Co-reporter:Zhongxi Xie, Xiaoran Deng, Bei Liu, Shanshan Huang, Pingan Ma, Zhiyao Hou, Ziyong Cheng, Jun Lin, and Shifang Luan
ACS Applied Materials & Interfaces September 13, 2017 Volume 9(Issue 36) pp:30414-30414
Publication Date(Web):August 23, 2017
DOI:10.1021/acsami.7b09124
Photoinduced reversible addition–fragmentation chain transfer (RAFT) polymerization generally adopts high-energy ultraviolet (UV) or blue light. In combination with photoredox catalyst, the excitation light wavelength was extended to the visible and even near-infrared (NIR) region for photoinduced electron transfer RAFT polymerization. In this report, we introduce for the first time a surface NIR-light-initiated RAFT polymerization on upconversion nanoparticles (UCNPs) without adding any photocatalyst and construct a functional inorganic core/polymer shell nanohybrid for application in cancer theranostics. The multilayer core–shell UCNPs (NaYF4:Yb/Tm@NaYbF4:Gd@NaNdF4:Yb@NaYF4), with surface anchorings of chain transfer agents, can serve as efficient NIR-to-UV light transducers for initiating the RAFT polymerization. A hierarchical double block copolymer brush, consisting of poly(acrylic acid) (PAA) and poly(oligo(ethylene oxide)methacrylate-co-2-(2-methoxy-ethoxy)ethyl methacrylate) (PEG for short), was grafted from the surface in sequence. The targeting arginine–glycine–aspartic (RGD) peptide was modified at the end of the copolymer through the trithiolcarbonate end group. After loading of doxorubicin, the UCNPs@PAA-b-PEG-RGD exhibited an enhanced U87MG cancer cell uptake efficiency and cytotoxicity. Besides, the unique upconversion luminescence of the nanohybrids was used for the autofluoresence-free cell imaging and labeling. Therefore, our strategy verified that UCNPs could efficiently activate RAFT polymerization by NIR photoirradiation and construct the complex nanohybrids, exhibiting prospective biomedical applications due to the low phototoxicity and deep penetration of NIR light.Keywords: cancer therapy; drug-delivery system; NIR light initiation; surface RAFT polymerization; upconversion nanoparticles;
Co-reporter:Xiaoming Liu, Weijie Xie, Ying Lü, Jingchun Feng, Xinghua Tang, Jun Lin, Yuhua Dai, Yu Xie, and Liushui Yan
Inorganic Chemistry November 20, 2017 Volume 56(Issue 22) pp:13829-13829
Publication Date(Web):October 30, 2017
DOI:10.1021/acs.inorgchem.7b01938
Up to now, orchestrating the coexistence of Eu2+ and Eu3+ activators in a single host lattice has been an extremely difficult task, especially for the appearance of the characteristic emission of Eu2+ and Eu3+ in order to generate white light. Nevertheless, here we demonstrate a new Eu2+/Eu3+ coactivated SrAl3BO7 nanocrystalline phosphor with abundant and excellent multichannel luminescence properties. A series of Eu2+/Eu3+ coactivated SrAl3BO7 nanocrystalline phosphors were prepared through a Pechini-type sol–gel method followed by a reduction process. With excitation of UV/NUV light, the prepared SrAl3BO7:Eu2+,Eu3+ phosphors show not only the characteristic f–f transitions of Eu3+ ion (5DJ → 7FJ,J′, J, J′ = 0–3), but also the 5d → 4f transitions of Eu2+ ion with comparable intensity from 400 to 700 nm in the whole visible spectral region. The luminescence color of the SrAl3BO7:Eu2+,Eu3+ phosphor can be tuned from blue, blue-green, white, and orange to orange-red by changing the excitation wavelength, the overall doping concentration of europium ions (Eu2+, Eu3+), and the relative ratio of Eu2+ to Eu3+ ions to some extent. A single-phase white-light emission has been realized in SrAl3BO7:Eu2+,Eu3+ phosphor. The obtained SrAl3BO7:Eu2+,Eu3+ phosphor has potential application in the area of NUV white-light-emitting diodes.
Co-reporter:Mengmeng Shang, Sisi Liang, Hongzhou Lian, and Jun Lin
Inorganic Chemistry June 5, 2017 Volume 56(Issue 11) pp:6131-6131
Publication Date(Web):May 8, 2017
DOI:10.1021/acs.inorgchem.7b00092
A series of Eu3+/Tb3+/Mn2+-ion-doped Ca19Ce(PO4)14 (CCPO) phosphors have been prepared via the conventional high-temperature solid-state reaction process. Under UV radiation, the CCPO host presents a broad blue emission band from Ce3+ ions, which are generated during the preparation process because of the formation of deficiency. The Eu3+-doped CCPO phosphors can exhibit magenta to red-orange emission as a result of the abnormal coexistence of Ce3+/Ce4+/Eu3+ and the metal–metal charge-transfer (MMCT) effect between Ce3+ and Eu3+. When Tb3+/Mn2+ are doped into the hosts, the samples excited with 300 nm UV light present multicolor emissions due to energy transfer (ET) from the host (Ce3+) to the activators with increasing activator concentrations. The emitting colors of CCPO:Tb3+ phosphors can be tuned from blue to green, and the CCPO:Mn2+ phosphors can emit red light. The ET mechanism from the host (Ce3+) to Tb3+/Mn2+ is demonstrated to be a dipole–quadrapole interaction for Ce3+ → Tb3+ and an exchange interaction for Ce3+ → Mn2+ in CCPO:Tb3+/Mn2+. Abundant emission colors containing white emission were obtained in the Tb3+- and Mn2+-codoped CCPO phosphors through control of the levels of doped Tb3+ and Mn2+ ions. The white-emitted CCPO:Tb3+/Mn2+ phosphor exhibited excellent thermal stability. The photoluminescence properties have shown that these materials might have potential for UV-pumped white-light-emitting diodes.
Co-reporter:Min Liu, Hui Liu, Shufen Sun, Xuejiao Li, Yanmin Zhou, Zhiyao Hou, and Jun Lin
Langmuir February 4, 2014 Volume 30(Issue 4) pp:1176-1182
Publication Date(Web):January 17, 2014
DOI:10.1021/la500131d
Porous hydroxyapatite (HAp) composite fibers functionalized with up-conversion (UC) luminescent and magnetic Na(Y/Gd)F4:Yb3+,Er3+ nanocrystals (NCs) have been fabricated via electrospinning. After transferring hydrophobic oleic acid-capped Na(Y/Gd)F4:Yb3+,Er3+ NCs into aqueous solution, these water-dispersible NCs were dispersed into precursor electrospun solution containing CTAB. Na(Y/Gd)F4:Yb3+,Er3+@HAp composite fibers were fabricated by the high temperature treatment of the electrospun Na(Y/Gd)F4:Yb3+,Er3+ NCs decorated precursor fibers. The biocompatibility test on MC 3T3-E1 cells using MTT assay shows that the HAp composite fibers have negligible cytotoxity, which reveals the HAp composite fibers could be a drug carrier for drug delivery. Because the contrast brightening is enhanced at increased concentrations of Gd3+, the HAp composite fibers can serve as T1 magnetic resonance imaging contrast agents. In addition, the composites uptaken by MC 3T3-E1 cells present the UC luminescent emission of Er3+ under the excitation of a 980 nm near-infrared laser. The above findings reveal Na(Y/Gd)F4:Yb3+,Er3+@HAp composite fibers have potential applications in drug storage/release and magnetic resonance/UC luminescence imaging.
Co-reporter:Jiating Xu, Piaoping Yang, Mingdi Sun, Huiting Bi, Bin Liu, Dan Yang, Shili Gai, Fei He, and Jun Lin
ACS Nano April 25, 2017 Volume 11(Issue 4) pp:4133-4133
Publication Date(Web):March 20, 2017
DOI:10.1021/acsnano.7b00944
Rare-earth-based upconversion nanotechnology has recently shown great promise for photodynamic therapy (PDT). However, the NIR-induced PDT is greatly restricted by overheating issues on normal bodies and low yields of reactive oxygen species (ROS, 1O2). Here, IR-808-sensitized upconversion nanoparticles (NaGdF4:Yb,Er@NaGdF4:Nd,Yb) were combined with mesoporous silica, which has Ce6 (red-light-excited photosensitizer) and MC540 (green-light-excited photosensitizer) loaded inside through covalent bond and electrostatic interaction, respectively. When irradiated by tissue-penetrable 808 nm light, the IR-808 greatly absorb 808 nm photons and then emit a broadband peak which overlaps perfectly with the absorption of Nd3+ and Yb3+. Thereafter, the Nd3+/Yb3+ incorporated shell synergistically captures the emitted NIR photons to illuminate NaGdF4:Yb,Er zone and then radiate ultrabright green and red emissions. The visible emissions simultaneously activate the dual-photosensitizer to produce a large amount of ROS and, importantly, low heating effects. The in vitro and in vivo experiments indicate that the dual-photosensitizer nanostructure has trimodal (UCL/CT/MRI) imaging functions and high anticancer effectiveness, suggesting its potential clinical application as an imaging-guided PDT technique.Keywords: bioimaging; dual-photosensitizer; IR-808; photodynamic therapy; upconversion;
Co-reporter:Ping’an Ma, Haihua Xiao, Chang Yu, Jianhua Liu, Ziyong Cheng, Haiqin Song, Xinyang Zhang, Chunxia Li, Jinqiang Wang, Zhen GuJun Lin
Nano Letters 2017 Volume 17(Issue 2) pp:
Publication Date(Web):January 31, 2017
DOI:10.1021/acs.nanolett.6b04269
Reactive oxygen species (ROS) plays a key role in therapeutic effects as well as side effects of platinum drugs. Cisplatin mediates activation of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX), which triggers oxygen (O2) to superoxide radical (O2•–) and its downstream H2O2. Through the Fenton’s reaction, H2O2 could be catalyzed by Fe2+/Fe3+ to the toxic hydroxyl radicals (•OH), which cause oxidative damages to lipids, proteins, and DNA. By taking the full advantage of Fenton’s chemistry, we herein demonstrated tumor site-specific conversion of ROS generation induced by released cisplatin and Fe2+/Fe3+ from iron-oxide nanocarriers with cisplatin(IV) prodrugs for enhanced anticancer activity but minimized systemic toxicity.Keywords: cisplatin; Drug delivery; Fenton’s reaction; iron oxide; reactive oxygen species;
Co-reporter:Lili Feng, Shili Gai, Fei He, Yunlu Dai, Chongna Zhong, Piaoping Yang, Jun Lin
Biomaterials 2017 Volume 147(Volume 147) pp:
Publication Date(Web):1 December 2017
DOI:10.1016/j.biomaterials.2017.09.011
Desirable nanosystem that could not only deliver drugs safely and effectively into tumor sites, but also be expected to serve as photosensitizer to realize the photodynamic therapeutic function, would be of great significance in the synergistic cancer therapy. To perform this task, a multifunctional nanosystem has been developed for markedly enhanced cancer therapeutic efficacy by loading chemotherapy agent (doxorubicin hydrochloride, DOX) and photosensitive drug chlorin e6 (Ce6) into the channels of mesoporous zirconium dioxide (ZrO2) layer which coats on Nd3+-doped upconversion nanoparticles (UCNPs). As a temperature sensitive phase change material (PCM), the loaded tetradecanol was served as switch for control release of DOX and reactive oxygen species (ROS) in the condition of enhanced temperature triggered by the near infrared (NIR) light irradiation. The hyperthermia generated from the UCNPs cores exposed to NIR laser could raise the temperature of tumor location to 47.8 °C. The as-synthesized UCNPs@ZrO2-Ce6/DOX/PCM nanosystem demonstrates an excellent in vivo synergistic effect by administrating into U14 tumor-bearing mice via intravenous injection, under mild NIR laser irradiation (0.5 W cm−2, 5 min break after 5 min irradiation). In a word, our experimental results indicate that the finely designed UCNPs@ZrO2-Ce6/DOX/PCM may act as an ideal nanoplatform for multiple imaging guided tumor therapy.
Co-reporter:Mengmeng Shang, Sisi Liang, Nianrui Qu, Hongzhou Lian, and Jun Lin
Chemistry of Materials 2017 Volume 29(Issue 4) pp:
Publication Date(Web):January 26, 2017
DOI:10.1021/acs.chemmater.6b05493
A series of promising cyan, green, and yellow emission (Ba, Sr)3(Si, Al)6(O, N)15:Eu2+ phosphors were synthesized by a Pechini-type sol–gel ammonolysis method. Variations in luminescence properties and crystal structure caused by the modification of phosphor composition were studied in detail. The prefired temperatures of the precursors play a key role in the process of forming the final products. Under UV light excitation, the as-prepared Ba3Si6O15:Eu2+ phosphor presents a strong cyan emission located at 498 nm. Moreover, the as-prepared oxynitride phosphors, Eu2+-activated (Ba1–ySry)3Si6–xAlxO15−μNδ (x = 0–1.2, y = 0–0.6), display a broader excitation band covering the entire visible region. Under blue light excitation, Ba3Si6–xAlxO15−μNδ:Eu2+ phosphors show a intense and narrow green emission at 520 nm, and the luminescent intensity can be enhanced by increasing Al content within a certain range. However, (Ba1–ySry)3Si6O15−μNδ:Eu2+phosphors exhibit green (520 nm) to yellow (554 nm) emission with increasing Sr content. Unexpectedly, Eu2+ doped Ba3Si6O9N4-type Ba3Si6O15−μNδ–1300 °C phosphor exhibits a bluish green emission and strong thermal quenching behavior. The (Ba1–ySry)3Si6–xAlxO15−μNδ:Eu2+ phosphors exhibit a small thermal quenching, and the quantum yields measured under 460 nm excitation could reach up to 89% for green Ba3Si6–xAlxO15−μNδ:Eu2+ phosphor and 71% for yellow (Ba1–ySry)3Si6xO15−μNδ:Eu2+ phosphor. White LEDs with tunable color temperature and higher color rendering index were fabricated by combining the prepared cyan Ba3Si6O15:Eu2+/green Ba2.91Eu0.09Si6–xAlxO15−μNδ (x = 0.06)/yellow (Ba0.97–ySry)3Eu0.09Si6O15−μNδ (y = 0.4) phosphor and a red phosphor with a UV or blue LED chip, indicating that they are promising phosphors for white LEDs.
Co-reporter:Bei Liu;Chunxia Li;Piaoping Yang;Zhiyao Hou
Advanced Materials 2017 Volume 29(Issue 18) pp:
Publication Date(Web):2017/05/01
DOI:10.1002/adma.201605434
808 nm-light-excited lanthanide (Ln3+)-doped nanoparticles (LnNPs) hold great promise for a wide range of applications, including bioimaging diagnosis and anticancer therapy. This is due to their unique properties, including their minimized overheating effect, improved penetration depth, relatively high quantum yields, and other common features of LnNPs. In this review, the progress of 808 nm-excited LnNPs is reported, including their i) luminescence mechanism, ii) luminescence enhancement, iii) color tuning, iv) diagnostic and v) therapeutic applications. Finally, the future outlook and challenges of 808 nm-excited LnNPs are presented.
Co-reporter:Bei Liu;Chunxia Li;Guanying Chen;Bin Liu;Xiaoran Deng;Yi Wei;Jun Xia;Bengang Xing;Ping'an Ma
Advanced Science 2017 Volume 4(Issue 8) pp:
Publication Date(Web):2017/08/01
DOI:10.1002/advs.201600540
Elaborately designed biocompatible nanoplatforms simultaneously achieving multimodal bioimaging and therapeutic functions are highly desirable for modern biomedical applications. Herein, uniform MoS2 nanoflowers with a broad size range of 80–180 nm have been synthesized through a facile, controllable, and scalable hydrothermal method. The strong absorbance of MoS2 nanoflowers at 808 nm imparts them with high efficiency and stability of photothermal conversion. Then a novel multifunctional composite of MoS2@Fe3O4-ICG/Pt(IV) (labeled as Mo@Fe-ICG/Pt) is designed by covalently grafting Fe3O4 nanoparticles with polyethylenimine (PEI) functionalized MoS2, and then loading indocyanine green molecules (ICG, photosensitizers) and platinum (IV) prodrugs (labeled as Pt(IV) prodrugs) on the surface of MoS2@Fe3O4. The resulting Mo@Fe-ICG/Pt nanocomposites can achieve excellent magnetic resonance/infrared thermal/photoacoustic trimodal biomaging as well as remarkably enhanced antitumor efficacy of combined photothermal therapy, photodynamic therapy, and chemotherapy triggered by a single 808 nm NIR laser, thus leading to an ideal nanoplatform for cancer diagnosis and treatment in future.
Co-reporter:Dan Yang;Guixin Yang;Piaoping Yang;Ruichan Lv;Shili Gai;Chunxia Li;Fei He
Advanced Functional Materials 2017 Volume 27(Issue 18) pp:
Publication Date(Web):2017/05/01
DOI:10.1002/adfm.201700371
Photodynamic therapy (PDT), as a minimally invasive and high-efficiency anticancer approach, has received extensive research attention recently. Despite plenty of effort devoted to exploring various types of photodynamic agents with strong near-infrared (NIR) absorbance for PDT and many encouraging progresses achieved in the area, effective and safe photodynamic photosensitizers with good biodegradability and biocompatibility are still highly expected. In this work, a novel nanocomposite has been developed by assembly of iron oxide (Fe3O4) nanoparticles (NPs) and Au nanoparticles on black phosphorus sheets (BPs@Au@Fe3O4), which shows a broad light absorption band and a photodegradable character. In vitro and in vivo assay indicates that BPs@Au@Fe3O4 nanoparticles are highly biocompatible and exhibit excellent tumor inhibition efficacy owing to a synergistic photothermal and photodynamic therapy mediated by a low-power NIR laser. Importantly, BPs@Au@Fe3O4 can anticipatorily suppress tumor growth by visualized synergistic therapy with the help of magnetic resonance imaging (MRI). This work presents the first combination application of the photodynamic and photothermal effect deriving from black phosphorus nanosheets and plasmonic photothermal effect from Au nanoparticles together with MRI from Fe3O4 NPs, which may open the new utilization of black phosphorus nanosheets in biomedicine, optoelectronic devices, and photocatalysis.
Co-reporter:Yi Wei;Xiaoran Deng;Zhongxi Xie;Xuechao Cai;Sisi Liang;Ping'an Ma;Zhiyao Hou;Ziyong Cheng
Advanced Functional Materials 2017 Volume 27(Issue 39) pp:
Publication Date(Web):2017/10/01
DOI:10.1002/adfm.201703535
AbstractOrganic/inorganic hybrid lead halide perovskites are promising optoelectronic materials due to their unique structure, excellent properties, and fascinating potential applications in lighting, photovoltaic, etc. However, perovskite materials are very sensitive to moisture and polar solvent, which greatly hinders their practical applications. Here, highly luminescent perovskite–polystyrene composite beads with uniform morphology are prepared via a simple swelling–shrinking strategy. This process is carried out only in nonpolar toluene and hexane without the addition of any polar reagents. As a result, the as-prepared composite beads not only retain high luminescence but also exhibit superior water-resistant property. The composites emit strong luminescence after being immersed into water over nine months. Moreover, even in some harsh environments such as acid/alkali aqueous solution, phosphate buffer solution, and Dulbecco's modified eagle medium biological buffers, they still preserve high luminescence. The applications in light-emitting diodes and cellular labeling agents are also carried out to demonstrate their ultrastability.
Co-reporter:Bin Liu;Xiaoran Deng;Zhongxi Xie;Ziyong Cheng;Piaoping Yang
Advanced Materials 2017 Volume 29(Issue 36) pp:
Publication Date(Web):2017/09/01
DOI:10.1002/adma.201604878
Oleic acid (OA) and/or oleylamine (OAm) are generally used as the surface ligands for stabilization of inorganic nanocrystals (NCs). The hydrophobic and inert surface of the NCs limits their applications such as in biomedical areas. Hence, surface modifications are essential in many physical and chemical processes. Here, a facile and versatile strategy is reported for the modification of NCs by ultraviolet-induced thiol–ene chemistry, in which thiol-terminated poly(ethylene glycol) (HSPEG) and its derivatives can react directly with double bonds in OA/OAm ligands to form covalent linking within one step. Through this strategy, various hydrophobic NCs with different compositions and morphologies are able to be transferred into water combining with functionalization of active groups. As a proof-of-concept, this strategy is successfully used to construct a sensor for detecting avidin based on upconverting luminescence analysis. Therefore, this strategy provides a new tool for designing and tuning the surface properties of NCs for different applications.
Co-reporter:Xiaoran Deng;Kai Li;Xuechao Cai;Bin Liu;Yi Wei;Kerong Deng;Zhongxi Xie;Zhijian Wu;Ping'an Ma;Zhiyao Hou;Ziyong Cheng
Advanced Materials 2017 Volume 29(Issue 36) pp:
Publication Date(Web):2017/09/01
DOI:10.1002/adma.201701266
It is of great importance in drug delivery to fabricate multifunctional nanocarriers with intelligent targeting properties, for cancer diagnosis and therapy. Herein, hollow-structured CuS@Cu2S@Au nanoshell/satellite nanoparticles are designed and synthesized for enhanced photothermal therapy and photoswitchable targeting theranostics. The remarkably improved photothermal conversion efficiency of CuS@Cu2S@Au under 808 nm near-infrared (NIR) laser irradiation can be explained by the reduced bandgap and more circuit paths for electron transitions for CuS and Cu2S modified with Au nanoparticles, as calculated by the Vienna ab initio simulation package, based on density functional theory. By modification of thermal-isomerization RGD targeting molecules and thermally sensitive copolymer on the surface of nanoparticles, the transition of the shielded/unshielded mode of RGD (Arg-Gly-Asp) targeting molecules and shrinking of the thermally sensitive polymer by NIR photoactivation can realize a photoswitchable targeting effect. After loading an anticancer drug doxorubicin in the cavity of CuS@Cu2S@Au, the antitumor therapy efficacy is greatly enhanced by combining chemo- and photothermal therapy. The reported nanohybrid can also act as a photoacoustic imaging agent and an NIR thermal imaging agent for real-time imaging, which provides a versatile platform for multifunctional theranostics and stimuli-responsive targeted cancer therapy.
Co-reporter:Yinyin Chen, Xiaoran Deng, Chunxia Li, Fei He, Bei Liu, Zhiyao Hou, Ziyong Cheng, Bengang Xing, Jun Lin
Nanomedicine: Nanotechnology, Biology and Medicine 2017 Volume 13, Issue 3(Issue 3) pp:
Publication Date(Web):1 April 2017
DOI:10.1016/j.nano.2016.12.004
Anticancer drug doxorubicin hydrochloride (DOX)-loaded photothermal nanocomposite MnFe2O4@mSiO2 with magnetic targeting and T1/T2-weighted dual-mode magnetic resonance imaging of MnFe2O4 core and NIR/pH-coupling sensitive mesoporous silica shell nanocarriers was designed and synthesized successfully. The anticancer drug DOX can be absorbed into mesoporous layer of MnFe2O4@mSiO2 nanocomposite, which shows obvious photothermal/chemo dual-modal synergistic therapies triggered by NIR/pH. Under 808 nm irradiation, MnFe2O4 can transform light into thermo, which can not only ablate tumor cells directly but also promote chemotherapy drugs releasing from mesoporous layer to kill tumor cells. The lower pH can also promote DOX releasing from mesoporous layer to enhance tumor inhibitory effect. It is confirmed that biocompatible DOX-MnFe2O4@mSiO2 nanocomposites can act as a potential multifunctional platform for effective magnetic targeting photothermal/chemo dual-modal synergistic therapies with enhanced anti-tumor efficacy and T1/T2-weighted dual-mode magnetic resonance imaging (MRI) applications in vivo.DOX-MnFe2O4@mSiO2 nanocomposites can act as a multifunctional platform for effective magnetic targeting photothermal/chemo dual-modal synergistic therapies and T1/T2-weighted dual-mode magnetic resonance imagings applications in vivo.Download high-res image (85KB)Download full-size image
Co-reporter:Kai Li, Hongzhou Lian, Yanqiu Han, Mengmeng Shang, Rik Van Deun, Jun Lin
Dyes and Pigments 2017 Volume 139(Volume 139) pp:
Publication Date(Web):1 April 2017
DOI:10.1016/j.dyepig.2016.12.059
•BaLu6(Si2O7)2(Si3O10):Ce3+,Tb3+ phosphors were synthesized for the first time.•Tunable color from blue to green was realized via energy transfer from Ce3+ to Tb3+.•The BaLu6(Si2O7)2(Si3O10):Ce3+,Tb3+ phosphors exhibited good thermal stability.•BaLu6(Si2O7)2(Si3O10):Ce3+,Tb3+ is a promising blue-green phosphor for LED.A series of novel blue-green emission phosphors BaLu6(Si2O7)2(Si3O10):Ce3+,Tb3+ (BLSO:Ce3+,Tb3+) were synthesized via the high-temperature solid-state reaction route. Many characterizations such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) were conducted to analyze the phase and structure of as-prepared samples. Photoluminescence (PL) properties illustrated that Ce3+ singly doped BLSO can produce a broad band ranging from 365 to 550 nm upon UV excitation, which overlapped the excitation spectrum of Tb3+ monitored at 550 nm emission. Energy transfer phenomenon from Ce3+ to Tb3+ in this kind of phosphor was demonstrated from the variations of emission spectra and the decrease of Ce3+ fluorescent decay lifetime in Ce3+-Tb3+ co-doped BLSO, based on which the emission color can be tuned from bright blue to green upon UV excitation. The energy transfer mechanism from Ce3+ to Tb3+ was determined to be electric dipole-quadrupole interaction. Moreover, the temperature-dependent PL of representative BLSO:0.18Ce3+,1.00Tb3+ was supplied in this manuscript, which indicated the good thermal stability of this kind of phosphor. The results show that BLSO:Ce3+,Tb3+ phosphors can be as a potential candidate of blue-green component in phosphor-converted UV LEDs.A series of novel blue-green emission phosphors BaLu6(Si2O7)2(Si3O10):Ce3+,Tb3+ (BLSO:Ce3+,Tb3+) have been synthesized and investigated.Download high-res image (201KB)Download full-size image
Co-reporter:Yi Wei;Hui Jia;Hui Xiao;Meng Meng Shang;Chun Che Lin;Chaochin Su;Ting-Shan Chan;Guo Gang Li
RSC Advances (2011-Present) 2017 vol. 7(Issue 4) pp:1899-1904
Publication Date(Web):2017/01/04
DOI:10.1039/C6RA26869B
Currently, developing single-phased white light phosphors based on a single-doped activator is an efficient approach to blends of bicolor/tricolor phosphors for realizing phosphor-converted white light emitting diodes (pc-WLEDs) with a high color rendering index (CRI) and low correlated color temperature (CCT). Here, we present high CRI (Ra = 93–95) and low CCT (3500–6000 K) white lights by cosubstituting [Ca2+–P5+] for [La3+–Si4+] in the solid solution Ca(8→2)La(2→8)(PO4)6−x(SiO4)xO2:Eu2+/Eu3+ (CLPSO_Eu). The results are attributed to the presence of multi Ca2+ sites due to possible mixing nanophases and the simultaneous occupancy of Ca2+ and La3+ sites by Eu, resulting in the mixing of blue (466 nm) and green emissions (540 nm) for Eu2+, and red emission (613 nm) for Eu3+, which were perfectly confirmed using X-ray Rietveld refinement, photoluminescence spectra and extended X-ray absorption fine structure. These findings not only imply that the as-prepared CLPSO_Eu are promising single-phased white light phosphor for near-UV based WLEDs but also offer a novel avenue to design high CRI white light phosphors based on a tunable Eu2+/Eu3+.
Co-reporter:Binbin Ding;Chang Yu;Chunxia Li;Xiaoran Deng;Jianxun Ding;Ziyong Cheng;Bengang Xing;Ping'an Ma
Nanoscale (2009-Present) 2017 vol. 9(Issue 43) pp:16937-16949
Publication Date(Web):2017/11/09
DOI:10.1039/C7NR04166G
Photothermal therapy (PTT) has attracted considerable attention in cancer treatment. Herein, the facile synthesis of copper iron sulfide (chalcopyrite, CuFeS2) nanoplates (NPs) with well-defined shape was achieved by a template-mediated method. Chitosan (CS), a linear cationic polysaccharide, was used to improve the physiological stability and biocompatibility. CuFeS2 NPs with strong near-infrared (NIR) absorbance enabled contrasts in photothermal and photoacoustic (PA) imaging. In vitro and in vivo tumor ablation studies further demonstrated that CS-functionalized CuFeS2 (CuFeS2-CS) NPs could convert 808 nm NIR light into heat for PTT with a photothermal conversion efficiency up to 30.5%, which was clearly higher than that of CuS NPs (only 21.4%). Furthermore, CuFeS2-CS NPs could also load cis-platinum pro-drug (CuFeS2-CS-Pt), and CuFeS2-CS-Pt showed a better synergistic therapeutic effect with respect to either chemotherapy or PTT.
Co-reporter:Mengmeng Zhu;Yuexiao Pan;Luqing Xi;Hongzhou Lian
Journal of Materials Chemistry C 2017 vol. 5(Issue 39) pp:10241-10250
Publication Date(Web):2017/10/12
DOI:10.1039/C7TC03805D
Mn4+-activated red phosphors have attracted considerable attention as promising red components in the spectra of white light emitting diodes (WLEDs) to achieve warm white light with superior performance. Herein, a novel red phosphor based on Mn4+-doped dodec-fluoride Li3Na3Al2F12:Mn4+ (LNAF:Mn) with microcubic morphology was obtained at room temperature. To elucidate the underlying relationship between the crystal structure and photoluminescence of LNAF:Mn, a phosphor LiNa2AlF6:Mn4+ with similar composition has been prepared, and their morphology and optical properties were comparatively investigated. The emission of the red phosphor LNAF:Mn is blue shifted compared to LiNa2AlF6:Mn4+ suggesting that the chromaticity coordinates of LANF:Mn are closer to the ideal red point (0.67, 0.33). The luminescence properties of LNAF:Mn have been improved by optimizing the synthetic conditions. This work exhibits a strategy to explore a novel Mn4+-doped fluoride except for the identified hexa-fluorides. Employing the as-prepared red LNAF:Mn as a red component, a high-performance WLED with a correlated color temperature (CCT) of 3874 K and a color rendering index (CRI) of 90.6 was obtained. This suggests the phosphor is a potential commercial red phosphor in warm WLEDs.
Co-reporter:Luqing Xi;Yuexiao Pan;Mengmeng Zhu;Hongzhou Lian
Journal of Materials Chemistry C 2017 vol. 5(Issue 36) pp:9255-9263
Publication Date(Web):2017/09/21
DOI:10.1039/C7TC02996A
A kind of red-emitting phosphor NaKSnF6:Mn4+ (NKSF:Mn) has been obtained from NaF and KF with a certain molecular ratio in HF solution at room temperature. The phosphor NKSF:Mn exhibits superior optical properties including high color purity with narrow-band emissions as well as better chromaticity coordinates compared to the red phosphors Na2SnF6:Mn4+ (NSF:Mn) and K2SnF6·H2O:Mn4+ (KSFH:Mn). The composition and structure of NKSF:Mn have been identified by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). The formation mechanism of NKSF:Mn is discussed and the morphology, thermal stability, and optical properties of NKSF:Mn have been investigated. The luminescence intensity of NKSF:Mn has been improved by optimizing synthetic parameters. A white light-emitting diode (WLED) fabricated using a blue GaN chip, a yellow YAG:Ce phosphor, and the as-prepared red phosphor NKSF:Mn exhibits superior warm white light with a color rendering index (CRI) of 90.3 at a correlated color temperature (CCT) of 3746 K.
Co-reporter:Bo Teng;Ping'an Ma;Chang Yu;Xinyang Zhang;Qingjie Feng;Lianji Wen;Chunxia Li;Ziyong Cheng;Dayong Jin
Journal of Materials Chemistry B 2017 vol. 5(Issue 2) pp:307-317
Publication Date(Web):2017/01/04
DOI:10.1039/C6TB02360F
Eukaryotic translation initiation factor (eIF) 4E is a valuable marker in cancer prognostics in many human cancers. Silencing eIF4E via delivery of siRNA may be able to overcome chemoresistance. Cisplatin, used as a first-line anti-cancer reagent, has been widely accepted for its great success in clinical applications but it is restricted due to severe side effects such as nephrotoxicity, peripheral neuropathy, and hearing loss. Moreover, platinum drug resistance is a major obstacle to its use. Platinum(IV) prodrugs (denoted as Pt(IV)) which could be reduced to Pt(II) by various reductants, including mercaptan and glutathione, within cancer cells have very limited toxicity and might overcome platinum resistance because of their chemical inertness. Moreover, combinational therapies that could sensitize the cancer cells to Pt drugs have received great attention nowadays around the world. Here we report a simple and effective upconversion nanoparticle carrier system loaded with both eIF4E siRNA and Pt(IV). We find that this theranostic system could sensitize laryngeal cancer cells to cisplatin based chemotherapy and allow bioimaging both in vitro and in vivo.
Co-reporter:Kerong Deng;Yinyin Chen;Chunxia Li;Xiaoran Deng;Zhiyao Hou;Ziyong Cheng;Yanqiu Han;Bengang Xing
Journal of Materials Chemistry B 2017 vol. 5(Issue 9) pp:1803-1814
Publication Date(Web):2017/03/01
DOI:10.1039/C6TB03233H
Near-infrared (NIR) light induced phototherapy has attracted considerable attention due to its deep therapeutic depth. To improve the therapeutic outcome and address non-selective side effects, the combination of complementary phototherapeutic strategies in a single nanoagent with precise targeting ability may provide an effective approach for cancer therapy. Thus we have developed an 808 nm NIR light triggered nanosystem based on IR806 dye functionalized MnFe2O4 (MFO-IR) for synchronous magnetic targeted and magnetic resonance (MR) imaging guided in vivo photodynamic/photothermal synergistic therapy. In this construction strategy, carboxylic acid functionalized NIR dye IR806 is explored as an 808 nm NIR-excited photosensitizer (PS) for the first time, which can also provide a conjugation site for MnFe2O4 nanoparticles (MFO NPs). Here, monodisperse MFO NPs have multiple capacities as dye carriers, targeting ligands, MRI contrast agents and photothermal agents. MFO-IR nanocomposites (NCs) with negligible toxicity present efficient NIR-mediated photothermal damage and ROS cytotoxicity via the relevant in vitro experimental investigations. With ideal magnetic targeting effects and remarkable NIR light-responsive properties, these MFO-IR NCs exhibit high in vivo tumor localization and could destroy subcutaneous solid tumors completely under an external magnetic field and 808 nm laser irradiation. Consequently, this magnetic nanosystem has great potential for simultaneous diagnosis and precise cancer phototherapy.
Co-reporter:Dongmei Wang;Bei Liu;Zewei Quan;Chunxia Li;Zhiyao Hou;Bengang Xing
Journal of Materials Chemistry B 2017 vol. 5(Issue 12) pp:2209-2230
Publication Date(Web):2017/03/22
DOI:10.1039/C6TB03117J
In recent years, near-infrared (NIR) light, as a powerful means of external stimulus, has attracted widespread attention in the field of tumor research. On one hand, NIR light-excited rare earth upconversion nanoparticles (UCNPs) have presented unique features in multimodal bioimaging, energy conversion and photocontrolled drug delivery. On the other hand, NIR-light-triggered photothermal therapy (PTT) is a minimally invasive approach in the fight against tumors, owing to its high spatial resolution, economic viability and improved target selectivity. Thus, the marrying of UCNPs and NIR photothermal agents could open new avenues in the construction of theranostic nanoplatforms. This review primarily focuses on the new advances in the design and the therapeutic applications of multifunctional UCNPs–NIR absorber nanoplatforms. The future challenges and prospects in this field are also addressed.
Co-reporter:Sisi Liang;Mengmeng Shang;Hongzhou Lian;Kai Li;Yang Zhang
Journal of Materials Chemistry C 2017 vol. 5(Issue 11) pp:2927-2935
Publication Date(Web):2017/03/16
DOI:10.1039/C6TC05499D
In order to improve the quality of lighting and display devices based on InGaN blue chips, blue light excitable red phosphor is an essential component. Here, we prepared a series of efficient red emitting phosphors of Mg14Ge5O24 doped with different concentrations of Mn4+ based on a conventional solid-state reaction. Crystal structure, composition, morphology, and luminescence properties of samples were characterized by utilizing Rietveld refinement, X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and PL quantum yields (QYs). Moreover, reflectance spectra, temperature-dependent photoluminescence behavior, and the fabricated WLEDs performances were studied in detail. An absolute photoluminescence quantum yield as high as 81% was obtained for the Mg14Ge5(1–0.2%)O24:0.2%Mn4+ phosphor with good thermal stability. The fabricated WLED with CCT = 2864 K and Ra = 80.6 was attained by combining the prepared red phosphor and YAG yellow phosphor with a blue LED chip, which was superior to the conventional YAG-type WLED. All the results indicate that Mg14Ge5O24:Mn4+ is a promising phosphor and widens the horizon for materials in WLED applications.
Co-reporter:Yunlu Dai;Huiting Bi;Xiaoran Deng;Chunxia Li;Fei He;Ping'an Ma;Piaoping Yang
Journal of Materials Chemistry B 2017 vol. 5(Issue 11) pp:2086-2095
Publication Date(Web):2017/03/15
DOI:10.1039/C7TB00224F
The design of stimuli-responsive drug delivery systems has attracted much attention to improve therapeutic efficacy for clinical applications. Here an 808 nm NIR light responsive dual-drug system was designed for cancer treatment both in vitro and in vivo. Mesoporous silica coated NaYF4:Yb0.4/Tm0.02@NaGdF4:Yb0.1@NaNdF4:Yb0.1 (UCNPs) with a core-shell structure (labeled as UCNPs@mSiO2) was prepared and loaded with the antitumor drug doxorubicin (DOX). The surface of the composite was functionalized with β-cyclodextrin rings bridged by the light cleavable platinum(IV) pro-drug, thus blocking DOX inside the mesopores of silica. When excited by 808 nm NIR light, the emitted UV light from the UCNPs was used to activate the platinum(IV) pro-drug to gain higher toxicity platinum(II) complexes and open the mesopores of silica (at the same time) to release DOX molecules. Both DOX and platinum(II) complexes can kill cancer cells. This dual-drug delivery system may represent a new avenue for the application of UCNPs in photoactivated cancer therapy.
Co-reporter:Luqing Xi;Yuexiao Pan;Mengmeng Zhu;Hongzhou Lian
Dalton Transactions 2017 vol. 46(Issue 40) pp:13835-13844
Publication Date(Web):2017/10/17
DOI:10.1039/C7DT03107F
A novel red phosphor, NaHF2:Mn4+ (NHF:Mn), was obtained via substituting Na+ located at the center of the octahedron coordinated with six F− ions with Mn4+ in the host lattice of NHF. The phase purity and the exact composition of the obtained NHF:Mn were confirmed by X-ray powder diffraction (XRD), Rietveld refinement, energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), and infrared (IR) spectroscopy, respectively. The luminescence intensity of NHF:Mn was enhanced by optimizing the synthetic conditions. A series of warm white light-emitting diodes (WLEDs) with a color rendering index (CRI) higher than 88.0 and correlated color temperatures (CCT) between 3146 and 5172 K were obtained by encapsulating the as-prepared red phosphor NHF:Mn with the yellow one Y3Al5O12:Ce3+ (YAG:Ce) on blue chips. The advantage of the synthetic strategy to obtain NHF:Mn can be extended to develop novel Mn4+ doped red phosphors via substituting for central ions with unequal electric charge in the centers of octahedra.
Co-reporter:Jiating Xu, Ye Kuang, Ruichan Lv, Piaoping Yang, Chunxia Li, Huiting Bi, Bin Liu, Dan Yang, Yunlu Dai, Shili Gai, Fei He, Bengang Xing, Jun Lin
Biomaterials 2017 Volume 130(Volume 130) pp:
Publication Date(Web):1 June 2017
DOI:10.1016/j.biomaterials.2017.03.041
Optimal nano-sized drug carrier requires long blood circulation, selective extravasation, and efficient cell uptake. Here we develop a charge-convertible nanoplatform based on Pt(IV) prodrug loaded NaYF4:Yb,Tm upconversion nanoparticles (UCNs), followed by coating a layer of PEG-PAH-DMMA polymer (UCNs-Pt(IV)@PEG-PAH-DMMA). The polymer endows the platform with high biocompatibility, initial nano-size for prolonged blood circulation and selective extravasation. Especially, the anionic polymer can response to the mild acidic stimulus (pH ∼6.5) of tumor extracellular microenvironment and experience charge-shifting to a cationic polymer, resulting in electrostatic repulsion and releases of positive UCNs-Pt(IV). The positive UCNs-Pt(IV) nanoparticles have high affinity to negative cell membrane, leading to efficacious cell internalization. Simultaneously, the ultraviolet (UV) light emitted from UCNs upon near-infrared (NIR) light irradiation, together with the reductive glutathione (GSH) in cancer cells efficiently activate the Pt(IV) prodrug to highly cytotoxic Pt(II), realizing NIR photon improved chemotherapy. The experimental results reveal the charge convertibility, low adverse effect and markedly enhanced tumor ablation efficacy upon NIR laser irradiation of this smart nanoplatform. Moreover, combining the inherent upconversion luminescence (UCL) and computed tomography (CT) imaging capabilities, an alliance of cancer diagnosis and therapy has been achieved.Download high-res image (340KB)Download full-size image
Co-reporter:Ruichan Lv, Dan Yang, Piaoping Yang, Jiating Xu, Fei He, Shili Gai, Chunxia Li, Yunlu Dai, Guixin Yang, and Jun Lin
Chemistry of Materials 2016 Volume 28(Issue 13) pp:4724
Publication Date(Web):June 15, 2016
DOI:10.1021/acs.chemmater.6b01720
A proper photosensitizer and increased penetration depth are still two major challenges in photodynamic therapy (PDT). The conventional ultraviolet/visible irradiation light has low tissue penetration, which thus limits its clinical application. Herein, we for the first time designed a novel multifunctional composite by integrating NaGdF4:Yb,Er@Yb@Nd@Yb upconversion nanoparticles (UCNPs) and black phosphorus sheets (BPS) for a single 808 nm laser light-mediated PDT. UCNPs, which served as the energy donor, were modified with poly(acrylic acid), and the BPS were stabilized by the PEG-NH2; then the two counterparts were integrated into the UCNPs–BPS composite via electrostatic interaction. Under 808 nm near-infrared light irradiation, the composite exhibits excellent antitumor efficiency because of the large amount of reactive oxygen species generated compared with those under 650 and 980 nm irradiations with the same pump power, which has evidently been confirmed by in vitro and in vivo results. In particular, our work may pave the way for the wide application of black phosphorus-based materials in theranostics.
Co-reporter:Lili Feng, Fei He, Bin Liu, Guixin Yang, Shili Gai, Piaoping Yang, Chunxia Li, Yunlu Dai, Ruichan Lv, and Jun Lin
Chemistry of Materials 2016 Volume 28(Issue 21) pp:7935
Publication Date(Web):October 10, 2016
DOI:10.1021/acs.chemmater.6b03598
Exploring novel photosensitizer (PS) with good stability and high light converting efficiency and designing novel structure to integrate deep penetrating near-infrared (NIR) light excitable up-conversion nanoparticles (UCNPs) and PS into one system are highly fascinating in the photodynamic therapy (PDT) field. In this study, a novel core–shell structured platform (UCNPs@g-C3N4–PEG) with all-in-one “smart” functions for simultaneous photodynamic therapy, photothermal therapy (PTT), and trimodal imaging properties has been rationally designed and fabricated. This system is composed of a core–shell–shell structured NaGdF4:Yb/Tm@NaGdF4:Yb@NaNdF4:Yb up-conversion luminescence (UCL) core and photoactive graphitic-phase carbon nitride (g-C3N4) mesoporous shell closely coated on individual core. This designed structure allows large specific surface area, high loading amount, close proximity to the UCL core, and almost no leakage of g-C3N4 PS, thus ensuring sufficient reactive oxygen species (ROS) to damage tumor cells. Excitation by 808 nm NIR light, the emitted ultraviolet, and visible light can activate g-C3N4 to generate significant amount of ROS and the doped Nd3+ ions give rise to obvious thermal effect, which leads to excellent antitumor efficiency due to the combined PDT and PTT effect. Considering the trimodal imaging properties (UCL, computed tomography, and magnetic resonance imaging), we achieved an imaging guided cancer phototherapy motivated by a single NIR laser.
Co-reporter:Bei Liu, Chunxia Li, Bengang Xing, Piaoping Yang and Jun Lin
Journal of Materials Chemistry A 2016 vol. 4(Issue 28) pp:4884-4894
Publication Date(Web):21 Jun 2016
DOI:10.1039/C6TB00799F
Integrated theranostic nanosystems that combine therapeutic methods with suitable medical imaging modality are highly needed in the improvement of cancer theranostic approaches. Herein, polydopamine (PDA)-shelled NaYF4:Yb,Er@NaYF4:Yb nanoparticles (UCNPs) capable of loading indocyanine green (ICG) molecules via electrostatic adsorption, hydrophobic interaction and π–π stacking were successfully designed and synthesized (UCNPs@PDA-ICG, denoted as UPI) for upconversion imaging and combined photothermal/photodynamic therapy (PTT/PDT) with enhanced antitumor efficacy. We have found that ICG in this novel anticancer nanoplatform can be triggered impressively by 808-nm irradiation to produce both a photothermal effect and cytotoxic reactive oxygen species (ROS), thus achieving a good PTT/PDT synergistic effect. Notably, compared with free ICG molecules, UPI nanocomposites show much higher photostability and thermal stability. Both in vitro and in vivo experiments show that the as-obtained UPI can ablate cancer cells effectively with 808-nm irradiation, revealing their great potential as a NIR-mediated dual-modal therapeutic platform. Meanwhile, the core of UCNPs can be used for UCL imaging. All these results demonstrate great potentiality of UPI as a novel type of theranostic agent for the treatment of tumors.
Co-reporter:Sisi Liang, Mengmeng Shang, Hongzhou Lian, Kai Li, Yang Zhang and Jun Lin
Journal of Materials Chemistry A 2016 vol. 4(Issue 26) pp:6409-6416
Publication Date(Web):13 Jun 2016
DOI:10.1039/C6TC01813K
In order to get efficient phosphors used in WLEDs to cover the shortage of red emission, highly saturated rare-earth-free red phosphors MGe4O9:Mn4+ (M = Sr, Ba) have been successfully fabricated by a solid state method at 1100 °C. The crystal structure properties including the phase purity were analyzed by means of X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Photoluminescence absolute quantum efficiencies as well as lifetimes were utilized to characterize samples. As for the photoluminescence properties, the excitation spectra of samples exhibit two broad absorption bands with peaks at about 300 nm and 430 nm, which could be excited by near-UV/blue LED excitation. The emission spectra exhibit sharp peaks ranging from 600 nm to 700 nm due to the 4Eg → 4A2g transition of Mn4+ ions. The optimal Mn4+ doping concentrations in both the SrGe4O9 and BaGe4O9 host are determined to be 0.5 mol%. The critical energy transfer distances of these phosphors are calculated to be about 19 Å, and the concentration quenching mechanism is proved to be the dipole–dipole interaction. With increasing temperature, the luminescence of MGe4O9:Mn4+ (M = Sr, Ba) phosphors gradually decreases and the BaGe4O9:Mn4+ sample with the quenching temperature (T0.5) of about 180 °C has better thermal stability than SrGe4O9:Mn4+ with T0.5 of about 100 °C. Based on a combination of a blue LED chip, YAG:Ce3+ and MGO:0.5%Mn4+ red phosphors, the warm WLED is fabricated to explore its possible application as a warm white light-emitting diode.
Co-reporter:Kai Li, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2016 vol. 4(Issue 24) pp:5507-5530
Publication Date(Web):18 Apr 2016
DOI:10.1039/C6TC00436A
Utilizing energy transfer (ET) between the sensitizer and acceptor in phosphors is a good way to obtain tunable emission color. Therefore, many researchers have devoted their interest to design phosphors with different emission colors via their energy transfer properties. It is well known that Ce3+ and Bi3+ are good sensitizers, while Mn2+, Dy3+, Eu3+ and Sm3+ can be useful activators. Further, Eu2+ and Tb3+ can be both good sensitizers and activators. Therefore, herein we summarise many recent ET systems consisting of Eu2+–Mn2+/Tb3+, Eu2+–Tb3+–Mn2+/Eu3+/Sm3+, Ce3+–Mn2+/Tb3+/Dy3+/Eu2+, Ce3+–Tb3+–Mn2+/Eu3+/Sm3+, Bi3+–Eu3+/Sm3+ and Tb3+–Eu3+/Sm3+, which show tunable emission color from ultraviolet to blue and green, blue to green, yellow, orange and pink/red, cyan to green, orange and pink/red, and green to yellow/orange and red. Based on this summary, this review will be a good reference to benefit the design and investigation of phosphors potentially applied in FEDs and LEDs with ET.
Co-reporter:Kai Li, Sisi Liang, Hongzhou Lian, Mengmeng Shang, Bengang Xing and Jun Lin
Journal of Materials Chemistry A 2016 vol. 4(Issue 16) pp:3443-3453
Publication Date(Web):17 Mar 2016
DOI:10.1039/C6TC00579A
A variety of Ce3+ and Tb3+-doped BaLu2Si3O10 (BLSO) phosphors were synthesized via the high-temperature solid-state reaction method. Many technologies, such as X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), solid-state NMR, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) measurements, were used to characterize the as-prepared samples. Lu4Si2O7N2 was generated when N3− replaced O2− in BLSO:Ce3+, which resulted in a shift of the emission band from the blue (423 nm) to the cyan (460 nm) region under UV excitation. It was speculated that energy transfer occurred in Ce3+ and Tb3+ co-doped BLSO via the spectral overlap between Ce3+ emission and Tb3+ excitation in singly-doped BLSO, demonstrated by the variation in the emission spectra and the decrease in the Ce3+ fluorescent lifetimes in Ce3+ and Tb3+ co-doped BLSO, which resulted in a color change from blue to green when the concentration ratio of Ce3+/Tb3+ in BLSO:Ce3+,Tb3+ was adjusted. The energy transfer mechanism was confirmed to be electric dipole–quadrupole interaction. Moreover, quantum yields (QYs), Commission Internationale de l'Eclairage (CIE) chromaticity coordinates and temperature-dependent PL properties have also been investigated in detail. The results show the potential of BLSO:Ce3+,Tb3+ compounds as candidates for phosphors in phosphor-converted LEDs.
Co-reporter:Ying Tian, Yi Wei, Yun Zhao, Zewei Quan, Guogang Li and Jun Lin
Journal of Materials Chemistry A 2016 vol. 4(Issue 6) pp:1281-1294
Publication Date(Web):30 Dec 2015
DOI:10.1039/C5TC03482E
A series of Ca5(PO4)3Cl (CPOCl):Ce3+/Eu2+,Tb3+/Mn2+ phosphors with apatite structures have been prepared via the Pechini sol–gel process. The structure refinement indicates that the as-prepared phosphors crystallized in a hexagonal phase with the space group of P63/m (176), and there are two kinds of cation sites (4f and 6h) in the host lattice to accommodate the doping ions. The emissions of Eu2+ and Ce3+ at different lattice sites in the CPOCl host have been identified and discussed. The red shifted emission of CPOCl:Ce3+ with increasing Ce3+ doping concentrations has been explained, which is mainly attributed to the occupation of 6h sites of Ce3+ ions at a high doping level. In addition, the transformation from chlorapatite structures to oxyapatite structures driven by charge balance with Ce3+ concentrations also contributes to this red shift. When codoping Tb3+/Mn2+ ions into these cation sites, efficient energy transfers from Ce3+/Eu2+ ions to Tb3+/Mn2+ ions were observed, and the corresponding energy transfer mechanisms have been revealed. Under 340–420 nm near-ultraviolet light (n-UV) excitation, highly efficient blue-green tunable emission from Ce3+/Eu2+ ions to Tb3+ ions and single-phase white emission from Ce3+, Mn2+-codoped CPOCl can be obtained. In addition, the thermal stability of CPOCl:Ce3+/Eu2+,Tb3+/Mn2+ phosphors has been investigated systematically. Based on these experimental results, the as-prepared CPOCl:Ce3+/Eu2+,Tb3+/Mn2+ phosphors can act as potential color-tunable and single-phase white emission phosphors for possible applications in n-UV based white LEDs.
Co-reporter:Bei Liu, Xinyang Zhang, Chunxia Li, Fei He, Yinyin Chen, Shanshan Huang, Dayong Jin, Piaoping Yang, Ziyong Cheng and Jun Lin
Nanoscale 2016 vol. 8(Issue 25) pp:12560-12569
Publication Date(Web):29 Oct 2015
DOI:10.1039/C5NR06322A
The combination of multi-theranostic modes in a controlled fashion has received tremendous attention for the construction of cooperative therapeutic systems in nanomedicine. Herein, we have synthesized a smart magnetically targeted nanocarrier system, Cu9S5@mSiO2@Fe3O4-PEG (labelled as CMF), which integrates NIR triggered photothermal therapy, pH/NIR-responsive chemotherapy and MR imaging into one nanoplatform to enhance the therapeutic efficacy. This new multifunctional paradigm has a uniform and monodisperse sesame ball-like structure by decorating tiny Fe3O4 nanoparticles on the surface of Cu9S5@mSiO2 before a further PEG modification to improve its hydrophilicity and biocompatibility. With doxorubicin (DOX) payload, the as-obtained CMF-DOX composites can simultaneously provide an intense heating effect and enhanced DOX release upon 980 nm NIR light exposure, achieving a combined chemo/photothermal therapy. Under the influence of an external magnetic field, the magnetically targeted synergistic therapeutic effect of CMF-DOX can lead to highly superior inhibition of animal H22 tumor in vivo when compared to any of the single approaches alone. The results revealed that this Cu9S5 based magnetically targeted chemo/photothermal synergistic nanocarrier system has great promise in future MR imaging assisted tumor targeted therapy of cancer.
Co-reporter:Xiaoran Deng, Yinyin Chen, Ziyong Cheng, Kerong Deng, Ping'an Ma, Zhiyao Hou, Bei Liu, Shanshan Huang, Dayong Jin and Jun Lin
Nanoscale 2016 vol. 8(Issue 12) pp:6837-6850
Publication Date(Web):22 Feb 2016
DOI:10.1039/C5NR08253F
Combining multi-model treatments within one single system has attracted great interest for the purpose of synergistic therapy. In this paper, hollow gold nanospheres (HAuNs) coated with a temperature-sensitive polymer, poly(oligo(ethylene oxide) methacrylate-co-2-(2-methoxyethoxy)ethyl methacrylate) (p(OEGMA-co-MEMA)), co-loaded with DOX and a photosensitizer Chlorin e6 (Ce6) were successfully synthesized. As high as 58% DOX and 6% Ce6 by weight could be loaded onto the HAuNs-p(OEGMA-co-MEMA) nanocomposites. The grafting polymer brushes outside the HAuNs play the role of “gate molecules” for controlled drug release by 650 nm laser radiation owing to the temperature-sensitive property of the polymer and the photothermal effect of HAuNs. The HAuNs-p(OEGMA-co-MEMA)-Ce6-DOX nanocomposites with 650 nm laser radiation show effective inhibition of cancer cells in vitro and enhanced anti-tumor efficacy in vivo. In contrast, control groups without laser radiation show little cytotoxicity. The nanocomposite demonstrates a way of “killing three birds with one stone”, that is, chemotherapy, photothermal and photodynamic therapy are triggered simultaneously by the 650 nm laser stimulation. Therefore, the nanocomposites show the great advantages of multi-modal synergistic effects for cancer therapy by a remote-controlled laser stimulus.
Co-reporter:Guogang Li, Chun Che Lin, Yi Wei, Zewei Quan, Ying Tian, Yun Zhao, Ting-Shan Chan and Jun Lin
Chemical Communications 2016 vol. 52(Issue 46) pp:7376-7379
Publication Date(Web):04 May 2016
DOI:10.1039/C6CC01969B
By cosubstituting [Ca2+–P5+] for [La3+–Si4+] in the Eu-doped Ca(2→8)La(8→2)(SiO4)6−x(PO4)xO2 (0 ≤ x ≤ 6) system, Eu3+ ions are controllably and gradually transformed to Eu2+. Thus, the emission colors consecutively changed from red to blue/green light. Furthermore, excellent warm-white lights with the low correlated color temperature (CCT) range of 3500–3800 K and a high color rendering index (Ra) (88.4–93.2) have been achieved by mixing the as-prepared phosphors at different cation cosubstitution ratios.
Co-reporter:Guogang Li, Yun Zhao, Yi Wei, Ying Tian, Zewei Quan and Jun Lin
Chemical Communications 2016 vol. 52(Issue 16) pp:3376-3379
Publication Date(Web):18 Jan 2016
DOI:10.1039/C5CC09782G
Here we report a novel Ca10(PO4)6O:Ce3+ phosphate phosphor, consisting of an apatite structure, whose emission peaks under excitation with near-ultra violet light were found to shift from 410 nm (blue light) to 510 nm (yellowish-green light) with an increasing Ce3+ doping level due to the Ce3+ at the different concentrations preferentially occupying different crystallographic sites.
Co-reporter:Kai Li, Sisi Liang, Mengmeng Shang, Hongzhou Lian, and Jun Lin
Inorganic Chemistry 2016 Volume 55(Issue 15) pp:7593-7604
Publication Date(Web):July 14, 2016
DOI:10.1021/acs.inorgchem.6b01040
A series of Ce3+, Tb3+, Eu3+ doped Ba2Y2(PO4)2(SiO4) (BYSPO) phosphors were synthesized via the high-temperature solid-state reaction route. X-ray diffraction, high-resolution transmission electron microscopy, Fourier transform infrared, solid-state NMR, photoluminescence (PL) including temperature-dependent PL, and fluorescent decay measurements were conducted to characterize and analyze as-prepared samples. BYSPO was obtained by the substitution of Y+SiO4 for Ba+PO4 in Ba3Y(PO4)3 (BYPO). The red shift of PL emission from 375 to 401 nm occurs by comparing BYSPO:0.14Ce3+ with BYPO:0.14Ce3+ under 323 nm UV excitation. More importantly, the excitation edge can be extended from 350 to 400 nm, which makes it be excited by UV/n-UV chips (330–410 nm). Tunable emission color from blue to green can be observed under 365 nm UV excitation based on the energy transfer from Ce3+ to Tb3+ ions after codoping Tb3+ into BYSPO:0.14Ce3+. Moreover, energy transfer from Tb3+ to Eu3+ ions also can be found in BYSPO:Tb3+,Eu3+ phosphors, resulting in the tunable color from green to orange red upon 377 nm UV excitation. Energy transfer properties were demonstrated by overlap of excitation spectra, variations of emission spectra, and decay times. In addition, energy transfer mechanisms from Ce3+ to Tb3+ and Tb3+ to Eu3+ in BYSPO were also discussed in detail. Quantum yields and CIE chromatic coordinates were also presented. Generally, the results suggest their potential applications in UV/n-UV pumped LEDs.
Co-reporter:Zhongxian Qiu, Hongzhou Lian, Mengmeng Shang, Shixun Lian and Jun Lin
CrystEngComm 2016 vol. 18(Issue 24) pp:4597-4603
Publication Date(Web):09 May 2016
DOI:10.1039/C6CE00832A
An unexpected spectral blue shift of the emission from yellow to green is observed for the solid solution phosphors Sr3−mCamB2O6:Eu2+ (m = 0–3), when larger Sr2+ ions are substituted by smaller Ca2+ ions in Sr3B2O6 lattices. The powder X-ray patterns of all the phases indicate a structural similarity to the end compounds and show a smooth variation of the structural parameters with composition in the full range. The linear structural evolution of the iso-structural Sr3−mCamB2O6 solid solutions obeying Vegard's rule has also been examined and verified by Rietveld refinement, high resolution transmission electron microscopy and Fourier transform infrared spectroscopy. The average bond lengths of the central cations to the coordinating anions and the distortion indexes of the coordination polyhedra are investigated. As a result, the symmetry of the coordination crystal field is found to be higher with increasing Ca content in the solid solutions phosphors, which should be primarily responsible for the continuous blue shift of the emission spectra of Sr2.96−mCamB2O6:0.04Eu2+ with the growth of the m value.
Co-reporter:Bei Liu, Chunxia Li, Ziyong Cheng, Zhiyao Hou, Shanshan Huang and Jun Lin
Biomaterials Science 2016 vol. 4(Issue 6) pp:890-909
Publication Date(Web):14 Mar 2016
DOI:10.1039/C6BM00076B
The near-infrared (NIR) region (700–1100 nm) is the so-called transparency “therapeutic window” for biological applications owing to its deeper tissue penetration and minimal damage to healthy tissues. In recent years, various NIR-based therapeutic and interventional strategies, such as NIR-triggered drug delivery, photothermal therapy (PTT) and photodynamic therapy (PDT), are under research in intensive preclinical and clinical investigations for cancer treatment. The NIR control in these cancer therapy systems is considered crucial to boost local effective tumor suppression while minimizing side effects, resulting in improved therapeutic efficacy. Some researchers even predict the NIR-triggered cancer therapy to be a new and exciting possibility for clinical nanomedicine applications. In this review, the rapid development of NIR light-responsive cancer therapy based on various smartly designed nanocomposites for deep tumor treatments is introduced. In detail, the use of NIR-sensitive materials for chemotherapy, PTT as well as PDT is highlighted, and the associated challenges and potential solutions are discussed. The applications of NIR-sensitive cancer therapy modalities summarized here can highlight their potential use as promising nanoagents for deep tumor therapy.
Co-reporter:Xuechao Cai, Jun Lin, and Maolin Pang
Crystal Growth & Design 2016 Volume 16(Issue 7) pp:3565-3568
Publication Date(Web):May 25, 2016
DOI:10.1021/acs.cgd.6b00313
Highly uniform Fe-MIL-88B micron particles with shape evolution from hexagonal bipyramids to bipyramidal hexagonal prism were obtained by a surfactant (polyvinylpyrrolidone, PVP) assisted modified solvothermal method. The modified solvothermal method further demonstrated its feasibility to produce highly uniform micron or nanosized MOF, which provides great opportunities for fabrication of new MOFs and investigation their potential applications in versatile research fields.
Co-reporter:Bei Liu, Chunxia Li, Zhongxi Xie, Zhiyao Hou, Ziyong Cheng, Dayong Jin and Jun Lin
Dalton Transactions 2016 vol. 45(Issue 33) pp:13061-13069
Publication Date(Web):21 Jan 2016
DOI:10.1039/C5DT04857E
Recently, incorporating multiple components into one nanostructured matrix to construct a multifunctional nanomedical platform has attracted more and more attention for simultaneous anticancer diagnosis and therapy. Herein, a novel anti-cancer nanoplatform has been successfully developed by coating a uniform shell of poly(acrylic acid) (PAA) on the surface of CuS-decorated upconversion nanoparticles (UCNPs). Benefiting from the enhanced 808 nm-excited UCL intensity of the multilayer UCNPs, the unique photothermal properties of CuS and the pH-responsive drug release capacity of the PAA shell, such a nanoplatform design of UCNPs-CuS@PAA (labeled UCP) offers a new route to achieve 808 nm-excited UCL imaging guided chemo/photothermal combination therapy. We have found that the combined chemo/photothermal therapy can significantly improve the therapeutic efficacy compared with chemotherapy or photothermal therapy (PTT) alone. Moreover, the pH/NIR-dependent drug delivery properties, 808 nm-excited UCL imaging, as well as in vitro/in vivo biocompatibility tests were also investigated in detail. These results show promising applications of UCP nanoparticles as a novel theranostic agent for the detection and treatment of tumors.
Co-reporter:Fei He, Chunxia Li, Xinyang Zhang, Yinyin Chen, Xiaoran Deng, Bei Liu, Zhiyao Hou, Shanshan Huang, Dayong Jin and Jun Lin
Dalton Transactions 2016 vol. 45(Issue 4) pp:1708-1716
Publication Date(Web):07 Dec 2015
DOI:10.1039/C5DT04191K
808 nm excited upconversion nanoparticles (UCNPs) have received extensive attention in the biomedical areas. However, one of the limitations of UCNPs is their lower luminescence efficiency. Aimed at this problem, a series of BaGdF5-based UCNPs were prepared by a layer-by-layer procedure. And UC luminescence properties are optimized by varying the doping concentration of rare earth ions, amount and types of shells. It is found that if the amount of core BaGdF5:20%Yb3+/2%Er3+ was fixed at 0.5 mmol, the optimized conditions of three shell layers are 0.3 mmol of BaGdF5:10%Yb3+, 0.5 mmol of BaNdF5 and 0.5 mmol of BaGdF5. Thus the UC luminescence intensity of the resultant nanoparticles BaGdF5:20%Yb3+/2%Er3+@BaGdF5:10%Yb3+@BaNdF5@BaGdF5 (Er@Yb@Nd@Gd) is enhanced more than four times compared with that of BaGdF5:20%Yb3+/2%Er3+@BaGdF5:10%Yb3+@BaNdF5 (Er@Yb@Nd). To further improve the biocompatibility and applications in the biological field, carboxymethyl chitosan (CMC), a type of biocompatible water-transfer agent, was used as a capping ligand to modify the surface of Er@Yb@Nd@Gd. An antitumor drug doxorubicin (DOX) was loaded to the CMC-modified Er@Yb@Nd@Gd nanocarriers by electrostatic interactions. The DOX can be selectively released in an acidic environment, which shows a pH-triggered drug release behavior. On the other hand, Er@Yb@Nd@Gd nanoparticles have excellent magnetic properties due to the presence of Gd components. T1-weighted magnetic resonance imaging (MRI) reveals the concentration-dependent brightening effect with longitudinal relaxivity (r1) as high as 43.77 s−1 (mM)−1, much higher than that of previous Gd3+-based counterparts. The results indicate that this multifunctional drug delivery system is expected to be a promising platform for simultaneous cancer therapy and bioimaging.
Co-reporter:Fei He, Yinyin Chen, Chunxia Li, Xiaoran Deng, Bin Liu, Bei Liu, Shanshan Huang, Zhiyao Hou, Ziyong Cheng and Jun Lin
RSC Advances 2016 vol. 6(Issue 70) pp:65600-65606
Publication Date(Web):28 Jun 2016
DOI:10.1039/C6RA10736B
A mixture of anticancer drug doxorubicin hydrochloride (DOX) and 1-tetradecanol (TD) are co-loaded into core–shell structured Cu9S5@mSiO2 nanoparticles to achieve bimodal tumor therapy with enhanced efficacy. TD, a kind of phase change molecule with a melting temperature (Tm) of 39 °C, acts as a gatekeeper to control DOX release. Cu9S5 is a kind of good photothermal agent and has the advantage of a high photothermal conversion efficiency, which has a thermal effect on TD. Cu9S5 NCs at a concentration of 312.5 ppm can elevate its temperature by 28.6 °C in 5 min when the system is irradiated by a 980 nm laser (0.5 W cm−2). When the temperature of the system is higher than 39 °C, TD can melt and DOX will release from the pores. Besides NIR-triggered release, the DOX release is also controlled by pH. Synergistic NIR-triggered and pH-triggered DOX release prevents the premature release of drug molecules (<4% of the whole loaded DOX in 24 h) in neutral conditions without irradiation. However, upon irradiation in acidic conditions (pH = 5.0), the release of the whole loaded DOX could reach 32.6%. Therefore, this versatile combination of photothermal therapy and chemotherapy makes the application of multifunctional drug delivery systems possible.
Co-reporter:Dongmei Wang, Jian Fan, Mengmeng Shang, Kai Li, Yang Zhang, Hongzhou Lian, Jun Lin
Optical Materials 2016 Volume 51() pp:162-170
Publication Date(Web):January 2016
DOI:10.1016/j.optmat.2015.11.029
•GdY(MoO4)3:RE3+ (RE = Eu, Dy, Sm, Tb) phosphor were synthesized via a Pechini-type sol–gel process.•Under the excitation, the GdY(MoO4)3:RE3+ phosphors exhibit the characteristic RE3+ emission.•The concentration quenching is not observed in the GdY(MoO4)3:xEu3+ system.•The emission intensities maximize at x = 0.05, 0.03, and 0.18 for Dy3+, Sm3+, and Tb3+ in the host.•The PL colors of GdY(MoO4)3:0.01Tb3+, xEu3+ samples can be tuned from green to red.GdY(MoO4)3:RE3+ (RE = Eu, Dy, Sm, Tb) phosphor were synthesized via a Pechini-type sol–gel process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) and cathodoluminescence (CL) spectra, and decay lifetimes etc were utilized to characterize the resulting samples. After annealed at 800 °C for 4 h in air, pure GdY(MoO4)3 phase can form. When the calcination temperature is further increased to 1100 °C, the crystallinity and luminescence intensity reach the best in our experiments. Under UV light and low-voltage electron beam excitation, the GdY(MoO4)3:Eu3+, GdY(MoO4)3:Dy3+, GdY(MoO4)3:Sm3+ and GdY(MoO4)3:Tb3+ phosphors exhibit the characteristic emission of Eu3+ (5D0-7F2, red), Dy3+ (4F9/2–6H13/2, yellow), Sm3+ (4G5/2–6H7/2, orange) and Tb3+ (5D4–7F5, green) with a high color purity, respectively. The Eu3+ and Tb3+ co-doping phosphors are capable of showing color-tunable emissions in the visible region under single-wavelength excitation. The luminescence mechanism and concentration quenching effect were discussed in detail.
Co-reporter:Guogang Li, Ying Tian, Yun Zhao and Jun Lin
Chemical Society Reviews 2015 vol. 44(Issue 23) pp:8688-8713
Publication Date(Web):30 Sep 2015
DOI:10.1039/C4CS00446A
Nowadays, phosphor converted white light-emitting diodes (pc-WLEDs) have been widely used in solid-state lighting and display areas due to their superior lifetime, efficiency, and reliability as well as significant reduction in power consumption. Phosphors are indispensable components of pc-WLED devices, and their luminescence properties determine the quality of WLED lighting and displays. In order to further achieve high luminous efficacy, chromatic stability, and color-rending properties in pc-WLEDs, much effort has been focused on improving current pc-WLED phosphors and developing novel pc-WLED phosphors recently. This review article concerns commonly used rare earth ion (Eu2+ and Ce3+) activated inorganic phosphors, highlighting the important effect of spectral tuning via local structural variations on improving the luminescence performance of phosphors. The main spectral tuning strategies are discussed in detail and summarized, including (1) doping level control; (2) cationic substitution; (3) anionic substitution; (4) cationic–anionic substitution; (5) the crystal-site engineering approach; (6) mixing of nanophases.
Co-reporter:Dongmei Yang, Ping'an Ma, Zhiyou Hou, Ziyong Cheng, Chunxia Li and Jun Lin
Chemical Society Reviews 2015 vol. 44(Issue 6) pp:1416-1448
Publication Date(Web):02 Jul 2014
DOI:10.1039/C4CS00155A
Lanthanide ion (Ln3+)-based upconversion nano/micromaterials that emit higher-energy visible light when excited by low-energy NIR light have aroused considerable attention in the forefront of materials science and biomedical fields, which stems from their unique optical and chemical properties including minimum photodamage to living organisms, low autofluorescence, high signal-to-noise ratio and detection sensitivity, and high penetration depth in biological or environmental samples. Thus, Ln3+-based upconversion materials are rising new stars and are quickly emerging as potential candidates to revolutionize novel biomedical applications. In this review article, we mainly focus on the recent progress in various chemical syntheses of Ln3+-based upconversion nanomaterials, with special emphasis on their application in stimuli-response controlled drug release and subsequent therapy. Functional groups that are introduced into the stimuli-responsive system can respond to external triggers, such as pH, temperature, light, and even magnetic fields, which can regulate the movement of the pharmaceutical cargo and release the drug at a desired time and in a desired area. This is crucial to boost drug efficacy in cancer treatment while minimizing the side effects of cytotoxic drugs. Many multifunctional (magnetic/upconversion luminescence and porous) composite materials based on Ln3+ have been designed for controlled drug delivery and multimodal bioimaging. Finally, the challenges and future opportunities for Ln3+-based upconversion materials are discussed.
Co-reporter:Fei He;Guixin Yang;Piaoping Yang;Yuxiu Yu;Ruichan Lv;Chunxia Li;Yunlu Dai;Shili Gai
Advanced Functional Materials 2015 Volume 25( Issue 25) pp:3966-3976
Publication Date(Web):
DOI:10.1002/adfm.201500464
The NIR light-induced imaging-guided cancer therapy is a promising route in the targeting cancer therapy field. However, up to now, the existing single-modality light-induced imaging effects are not enough to meet the higher diagnosis requirement. Thus, the multifunctional cancer therapy platform with multimode light-induced imaging effects is highly desirable. In this work, captopril stabilized-Au nanoclusters Au25(Capt)18−(Au25) are assembled into the mesoporous silica shell coating outside of Nd3+-sensitized upconversion nanoparticles (UCNPs) for the first time. The newly formed Au25 shell exhibits considerable photothermal effects, bringing about the photothermal imaging and photoacoustic imaging properties, which couple with the upconversion luminescence imaging. More importantly, the three light-induced imaging effects can be simultaneously achieved by exciting with a single NIR light (808 nm), which is also the triggering factor for the photothermal and photodynamic cancer therapy. Besides, the nanoparticles can also present the magnetic resonance and computer tomography imaging effects due to the Gd3+ and Yb3+ ions in the UCNPs. Furthermore, due to the photodynamic and the photothermal effects, the nanoparticles possess efficient in vivo tumor growth inhibition under the single irradiation of 808 nm light. The multifunctional cancer therapy platform with multimode imaging effects realizes a true sense of light-induced imaging-guided cancer therapy.
Co-reporter:Bei Liu;Yinyin Chen;Chunxia Li;Fei He;Zhiyao Hou;Shanshan Huang;Haomiao Zhu;Xueyuan Chen
Advanced Functional Materials 2015 Volume 25( Issue 29) pp:4717-4729
Publication Date(Web):
DOI:10.1002/adfm.201501582
In this work, a simple method is demonstrated for the synthesis of multifunctional core–shell nanoparticles NaYF4:Yb,Er@NaYF4:Yb@NaNdF4:Yb@NaYF4:Yb@PAA (labeled as Er@Y@Nd@Y@PAA or UCNP@PAA), which contain a highly effective 808-nm-to-visible UCNP core and a thin shell of poly(acrylic acid) (PAA) to achieve upconversion bioimaging and pH-sensitive anticancer chemotherapy simultaneously. The core–shell Nd3+-sensitized UCNPs are optimized by varying the shell number, core size, and host lattices. The final optimized Er@Y@Nd@Y nanoparticle composition shows a significantly improved upconversion luminescence intensity, that is, 12.8 times higher than Er@Y@Nd nanoparticles. After coating the nanocomposites with a thin layer of PAA, the resulting UCNP@PAA nanocomposite perform well as a pH-responsive nanocarrier and show clear advantages over UCNP@mSiO2, which are evidenced by in vitro/in vivo experiments. Histological analysis also reveals that no pathological changes or inflammatory responses occur in the heart, lungs, kidneys, liver, and spleen. In summary, this study presents a major step forward towards a new therapeutic and diagnostic treatment of tumors by using 808-nm excited UCNPs to replace the traditional 980-nm excitation.
Co-reporter:Kerong Deng;Zhiyao Hou;Xiaoran Deng;Piaoping Yang;Chunxia Li
Advanced Functional Materials 2015 Volume 25( Issue 47) pp:7280-7290
Publication Date(Web):
DOI:10.1002/adfm.201503046
A novel nanoplatform based on tungsten oxide (W18O49, WO) and indocyanine green (ICG) for dual-modal photothermal therapy (PTT) and photodynamic therapy (PDT) has been successfully constructed. In this design, the hierarchical unique nanorod-bundled W18O49 nanostructures play roles in being not only as an efficient photothermal agent for PTT but also as a potential nanovehicle for ICG molecules via electrostatic adsorption after modified with trimethylammonium groups on their surface. It is found that the ability of ICG to produce cytotoxic reactive oxygen species for PDT is well maintained after being attached on the WO, thus the as-obtained WO@ICG can achieve a synergistic effect of combined PTT and PDT under single 808 nm near-infrared (NIR) laser excitation. Notably, compared with PTT or PDT alone, the enhanced HeLa cells lethality of the 808 nm laser triggered dual-modal therapy is observed. The in vivo animal experiments have shown that WO@ICG has effective solid tumor ablation effect with 808 nm NIR light irradiation, revealing the potential of these nanocomposites as a NIR-mediated dual-modal therapeutic platform for cancer treatment.
Co-reporter:Ruichan Lv, Chongna Zhong, Rumin Li, Piaoping Yang, Fei He, Shili Gai, Zhiyao Hou, Guixin Yang, and Jun Lin
Chemistry of Materials 2015 Volume 27(Issue 5) pp:1751
Publication Date(Web):February 9, 2015
DOI:10.1021/cm504566f
As a potential photosensitizer for photodynamic therapy (PDT), pure titanium dioxide has the drawbacks of low tissue penetration and possible damage to skin due to the triggered UV light. To realize near-infrared (NIR) laser-induced multimodal imaging guided therapy, we constructed a multifunctional core–shell structure (TiO2@Y2Ti2O7@YOF:Yb,Tm) by a facile coprecipitation route, followed by an annealing process. Under a single NIR laser irradiation, the highly cytotoxic reactive oxygen species (ROS) required for PDT can be generated due to the energy transfer from YOF:Yb,Tm to the Y2Ti2O7 photocatalyst which is responsive to blue emission (visible light), and the thermal effect can be simultaneously produced due to the nonradiative transition and the recombination of electron–hole pairs. The NIR light induced PDT and photothermal therapy (PTT) can efficiently suppress tumor growth, which was evidenced by both in vitro and in vivo results. Moreover, the rare earth ions in the composite make the material have good up-conversion luminescence (UCL) imaging and CT imaging properties, thus achieving the target of synergistic PDT and PTT therapy under the multimodal imaging guidance.
Co-reporter:Guixin Yang, Dan Yang, Piaoping Yang, Ruichan Lv, Chunxia Li, Chongna Zhong, Fei He, Shili Gai, and Jun Lin
Chemistry of Materials 2015 Volume 27(Issue 23) pp:7957
Publication Date(Web):November 12, 2015
DOI:10.1021/acs.chemmater.5b03136
To solve the issue of limited penetration depth and overheating of the excited 980 nm near-infrared (NIR) light, and unstable and insufficient loading amount of photosensitizers (PSs) in photodynamic therapy (PDT), we have constructed a well-defined core–shell structured NaGdF4:Yb/Tm@NaGdF4:Yb@NaNdF4:Yb@NaGdF4@mSiO2@TiO2 (UCNPs@mSiO2@TiO2) nanocomposite by coating a layer of TiO2 PSs/photocatalyst on an effective 808 nm-to-UV/visible upconversion luminescent (UCL) core to achieve simultaneous multiple bioimaging and efficient PDT. The design of quenching-shield layer can eliminate the back energy transfer from activator Tm3+ to sensitized Nd3+, thus significantly improving the UCL emission. The high surface area of mesoporous silica-coated UCNPs facilitates the stable and high loading amount of anatase TiO2. In vivo results indicate that 808 nm NIR light-mediated PDT using UCNPs@mSiO2@TiO2 as photosensitizers shows much higher antitumor efficacy than those with 980 nm and UV irradiations due to the higher tissue penetration depth. Meanwhile, the platform itself as an imaging nanoprobe endows the sample with multiple imaging (UCL/CT/MRI) properties. Our work makes great progress toward the integrity of diagnosis and PDT induced by a single 808 nm NIR light.
Co-reporter:Ruichan Lv, Piaoping Yang, Fei He, Shili Gai, Guixin Yang, and Jun Lin
Chemistry of Materials 2015 Volume 27(Issue 2) pp:483
Publication Date(Web):December 9, 2014
DOI:10.1021/cm503647k
To integrate photothermal therapy (PTT) with chemotherapy for improved antitumor efficiency, we designed a novel multifunctional composite by attaching CuxS nanoparticles onto the surface of Y2O3:Yb/Er hollow spheres through a combined coprecipitation and subsequent hydrothermal route. By altering the initial pH values for the synthesis of precursors, the size and structure properties of the final composites can controllably be tuned. The conjugated folic acid (FA) makes the composite recognize the targeted cancer cells and the attached CuxS nanoparticles endow the composite with photothermal function. It is found that the release of doxorubicin (DOX) from the functional carrier could be triggered by both pH value and near-infrared (NIR) radiation. In particular, both PTT and chemotherapy can be simultaneously driven by 980 nm laser irradiation. The synergistic therapeutic effect based on PTT and chemotherapy can lead to low in vitro viability of 12.9% and highly strong inhibition of animal H22 tumor in vivo, which is superior to any individual therapy. Moreover, the composite exhibits the clear in vivo red up-conversion luminescence (UCL). This multifunctional nanocarrier can be applicable as bioimaging agent and effective antitumor agent for the synergistic interaction between PTT and the enhanced chemotherapy.
Co-reporter:Bei Liu, Chunxia Li, Ping'an Ma, Yinyin Chen, Yuanxin Zhang, Zhiyao Hou, Shanshan Huang and Jun Lin
Nanoscale 2015 vol. 7(Issue 5) pp:1839-1848
Publication Date(Web):01 Dec 2014
DOI:10.1039/C4NR05342G
A low toxic multifunctional nanoplatform, integrating both mutimodal diagnosis methods and antitumor therapy, is highly desirable to assure its antitumor efficiency. In this work, we show a convenient and adjustable synthesis of multifunctional nanoparticles NaYF4:Yb, Er@mSiO2@Fe3O4-PEG (MFNPs) based on different sizes of up-conversion nanoparticles (UCNPs). With strong up-conversion fluorescence offered by UCNPs, superparamagnetism properties attributed to Fe3O4 nanoparticles and porous structure coming from the mesoporous SiO2 shell, the as-obtained MFNPs can be utilized not only as a contrast agent for dual modal up-conversion luminescence (UCL)/magnetic resonance (MR) bio-imaging, but can also achieve an effective magnetically targeted antitumor chemotherapy both in vitro and in vivo. Furthermore, the UCL intensity of UCNPs and the magnetic properties of Fe3O4 in the MFNPs were carefully balanced. Silica coating and further PEG modifying can improve the hydrophilicity and biocompatibility of the as-synthesized MFNPs, which was confirmed by the in vitro/in vivo biocompatibility and in vivo long-time bio-distributions tests. Those results revealed that the UCNPs based magnetically targeted drug carrier system we synthesized has great promise in the future for multimodal bio-imaging and targeted cancer therapy.
Co-reporter:Arif Gulzar, Shili Gai, Piaoping Yang, Chunxia Li, Mohd Bismillah Ansari and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 44) pp:8599-8622
Publication Date(Web):03 Sep 2015
DOI:10.1039/C5TB00757G
In the last decade, using polymer and mesoporous silica materials as efficient drug delivery carriers has attracted great attention. Although the development and application of them involves some inevitable barriers, such as chronic toxicities, long-term stability, understanding of the biological fate and physiochemical properties, biodistribution, effect in the biological environment, circulation properties and targeting efficacy in vivo. The construction of stimuli responsive drug carriers using biologically safe materials, followed by hydrophilic modification, bioconjugation, targeting functionalization, and detailed safety analysis in small/large animal models may be the best way to overcome these barriers. Huge progress has been made in stimuli responsive drug delivery systems based on polymer and mesoporous silica materials, mainly including pH-, thermo-, light-, enzyme-, redox-, magnetic field- and ultrasound-responsive drug delivery systems, all of which are highlighted in this review.
Co-reporter:Yinyin Chen, Bei Liu, Xiaoran Deng, Shanshan Huang, Zhiyao Hou, Chunxia Li and Jun Lin
Nanoscale 2015 vol. 7(Issue 18) pp:8574-8583
Publication Date(Web):02 Apr 2015
DOI:10.1039/C5NR00829H
Core–shell structured Nd3+-sensitized NaYF4:Yb/Nd/Er@NaYF4:Nd@mSiO2 nanoparticles (NPs) were designed and synthesized. The NaYF4:Yb/Nd/Er@NaYF4:Nd core imparts the nanomaterials with luminescence properties for upconversion optical imaging under 808 nm laser irradiation, whereas the mesoporous SiO2 shell allows the nanomaterials to be loaded with anticancer drug doxorubicin (DOX). In vivo toxicity assessment has confirmed that the NPs have low systematic toxicity in healthy mice. In vivo antitumor activity shows that the nanocomposites exhibit greater antitumor efficacy than pure DOX. As a result, the composite nanomaterials can serve as nanotheranostic materials for synchronous upconversion luminescence imaging under 808 nm laser irradiation, and as anticancer drug delivery vehicles, so as to integrate the diagnosis and treatment of cancers in vivo.
Co-reporter:Kai Li, Mengjiao Xu, Jian Fan, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 44) pp:11618-11628
Publication Date(Web):08 Oct 2015
DOI:10.1039/C5TC02759D
A series of Eu2+,Mn2+-doped Na3LuSi2O7 (NLSO) phosphors have been prepared via the high-temperature solid-state reaction route. X-ray diffraction (XRD), Raman and Fourier transform infrared (FT-IR) spectra, fluorescent decay times, photoluminescence (PL) including temperature-dependent PL properties and scanning electron microscopy (SEM) were used to characterize the as-prepared samples. In Eu2+ singly-doped NLSO samples, an intense green emission is presented under UV excitation. A tunable color from green to yellowish-orange was generated when Mn2+ ions were co-doped into the NLSO:Eu2+, which is based on the energy transfer from Eu2+ to Mn2+ ions. The energy transfer from Eu2+ to Mn2+ ions can be speculated to be due to the wide spectral overlap between the Eu2+ emission and Mn2+ excitation spectra in Eu2+ or Mn2+ singly-doped NLSO samples. This is demonstrated by the similar excitation spectra of the Eu2+ and Mn2+ emission bands and the decreases in Eu2+ emission intensity and decay lifetime with the increase of Mn2+ concentration in the NLSO:Eu2+,Mn2+ samples. The energy transfer mechanism from Eu2+ to Mn2+ ions was determined to be a dipole–quadrupole interaction by the concentration quenching and spectral overlap methods. The maximum quantum yield can reach 51.5% for NLSO:0.01Eu2+,0.12Mn2+. The above results indicate that NLSO:Eu2+,Mn2+ could be a candidate as a green to yellowish-orange component for UV-excited w-LEDs.
Co-reporter:Kai Li, Jian Fan, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 38) pp:9989-9998
Publication Date(Web):04 Sep 2015
DOI:10.1039/C5TC01993A
A series of Bi3+,Eu3+-doped Sr2Y8(SiO4)6O2 (SYSO) phosphors were synthesized by the Pechini-type sol–gel route. XRD patterns, Rietveld refinement, FT-IR spectra, photoluminescence spectra (PL), fluorescence decay time, and quantum yields (QYs) were utilized to characterize the as-prepared samples. Intense blue-green emission due to the 3P1 → 1S0 transition of Bi3+ ions is produced under UV excitation in Bi3+ singly doped SYSO samples. Spectral analysis illustrates that two kinds of Bi3+ ions are generated by occupying the two kinds of sites (4f and 6h) available for Y in SYSO, denoted as Bi3+(1) and Bi3+(2), corresponding to the two main emission bands at around 413 and 493 nm, respectively. A wide spectral overlap between Bi3+ emission and Eu3+ excitation spectra results in the energy transfer from Bi3+ to Eu3+. This has been demonstrated via the excitation spectra monitored at Bi3+ and Eu3+ emission bands, and the PL emission spectra and decay time of Bi3+ in SYSO:Bi3+,Eu3+ phosphors. The energy transfer mechanism is determined to be dipole–quadrupole interaction. The critical distance of energy transfer from Bi3+ to Eu3+ ions is calculated to be 12.78 Å based on the concentration quenching method, which is in good agreement with that of the spectral overlap route (10.03–13.37 Å). Moreover, the QYs, CIE chromaticity and thermal quenching properties have also been investigated. White emission color can be realized with the CIE coordinates (0.325, 0.311) and QY 52% for SYSO:0.08Bi3+,0.48Eu3+. The above results suggest that SYSO:Bi3+,Eu3+ can be a potential single-component white-emitting phosphor for UV w-LEDs.
Co-reporter:Mengmeng Shang, Jing Wang, Jian Fan, Hongzhou Lian, Yang Zhang and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 36) pp:9306-9317
Publication Date(Web):13 Aug 2015
DOI:10.1039/C5TC01864A
Nitride phosphors have drawn much interest because of their outstanding thermal and chemical stability and interesting photoluminescence properties. Currently, it remains a challenge to synthesize these phosphors through a convenient chemical route. Herein we propose a general and convenient strategy based on hydrothermal-ammonolysis reaction to successfully prepare zinc germanium nitride (ZnGeN2) and Mn2+ doped ZnGeN2 phosphors. The crystal structure, composition, morphology, luminescence and reflectance spectra, quantum efficiency, and the temperature-dependent photoluminescence behavior were studied respectively. The phase formation and crystal structure of ZnGeN2 were confirmed from powder X-ray diffraction and Rietveld refinement. EDX analysis confirmed the actual atomic ratios of Zn/Ge and N/Ge and suggested the presence of Ge vacancy defects in the ZnGeN2 host, which is associated with its yellow emission at 595 nm with a FWHM of 143 nm under UV light excitation. For Mn2+ doped ZnGeN2 phosphor, it exhibits an intense red emission due to the 4T1g → 6A1g transition of Mn2+ ions. The unusual red emission of Mn2+ at the tetrahedral Zn2+ sites is attributed to the strong nephelauxetic effect and crystal field between Mn2+ and the tetrahedrally coordinated N3−. Moreover, the PL intensity of ZnGeN2:Mn2+ phosphors can be enhanced by Mg2+ ions partially substituting for Zn2+ ions in a certain concentration range. The optimal Mn2+ doping concentration in the ZnGeN2 host is 0.4 mol%. The critical energy transfer distance of this phosphor is calculated to be about 27.99 Å and the concentration quenching mechanism is proved to be the dipole–dipole interaction. With increasing temperature, the luminescence of ZnGeN2:Mn2+ phosphors gradually decreases and the FWHM of the emission band broadens from 54 nm to 75 nm. The corresponding activation energy Ea was reckoned to be 0.395 eV. And the nonradiative transition probability increases with the increasing temperature, finally leading to the lifetime decrease with the increase of the temperature.
Co-reporter:Xiaoyong Huang and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 29) pp:7652-7657
Publication Date(Web):01 Jul 2015
DOI:10.1039/C5TC01438G
In recent years, intensive research efforts around the world have been devoted to lanthanide-doped upconversion nanoparticles because of their promising application in biological imaging. However, the overheating issue caused upon 980 nm laser irradiation in conventional Yb3+-based nanoparticles is needed to be addressed, and thus Nd3+/Yb3+-based upconversion nanoparticles with 808 nm excitation are investigated as promising alternatives because they can significantly decrease the optical absorption of water. Due to the cascade sensitization process, Nd3+/Yb3+-based upconversion nanoparticles, however, always suffer from the intrinsic low luminescence efficiency. To solve this problem, here we proposed the active-core/active-shell nanostructured design as an effective strategy for upconversion improvement of Nd3+/Yb3+-based upconversion nanoparticles. We found that after growing an optimized active-shell containing both Nd3+ and Yb3+ ions, a maximum 522-fold enhancement in upconversion luminescence was realized upon excitation at 808 nm. These findings would be of great importance to the community developing high-performance upconversion nanoparticles for bioimaging applications.
Co-reporter:Kai Li, Mengmeng Shang, Yang Zhang, Jian Fan, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 27) pp:7096-7104
Publication Date(Web):29 May 2015
DOI:10.1039/C5TC00927H
Co-doping of Ce3+/Eu2+, Tb3+, Mn2+ ions into a single-component host is commonly used to achieve white-light phosphors through energy transfer, which present good color stability and high color rendering index (CRI) values. In this work, a series of single-component trichromatic white-light-emitting Ca9Bi(PO4)7(CBPO):Ce3+,Tb3+,Mn2+ phosphors were synthesized and investigated. The crystal structure, luminescence properties and energy transfer behavior are discussed in detail. The energy transfer process from Ce3+ to Tb3+/Mn2+ has been demonstrated to be a resonant type via the dipole–dipole–quadrupole–quadrupole interaction mechanism, respectively, which makes the emission color shift from purple-blue to green/red with the corresponding Commission Internationale de L'Eclairage (CIE) chromaticity coordinates from (0.166, 0.011) to (0.260, 0.569) and (0.582, 0.287), respectively. Additionally, the white light emission by controlling the concentration ratio of Tb3+ and Mn2+ ions has been acquired in the CBPO:0.08Ce3+,0.22Tb3+,0.11Mn2+ sample with the CIE chromaticity coordinates of (0.375, 0.310) and an absolute quantum yield of 50% upon 292 nm excitation. The maximum quantum yield is 84% for CBPO:0.08Ce3+,0.90Tb3+. The good thermal stability of the CBPO:0.08Ce3+,0.22Tb3+,0.11Mn2+ sample shows about 83.6% at 150 °C of its initial PL intensity at room temperature, which attracts more attention. The results suggest that the present phosphors can be potentially applied as candidates of single-component white-light phosphors for UV-pumped w-LEDs.
Co-reporter:Kai Li, Ju Xu, Xuechao Cai, Jian Fan, Yang Zhang, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 24) pp:6341-6349
Publication Date(Web):26 May 2015
DOI:10.1039/C5TC00796H
A series of Eu2+ singly doped α-Ca1.65Sr0.35SiO4:Eu2+ phosphors have been synthesized via the high-temperature solid-state reaction method. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), diffuse reflectance spectroscopy and photoluminescence (PL) including temperature-dependent PL were used to characterize the as-prepared samples. The XRD patterns and Rietveld refinement of the presented sample show the pure phase of the as-prepared samples. All of the phosphors exhibit intense and broad absorption bands in the ultraviolet and near ultraviolet (n-UV) range, and produce bright green emission upon 365 nm UV radiation. The critical concentration of Eu2+ for the maximum intensity was determined to be about 1 mol% in α-Ca1.65Sr0.35SiO4:Eu2+ after optimizing the composition. The energy transfer mechanism between Eu2+ was demonstrated to be dipole–dipole interaction. Besides, the fluorescence decay curves, the temperature dependent PL and CIE value of α-Ca1.65Sr0.35SiO4:Eu2+ phosphors were investigated. It is reasonable that the decay times of samples decrease with increasing Eu2+ content. The CIE chromaticity coordinates shift from green (0.197, 0.395) to the border between the green and yellow (0.242, 0.547) region, which agree with the corresponding emission spectra. The maximum quantum yield is 69% for α-Ca1.65Sr0.345SiO4:0.005Eu2+. The thermal stability of luminescence of selected α-Ca1.65Sr0.34SiO4:0.01Eu2+ was also investigated and compared with that of the commercial green phosphor, which shows its good performance. The above results suggest that it is a good candidate for green-emitting phosphors applied in UV/n-UV pumped w-LEDs.
Co-reporter:Xiaoyun Mi, Jiacheng Sun, Peng Zhou, Hongyan Zhou, Di Song, Kai Li, Mengmeng Shang and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 17) pp:4471-4481
Publication Date(Web):27 Jan 2015
DOI:10.1039/C4TC02433H
Ca8MgLu(PO4)7:Ce3+,Tb3+,Mn2+ (abbreviated as CMLP:Ce3+,Tb3+,Mn2+) phosphors were synthesized by a high-temperature solid-state method. X-ray diffraction (XRD), photoluminescence (PL) spectra, GSAS structural refinement, and absolute quantum yield and lifetimes were used to characterize the samples. Increasing the Ce3+ doping concentration in the CMLP host shifts the emission peak from 360 to 374 nm. Under UV excitation, the energy transfers (ETs) from Ce3+ to Tb3+ and from Ce3+ to Mn2+ in the CMLP host occurred mainly via a dipole–quadrupole mechanism, and the critical distances of the ion pairs (RC) were calculated by the quenching concentration method and spectral overlap method, respectively. The emission colors of the CMLP:Ce3+,Tb3+,Mn2+ samples could be adjusted from blue to green, and eventually to orange–red by the ET between Ce3+ and Tb3+/Mn2+. Moreover, a white light emission tunable over a wide range was obtained by precisely controlling the contents of Ce3+, Tb3+ and Mn2+. Temperature dependent luminescence spectra proved the good thermal stability of the as-prepared phosphor. Based on the good PL properties and varied hues of the CMLP host achieved by adjusting the doping concentration of the activators (Ce3+, Tb3+, Mn2+), CMLP might be promising as a host material for solid-state lighting and display fields.
Co-reporter:Yang Zhang, Xuejiao Li, Kai Li, Hongzhou Lian, Mengmeng Shang and Jun Lin
Journal of Materials Chemistry A 2015 vol. 3(Issue 14) pp:3294-3303
Publication Date(Web):10 Feb 2015
DOI:10.1039/C5TC00152H
Ba2(1−x)Zr2Si3O12 (BZSO):xEu2+ (x = 0.005–0.06) phosphors have been prepared by a high temperature solid state reaction. Using X-ray powder diffraction, the structural properties including the phase purity were analyzed through Rietveld analysis. The BZSO:Eu2+ phosphors exhibit a broad excitation band ranging from 200 to 450 nm, and an intense asymmetric green emission band centered at 501 nm under an excitation of 365 nm. The optimum doping concentration of Eu2+ was found for x = 0.03. The detailed energy transfer mechanism among Eu2+ in BZSO is found to be a dipole–dipole mechanism, and the critical distance (RC) for the Eu2+ ions calculated by the concentration quenching and spectral overlap methods are 20.45 and 25.83 Å, respectively. Furthermore, the unexpected blue shift (from green to cyan) in the emission and the increase in the thermal quenching barrier upon cation substitutions (Ca2+/Sr2+ for Ba2+) in the BZSO:0.03Eu2+ system have been investigated, which is due to the variation of the crystal field strength that the 5d orbital of the Eu2+ ion experiences. The underlying mechanism is ascribed to the differences between the average structure and the local coordination environments on the activator ions (Eu2+), as confirmed by the refinement results. Considering the merits of the near-UV light excitation, broad band emission, and good thermal stability, these materials have a potential application as white light emitting diode phosphors.
Co-reporter:Yang Zhang, Xuejiao Li, Kai Li, Hongzhou Lian, Mengmeng Shang, and Jun Lin
ACS Applied Materials & Interfaces 2015 Volume 7(Issue 4) pp:2715
Publication Date(Web):January 15, 2015
DOI:10.1021/am508859c
In this article, Eu-activated CaYAlO4 aluminate phosphors were synthesized by a solid-state reaction. Under UV light excitation, characteristic red line emission of Eu3+ was detected in the range of 570–650 nm. In addition, we introduced crystal-site engineering approach into the CaYAlO4 host through incorporation of Si4+–Ca2+ to replace Al3+–Y3+, which would shrink the AlO6 octahedrons, accompanied by the expansion of CaO9 polyhedron, and then enable the partial reduction of Eu3+ to Eu2+. The crystal structure and underlying mechanism have been clarified on the basis of the Rietveld refinement analysis. The PL spectra of Ca0.99+xY1–xAl1–xSixO4:Eu0.01 (x = 0–0.30) exhibit both green emission of Eu2+ (4f65d1–4f7, broadband around 503 nm) and red-orange emission of Eu3+ (5D0–7F1,2, 593 and 624 nm) under UV light excitation with a quantum yield of 38.5%. The CIE coordinates of Ca0.99+xY1–xAl1–xSixO4:Eu0.01 (x = 0–0.30) phosphors are regularly shifted from (0.482, 0.341) to (0.223, 0.457) with increasing x, which would expand the application of Eu. Furthermore, this investigation reveals the correlations of structure and property of luminescent materials, which would shed light on the development of novel phosphors suitable for lighting and display applications.Keywords: crystal-site engineering; phosphors; Rietveld refinement; structure and property; tunable emission; WLEDs
Co-reporter:Yuanxin Zhang, Zhiyao Hou, Yakun Ge, Kerong Deng, Bei Liu, Xuejiao Li, Quanshun Li, Ziyong Cheng, Ping’an Ma, Chunxia Li, and Jun Lin
ACS Applied Materials & Interfaces 2015 Volume 7(Issue 37) pp:20696
Publication Date(Web):September 1, 2015
DOI:10.1021/acsami.5b05522
Near-infrared light is an attractive stimulus due to its noninvasive and deep tissue penetration. Particularly, NIR light is utilized for cancer thermotherapy and on-demand release of drugs by the disruption of the delivery carriers. Here we have prepared a novel NIR-responsive DNA-hybrid-gated nanocarrier based on mesoporous silica-coated Cu1.8S nanoparticles. Cu1.8S nanoparticles, possessing high photothermal conversion efficiency under a 980 nm laser, were chosen as photothermal agents. The mesoporous silica structure could be used for drug storage/delivery and modified with aptamer-modified GC-rich DNA-helix as gatekeepers, drug vectors, and targeting ligand. Simultaneously, the as-produced photothermal effect caused denaturation of DNA double strands, which triggered the drug release of the DNA-helix-loaded hydrophilic drug doxorubicin and mesopore-loaded hydrophobic drug curcumin, resulting in a synergistic therapeutic effect. The Cu1.8S@mSiO2 nanocomposites endocytosed by cancer cells through the aptamer-mediated mode are able to generate rational release of doxorubicin/curcumin under NIR irradiation, strongly enhancing the synergistic growth-inhibitory effect of curcumin against doxorubicin in MCF-7 cells, which is associated with a strong mitochondrial-mediated cell apoptosis progression. The underlying mechanism of apoptosis showed a strong synergistic inhibitory effect both on the expression of Bcl-2, Bcl-xL, Mcl-1, and upregulated caspase 3/9 activity and on the expression level of Bak and Bax. Therefore, Cu1.8S@mSiO2 with efficient synergistic therapeutic efficiency is a potential multifunctional cancer therapy nanoplatform.Keywords: aptamer; copper sulfide; mesoporous silica; NIR light; photothermal conversion; synergistic effect
Co-reporter:Kai Li; Xiaoming Liu; Yang Zhang; Xuejiao Li; Hongzhou Lian
Inorganic Chemistry 2015 Volume 54(Issue 1) pp:323-333
Publication Date(Web):December 11, 2014
DOI:10.1021/ic502493c
A series of Ln3+ (Ln3+ = Eu3+/Tb3+/Dy3+/Sm3+) ion doped CaNb2O6 (CNO) phosphors have been prepared via the conventional high-temperature solid-state reaction route. The X-ray diffraction (XRD) and structure refinement, diffuse reflection, photoluminescence (PL), and fluorescent decay curves were used to characterize the as-prepared samples. Under UV radiation, the CNO host present a broad emission band from about 355 to 605 nm centered around 460 nm originating from the NbO6 octahedral groups, which has spectral overlaps with the excitation of f–f transitions of Eu3+/Tb3+/Dy3+/Sm3+ in CNO:Eu3+/Tb3+/Dy3+/Sm3+ samples. They show both host emission and respective emission lines derived from the characteristic f–f transitions of activators, which present different emission colors owing to the energy transfer from the NbO6 group in the host to Eu3+/Tb3+/Dy3+/Sm3+ with increasing activator concentrations. The decreases of decay lifetimes of host emissions in CNO:Eu3+/Tb3+/Dy3+/Sm3+ demonstrate the energy transfer from the hosts to Eu3+/Tb3+/Dy3+/Sm3+. The energy transfer mechanisms in CNO:Eu3+/Tb3+/Dy3+ phosphors have been determined to be a resonant type via dipole–dipole mechanisms. For CNO:Sm3+, the metal–metal charge transfer transition (MMCT) might contribute to the different variations of decay lifetimes and emission intensity from CNO:Eu3+/Tb3+/Dy3+ samples. The best quantum efficiency is 71.2% for CNO:0.01/0.02Dy3+. The PL properties of as-prepared materials indicate the promising application in UV-pumped white-emitting lighting diodes field.
Co-reporter:Kai Li; Mengmeng Shang; Hongzhou Lian
Inorganic Chemistry 2015 Volume 54(Issue 16) pp:7992-8002
Publication Date(Web):August 6, 2015
DOI:10.1021/acs.inorgchem.5b01197
A series of Ce3+-doped α-Ca1.65Sr0.35SiO4 (CSSO) phosphors without and with the substitutions of Si by Al/Ga/B were synthesized via the high-temperature solid-state reaction process. X-ray diffraction patterns and Rietveld refinements were used to demonstrate the successful incorporations of Al/Ga/B into CSSO:Ce3+. Without Al/Ga/B, the Ce3+ singly doped CSSO phosphors present intense blue emission, which correspond to the broad emission bands in visible region with the wavelength range from 360 to 580 nm upon 350 nm excitation. The optimal emission intensity occurs in CSSO:0.05Ce3+ sample with the emission peak wavelength at 436 nm. With the introduction of Al/Ga/B into the CSSO:0.05Ce3+, the emission peak shifts from 436 to 457/465/446 nm under 365 nm excitation, respectively. The red shift of Ce3+ emission is attributed to the polyhedral distortion of the cations, resulting in the enhancement of crystal field spitting due to the variations of the adjacent (Al/Ga/B,Si)O4 polyhedron. Moreover, the temperature-dependent photoluminescence was determined to be of light impact to CSSO:Ce3+ with the introduction of Al/Ga/B. This research is useful for enriching the emission colors of Ce3+-activated phosphors.
Co-reporter:Yinyin Chen, Zhiyao Hou, Bei Liu, Shanshan Huang, Chunxia Li and Jun Lin
Dalton Transactions 2015 vol. 44(Issue 7) pp:3118-3127
Publication Date(Web):15 Dec 2014
DOI:10.1039/C4DT03113J
A composite antitumor drug carrier platform, in which antitumor drug doxorubicin (DOX) loaded core–shell structured Cu9S5@mSiO2 nanoparticles were incorporated into poly(ε-caprolactone) and gelatin to form nanofibrous fabrics using an electrospinning process, was successfully assembled. The resultant multifunctional spun pieces could be implanted directly to the tumor site of mice using surgical procedures to achieve the orthotopic synergistic therapy combining the chemotherapy of the controlled release of DOX from mesoporous SiO2 with the photothermal treatment through the performance of the photothermal transformation of Cu9S5 under 980 nm laser irradiation in vivo. The experimental results in vivo demonstrated that the synergistic chemotherapy/photothermal treatment of DOX loaded Cu9S5@mSiO2 composite fibers under 980 nm laser irradiation has a more efficient tumor suppression effect, compared with a single chemotherapy of DOX loaded Cu9S5@mSiO2 composite fibers without the 980 nm laser irradiation or a single photothermal treatment from Cu9S5@mSiO2 composite fibers under 980 nm laser irradiation.
Co-reporter:Kai Li, Hongzhou Lian, Mengmeng Shang and Jun Lin
Dalton Transactions 2015 vol. 44(Issue 47) pp:20542-20550
Publication Date(Web):27 Oct 2015
DOI:10.1039/C5DT03565A
A series of novel color-tunable Ba3Y4O9:Bi3+,Eu3+ phosphors were prepared for the first time via the high-temperature solid-state reaction route. The effect of Bi3+ concentration on the emission intensity of Ba3Y4O9:Bi3+ was investigated. The emission spectra of the Ba3Y4O9:Bi3+,Eu3+ phosphors present both a greenish yellow band of Bi3+ emission centered at 523 nm, and many characteristic emission lines of Eu3+, derived from the allowed 3P1–1S0 transition of the Bi3+ ion and the 5D0–7FJ transition of the Eu3+ ion, respectively. The energy transfer phenomenon from Bi3+ to Eu3+ ions is observed under UV excitation in Bi3+, Eu3+ co-doped Ba3Y4O9 phosphors, and their transfer mechanism is demonstrated to be a resonant type via dipole–quadrupole interaction. The critical distance between Bi3+ and Eu3+ for the energy transfer effect was calculated via the concentration quenching and spectral overlap methods. Results show that color tuning from greenish yellow to orange red can be realized by adjusting the mole ratio of Bi3+ and Eu3+ concentrations based on the principle of energy transfer. Moreover, temperature-dependent PL properties, CIE chromaticity coordinates and quantum yields of Ba3Y4O9:Bi3+,Eu3+ phosphors were also supplied. It is illustrated that the as-prepared Ba3Y4O9:Bi3+,Eu3+ phosphors can be potential candidates for color-tunable phosphors applied in UV-pumped LEDs.
Co-reporter:Yang Zhang, Xiaoming Liu, Xuejiao Li, Kai Li, Hongzhou Lian, Mengmeng Shang and Jun Lin
Dalton Transactions 2015 vol. 44(Issue 17) pp:7743-7747
Publication Date(Web):05 Dec 2014
DOI:10.1039/C4DT03095H
We demonstrate a strategy to manipulate the valence state of Eu in CaGdAlO4 based on breaking down geometrical restrictions on the activators. This strategy could promote the search for novel phosphors for white light emission diodes (WLEDs).
Co-reporter:Kai Li, Yang Zhang, Xuejiao Li, Mengmeng Shang, Hongzhou Lian and Jun Lin
Dalton Transactions 2015 vol. 44(Issue 10) pp:4683-4692
Publication Date(Web):26 Jan 2015
DOI:10.1039/C4DT03720K
A series of Eu2+ and Tb3+ singly-doped and co-doped β-Ca3(PO4)2 phosphors have been synthesized via the high-temperature solid-state reaction method. Thermogravimetric (TG) analysis, fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) patterns and Rietveld refinements, photoluminescence (PL) spectra including temperature-dependent PL and quantum efficiency, and fluorescence decay lifetimes have been used to characterise the as-prepared samples. Under UV excitation, β-Ca3(PO4)2:Eu2+ presents a broad emission band centered at 415 nm, which can be decomposed into five symmetrical bands peaking at 390, 408, 421, 435 and 511 nm based on the substitution of five kinds of Ca2+ sites by Eu2+ ions. β-Ca3(PO4)2:Tb3+ shows characteristic emission lines under Tb3+ 4f–5d transition excitation around 223 nm. In β-Ca3(PO4)2:Eu2+, Tb3+ phosphors, similar excitation spectra monitored at 415 and 547 nm have been observed, which illustrates the possibility of energy transfer from Eu2+ to Tb3+ ions. The variations in the emission spectra and decay lifetimes further demonstrate the existence of energy transfer from Eu2+ to Tb3+ ions under UV excitation. The energy transfer mechanism has been confirmed to be dipole–quadrupole, which can be validated via the agreement of critical distances obtained from the concentration quenching (12.11 Å) and spectrum overlap methods (9.9–13.2 Å). The best quantum efficiency can reach 90% for the β-Ca3(PO4)2:0.01Eu2+, 0.15Tb3+ sample under 280 nm excitation. These results show that the developed phosphors may possess potential applications in UV-pumped white light-emitting diodes.
Co-reporter:Shanshan Huang, Ziyong Cheng, Yinyin Chen, Bei Liu, Xiaoran Deng, Ping'an Ma and Jun Lin
RSC Advances 2015 vol. 5(Issue 52) pp:41985-41993
Publication Date(Web):11 May 2015
DOI:10.1039/C5RA01750E
Mesoporous silica nanoparticles (MSNs) were firstly functionalized with upconversion luminescent Gd2O3:Yb3+,Er3+ via the Pechini sol–gel method. Then, polyelectrolyte multilayers (PEM) composed of poly(allyamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) were coated onto the Gd2O3:Yb3+,Er3+@MSNs using a layer-by-layer (LbL) technique to achieve the pH-responsive properties of the nanocarriers. PEM@Gd2O3:Yb3+,Er3+@MSNs loaded with doxorubicin hydrochloride (DOX) showed pH-responsive release and higher cytotoxicity towards MCF-7 breast cancer cells in vitro. Nanocomposites functionalized with Gd2O3:Yb3+,Er3+ can serve as T1-weighted magnetic resonance imaging (MRI) contrast agents. Nanoparticles emitting red signals under 980 nm laser excitation are suitable for use in potential bioimaging applications. The upconversion luminescent (UCL) intensity of PEM-coated nanocomposites can be adjusted by controlling the number of layers of the PAH/PSS coating. The PEM@Gd2O3:Yb3+,Er3+@MSNs can be used as a potential drug delivery system for MRI, UCL imaging, and pH-responsive chemotherapy.
Co-reporter:Yinyin Chen, Chunxia Li, Zhiyao Hou, Shanshan Huang, Bei Liu, Fei He, Laoyong Luo and Jun Lin
New Journal of Chemistry 2015 vol. 39(Issue 6) pp:4987-4993
Publication Date(Web):16 Apr 2015
DOI:10.1039/C5NJ00327J
A nanocomposite fabricated by electrostatic spinning, which incorporated polyaniline nanoparticles into poly(ε-caprolactone) and gelatin (PG), was used to form nanofiber fabrics. Polyaniline nanoparticles have a strong optical absorption at near-infrared (NIR) wavelengths and can convert optical energy into thermal energy under 808 nm laser irradiation, allowing them to ablate tumor cells thermally. Pieces of the nanocomposite were surgically implanted into tumors in mice, and orthotopic photothermal therapy was performed. The experimental results in vivo suggested that polyaniline PG can inhibit tumor growth efficiently by converting optical energy into thermal energy to ablate tumor cells.
Co-reporter:Mengmeng Shang, Jian Fan, Yang Zhang, Hongzhou Lian, Jun Lin
Inorganic Chemistry Communications 2015 Volume 52() pp:73-76
Publication Date(Web):February 2015
DOI:10.1016/j.inoche.2015.01.003
•The novel garnet-based phosphors were synthesized by solid state reaction and investigated the luminescent properties.•The311/122-YAMSO:Ce3 +, Mn2 + phosphors exhibit a blue emission of Ce3 + ion and a orange-red emission of Mn2 + ion.•The emitting colors can be tuned from cool to warm white by adjusting the Mn2+ concentration through energy transfer.Presently considerable interest in single-phase white-emitting for ultraviolet light-emitting diodes is stimulated. Here we report the effective single-phase phosphors based on YAG-garnet structure, which exhibit varied hues from blue through white and eventually orange by tuning the relative proportion of Ce3 +/Mn2 + excited at ultraviolet.White-light generation and full-colors were obtained in single-phase garnet-based Y3Al5 − 2xMgxSixO12:Ce3 +, Mn2 + (Mg2 +–Si4 + replacing Al(1)3 +–Al(2)3 + in garnet-Y3Al5O12 host lattice on octahedron and tetrahedral sites, x = 1 and 2) phosphors using energy transfer principle.
Co-reporter:Xiaoran Deng, Yunlu Dai, Jianhua Liu, Ying Zhou, Ping'an Ma, Ziyong Cheng, Yinyin Chen, Kerong Deng, Xuejiao Li, Zhiyao Hou, Chunxia Li, Jun Lin
Biomaterials 2015 50() pp: 154-163
Publication Date(Web):May 2015
DOI:10.1016/j.biomaterials.2015.01.040
Co-reporter:Yinyin Chen;Shi Liu;Zhiyao Hou;Pingan Ma;Dongmei Yang;Chunxia Li
Nano Research 2015 Volume 8( Issue 6) pp:1917-1931
Publication Date(Web):2015 June
DOI:10.1007/s12274-014-0701-y
A multifunctional, dual-drug carrier platform was successfully constructed. Core-shell structured NaGdF4:Yb/Er@NaGdF4:Yb@mSiO2-polyethylene glycol (abbreviated as UCNPS) nanoparticles loaded with the antitumor drug, doxorubicin (DOX) were incorporated into poly(ɛ-caprolactone) (PCL) and gelatin loaded with antiphlogistic drug, indomethacin (MC) to form nanofibrous fabrics (labeled as MC/UCNPS/DOX) via electrospinning process. The resultant multifunctional spinning pieces can be surgically implanted directly at the tumor site of mice as an orthotopic chemotherapy by controlled-release DOX from mesoporous silicon dioxide (SiO2) and upconversion fluorescence/magnetic resonance dual-model imaging through NaGdF4:Yb/Er@NaGdF4:Yb embedded in MC/UCNPS/DOX in vivo.
Co-reporter:Ruichan Lv, Piaoping Yang, Fei He, Shili Gai, Chunxia Li, Yunlu Dai, Guixin Yang, and Jun Lin
ACS Nano 2015 Volume 9(Issue 2) pp:1630
Publication Date(Web):January 12, 2015
DOI:10.1021/nn5063613
To integrate photodynamic therapy (PDT) with photothermal therapy (PTT) and chemotherapy for enhanced antitumor efficiency, we developed a mild and rational route to synthesize novel multifunctional GdOF:Ln@SiO2 (Ln = 10%Yb/1%Er/4%Mn) mesoporous capsules using strong up-conversion luminescent (UCL) GdOF:Ln as cores and mesoporous silica layer as shells, followed by modification with varied functional groups onto the framework. It was found that due to the codoped Yb/Er/Mn in GdOF, the markedly enhanced red emission can efficiently transfer energy to the conjugated PDT agent (ZnPc) which produces high singlet oxygen, and the incorporated carbon dots outside the shell can generate obvious thermal effect under 980 nm laser irradiation and also prevent the premature leaking of ZnPc. Simultaneously, the as-produced thermal effect can obviously enhance the doxorubicin (DOX) release, which greatly improves the chemotherapy, resulting in a synergistic therapeutic effect. The system exhibits drastically enhanced therapeutic efficiency against tumor growth, as demonstrated both in vitro and in vivo. Especially, the doped rare earth ions in the host endow the material with excellent UCL imaging, magnetic resonance imaging (MRI), and computed tomography (CT) imaging properties, thus realizing the target of multimodal imaging guided multiple therapies.Keywords: bioimaging; GdOF; photodynamic therapy; photothermal therapy; up-conversion;
Co-reporter:Zhiyao Hou, Yuanxin Zhang, Kerong Deng, Yinyin Chen, Xuejiao Li, Xiaoran Deng, Ziyong Cheng, Hongzhou Lian, Chunxia Li, and Jun Lin
ACS Nano 2015 Volume 9(Issue 3) pp:2584
Publication Date(Web):February 18, 2015
DOI:10.1021/nn506107c
Photodynamic therapy (PDT) is a promising antitumor treatment that is based on the photosensitizers that inhibit cancer cells by yielding reactive oxygen species (ROS) after irradiation of light with specific wavelengths. As a potential photosensitizer, titanium dioxide (TiO2) exhibits minimal dark cytotoxicity and excellent ultraviolet (UV) light triggered cytotoxicity, but is challenged by the limited tissue penetration of UV light. Herein, a novel near-infrared (NIR) light activated photosensitizer for PDT based on TiO2-coated upconversion nanoparticle (UCNP) core/shell nanocomposites (UCNPs@TiO2 NCs) is designed. NaYF4:Yb3+,Tm3+@NaGdF4:Yb3+ core/shell UCNPs can efficiently convert NIR light to UV emission that matches well with the absorption of TiO2 shells. The UCNPs@TiO2 NCs endocytosed by cancer cells are able to generate intracellular ROS under NIR irradiation, decreasing the mitochondrial membrane potential to release cytochrome c into the cytosol and then activating caspase 3 to induce cancer cell apoptosis. NIR light triggered PDT of tumor-bearing mice with UCNPs@TiO2 as photosensitizers can suppress tumor growth efficiently due to the better tissue penetration than UV irradiation. On the basis of the evidence of in vitro and in vivo results, UCNPs@TiO2 NCs could serve as an effective photosensitizer for NIR light mediated PDT in antitumor therapy.Keywords: core/shell structure; mitochondria-involved apoptosis; NIR light mediated; photodynamic therapy; titanium dioxide; upconversion nanoparticles;
Co-reporter:Mengmeng Shang, Chunxia Li and Jun Lin
Chemical Society Reviews 2014 vol. 43(Issue 5) pp:1372-1386
Publication Date(Web):17 Dec 2013
DOI:10.1039/C3CS60314H
White light-emitting diodes (WLEDs) as new solid-state light sources have a greatly promising application in the field of lighting and display. So far much effort has been devoted to exploring novel luminescent materials for WLEDs. Currently the major challenges in WLEDs are to achieve high luminous efficacy, high chromatic stability, brilliant color-rending properties, and price competitiveness against fluorescent lamps, which rely critically on the phosphor properties. In recent years, numerous efforts have been made to develop single-phase white-light-emitting phosphors for near-ultraviolet or ultraviolet excitation to solve the above challenges with certain achievements. This review article highlights the current methods to realize the white light emission in a single-phase host, including: (1) doping a single rare earth ion (Eu3+, Eu2+ or Dy3+) into appropriate single-phase hosts; (2) co-doping various luminescent ions with different emissions into a single matrix simultaneously, such as Tm3+/Tb3+/Eu3+, Tm3+/Dy3+, Yb3+/Er3+/Tm3+etc.; (3) codoping different ions in one host to control emission color via energy transfer processes; and (4) controlling the concentration of the defect and reaction conditions of defect-related luminescent materials.
Co-reporter:Guogang Li and Jun Lin
Chemical Society Reviews 2014 vol. 43(Issue 20) pp:7099-7131
Publication Date(Web):24 Jun 2014
DOI:10.1039/C4CS00109E
Nowadays there are several technologies used for flat panel displays (FPDs) and the development of FPDs with enhanced energy efficiency and improved display quality is strongly required. Field emission displays (FEDs) have been considered as one of the most promising next generation flat panel display technologies due to their excellent display performance and low energy consumption. For the development of FEDs, phosphors are irreplaceable components. In the past decade, the study of highly efficient low-voltage cathodoluminescent materials, namely FED phosphors, has become the focus of enhancing energy efficiency and realizing high-quality displays. This review summaries the recent progress in the chemical synthesis and improvement of novel, rare-earth and transition metal ions activated inorganic cathodoluminescent materials in powder and thin film forms. The discussion is focused on the modification of morphology, size, surface, composition and conductivity of phosphors and the corresponding effects on their cathodoluminescent properties. Special emphases are given to the selection of host and luminescent centers, the adjustment of emission colors through doping concentration optimization, energy transfer and mono- or co-doping activator ions, the improvement of chromaticity, color stability and color gamut as well as the saturation behavior and the degradation behavior of phosphors under the excitation of a low-voltage electron beam. Finally, the research prospects and future directions of FED phosphors are discussed with recommendations to facilitate the further study of new and highly efficient low-voltage cathodoluminescent materials.
Co-reporter:Yang Zhang;Zhijian Wu;Dongling Geng;Xiaojiao Kang;Mengmeng Shang;Xuejiao Li;Hongzhou Lian;Ziyong Cheng
Advanced Functional Materials 2014 Volume 24( Issue 42) pp:6581-6593
Publication Date(Web):
DOI:10.1002/adfm.201402092
ZnGa2O4 and ZnGa2O4: Mn2+/Eu3+ with uniform nanosphere (diameter about 400 nm) morphology have been synthesized via a facile hydrothermal approach. XRD, Raman spectra, XPS, FT-IR, SEM, TEM, photoluminescence (PL), and cathodoluminescecne (CL) spectra are used to characterize the resulting samples. The controlled experiments indicate the dosage of trisodium citrate and pH values are responsible for shape determination of the ZnGa2O4 products. The possible fast crystallization–dissolution–recrystallization formation mechanism for these nanospheres is presented. Under UV light and low-voltage electron beam excitation, ZnGa2O4, ZnGa2O4: Mn2+ and ZnGa2O4: Eu3+ emit bright blue, green, and red luminescence, respectively. Based on density functional theory calculations from first principles, the green and red emission are caused by the Mn 3d and Eu 4f electronic structures, respectively. Besides, the dependence of the CL intensity on the calcination temperature and electrical conductivity of the samples is presented. The ZnGa2O4: Mn2+ nanospheres have a higher CL intensity than that of bulk samples under the same excitation condition. The realization of three primary colors from a single host material suggests that full color display based on ZnGa2O4 nanospheres might be achievable, showing that these materials have potential applications in lighting and display fields.
Co-reporter:Hongzhou Lian, Yunlu Dai, Dongmei Yang, Ziyong Cheng, Chunxia Li, Zhiyao Hou, Mengmeng Shang and Jun Lin
Nanoscale 2014 vol. 6(Issue 16) pp:9703-9712
Publication Date(Web):16 Jun 2014
DOI:10.1039/C4NR02023E
Oil-dispersible monodispersed NaCeF4, NaCeF4:Tb3+ and NaCeF4:Yb3+ nanoparticles were prepared through a thermal decomposition method. Phase purity, morphology and luminescence properties were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and high resolution TEM (HRTEM), and photoluminescence (PL) spectra, respectively. The starting amount of NaF is crucial for phase purity, and the reaction time had an effect on the morphology of the products. Products with rectangles, rods, and their mixtures could be obtained at different reaction times. Under UV excitation, energy transfer from Ce3+ to lanthanide ions Tb3+ and Yb3+ could be observed in both NaCeF4:Tb3+ and NaCeF4:Yb3+. Energy transfer from Ce3+ to Tb3+ was proposed to be of a resonant type (ET) by luminescent dynamic studies with a theoretically calculated efficiency of up to 93%. Energy transfer from Ce3+ to Yb3+ was demonstrated to be a cooperative (CET) process, and the CET efficiency and total theoretical quantum efficiency were found to be 79% and 158%, respectively.
Co-reporter:Xuejiao Li, Yang Zhang, Dongling Geng, Jianshe Lian, Guo Zhang, Zhiyao Hou and Jun Lin
Journal of Materials Chemistry A 2014 vol. 2(Issue 46) pp:9924-9933
Publication Date(Web):07 Oct 2014
DOI:10.1039/C4TC01909A
Eu3+ and/or Tb3+-doped CaGdAlO4 phosphor samples were synthesized via a conventional high temperature solid-state reaction process. X-Ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) as well as cathodoluminescence (CL) spectra were used to characterize the samples. For CaGdAlO4:Tb3+, the concentration of doped Tb3+ has a significant effect on the 5D3/5D4 emission intensity due to the dipole–dipole cross-relaxation mechanism from 5D3 to 5D4. Under the 4f8 → 4f75d excitation of Tb3+ or low-voltage electron beam excitation, the CaGdAlO4:Tb3+ samples show tunable luminescence from blue to cyan and then to green with the variation of the Tb3+-doping concentration. For CaGdAlO4:Eu3+, the samples exhibit a reddish-orange emission corresponding to the 5D0,1 → 7F0,1,2,3 transitions of Eu3+. Energy transfer can take place from Tb3+ to Eu3+ when they are codoped in one host. Furthermore, for CaGdAlO4:Tb3+/Eu3+, a white emission can be realized in the single phase CaGdAlO4 host by reasonably adjusting the doping concentrations of Tb3+ and Eu3+ under low-voltage electron beam excitation. Due to the excellent PL, CL properties and good CIE chromaticity coordinates, the as-prepared Tb3+/Eu3+-doped CaGdAlO4 nanocrystalline phosphors have potential applications in field emission display devices.
Co-reporter:Ruichan Lv, Piaoping Yang, Yunlu Dai, Shili Gai, Fei He, and Jun Lin
ACS Applied Materials & Interfaces 2014 Volume 6(Issue 17) pp:15550
Publication Date(Web):August 20, 2014
DOI:10.1021/am504347e
Uniform Na5Lu9F32 hollow mesoporous spheres (HMSs) have been successfully prepared by a facile and mild (50 °C for 5 h) coprecipitation process, and Au nanocrystals (NCs) with particle size of about 10 nm were conjugated to poly(ether imide) (PEI) modified HMSs by electrostatic interaction. Compared with Na5Lu9F32:Yb/Er HMSs, the up-conversion (UC) luminescence intensity of Na5Lu9F32:Yb/Er@Au HMSs was much higher under low pump power due to the local field enhancement (LFE) of Au NCs, and there is a surface plasmon resonance (SPR) effect with nonradiative transitions which generates a thermal effect. These two effects have been proved by theoretical discrete-dipole approximation (DDA) simulation. The good biocompatibility of Na5Lu9F32:Yb/Er@Au HMSs indicates them as a promising candidate in the biological field. Particularly, under near-infrared (NIR) laser irradiation, a rapid doxorubicin (DOX) release was achieved due to the thermal effect of Au NCs. In this case, Na5Lu9F32:Yb/Er@Au HMSs exhibit an apparent NIR light-controlled “on/off” drug release pattern. In addition, UC luminescent images uptaken by cells show brighter green and red emission under NIR laser excitation. Therefore, this novel multifunctional (mesoporous, enhanced UC luminescent, and light-triggered drug release) material should be potential as a suitable targeted cancer therapy carrier and bioimaging.Keywords: hollow; light-triggered; mesoporous; up-conversion luminescence
Co-reporter:Dongling Geng, Hongzhou Lian, Mengmeng Shang, Yang Zhang, and Jun Lin
Inorganic Chemistry 2014 Volume 53(Issue 4) pp:2230-2239
Publication Date(Web):January 28, 2014
DOI:10.1021/ic402916b
Ce3+- and/or Mn2+-activated Y10(Si6O22N2)O2 phosphors have been prepared via a soft-chemical ammonolysis method. Structure refinement, scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared, and thermogravimetry analysis have been employed to characterize the phase purity, crystal structure, morphology, crystallization condition, chemical composition, and thermal stability of the products. The photoluminescence and cathodoluminescence properties for Ce3+- and Mn2+-doped Y10(Si6O22N2)O2 phosphors were studied in detail. For Ce3+/Mn2+ singly doped Y10(Si6O22N2)O2 phosphors, typical emissions of Ce3+ (blue) and Mn2+ (reddish-orange) ions can be observed. Especially, Ce3+ emission at different lattice sites 4f and 6h has been identified and discussed. Energy transfer from Ce3+(I) and Ce3+(II) to Mn2+ ions in Y10(Si6O22N2)O2:Ce3+,Mn2+ samples has been validated and confirmed by the photoluminescence spectra and luminescence decay times. A color-tunable emission in Y10(Si6O22N2)O2:Ce3+,Mn2+ phosphors can be achieved by an energy-transfer process and a change in the doping concentration of the activators. The temperature-dependent photoluminescence properties and degradation property of cathodoluminescence under continuous electron bombardment of as-synthesized phosphors prove that the Y10(Si6O22N2)O2 host has good stability. Therefore, the Y10(Si6O22N2)O2:Ce3+,Mn2+ phosphors may potentially serve as single-phase blue/reddish-orange phosphors for white-light-emitting diodes and field-emission displays.
Co-reporter:Mengmeng Shang, Jian Fan, Hongzhou Lian, Yang Zhang, Dongling Geng, and Jun Lin
Inorganic Chemistry 2014 Volume 53(Issue 14) pp:7748-7755
Publication Date(Web):June 27, 2014
DOI:10.1021/ic501063j
The influence of Mg2+–Si4+/Ge4+ incorporation into Ce3+-doped Y3Al5O12 garnet phosphors on the crystal structure and luminescence properties is described in this work. X-ray diffraction with Rietveld refinements, photoluminescence spectra, absolute quantum yield, thermal quenching behavior, and lifetimes were utilized to characterize samples. The introduction of Mg2+–Si4+/Ge4+ leads to an obvious red shift of emission wavelength under the excitation of blue light, especially for the series of Mg2+–Si4+ substitutions, which is suited for white light-emitting diodes (LEDs) with low color temperatures and good color rendering using only a single phosphor. More interestingly, an additional emission band locating at high-energy was observed with ultraviolet excitation, which is different than previous literature. Under the excitation of ultraviolet, the emission color for the Mg2+–Si4+ substitutions can be tuned from yellow-green to blue, which is expected to obtain single-phased phosphors with white emission excited with UV-LED chip. The usual Ce3+ emission band at low energy has stronger quenching at high temperatures. The mechanisms for the observed phenomena are discussed.
Co-reporter:Kai Li, Jian Fan, Xiaoyun Mi, Yang Zhang, Hongzhou Lian, Mengmeng Shang, and Jun Lin
Inorganic Chemistry 2014 Volume 53(Issue 22) pp:12141-12150
Publication Date(Web):November 6, 2014
DOI:10.1021/ic502058r
Co-reporter:Kai Li, Mengmeng Shang, Dongling Geng, Hongzhou Lian, Yang Zhang, Jian Fan, and Jun Lin
Inorganic Chemistry 2014 Volume 53(Issue 13) pp:6743-6751
Publication Date(Web):June 6, 2014
DOI:10.1021/ic500545y
A series of β-Na2Ca4(PO4)2(SiO4) (β-NCPS):A (A = Eu2+, Dy3+, Ce3+/Tb3+) phosphors were prepared via a high-temperature solid-state reaction route. The X-ray diffraction, Fourier transform infrared, photoluminescence (PL), cathodoluminescence (CL) properties, fluorescent lifetimes, and absolute quantum yield were exploited to characterize the samples. Under UV radiation, the β-NCPS:Eu2+ phosphors present bright green emissions, and the β-NCPS:Ce3+ phosphors show strong blue emissions, which are attributed to their 4f65d1 → 4f7 and 5d–4f allowed transitions, respectively. The β-NCPS:Ce3+, Tb3+ phosphors display intense tunable color from blue to green and high absolute quantum yields (81% for β-NCPS:0.12Ce3+ and 83% for β-NCPS:0.12Ce3+, 0.08Tb3+) when excited at 365 nm. Simultaneously, the energy transfer from Ce3+ to Tb3+ ions is deduced from the spectral overlap between Ce3+ emission and Tb3+ excitation spectra and demonstrated by the change of emission spectra and decay lifetimes. Moreover, the energy-transfer mechanism from Ce3+ to Tb3+ ions is confirmed to be exchange interaction according to the discussion of expression from Dexter and Reisfeld. Under a low-voltage electron-beam excitation, the β-NCPS:A (A = Eu2+, Dy3+, Ce3+/Tb3+) phosphors exhibit their characteristic emissions, and the emission profiles of β-NCPS:Ce3+,Tb3+ phosphors are obviously different from those of the PL spectra; this difference might be ascribed to their different luminescence mechanisms. These results in PL and CL properties suggest that β-NCPS:A (A = Eu2+, Dy3+, Ce3+/Tb3+) phosphors are potential candidates for solid-state lighting and field-emission displays.
Co-reporter:Yang Zhang, Xuejiao Li, Dongling Geng, Mengmeng Shang, Hongzhou Lian, Ziyong Cheng and Jun Lin
CrystEngComm 2014 vol. 16(Issue 11) pp:2196-2204
Publication Date(Web):13 Dec 2013
DOI:10.1039/C3CE42323A
Uniform YOF nano/micro-crystals with nanosphere and micro-rod morphologies have been synthesized by simply modulating the pH values of the initial solution through a facile hydrothermal route without using any morphology controlling agent. The possible formation mechanism of the micro-rods has been proposed based on a series of time-dependent experiments. XRD, FT-IR, TG-DTA, Raman spectra, SEM and TEM, as well as down-conversion (DC) luminescence (photoluminescence, cathodoluminescence) and up-conversion (UC) luminescence spectra are used to characterize the resulting YOF samples. The results of the DC and UC luminescence properties prove that the as-synthesized YOF are excellent host lattices for rare earth luminescence. Among the different morphologies, YOFs with a micro-rod morphology present the strongest luminescence intensity which may be due to the larger size and the fewer quenching sites, confirmed by the results of morphology-dependent luminescence intensity.
Co-reporter:Yuan Wu, Dongmei Yang, Xiaojiao Kang, Yang Zhang, Shanshan Huang, Chunxia Li and Jun Lin
CrystEngComm 2014 vol. 16(Issue 6) pp:1056-1063
Publication Date(Web):25 Nov 2013
DOI:10.1039/C3CE41854E
LaF3:Yb3+/Er3+ upconversion (UC) crystals with self-assembling microstructures have been synthesized via a simple one-pot ionothermal method. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy were used to characterize the samples. The samples crystallize in the pure hexagonal phase and self-assemble into the aligned arrays like a string of pearls. The effects of reaction temperature, reaction time, the volume ratio of ionic liquid (IL)/water in the mixed solvent and solvent composition on the size and morphology of the products have been studied in detail and a possible formation mechanism has also been proposed. The results indicate that the adoption of water–IL solvent mixture as reaction medium facilitates the particle morphology control. Furthermore, a bright yellowish-green emission can be obtained from the LaF3:Yb3+/Er3+ under 980 nm laser excitation. Such a material shows potential applications in color displays, light-emitting diodes, and optical storage.
Co-reporter:Yang Zhang, Xuejiao Li, Xiaojiao Kang, Zhiyao Hou and Jun Lin
Physical Chemistry Chemical Physics 2014 vol. 16(Issue 22) pp:10779-10787
Publication Date(Web):09 Apr 2014
DOI:10.1039/C4CP00817K
In this paper, well defined GdOF:Yb3+/Er3+, Tm3+, Ho3+ nano/submicrocrystals with multiform morphologies were prepared via the urea-based precipitation method without using any surfactants. The morphologies of the GdOF products, including spindles and spheres with different sizes (30–550 nm), could be easily modulated by changing the fluorine sources, and the possible formation mechanism has been presented. XRD, FT-IR, SEM, TEM, as well as up-conversion (UC) photoluminescence spectra were used to characterize the prepared samples. Under 980 nm NIR excitation, the relative emission intensities and emission colors of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ doped GdOF could be precisely adjusted over a wide range by tuning the Yb3+ doping concentration. The strategies for color tuning of UC emission proposed in the current system may be helpful to achieve efficient multicolor luminescence under 980 nm laser excitation. In addition, the corresponding UC mechanisms in the co-doping GdOF systems were analyzed in detail based on the emission spectra and the plot of luminescence intensity to pump power.
Co-reporter:Suwen Li, Xuejiao Li, Yi Jiang, Zhiyao Hou, Ziyong Cheng, Pingan Ma, Chunxia Li and Jun Lin
RSC Advances 2014 vol. 4(Issue 98) pp:55100-55107
Publication Date(Web):17 Oct 2014
DOI:10.1039/C4RA09266J
Highly dispersible LaF3:x% Tb3+ (x = 1, 3, 5, 8, 10) nanoparticles capped with citrate ligands have been prepared and functionalized by salicylate and 5-sulfosalicylate, respectively. The structure, morphology, photoluminescence properties, fluorescence dynamics and ligand sensitization mechanism have been studied systemically. Monitoring the characteristic emission of the Tb3+ 5D4–7F5 transition, the broad absorption bands in the UV domain are obtained with the functionalized nanoparticles. Under excitation of the π–π* electron transition absorption of salicylate (or 5-sulfosalicylate), the enhanced luminescence of Tb3+ ions is achieved in the functionalized nanoparticles. The ligand sensitization is potentially interpreted by a dipole–dipole sensitization mechanism. The luminescence lifetimes of Tb3+ ions in the nanoparticles functionalized by aromatic carboxylate acids are longer than the ones in LaF3:Tb3+ nanoparticles capped with citrate ligands.
Co-reporter:Dongling Geng;Kai Li;Hongzhou Lian;Mengmeng Shang;Yang Zhang;Zhijian Wu
European Journal of Inorganic Chemistry 2014 Volume 2014( Issue 11) pp:1955-1964
Publication Date(Web):
DOI:10.1002/ejic.201400001
Abstract
Ce3+-, Tb3+-, and Dy3+-activated Y4Si2N2O7 phosphors have been prepared by the Pechini-type sol–gel method followed by ammonolysis of the precursors. The phase purity, morphology, crystallization condition, chemical composition, and thermal stability of the products have been studied carefully by X-ray diffraction (XRD), energy-dispersive X-ray (EDX), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), fourier-transform infrared (FTIR), and thermogravimetry analysis (TGA) techniques. The photoluminescence (PL) and cathodoluminescence (CL) properties of Ce3+-, Tb3+-, and Dy3+-doped Y4Si2N2O7 phosphors were also investigated. The electronic structure of Y4Si2N2O7 has been investigated by density-functional theory methods. The calculations revealed that the nitrogen atom contributes more excited electrons than the O atom. The band gap has been calculated through the reflection spectrum of the Y4Si2N2O7 host. For Ce3+/Tb3+/Dy3+ singly doped Y4Si2N2O7 products, the phosphors give the typical emissions of the activators. The energy transfers from Ce3+ to Tb3+ and Dy3+ ions have been found and demonstrated through the PL spectra and luminescence decay times. The emission color of Y4Si2N2O7:Ce3+, Tb3+ and Y4Si2N2O7:Ce3+, Dy3+ samples can be tuned by energy transfer processes. Additionally, the temperature-dependent PL properties and the degradation property of CL under continuous electron bombardment of the as-synthesized phosphors prove that the Y4Si2N2O7 host has good stability. Therefore, the Y4Si2N2O7:Ce3+, Tb3+, Dy3+ phosphors could serve as a promising candidate for UV W-LEDs and FEDs.
Co-reporter:Bei Liu;Chunxia Li;Dongmei Yang;Zhiyao Hou;Ping'an Ma;Ziyong Cheng;Hongzhou Lian;Shanshan Huang
European Journal of Inorganic Chemistry 2014 Volume 2014( Issue 11) pp:1906-1913
Publication Date(Web):
DOI:10.1002/ejic.201301460
Abstract
We present the fabrication, upconversion-luminescence cell imaging, and drug-storage/release properties of upconversion-luminescent core/mesoporous-silica-shell-structured β-NaYF4:Yb3+,Er3+@SiO2@mSiO2 composite nanospheres with a size of 80 nm. The biocompatibility test on L929 fibroblast cells using a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay reveals the low cytotoxicity of the system. The drug-storage and in vitro release tests indicate that these multifunctional nanomaterials have controlled drug-loading and -release properties for ibuprofen (IBU). Moreover, the upconversion (UC) emission intensity of IBU-β-NaYF4:Yb3+,Er3+@SiO2@mSiO2 composite nanospheres increases gradually along with the released amount of IBU. Additionally, upconversion luminescence images of β-NaYF4:Yb3+,Er3+@SiO2@mSiO2 uptaken by cells show clear green emission under 980 nm infrared laser excitation. These findings make these material promising for applications in the bioimaging, drug delivery, and disease therapy fields on the basis of its upconversion-luminescent and mesoporous properties.
Co-reporter:Xiaoyun Mi, Kai Du, Kai Huang, Peng Zhou, Dongling Geng, Yang Zhang, Mengmeng Shang, Jun Lin
Materials Research Bulletin 2014 60() pp: 72-78
Publication Date(Web):
DOI:10.1016/j.materresbull.2014.08.017
Co-reporter:Dongmei Yang, Yunlu Dai, Jianhua Liu, Ying Zhou, Yinyin Chen, Chunxia Li, Ping'an Ma, Jun Lin
Biomaterials 2014 35(6) pp: 2011-2023
Publication Date(Web):
DOI:10.1016/j.biomaterials.2013.11.018
Co-reporter:Ziyong Cheng, Yunlu Dai, Xiaojiao Kang, Chunxia Li, Shanshan Huang, Hongzhou Lian, Zhiyao Hou, Pingan Ma, Jun Lin
Biomaterials 2014 35(24) pp: 6359-6368
Publication Date(Web):
DOI:10.1016/j.biomaterials.2014.04.029
Co-reporter:Yang Zhang ; Dongling Geng ; Xuejiao Li ; Jian Fan ; Kai Li ; Hongzhou Lian ; Mengmeng Shang
The Journal of Physical Chemistry C 2014 Volume 118(Issue 31) pp:17983-17991
Publication Date(Web):July 8, 2014
DOI:10.1021/jp504437f
Eu3+-/Er3+-activated YTiTaO6 phosphors have been prepared via conventional solid state reaction process. X-ray diffraction (XRD) and structure refinement, Raman spectra, X-ray photoelectron Spectrum (XPS), photoluminescence (PL) spectra, cathodoluminescence (CL) spectra, and lifetimes were utilized to characterize the synthesized samples. Under UV light excitation, the YTiTaO6 sample shows broad band emission centered near 505 nm due to the Ta(Ti)O6 polyhedron. Eu3+ and Er3+ ions doped YTiTaO6 samples show strong line emissions coming from the characteristic f–f transitions. The energy transfer from the Ta(Ti)O6 group of the host to Eu3+ and Er3+ in YTiTaO6 phosphors has been demonstrated to be a resonant type via a dipole–dipole mechanism, and the critical distance (RC) for host emission to Eu3+ and Er3+ calculated by concentration quenching method are 10.02 and 18.86 Å, respectively. Under the low voltage electron beam excitation, the CL spectra of YTiTaO6, YTiTaO6: Eu3+, and YTiTaO6: Er3+ samples are similar to their PL spectra, exhibiting bluish-green, red, and green luminescence, respectively, which indicates that these materials might be promising for application in solid-state lighting and field-emission displays.
Co-reporter:Min Liu, Hui Liu, Shufen Sun, Xuejiao Li, Yanmin Zhou, Zhiyao Hou, and Jun Lin
Langmuir 2014 Volume 30(Issue 4) pp:1176-1182
Publication Date(Web):January 17, 2014
DOI:10.1021/la500131d
Porous hydroxyapatite (HAp) composite fibers functionalized with up-conversion (UC) luminescent and magnetic Na(Y/Gd)F4:Yb3+,Er3+ nanocrystals (NCs) have been fabricated via electrospinning. After transferring hydrophobic oleic acid-capped Na(Y/Gd)F4:Yb3+,Er3+ NCs into aqueous solution, these water-dispersible NCs were dispersed into precursor electrospun solution containing CTAB. Na(Y/Gd)F4:Yb3+,Er3+@HAp composite fibers were fabricated by the high temperature treatment of the electrospun Na(Y/Gd)F4:Yb3+,Er3+ NCs decorated precursor fibers. The biocompatibility test on MC 3T3-E1 cells using MTT assay shows that the HAp composite fibers have negligible cytotoxity, which reveals the HAp composite fibers could be a drug carrier for drug delivery. Because the contrast brightening is enhanced at increased concentrations of Gd3+, the HAp composite fibers can serve as T1 magnetic resonance imaging contrast agents. In addition, the composites uptaken by MC 3T3-E1 cells present the UC luminescent emission of Er3+ under the excitation of a 980 nm near-infrared laser. The above findings reveal Na(Y/Gd)F4:Yb3+,Er3+@HAp composite fibers have potential applications in drug storage/release and magnetic resonance/UC luminescence imaging.
Co-reporter:Lin Wang, Jianhua Liu, Yunlu Dai, Qiang Yang, Yuanxin Zhang, Piaoping Yang, Ziyong Cheng, Hongzhou Lian, Chunxia Li, Zhiyao Hou, Ping’an Ma, and Jun Lin
Langmuir 2014 Volume 30(Issue 43) pp:13042-13051
Publication Date(Web):2017-2-22
DOI:10.1021/la503444g
Nanoparticles have been explored as nonviral gene carriers for years because of the simplicity of surface modification and lack of immune response. Lanthanide-based upconversion nanoparticles (UCNPs) are becoming attractive candidates for biomedical applications in virtue of their unique optical properties and multimodality imaging ability. Here, we report a UCNPs-based structure with polyethylenimine coating for both efficient gene transfection and trimodality imaging. Cytotoxicity tests demonstrated that the nanoparticles exhibited significantly decreased cytotoxicity compared to polyethylenimine polymer. Further, in vitro studies revealed that the gene carriers are able to transfer the enhanced green fluorescence protein (EGFP) plasmid DNA into Hela cells in higher transfection efficiency than PEI. Gene silencing was also examined by delivering bcl-2 siRNA into Hela cells, resulting in significant downregulation of target bcl-2 mRNA. More importantly, we demonstrated the feasibility of upconversion gene carriers to serve as effective contrast agents for MRI/CT/UCL trimodality imaging both in vitro and in vivo. The facile fabrication process, great biocompatibility, enhanced gene transfection efficiency, and great bioimaging ability can make it promising for application in gene therapy.
Co-reporter:Yunlu Dai ; Haihua Xiao ; Jianhua Liu ; Qinghai Yuan ; Ping’an Ma ; Dongmei Yang ; Chunxia Li ; Ziyong Cheng ; Zhiyao Hou ; Piaoping Yang
Journal of the American Chemical Society 2013 Volume 135(Issue 50) pp:18920-18929
Publication Date(Web):November 26, 2013
DOI:10.1021/ja410028q
Controlling anticancer drug activity and release on demand is very significant in cancer therapy. The photoactivated platinum(IV) pro-drug is stable in the dark and can be activated by UV light. In this study, we develop a multifunctional drug delivery system combining upconversion luminescence/magnetic resonance/computer tomography trimodality imaging and NIR-activated platinum pro-drug delivery. We use the core–shell structured upconversion nanoparticles to convert the absorbed NIR light into UV to activate the trans-platinum(IV) pro-drug, trans,trans,trans-[Pt(N3)2(NH3)(py)(O2CCH2CH2COOH)2]. Compared with using the UV directly, the NIR has a higher tissue penetration depth and is less harmful to health. Meanwhile, the upconversion nanoparticles can effectively deliver the platinum(IV) pro-drugs into the cells by endocytosis. The mice treated with pro-drug-conjugated nanoparticles under near-infrared (NIR) irradiation demonstrated better inhibition of tumor growth than that under direct UV irradiation. This multifunctional nanocomposite could be used as multimodality bioimaging contrast agents and transducers by converting NIR light into UV for control of drug activity in practical cancer therapy.
Co-reporter:Yang Zhang ; Dongling Geng ; Xiaojiao Kang ; Mengmeng Shang ; Yuan Wu ; Xuejiao Li ; Hongzhou Lian ; Ziyong Cheng
Inorganic Chemistry 2013 Volume 52(Issue 22) pp:12986-12994
Publication Date(Web):November 6, 2013
DOI:10.1021/ic401501t
YOF:Ln3+ (Ln = Tb, Eu, Tm, Dy, Ho, Sm) nano-/microstructures with a variety of novel and well-defined morphologies, including nanospheres, nanorod bundles, and microspindles, have been prepared through a convenient modified urea-based homogeneous precipitation (UBHP) technique followed by a heat treatment. The sizes and morphologies of the YOF products could be easily modulated by changing the pH values and fluoride sources. XRD, TG-DTA, FT-IR, SEM, and TEM, as well as photoluminescence (PL) and cathodoluminescence (CL) spectra, were used to characterize the prepared samples. The YOF:Ln3+ nanospheres show the characteristic f–f transitions of Ln3+ (Ln = Tb, Eu, Tm, Dy, Ho, Sm) ions and give bright green, red, blue, yellow, blue-green, and yellow-orange emission, respectively, under UV light and low-voltage electron beam excitation. Furthermore, YOF:0.03Tb3+ phosphors exhibit green luminescence with superior properties in comparison with the commercial phosphor ZnO:Zn to a degree, which is advantageous for improving display quality. Because of the simultaneous luminescence of Ln3+ in the YOF host, the luminescence colors of YOF:Ln3+ phosphors can be precisely adjusted by changing the doped Ln3+ ions and corresponding concentrations, which makes these materials hold great promise for applications in field-emission displays.
Co-reporter:Dongling Geng ; Mengmeng Shang ; Yang Zhang ; Hongzhou Lian
Inorganic Chemistry 2013 Volume 52(Issue 23) pp:13708-13718
Publication Date(Web):November 4, 2013
DOI:10.1021/ic402305x
A series of single-phase phosphors based on KNaCa2(PO4)2 (KNCP):A (A = Ce3+, Eu2+, Tb3+, Mn2+, Sm3+) have been prepared via the Pechini-type sol–gel method. Photoluminescence (PL) and cathodoluminescence (CL) properties of Ce3+-, Eu2+-, Tb3+-, Mn2+-, and Sm3+-activated KNCP phosphors were investigated. For the A singly doped KNCP samples, they exhibit the characteristic emissions of the A activator. Na+ ions exhibit the best charge compensation result among Li+, Na+, and K+ ions for Ce3+-, Tb3+-, and Sm3+-doped KNCP samples. The energy transfers from Ce3+ to Tb3+ and Mn2+ ions as well as Eu2+ to Tb3+ and Mn2+ have been validated. The emission colors of KNCP:Ce3+/Eu2+, Tb3+/Mn2+, Na+ samples can be adjusted by energy transfer process and changing the Tb3+/Mn2+ concentration. More importantly, white light emission in KNCP:Eu2+, Mn2+ system has been obtained. The KNCP:Tb3+, Na+ sample shows tunable luminescence from blue to cyan and then to green with the change of Tb3+ concentration due to the cross-relaxation from 5D3 to 5D4. A white emission can also be realized in the single-phase KNCP host by reasonably adjusting the doping concentrations of Tb3+ and Sm3+ (reddish-orange emission) under low-voltage electron beam excitation. Additionally, the temperature-dependent PL properties of as-prepared phosphors reveal that the KNCP host has good thermal stability. Therefore, the KNCP:A (A = Ce3+, Eu2+, Tb3+, Mn2+, Sm3+) phosphors could be regarded as good candidates for UV W-LEDs and FEDs.
Co-reporter:Dongling Geng, Mengmeng Shang, Yang Zhang, Hongzhou Lian and Jun Lin
Dalton Transactions 2013 vol. 42(Issue 43) pp:15372-15380
Publication Date(Web):14 Aug 2013
DOI:10.1039/C3DT51670A
Eu2+ singly and Eu2+/Mn2+ co-doped Na2SrMg(PO4)2 (NSMP) phosphors have been prepared via a high-temperature solid-state reaction process. Upon UV excitation of 260–360 nm, the NSMP:xEu2+ phosphors exhibit a violet band located at 399 nm and a blue band centered at 445 nm, which originate from Eu2+ ions occupying two different crystallographic sites: Eu2+(I) and Eu2+(II), respectively. Excitation wavelengths longer than 380 nm can selectively excite Eu2+(II) to emit blue light. Energy transfer processes in the Eu2+(I)–Eu2+(II) and Eu2+–Mn2+ pairs have been observed and investigated by luminescence spectra and decay curves. The emission color of as-prepared samples can be tuned by changing the relative concentrations of Eu2+ and Mn2+ ions and adjusting the excitation wavelength. Under UV excitation of 323 nm, the absolute quantum yield of NSMP:0.005Eu2+ is 91%, which is higher than most of the other Eu2+-doped phosphors reported previously. The temperature dependent luminescence properties and decay curves (4.3–450 K) of NSMP:Eu2+ and NSMP:Eu2+, Mn2+ phosphors have been studied in detail. Thermal quenching of Eu2+ has been observed while the emission band of Mn2+ shows a blue-shift and an abnormal increase of intensity with increasing temperature. The unusual thermal quenching behavior indicates that the NSMP compound can serve as a good lattice host for Mn2+ ions which can be used as a red-emitting phosphor. Additionally, the lifetimes for Eu2+(I) and Eu2+(II) increase with increasing temperatures.
Co-reporter:Yang Zhang, Xiaojiao Kang, Dongling Geng, Mengmeng Shang, Yuan Wu, Xuejiao Li, Hongzhou Lian, Ziyong Cheng and Jun Lin
Dalton Transactions 2013 vol. 42(Issue 39) pp:14140-14148
Publication Date(Web):22 Jul 2013
DOI:10.1039/C3DT51576A
GdOF:Ln3+ (Ln = Eu, Tb, Tm, Dy, Ho and Sm) microspheres (1.5 μm) with high uniformity and monodispersity have been synthesized via a facile hydrothermal method followed by heat treatment (600 °C). X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), as well as photoluminescence (PL) and cathodoluminescence (CL) spectra are used to characterize the resulting samples. A series of controlled experiments indicate that sodium citrate (Cit3−) as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the dosage of Cit3− and pH values in the initial solution. The possible formation mechanism for these microspheres has been presented. Under UV light and low-voltage electron beam excitation, GdOF:Ln3+ microspheres show the characteristic f–f transitions of Ln3+ (Eu, Tb/Ho, Tm, Dy and Sm) ions and give bright red, green, blue, yellow and yellowish-orange emission, respectively. In addition, multicolored luminescence containing white emission have been successfully confected for co-doped GdOF:Ln3+ phosphors by changing the doped Ln3+ ions and adjusting their doping concentrations due to the simultaneous luminescence of Ln3+ in the GdOF host, making these materials have potential applications in field-emission display devices.
Co-reporter:Zhiyao Hou, Kerong Deng, Chunxia Li, Xiaoran Deng, Hongzhou Lian, Ziyong Cheng, Dayong Jin, Jun Lin
Biomaterials (September 2016) Volume 101() pp:32-46
Publication Date(Web):September 2016
DOI:10.1016/j.biomaterials.2016.05.024
The current near-infrared (NIR) light-induced photodynamic therapy (PDT) can enhance the tissue penetration depth to trigger photosensitizers (PSs) far from the surface. NIR-mediated PDT is still challenged by overheating effect on normal tissues, limited tumor selectivity and low reactive oxygen species (ROS) yields. Here we construct a dual-agent photosensitizing nanoplatform by combining UV-blue upconversion emitting NaYF4:Yb/Tm@NaYF4:Yb@NaNdF4:Yb@NaYF4 (labeled as UCNPs) multi-shell nanocrystals with titanium dioxide (TiO2, UV-light-excited PS) and hypocrellin A (HA, blue-light-excited PS), which can induce cancer cell apoptosis by 808 nm light-triggered and hyaluronic acid (Hyal)-targeted PDT. In this construction strategy, the crystallized TiO2 shells on the surface of UCNPs can play dual roles as UV-light excited PS and conjugation site for Hyal, and then Hyal is served as targeting-ligand as well as the carrier of HA simultaneously. The step-by-step reactive mode of loading PSs and modifying targeting-ligands is a controllable and ordered design based on the use of one intermediate product as the reaction site for the next component. The Nd3+-sensitized UCNPs with quenching reduction layer can efficiently convert 808 nm NIR light to UV-blue emission for simultaneous activation of two PSs with enhanced intracellular ROS generation. Through the in vitro and in vivo experiment results, the dual-photosensitizers nanoplatform presents enhanced anti-tumor efficacy by effective targeting cellular uptake and taking full advantage of upconversion emission, which may make a major step toward next generation of NIR-mediated PDT.
Co-reporter:Zhiyao Hou, Kerong Deng, Chunxia Li, Xiaoran Deng, Hongzhou Lian, Ziyong Cheng, Dayong Jin, Jun Lin
Biomaterials (September 2016) Volume 101() pp:
Publication Date(Web):1 September 2016
DOI:10.1016/j.biomaterials.2016.05.024
The current near-infrared (NIR) light-induced photodynamic therapy (PDT) can enhance the tissue penetration depth to trigger photosensitizers (PSs) far from the surface. NIR-mediated PDT is still challenged by overheating effect on normal tissues, limited tumor selectivity and low reactive oxygen species (ROS) yields. Here we construct a dual-agent photosensitizing nanoplatform by combining UV-blue upconversion emitting NaYF4:Yb/Tm@NaYF4:Yb@NaNdF4:Yb@NaYF4 (labeled as UCNPs) multi-shell nanocrystals with titanium dioxide (TiO2, UV-light-excited PS) and hypocrellin A (HA, blue-light-excited PS), which can induce cancer cell apoptosis by 808 nm light-triggered and hyaluronic acid (Hyal)-targeted PDT. In this construction strategy, the crystallized TiO2 shells on the surface of UCNPs can play dual roles as UV-light excited PS and conjugation site for Hyal, and then Hyal is served as targeting-ligand as well as the carrier of HA simultaneously. The step-by-step reactive mode of loading PSs and modifying targeting-ligands is a controllable and ordered design based on the use of one intermediate product as the reaction site for the next component. The Nd3+-sensitized UCNPs with quenching reduction layer can efficiently convert 808 nm NIR light to UV-blue emission for simultaneous activation of two PSs with enhanced intracellular ROS generation. Through the in vitro and in vivo experiment results, the dual-photosensitizers nanoplatform presents enhanced anti-tumor efficacy by effective targeting cellular uptake and taking full advantage of upconversion emission, which may make a major step toward next generation of NIR-mediated PDT.
Co-reporter:Fei He, Lili Feng, Piaoping Yang, Bin Liu, Shili Gai, Guixin Yang, Yunlu Dai, Jun Lin
Biomaterials (October 2016) Volume 105() pp:77-88
Publication Date(Web):October 2016
DOI:10.1016/j.biomaterials.2016.07.031
Upon near-infrared (NIR) light irradiation, the Nd3+ doping derived down-conversion luminescence (DCL) in NIR region and thermal effect are extremely fascinating in bio-imaging and photothermal therapy (PTT) fields. However, the concentration quenching induced opposite changing trend of the two properties makes it difficult to get desired DCL and thermal effect together in one single particle. In this study, we firstly designed a unique NaGdF4:0.3%Nd@NaGdF4@NaGdF4:10%Yb/1%Er@NaGdF4:10%Yb @NaNdF4:10%Yb multiple core-shell structure. Here the inert two layers (NaGdF4 and NaGdF4:10%Yb) can substantially eliminate the quenching effects, thus achieving markedly enhanced NIR-to-NIR DCL, NIR-to-Vis up-conversion luminescence (UCL), and thermal effect under a single 808 nm light excitation simultaneously. The UCL excites the attached photosensitive drug (Au25 nanoclusters) to generate singlet oxygen (1O2) for photodynamic therapy (PDT), while DCL with strong NIR emission serves as probe for sensitive deep-tissue imaging. The in vitro and in vivo experimental results demonstrate the excellent cancer inhibition efficacy of this platform due to a synergistic effect arising from the combined PTT and PDT. Furthermore, multimodal imaging including fluorescence imaging (FI), photothermal imaging (PTI), and photoacoustic imaging (PAI) has been obtained, which is used to monitor the drug delivery process, internal structure of tumor and photo-therapeutic process, thus achieving the target of imaging-guided cancer therapy.
Co-reporter:Fei He, Lili Feng, Piaoping Yang, Bin Liu, Shili Gai, Guixin Yang, Yunlu Dai, Jun Lin
Biomaterials (October 2016) Volume 105() pp:
Publication Date(Web):1 October 2016
DOI:10.1016/j.biomaterials.2016.07.031
Upon near-infrared (NIR) light irradiation, the Nd3+ doping derived down-conversion luminescence (DCL) in NIR region and thermal effect are extremely fascinating in bio-imaging and photothermal therapy (PTT) fields. However, the concentration quenching induced opposite changing trend of the two properties makes it difficult to get desired DCL and thermal effect together in one single particle. In this study, we firstly designed a unique NaGdF4:0.3%Nd@NaGdF4@NaGdF4:10%Yb/1%Er@NaGdF4:10%Yb @NaNdF4:10%Yb multiple core-shell structure. Here the inert two layers (NaGdF4 and NaGdF4:10%Yb) can substantially eliminate the quenching effects, thus achieving markedly enhanced NIR-to-NIR DCL, NIR-to-Vis up-conversion luminescence (UCL), and thermal effect under a single 808 nm light excitation simultaneously. The UCL excites the attached photosensitive drug (Au25 nanoclusters) to generate singlet oxygen (1O2) for photodynamic therapy (PDT), while DCL with strong NIR emission serves as probe for sensitive deep-tissue imaging. The in vitro and in vivo experimental results demonstrate the excellent cancer inhibition efficacy of this platform due to a synergistic effect arising from the combined PTT and PDT. Furthermore, multimodal imaging including fluorescence imaging (FI), photothermal imaging (PTI), and photoacoustic imaging (PAI) has been obtained, which is used to monitor the drug delivery process, internal structure of tumor and photo-therapeutic process, thus achieving the target of imaging-guided cancer therapy.
Co-reporter:Sisi Liang, Mengmeng Shang, Hongzhou Lian, Kai Li, Yang Zhang and Jun Lin
Journal of Materials Chemistry A 2017 - vol. 5(Issue 11) pp:NaN2935-2935
Publication Date(Web):2017/02/24
DOI:10.1039/C6TC05499D
In order to improve the quality of lighting and display devices based on InGaN blue chips, blue light excitable red phosphor is an essential component. Here, we prepared a series of efficient red emitting phosphors of Mg14Ge5O24 doped with different concentrations of Mn4+ based on a conventional solid-state reaction. Crystal structure, composition, morphology, and luminescence properties of samples were characterized by utilizing Rietveld refinement, X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and PL quantum yields (QYs). Moreover, reflectance spectra, temperature-dependent photoluminescence behavior, and the fabricated WLEDs performances were studied in detail. An absolute photoluminescence quantum yield as high as 81% was obtained for the Mg14Ge5(1–0.2%)O24:0.2%Mn4+ phosphor with good thermal stability. The fabricated WLED with CCT = 2864 K and Ra = 80.6 was attained by combining the prepared red phosphor and YAG yellow phosphor with a blue LED chip, which was superior to the conventional YAG-type WLED. All the results indicate that Mg14Ge5O24:Mn4+ is a promising phosphor and widens the horizon for materials in WLED applications.
Co-reporter:Dongmei Wang, Bei Liu, Zewei Quan, Chunxia Li, Zhiyao Hou, Bengang Xing and Jun Lin
Journal of Materials Chemistry A 2017 - vol. 5(Issue 12) pp:NaN2230-2230
Publication Date(Web):2017/02/06
DOI:10.1039/C6TB03117J
In recent years, near-infrared (NIR) light, as a powerful means of external stimulus, has attracted widespread attention in the field of tumor research. On one hand, NIR light-excited rare earth upconversion nanoparticles (UCNPs) have presented unique features in multimodal bioimaging, energy conversion and photocontrolled drug delivery. On the other hand, NIR-light-triggered photothermal therapy (PTT) is a minimally invasive approach in the fight against tumors, owing to its high spatial resolution, economic viability and improved target selectivity. Thus, the marrying of UCNPs and NIR photothermal agents could open new avenues in the construction of theranostic nanoplatforms. This review primarily focuses on the new advances in the design and the therapeutic applications of multifunctional UCNPs–NIR absorber nanoplatforms. The future challenges and prospects in this field are also addressed.
Co-reporter:Bo Teng, Ping'an Ma, Chang Yu, Xinyang Zhang, Qingjie Feng, Lianji Wen, Chunxia Li, Ziyong Cheng, Dayong Jin and Jun Lin
Journal of Materials Chemistry A 2017 - vol. 5(Issue 2) pp:NaN317-317
Publication Date(Web):2016/11/24
DOI:10.1039/C6TB02360F
Eukaryotic translation initiation factor (eIF) 4E is a valuable marker in cancer prognostics in many human cancers. Silencing eIF4E via delivery of siRNA may be able to overcome chemoresistance. Cisplatin, used as a first-line anti-cancer reagent, has been widely accepted for its great success in clinical applications but it is restricted due to severe side effects such as nephrotoxicity, peripheral neuropathy, and hearing loss. Moreover, platinum drug resistance is a major obstacle to its use. Platinum(IV) prodrugs (denoted as Pt(IV)) which could be reduced to Pt(II) by various reductants, including mercaptan and glutathione, within cancer cells have very limited toxicity and might overcome platinum resistance because of their chemical inertness. Moreover, combinational therapies that could sensitize the cancer cells to Pt drugs have received great attention nowadays around the world. Here we report a simple and effective upconversion nanoparticle carrier system loaded with both eIF4E siRNA and Pt(IV). We find that this theranostic system could sensitize laryngeal cancer cells to cisplatin based chemotherapy and allow bioimaging both in vitro and in vivo.
Co-reporter:Kerong Deng, Yinyin Chen, Chunxia Li, Xiaoran Deng, Zhiyao Hou, Ziyong Cheng, Yanqiu Han, Bengang Xing and Jun Lin
Journal of Materials Chemistry A 2017 - vol. 5(Issue 9) pp:NaN1814-1814
Publication Date(Web):2017/01/25
DOI:10.1039/C6TB03233H
Near-infrared (NIR) light induced phototherapy has attracted considerable attention due to its deep therapeutic depth. To improve the therapeutic outcome and address non-selective side effects, the combination of complementary phototherapeutic strategies in a single nanoagent with precise targeting ability may provide an effective approach for cancer therapy. Thus we have developed an 808 nm NIR light triggered nanosystem based on IR806 dye functionalized MnFe2O4 (MFO-IR) for synchronous magnetic targeted and magnetic resonance (MR) imaging guided in vivo photodynamic/photothermal synergistic therapy. In this construction strategy, carboxylic acid functionalized NIR dye IR806 is explored as an 808 nm NIR-excited photosensitizer (PS) for the first time, which can also provide a conjugation site for MnFe2O4 nanoparticles (MFO NPs). Here, monodisperse MFO NPs have multiple capacities as dye carriers, targeting ligands, MRI contrast agents and photothermal agents. MFO-IR nanocomposites (NCs) with negligible toxicity present efficient NIR-mediated photothermal damage and ROS cytotoxicity via the relevant in vitro experimental investigations. With ideal magnetic targeting effects and remarkable NIR light-responsive properties, these MFO-IR NCs exhibit high in vivo tumor localization and could destroy subcutaneous solid tumors completely under an external magnetic field and 808 nm laser irradiation. Consequently, this magnetic nanosystem has great potential for simultaneous diagnosis and precise cancer phototherapy.
Co-reporter:Yunlu Dai, Huiting Bi, Xiaoran Deng, Chunxia Li, Fei He, Ping'an Ma, Piaoping Yang and Jun Lin
Journal of Materials Chemistry A 2017 - vol. 5(Issue 11) pp:NaN2095-2095
Publication Date(Web):2017/02/21
DOI:10.1039/C7TB00224F
The design of stimuli-responsive drug delivery systems has attracted much attention to improve therapeutic efficacy for clinical applications. Here an 808 nm NIR light responsive dual-drug system was designed for cancer treatment both in vitro and in vivo. Mesoporous silica coated NaYF4:Yb0.4/Tm0.02@NaGdF4:Yb0.1@NaNdF4:Yb0.1 (UCNPs) with a core-shell structure (labeled as UCNPs@mSiO2) was prepared and loaded with the antitumor drug doxorubicin (DOX). The surface of the composite was functionalized with β-cyclodextrin rings bridged by the light cleavable platinum(IV) pro-drug, thus blocking DOX inside the mesopores of silica. When excited by 808 nm NIR light, the emitted UV light from the UCNPs was used to activate the platinum(IV) pro-drug to gain higher toxicity platinum(II) complexes and open the mesopores of silica (at the same time) to release DOX molecules. Both DOX and platinum(II) complexes can kill cancer cells. This dual-drug delivery system may represent a new avenue for the application of UCNPs in photoactivated cancer therapy.
Co-reporter:Bei Liu, Chunxia Li, Ziyong Cheng, Zhiyao Hou, Shanshan Huang and Jun Lin
Biomaterials Science (2013-Present) 2016 - vol. 4(Issue 6) pp:NaN909-909
Publication Date(Web):2016/03/14
DOI:10.1039/C6BM00076B
The near-infrared (NIR) region (700–1100 nm) is the so-called transparency “therapeutic window” for biological applications owing to its deeper tissue penetration and minimal damage to healthy tissues. In recent years, various NIR-based therapeutic and interventional strategies, such as NIR-triggered drug delivery, photothermal therapy (PTT) and photodynamic therapy (PDT), are under research in intensive preclinical and clinical investigations for cancer treatment. The NIR control in these cancer therapy systems is considered crucial to boost local effective tumor suppression while minimizing side effects, resulting in improved therapeutic efficacy. Some researchers even predict the NIR-triggered cancer therapy to be a new and exciting possibility for clinical nanomedicine applications. In this review, the rapid development of NIR light-responsive cancer therapy based on various smartly designed nanocomposites for deep tumor treatments is introduced. In detail, the use of NIR-sensitive materials for chemotherapy, PTT as well as PDT is highlighted, and the associated challenges and potential solutions are discussed. The applications of NIR-sensitive cancer therapy modalities summarized here can highlight their potential use as promising nanoagents for deep tumor therapy.
Co-reporter:Dongmei Yang, Ping'an Ma, Zhiyou Hou, Ziyong Cheng, Chunxia Li and Jun Lin
Chemical Society Reviews 2015 - vol. 44(Issue 6) pp:NaN1448-1448
Publication Date(Web):2014/07/02
DOI:10.1039/C4CS00155A
Lanthanide ion (Ln3+)-based upconversion nano/micromaterials that emit higher-energy visible light when excited by low-energy NIR light have aroused considerable attention in the forefront of materials science and biomedical fields, which stems from their unique optical and chemical properties including minimum photodamage to living organisms, low autofluorescence, high signal-to-noise ratio and detection sensitivity, and high penetration depth in biological or environmental samples. Thus, Ln3+-based upconversion materials are rising new stars and are quickly emerging as potential candidates to revolutionize novel biomedical applications. In this review article, we mainly focus on the recent progress in various chemical syntheses of Ln3+-based upconversion nanomaterials, with special emphasis on their application in stimuli-response controlled drug release and subsequent therapy. Functional groups that are introduced into the stimuli-responsive system can respond to external triggers, such as pH, temperature, light, and even magnetic fields, which can regulate the movement of the pharmaceutical cargo and release the drug at a desired time and in a desired area. This is crucial to boost drug efficacy in cancer treatment while minimizing the side effects of cytotoxic drugs. Many multifunctional (magnetic/upconversion luminescence and porous) composite materials based on Ln3+ have been designed for controlled drug delivery and multimodal bioimaging. Finally, the challenges and future opportunities for Ln3+-based upconversion materials are discussed.
Co-reporter:Yang Zhang, Xiaojiao Kang, Dongling Geng, Mengmeng Shang, Yuan Wu, Xuejiao Li, Hongzhou Lian, Ziyong Cheng and Jun Lin
Dalton Transactions 2013 - vol. 42(Issue 39) pp:NaN14148-14148
Publication Date(Web):2013/07/22
DOI:10.1039/C3DT51576A
GdOF:Ln3+ (Ln = Eu, Tb, Tm, Dy, Ho and Sm) microspheres (1.5 μm) with high uniformity and monodispersity have been synthesized via a facile hydrothermal method followed by heat treatment (600 °C). X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), as well as photoluminescence (PL) and cathodoluminescence (CL) spectra are used to characterize the resulting samples. A series of controlled experiments indicate that sodium citrate (Cit3−) as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the dosage of Cit3− and pH values in the initial solution. The possible formation mechanism for these microspheres has been presented. Under UV light and low-voltage electron beam excitation, GdOF:Ln3+ microspheres show the characteristic f–f transitions of Ln3+ (Eu, Tb/Ho, Tm, Dy and Sm) ions and give bright red, green, blue, yellow and yellowish-orange emission, respectively. In addition, multicolored luminescence containing white emission have been successfully confected for co-doped GdOF:Ln3+ phosphors by changing the doped Ln3+ ions and adjusting their doping concentrations due to the simultaneous luminescence of Ln3+ in the GdOF host, making these materials have potential applications in field-emission display devices.
Co-reporter:Dongling Geng, Mengmeng Shang, Yang Zhang, Hongzhou Lian and Jun Lin
Dalton Transactions 2013 - vol. 42(Issue 43) pp:NaN15380-15380
Publication Date(Web):2013/08/14
DOI:10.1039/C3DT51670A
Eu2+ singly and Eu2+/Mn2+ co-doped Na2SrMg(PO4)2 (NSMP) phosphors have been prepared via a high-temperature solid-state reaction process. Upon UV excitation of 260–360 nm, the NSMP:xEu2+ phosphors exhibit a violet band located at 399 nm and a blue band centered at 445 nm, which originate from Eu2+ ions occupying two different crystallographic sites: Eu2+(I) and Eu2+(II), respectively. Excitation wavelengths longer than 380 nm can selectively excite Eu2+(II) to emit blue light. Energy transfer processes in the Eu2+(I)–Eu2+(II) and Eu2+–Mn2+ pairs have been observed and investigated by luminescence spectra and decay curves. The emission color of as-prepared samples can be tuned by changing the relative concentrations of Eu2+ and Mn2+ ions and adjusting the excitation wavelength. Under UV excitation of 323 nm, the absolute quantum yield of NSMP:0.005Eu2+ is 91%, which is higher than most of the other Eu2+-doped phosphors reported previously. The temperature dependent luminescence properties and decay curves (4.3–450 K) of NSMP:Eu2+ and NSMP:Eu2+, Mn2+ phosphors have been studied in detail. Thermal quenching of Eu2+ has been observed while the emission band of Mn2+ shows a blue-shift and an abnormal increase of intensity with increasing temperature. The unusual thermal quenching behavior indicates that the NSMP compound can serve as a good lattice host for Mn2+ ions which can be used as a red-emitting phosphor. Additionally, the lifetimes for Eu2+(I) and Eu2+(II) increase with increasing temperatures.
Co-reporter:Bei Liu, Chunxia Li, Bengang Xing, Piaoping Yang and Jun Lin
Journal of Materials Chemistry A 2016 - vol. 4(Issue 28) pp:NaN4894-4894
Publication Date(Web):2016/06/21
DOI:10.1039/C6TB00799F
Integrated theranostic nanosystems that combine therapeutic methods with suitable medical imaging modality are highly needed in the improvement of cancer theranostic approaches. Herein, polydopamine (PDA)-shelled NaYF4:Yb,Er@NaYF4:Yb nanoparticles (UCNPs) capable of loading indocyanine green (ICG) molecules via electrostatic adsorption, hydrophobic interaction and π–π stacking were successfully designed and synthesized (UCNPs@PDA-ICG, denoted as UPI) for upconversion imaging and combined photothermal/photodynamic therapy (PTT/PDT) with enhanced antitumor efficacy. We have found that ICG in this novel anticancer nanoplatform can be triggered impressively by 808-nm irradiation to produce both a photothermal effect and cytotoxic reactive oxygen species (ROS), thus achieving a good PTT/PDT synergistic effect. Notably, compared with free ICG molecules, UPI nanocomposites show much higher photostability and thermal stability. Both in vitro and in vivo experiments show that the as-obtained UPI can ablate cancer cells effectively with 808-nm irradiation, revealing their great potential as a NIR-mediated dual-modal therapeutic platform. Meanwhile, the core of UCNPs can be used for UCL imaging. All these results demonstrate great potentiality of UPI as a novel type of theranostic agent for the treatment of tumors.
Co-reporter:Arif Gulzar, Shili Gai, Piaoping Yang, Chunxia Li, Mohd Bismillah Ansari and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 44) pp:NaN8622-8622
Publication Date(Web):2015/09/03
DOI:10.1039/C5TB00757G
In the last decade, using polymer and mesoporous silica materials as efficient drug delivery carriers has attracted great attention. Although the development and application of them involves some inevitable barriers, such as chronic toxicities, long-term stability, understanding of the biological fate and physiochemical properties, biodistribution, effect in the biological environment, circulation properties and targeting efficacy in vivo. The construction of stimuli responsive drug carriers using biologically safe materials, followed by hydrophilic modification, bioconjugation, targeting functionalization, and detailed safety analysis in small/large animal models may be the best way to overcome these barriers. Huge progress has been made in stimuli responsive drug delivery systems based on polymer and mesoporous silica materials, mainly including pH-, thermo-, light-, enzyme-, redox-, magnetic field- and ultrasound-responsive drug delivery systems, all of which are highlighted in this review.
Co-reporter:Kai Li, Ju Xu, Xuechao Cai, Jian Fan, Yang Zhang, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 24) pp:NaN6349-6349
Publication Date(Web):2015/05/26
DOI:10.1039/C5TC00796H
A series of Eu2+ singly doped α-Ca1.65Sr0.35SiO4:Eu2+ phosphors have been synthesized via the high-temperature solid-state reaction method. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), diffuse reflectance spectroscopy and photoluminescence (PL) including temperature-dependent PL were used to characterize the as-prepared samples. The XRD patterns and Rietveld refinement of the presented sample show the pure phase of the as-prepared samples. All of the phosphors exhibit intense and broad absorption bands in the ultraviolet and near ultraviolet (n-UV) range, and produce bright green emission upon 365 nm UV radiation. The critical concentration of Eu2+ for the maximum intensity was determined to be about 1 mol% in α-Ca1.65Sr0.35SiO4:Eu2+ after optimizing the composition. The energy transfer mechanism between Eu2+ was demonstrated to be dipole–dipole interaction. Besides, the fluorescence decay curves, the temperature dependent PL and CIE value of α-Ca1.65Sr0.35SiO4:Eu2+ phosphors were investigated. It is reasonable that the decay times of samples decrease with increasing Eu2+ content. The CIE chromaticity coordinates shift from green (0.197, 0.395) to the border between the green and yellow (0.242, 0.547) region, which agree with the corresponding emission spectra. The maximum quantum yield is 69% for α-Ca1.65Sr0.345SiO4:0.005Eu2+. The thermal stability of luminescence of selected α-Ca1.65Sr0.34SiO4:0.01Eu2+ was also investigated and compared with that of the commercial green phosphor, which shows its good performance. The above results suggest that it is a good candidate for green-emitting phosphors applied in UV/n-UV pumped w-LEDs.
Co-reporter:Yang Zhang, Xuejiao Li, Xiaojiao Kang, Zhiyao Hou and Jun Lin
Physical Chemistry Chemical Physics 2014 - vol. 16(Issue 22) pp:
Publication Date(Web):
DOI:10.1039/C4CP00817K
Co-reporter:Xuejiao Li, Yang Zhang, Dongling Geng, Jianshe Lian, Guo Zhang, Zhiyao Hou and Jun Lin
Journal of Materials Chemistry A 2014 - vol. 2(Issue 46) pp:NaN9933-9933
Publication Date(Web):2014/10/07
DOI:10.1039/C4TC01909A
Eu3+ and/or Tb3+-doped CaGdAlO4 phosphor samples were synthesized via a conventional high temperature solid-state reaction process. X-Ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) as well as cathodoluminescence (CL) spectra were used to characterize the samples. For CaGdAlO4:Tb3+, the concentration of doped Tb3+ has a significant effect on the 5D3/5D4 emission intensity due to the dipole–dipole cross-relaxation mechanism from 5D3 to 5D4. Under the 4f8 → 4f75d excitation of Tb3+ or low-voltage electron beam excitation, the CaGdAlO4:Tb3+ samples show tunable luminescence from blue to cyan and then to green with the variation of the Tb3+-doping concentration. For CaGdAlO4:Eu3+, the samples exhibit a reddish-orange emission corresponding to the 5D0,1 → 7F0,1,2,3 transitions of Eu3+. Energy transfer can take place from Tb3+ to Eu3+ when they are codoped in one host. Furthermore, for CaGdAlO4:Tb3+/Eu3+, a white emission can be realized in the single phase CaGdAlO4 host by reasonably adjusting the doping concentrations of Tb3+ and Eu3+ under low-voltage electron beam excitation. Due to the excellent PL, CL properties and good CIE chromaticity coordinates, the as-prepared Tb3+/Eu3+-doped CaGdAlO4 nanocrystalline phosphors have potential applications in field emission display devices.
Co-reporter:Kai Li, Mengjiao Xu, Jian Fan, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 44) pp:NaN11628-11628
Publication Date(Web):2015/10/08
DOI:10.1039/C5TC02759D
A series of Eu2+,Mn2+-doped Na3LuSi2O7 (NLSO) phosphors have been prepared via the high-temperature solid-state reaction route. X-ray diffraction (XRD), Raman and Fourier transform infrared (FT-IR) spectra, fluorescent decay times, photoluminescence (PL) including temperature-dependent PL properties and scanning electron microscopy (SEM) were used to characterize the as-prepared samples. In Eu2+ singly-doped NLSO samples, an intense green emission is presented under UV excitation. A tunable color from green to yellowish-orange was generated when Mn2+ ions were co-doped into the NLSO:Eu2+, which is based on the energy transfer from Eu2+ to Mn2+ ions. The energy transfer from Eu2+ to Mn2+ ions can be speculated to be due to the wide spectral overlap between the Eu2+ emission and Mn2+ excitation spectra in Eu2+ or Mn2+ singly-doped NLSO samples. This is demonstrated by the similar excitation spectra of the Eu2+ and Mn2+ emission bands and the decreases in Eu2+ emission intensity and decay lifetime with the increase of Mn2+ concentration in the NLSO:Eu2+,Mn2+ samples. The energy transfer mechanism from Eu2+ to Mn2+ ions was determined to be a dipole–quadrupole interaction by the concentration quenching and spectral overlap methods. The maximum quantum yield can reach 51.5% for NLSO:0.01Eu2+,0.12Mn2+. The above results indicate that NLSO:Eu2+,Mn2+ could be a candidate as a green to yellowish-orange component for UV-excited w-LEDs.
Co-reporter:Kai Li, Jian Fan, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 38) pp:NaN9998-9998
Publication Date(Web):2015/09/04
DOI:10.1039/C5TC01993A
A series of Bi3+,Eu3+-doped Sr2Y8(SiO4)6O2 (SYSO) phosphors were synthesized by the Pechini-type sol–gel route. XRD patterns, Rietveld refinement, FT-IR spectra, photoluminescence spectra (PL), fluorescence decay time, and quantum yields (QYs) were utilized to characterize the as-prepared samples. Intense blue-green emission due to the 3P1 → 1S0 transition of Bi3+ ions is produced under UV excitation in Bi3+ singly doped SYSO samples. Spectral analysis illustrates that two kinds of Bi3+ ions are generated by occupying the two kinds of sites (4f and 6h) available for Y in SYSO, denoted as Bi3+(1) and Bi3+(2), corresponding to the two main emission bands at around 413 and 493 nm, respectively. A wide spectral overlap between Bi3+ emission and Eu3+ excitation spectra results in the energy transfer from Bi3+ to Eu3+. This has been demonstrated via the excitation spectra monitored at Bi3+ and Eu3+ emission bands, and the PL emission spectra and decay time of Bi3+ in SYSO:Bi3+,Eu3+ phosphors. The energy transfer mechanism is determined to be dipole–quadrupole interaction. The critical distance of energy transfer from Bi3+ to Eu3+ ions is calculated to be 12.78 Å based on the concentration quenching method, which is in good agreement with that of the spectral overlap route (10.03–13.37 Å). Moreover, the QYs, CIE chromaticity and thermal quenching properties have also been investigated. White emission color can be realized with the CIE coordinates (0.325, 0.311) and QY 52% for SYSO:0.08Bi3+,0.48Eu3+. The above results suggest that SYSO:Bi3+,Eu3+ can be a potential single-component white-emitting phosphor for UV w-LEDs.
Co-reporter:Mengmeng Shang, Jing Wang, Jian Fan, Hongzhou Lian, Yang Zhang and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 36) pp:NaN9317-9317
Publication Date(Web):2015/08/13
DOI:10.1039/C5TC01864A
Nitride phosphors have drawn much interest because of their outstanding thermal and chemical stability and interesting photoluminescence properties. Currently, it remains a challenge to synthesize these phosphors through a convenient chemical route. Herein we propose a general and convenient strategy based on hydrothermal-ammonolysis reaction to successfully prepare zinc germanium nitride (ZnGeN2) and Mn2+ doped ZnGeN2 phosphors. The crystal structure, composition, morphology, luminescence and reflectance spectra, quantum efficiency, and the temperature-dependent photoluminescence behavior were studied respectively. The phase formation and crystal structure of ZnGeN2 were confirmed from powder X-ray diffraction and Rietveld refinement. EDX analysis confirmed the actual atomic ratios of Zn/Ge and N/Ge and suggested the presence of Ge vacancy defects in the ZnGeN2 host, which is associated with its yellow emission at 595 nm with a FWHM of 143 nm under UV light excitation. For Mn2+ doped ZnGeN2 phosphor, it exhibits an intense red emission due to the 4T1g → 6A1g transition of Mn2+ ions. The unusual red emission of Mn2+ at the tetrahedral Zn2+ sites is attributed to the strong nephelauxetic effect and crystal field between Mn2+ and the tetrahedrally coordinated N3−. Moreover, the PL intensity of ZnGeN2:Mn2+ phosphors can be enhanced by Mg2+ ions partially substituting for Zn2+ ions in a certain concentration range. The optimal Mn2+ doping concentration in the ZnGeN2 host is 0.4 mol%. The critical energy transfer distance of this phosphor is calculated to be about 27.99 Å and the concentration quenching mechanism is proved to be the dipole–dipole interaction. With increasing temperature, the luminescence of ZnGeN2:Mn2+ phosphors gradually decreases and the FWHM of the emission band broadens from 54 nm to 75 nm. The corresponding activation energy Ea was reckoned to be 0.395 eV. And the nonradiative transition probability increases with the increasing temperature, finally leading to the lifetime decrease with the increase of the temperature.
Co-reporter:Xiaoyong Huang and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 29) pp:NaN7657-7657
Publication Date(Web):2015/07/01
DOI:10.1039/C5TC01438G
In recent years, intensive research efforts around the world have been devoted to lanthanide-doped upconversion nanoparticles because of their promising application in biological imaging. However, the overheating issue caused upon 980 nm laser irradiation in conventional Yb3+-based nanoparticles is needed to be addressed, and thus Nd3+/Yb3+-based upconversion nanoparticles with 808 nm excitation are investigated as promising alternatives because they can significantly decrease the optical absorption of water. Due to the cascade sensitization process, Nd3+/Yb3+-based upconversion nanoparticles, however, always suffer from the intrinsic low luminescence efficiency. To solve this problem, here we proposed the active-core/active-shell nanostructured design as an effective strategy for upconversion improvement of Nd3+/Yb3+-based upconversion nanoparticles. We found that after growing an optimized active-shell containing both Nd3+ and Yb3+ ions, a maximum 522-fold enhancement in upconversion luminescence was realized upon excitation at 808 nm. These findings would be of great importance to the community developing high-performance upconversion nanoparticles for bioimaging applications.
Co-reporter:Kai Li, Mengmeng Shang, Yang Zhang, Jian Fan, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 27) pp:NaN7104-7104
Publication Date(Web):2015/05/29
DOI:10.1039/C5TC00927H
Co-doping of Ce3+/Eu2+, Tb3+, Mn2+ ions into a single-component host is commonly used to achieve white-light phosphors through energy transfer, which present good color stability and high color rendering index (CRI) values. In this work, a series of single-component trichromatic white-light-emitting Ca9Bi(PO4)7(CBPO):Ce3+,Tb3+,Mn2+ phosphors were synthesized and investigated. The crystal structure, luminescence properties and energy transfer behavior are discussed in detail. The energy transfer process from Ce3+ to Tb3+/Mn2+ has been demonstrated to be a resonant type via the dipole–dipole–quadrupole–quadrupole interaction mechanism, respectively, which makes the emission color shift from purple-blue to green/red with the corresponding Commission Internationale de L'Eclairage (CIE) chromaticity coordinates from (0.166, 0.011) to (0.260, 0.569) and (0.582, 0.287), respectively. Additionally, the white light emission by controlling the concentration ratio of Tb3+ and Mn2+ ions has been acquired in the CBPO:0.08Ce3+,0.22Tb3+,0.11Mn2+ sample with the CIE chromaticity coordinates of (0.375, 0.310) and an absolute quantum yield of 50% upon 292 nm excitation. The maximum quantum yield is 84% for CBPO:0.08Ce3+,0.90Tb3+. The good thermal stability of the CBPO:0.08Ce3+,0.22Tb3+,0.11Mn2+ sample shows about 83.6% at 150 °C of its initial PL intensity at room temperature, which attracts more attention. The results suggest that the present phosphors can be potentially applied as candidates of single-component white-light phosphors for UV-pumped w-LEDs.
Co-reporter:Yang Zhang, Xuejiao Li, Kai Li, Hongzhou Lian, Mengmeng Shang and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 14) pp:NaN3303-3303
Publication Date(Web):2015/02/10
DOI:10.1039/C5TC00152H
Ba2(1−x)Zr2Si3O12 (BZSO):xEu2+ (x = 0.005–0.06) phosphors have been prepared by a high temperature solid state reaction. Using X-ray powder diffraction, the structural properties including the phase purity were analyzed through Rietveld analysis. The BZSO:Eu2+ phosphors exhibit a broad excitation band ranging from 200 to 450 nm, and an intense asymmetric green emission band centered at 501 nm under an excitation of 365 nm. The optimum doping concentration of Eu2+ was found for x = 0.03. The detailed energy transfer mechanism among Eu2+ in BZSO is found to be a dipole–dipole mechanism, and the critical distance (RC) for the Eu2+ ions calculated by the concentration quenching and spectral overlap methods are 20.45 and 25.83 Å, respectively. Furthermore, the unexpected blue shift (from green to cyan) in the emission and the increase in the thermal quenching barrier upon cation substitutions (Ca2+/Sr2+ for Ba2+) in the BZSO:0.03Eu2+ system have been investigated, which is due to the variation of the crystal field strength that the 5d orbital of the Eu2+ ion experiences. The underlying mechanism is ascribed to the differences between the average structure and the local coordination environments on the activator ions (Eu2+), as confirmed by the refinement results. Considering the merits of the near-UV light excitation, broad band emission, and good thermal stability, these materials have a potential application as white light emitting diode phosphors.
Co-reporter:Kai Li, Mengmeng Shang, Hongzhou Lian and Jun Lin
Journal of Materials Chemistry A 2016 - vol. 4(Issue 24) pp:NaN5530-5530
Publication Date(Web):2016/04/18
DOI:10.1039/C6TC00436A
Utilizing energy transfer (ET) between the sensitizer and acceptor in phosphors is a good way to obtain tunable emission color. Therefore, many researchers have devoted their interest to design phosphors with different emission colors via their energy transfer properties. It is well known that Ce3+ and Bi3+ are good sensitizers, while Mn2+, Dy3+, Eu3+ and Sm3+ can be useful activators. Further, Eu2+ and Tb3+ can be both good sensitizers and activators. Therefore, herein we summarise many recent ET systems consisting of Eu2+–Mn2+/Tb3+, Eu2+–Tb3+–Mn2+/Eu3+/Sm3+, Ce3+–Mn2+/Tb3+/Dy3+/Eu2+, Ce3+–Tb3+–Mn2+/Eu3+/Sm3+, Bi3+–Eu3+/Sm3+ and Tb3+–Eu3+/Sm3+, which show tunable emission color from ultraviolet to blue and green, blue to green, yellow, orange and pink/red, cyan to green, orange and pink/red, and green to yellow/orange and red. Based on this summary, this review will be a good reference to benefit the design and investigation of phosphors potentially applied in FEDs and LEDs with ET.
Co-reporter:Kai Li, Sisi Liang, Hongzhou Lian, Mengmeng Shang, Bengang Xing and Jun Lin
Journal of Materials Chemistry A 2016 - vol. 4(Issue 16) pp:NaN3453-3453
Publication Date(Web):2016/03/17
DOI:10.1039/C6TC00579A
A variety of Ce3+ and Tb3+-doped BaLu2Si3O10 (BLSO) phosphors were synthesized via the high-temperature solid-state reaction method. Many technologies, such as X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), solid-state NMR, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) measurements, were used to characterize the as-prepared samples. Lu4Si2O7N2 was generated when N3− replaced O2− in BLSO:Ce3+, which resulted in a shift of the emission band from the blue (423 nm) to the cyan (460 nm) region under UV excitation. It was speculated that energy transfer occurred in Ce3+ and Tb3+ co-doped BLSO via the spectral overlap between Ce3+ emission and Tb3+ excitation in singly-doped BLSO, demonstrated by the variation in the emission spectra and the decrease in the Ce3+ fluorescent lifetimes in Ce3+ and Tb3+ co-doped BLSO, which resulted in a color change from blue to green when the concentration ratio of Ce3+/Tb3+ in BLSO:Ce3+,Tb3+ was adjusted. The energy transfer mechanism was confirmed to be electric dipole–quadrupole interaction. Moreover, quantum yields (QYs), Commission Internationale de l'Eclairage (CIE) chromaticity coordinates and temperature-dependent PL properties have also been investigated in detail. The results show the potential of BLSO:Ce3+,Tb3+ compounds as candidates for phosphors in phosphor-converted LEDs.
Co-reporter:Ying Tian, Yi Wei, Yun Zhao, Zewei Quan, Guogang Li and Jun Lin
Journal of Materials Chemistry A 2016 - vol. 4(Issue 6) pp:NaN1294-1294
Publication Date(Web):2015/12/30
DOI:10.1039/C5TC03482E
A series of Ca5(PO4)3Cl (CPOCl):Ce3+/Eu2+,Tb3+/Mn2+ phosphors with apatite structures have been prepared via the Pechini sol–gel process. The structure refinement indicates that the as-prepared phosphors crystallized in a hexagonal phase with the space group of P63/m (176), and there are two kinds of cation sites (4f and 6h) in the host lattice to accommodate the doping ions. The emissions of Eu2+ and Ce3+ at different lattice sites in the CPOCl host have been identified and discussed. The red shifted emission of CPOCl:Ce3+ with increasing Ce3+ doping concentrations has been explained, which is mainly attributed to the occupation of 6h sites of Ce3+ ions at a high doping level. In addition, the transformation from chlorapatite structures to oxyapatite structures driven by charge balance with Ce3+ concentrations also contributes to this red shift. When codoping Tb3+/Mn2+ ions into these cation sites, efficient energy transfers from Ce3+/Eu2+ ions to Tb3+/Mn2+ ions were observed, and the corresponding energy transfer mechanisms have been revealed. Under 340–420 nm near-ultraviolet light (n-UV) excitation, highly efficient blue-green tunable emission from Ce3+/Eu2+ ions to Tb3+ ions and single-phase white emission from Ce3+, Mn2+-codoped CPOCl can be obtained. In addition, the thermal stability of CPOCl:Ce3+/Eu2+,Tb3+/Mn2+ phosphors has been investigated systematically. Based on these experimental results, the as-prepared CPOCl:Ce3+/Eu2+,Tb3+/Mn2+ phosphors can act as potential color-tunable and single-phase white emission phosphors for possible applications in n-UV based white LEDs.
Co-reporter:Xiaoyun Mi, Jiacheng Sun, Peng Zhou, Hongyan Zhou, Di Song, Kai Li, Mengmeng Shang and Jun Lin
Journal of Materials Chemistry A 2015 - vol. 3(Issue 17) pp:NaN4481-4481
Publication Date(Web):2015/01/27
DOI:10.1039/C4TC02433H
Ca8MgLu(PO4)7:Ce3+,Tb3+,Mn2+ (abbreviated as CMLP:Ce3+,Tb3+,Mn2+) phosphors were synthesized by a high-temperature solid-state method. X-ray diffraction (XRD), photoluminescence (PL) spectra, GSAS structural refinement, and absolute quantum yield and lifetimes were used to characterize the samples. Increasing the Ce3+ doping concentration in the CMLP host shifts the emission peak from 360 to 374 nm. Under UV excitation, the energy transfers (ETs) from Ce3+ to Tb3+ and from Ce3+ to Mn2+ in the CMLP host occurred mainly via a dipole–quadrupole mechanism, and the critical distances of the ion pairs (RC) were calculated by the quenching concentration method and spectral overlap method, respectively. The emission colors of the CMLP:Ce3+,Tb3+,Mn2+ samples could be adjusted from blue to green, and eventually to orange–red by the ET between Ce3+ and Tb3+/Mn2+. Moreover, a white light emission tunable over a wide range was obtained by precisely controlling the contents of Ce3+, Tb3+ and Mn2+. Temperature dependent luminescence spectra proved the good thermal stability of the as-prepared phosphor. Based on the good PL properties and varied hues of the CMLP host achieved by adjusting the doping concentration of the activators (Ce3+, Tb3+, Mn2+), CMLP might be promising as a host material for solid-state lighting and display fields.
Co-reporter:Sisi Liang, Mengmeng Shang, Hongzhou Lian, Kai Li, Yang Zhang and Jun Lin
Journal of Materials Chemistry A 2016 - vol. 4(Issue 26) pp:NaN6416-6416
Publication Date(Web):2016/06/13
DOI:10.1039/C6TC01813K
In order to get efficient phosphors used in WLEDs to cover the shortage of red emission, highly saturated rare-earth-free red phosphors MGe4O9:Mn4+ (M = Sr, Ba) have been successfully fabricated by a solid state method at 1100 °C. The crystal structure properties including the phase purity were analyzed by means of X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Photoluminescence absolute quantum efficiencies as well as lifetimes were utilized to characterize samples. As for the photoluminescence properties, the excitation spectra of samples exhibit two broad absorption bands with peaks at about 300 nm and 430 nm, which could be excited by near-UV/blue LED excitation. The emission spectra exhibit sharp peaks ranging from 600 nm to 700 nm due to the 4Eg → 4A2g transition of Mn4+ ions. The optimal Mn4+ doping concentrations in both the SrGe4O9 and BaGe4O9 host are determined to be 0.5 mol%. The critical energy transfer distances of these phosphors are calculated to be about 19 Å, and the concentration quenching mechanism is proved to be the dipole–dipole interaction. With increasing temperature, the luminescence of MGe4O9:Mn4+ (M = Sr, Ba) phosphors gradually decreases and the BaGe4O9:Mn4+ sample with the quenching temperature (T0.5) of about 180 °C has better thermal stability than SrGe4O9:Mn4+ with T0.5 of about 100 °C. Based on a combination of a blue LED chip, YAG:Ce3+ and MGO:0.5%Mn4+ red phosphors, the warm WLED is fabricated to explore its possible application as a warm white light-emitting diode.
Co-reporter:Kai Li, Hongzhou Lian, Mengmeng Shang and Jun Lin
Dalton Transactions 2015 - vol. 44(Issue 47) pp:NaN20550-20550
Publication Date(Web):2015/10/27
DOI:10.1039/C5DT03565A
A series of novel color-tunable Ba3Y4O9:Bi3+,Eu3+ phosphors were prepared for the first time via the high-temperature solid-state reaction route. The effect of Bi3+ concentration on the emission intensity of Ba3Y4O9:Bi3+ was investigated. The emission spectra of the Ba3Y4O9:Bi3+,Eu3+ phosphors present both a greenish yellow band of Bi3+ emission centered at 523 nm, and many characteristic emission lines of Eu3+, derived from the allowed 3P1–1S0 transition of the Bi3+ ion and the 5D0–7FJ transition of the Eu3+ ion, respectively. The energy transfer phenomenon from Bi3+ to Eu3+ ions is observed under UV excitation in Bi3+, Eu3+ co-doped Ba3Y4O9 phosphors, and their transfer mechanism is demonstrated to be a resonant type via dipole–quadrupole interaction. The critical distance between Bi3+ and Eu3+ for the energy transfer effect was calculated via the concentration quenching and spectral overlap methods. Results show that color tuning from greenish yellow to orange red can be realized by adjusting the mole ratio of Bi3+ and Eu3+ concentrations based on the principle of energy transfer. Moreover, temperature-dependent PL properties, CIE chromaticity coordinates and quantum yields of Ba3Y4O9:Bi3+,Eu3+ phosphors were also supplied. It is illustrated that the as-prepared Ba3Y4O9:Bi3+,Eu3+ phosphors can be potential candidates for color-tunable phosphors applied in UV-pumped LEDs.
Co-reporter:Yang Zhang, Xiaoming Liu, Xuejiao Li, Kai Li, Hongzhou Lian, Mengmeng Shang and Jun Lin
Dalton Transactions 2015 - vol. 44(Issue 17) pp:NaN7747-7747
Publication Date(Web):2014/12/05
DOI:10.1039/C4DT03095H
We demonstrate a strategy to manipulate the valence state of Eu in CaGdAlO4 based on breaking down geometrical restrictions on the activators. This strategy could promote the search for novel phosphors for white light emission diodes (WLEDs).
Co-reporter:Kai Li, Yang Zhang, Xuejiao Li, Mengmeng Shang, Hongzhou Lian and Jun Lin
Dalton Transactions 2015 - vol. 44(Issue 10) pp:NaN4692-4692
Publication Date(Web):2015/01/26
DOI:10.1039/C4DT03720K
A series of Eu2+ and Tb3+ singly-doped and co-doped β-Ca3(PO4)2 phosphors have been synthesized via the high-temperature solid-state reaction method. Thermogravimetric (TG) analysis, fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) patterns and Rietveld refinements, photoluminescence (PL) spectra including temperature-dependent PL and quantum efficiency, and fluorescence decay lifetimes have been used to characterise the as-prepared samples. Under UV excitation, β-Ca3(PO4)2:Eu2+ presents a broad emission band centered at 415 nm, which can be decomposed into five symmetrical bands peaking at 390, 408, 421, 435 and 511 nm based on the substitution of five kinds of Ca2+ sites by Eu2+ ions. β-Ca3(PO4)2:Tb3+ shows characteristic emission lines under Tb3+ 4f–5d transition excitation around 223 nm. In β-Ca3(PO4)2:Eu2+, Tb3+ phosphors, similar excitation spectra monitored at 415 and 547 nm have been observed, which illustrates the possibility of energy transfer from Eu2+ to Tb3+ ions. The variations in the emission spectra and decay lifetimes further demonstrate the existence of energy transfer from Eu2+ to Tb3+ ions under UV excitation. The energy transfer mechanism has been confirmed to be dipole–quadrupole, which can be validated via the agreement of critical distances obtained from the concentration quenching (12.11 Å) and spectrum overlap methods (9.9–13.2 Å). The best quantum efficiency can reach 90% for the β-Ca3(PO4)2:0.01Eu2+, 0.15Tb3+ sample under 280 nm excitation. These results show that the developed phosphors may possess potential applications in UV-pumped white light-emitting diodes.
Co-reporter:Yinyin Chen, Zhiyao Hou, Bei Liu, Shanshan Huang, Chunxia Li and Jun Lin
Dalton Transactions 2015 - vol. 44(Issue 7) pp:NaN3127-3127
Publication Date(Web):2014/12/15
DOI:10.1039/C4DT03113J
A composite antitumor drug carrier platform, in which antitumor drug doxorubicin (DOX) loaded core–shell structured Cu9S5@mSiO2 nanoparticles were incorporated into poly(ε-caprolactone) and gelatin to form nanofibrous fabrics using an electrospinning process, was successfully assembled. The resultant multifunctional spun pieces could be implanted directly to the tumor site of mice using surgical procedures to achieve the orthotopic synergistic therapy combining the chemotherapy of the controlled release of DOX from mesoporous SiO2 with the photothermal treatment through the performance of the photothermal transformation of Cu9S5 under 980 nm laser irradiation in vivo. The experimental results in vivo demonstrated that the synergistic chemotherapy/photothermal treatment of DOX loaded Cu9S5@mSiO2 composite fibers under 980 nm laser irradiation has a more efficient tumor suppression effect, compared with a single chemotherapy of DOX loaded Cu9S5@mSiO2 composite fibers without the 980 nm laser irradiation or a single photothermal treatment from Cu9S5@mSiO2 composite fibers under 980 nm laser irradiation.
Co-reporter:Bei Liu, Chunxia Li, Zhongxi Xie, Zhiyao Hou, Ziyong Cheng, Dayong Jin and Jun Lin
Dalton Transactions 2016 - vol. 45(Issue 33) pp:NaN13069-13069
Publication Date(Web):2016/01/21
DOI:10.1039/C5DT04857E
Recently, incorporating multiple components into one nanostructured matrix to construct a multifunctional nanomedical platform has attracted more and more attention for simultaneous anticancer diagnosis and therapy. Herein, a novel anti-cancer nanoplatform has been successfully developed by coating a uniform shell of poly(acrylic acid) (PAA) on the surface of CuS-decorated upconversion nanoparticles (UCNPs). Benefiting from the enhanced 808 nm-excited UCL intensity of the multilayer UCNPs, the unique photothermal properties of CuS and the pH-responsive drug release capacity of the PAA shell, such a nanoplatform design of UCNPs-CuS@PAA (labeled UCP) offers a new route to achieve 808 nm-excited UCL imaging guided chemo/photothermal combination therapy. We have found that the combined chemo/photothermal therapy can significantly improve the therapeutic efficacy compared with chemotherapy or photothermal therapy (PTT) alone. Moreover, the pH/NIR-dependent drug delivery properties, 808 nm-excited UCL imaging, as well as in vitro/in vivo biocompatibility tests were also investigated in detail. These results show promising applications of UCP nanoparticles as a novel theranostic agent for the detection and treatment of tumors.
Co-reporter:Fei He, Chunxia Li, Xinyang Zhang, Yinyin Chen, Xiaoran Deng, Bei Liu, Zhiyao Hou, Shanshan Huang, Dayong Jin and Jun Lin
Dalton Transactions 2016 - vol. 45(Issue 4) pp:NaN1716-1716
Publication Date(Web):2015/12/07
DOI:10.1039/C5DT04191K
808 nm excited upconversion nanoparticles (UCNPs) have received extensive attention in the biomedical areas. However, one of the limitations of UCNPs is their lower luminescence efficiency. Aimed at this problem, a series of BaGdF5-based UCNPs were prepared by a layer-by-layer procedure. And UC luminescence properties are optimized by varying the doping concentration of rare earth ions, amount and types of shells. It is found that if the amount of core BaGdF5:20%Yb3+/2%Er3+ was fixed at 0.5 mmol, the optimized conditions of three shell layers are 0.3 mmol of BaGdF5:10%Yb3+, 0.5 mmol of BaNdF5 and 0.5 mmol of BaGdF5. Thus the UC luminescence intensity of the resultant nanoparticles BaGdF5:20%Yb3+/2%Er3+@BaGdF5:10%Yb3+@BaNdF5@BaGdF5 (Er@Yb@Nd@Gd) is enhanced more than four times compared with that of BaGdF5:20%Yb3+/2%Er3+@BaGdF5:10%Yb3+@BaNdF5 (Er@Yb@Nd). To further improve the biocompatibility and applications in the biological field, carboxymethyl chitosan (CMC), a type of biocompatible water-transfer agent, was used as a capping ligand to modify the surface of Er@Yb@Nd@Gd. An antitumor drug doxorubicin (DOX) was loaded to the CMC-modified Er@Yb@Nd@Gd nanocarriers by electrostatic interactions. The DOX can be selectively released in an acidic environment, which shows a pH-triggered drug release behavior. On the other hand, Er@Yb@Nd@Gd nanoparticles have excellent magnetic properties due to the presence of Gd components. T1-weighted magnetic resonance imaging (MRI) reveals the concentration-dependent brightening effect with longitudinal relaxivity (r1) as high as 43.77 s−1 (mM)−1, much higher than that of previous Gd3+-based counterparts. The results indicate that this multifunctional drug delivery system is expected to be a promising platform for simultaneous cancer therapy and bioimaging.
Co-reporter:Mengmeng Shang, Chunxia Li and Jun Lin
Chemical Society Reviews 2014 - vol. 43(Issue 5) pp:NaN1386-1386
Publication Date(Web):2013/12/17
DOI:10.1039/C3CS60314H
White light-emitting diodes (WLEDs) as new solid-state light sources have a greatly promising application in the field of lighting and display. So far much effort has been devoted to exploring novel luminescent materials for WLEDs. Currently the major challenges in WLEDs are to achieve high luminous efficacy, high chromatic stability, brilliant color-rending properties, and price competitiveness against fluorescent lamps, which rely critically on the phosphor properties. In recent years, numerous efforts have been made to develop single-phase white-light-emitting phosphors for near-ultraviolet or ultraviolet excitation to solve the above challenges with certain achievements. This review article highlights the current methods to realize the white light emission in a single-phase host, including: (1) doping a single rare earth ion (Eu3+, Eu2+ or Dy3+) into appropriate single-phase hosts; (2) co-doping various luminescent ions with different emissions into a single matrix simultaneously, such as Tm3+/Tb3+/Eu3+, Tm3+/Dy3+, Yb3+/Er3+/Tm3+etc.; (3) codoping different ions in one host to control emission color via energy transfer processes; and (4) controlling the concentration of the defect and reaction conditions of defect-related luminescent materials.
Co-reporter:Guogang Li, Ying Tian, Yun Zhao and Jun Lin
Chemical Society Reviews 2015 - vol. 44(Issue 23) pp:NaN8713-8713
Publication Date(Web):2015/09/30
DOI:10.1039/C4CS00446A
Nowadays, phosphor converted white light-emitting diodes (pc-WLEDs) have been widely used in solid-state lighting and display areas due to their superior lifetime, efficiency, and reliability as well as significant reduction in power consumption. Phosphors are indispensable components of pc-WLED devices, and their luminescence properties determine the quality of WLED lighting and displays. In order to further achieve high luminous efficacy, chromatic stability, and color-rending properties in pc-WLEDs, much effort has been focused on improving current pc-WLED phosphors and developing novel pc-WLED phosphors recently. This review article concerns commonly used rare earth ion (Eu2+ and Ce3+) activated inorganic phosphors, highlighting the important effect of spectral tuning via local structural variations on improving the luminescence performance of phosphors. The main spectral tuning strategies are discussed in detail and summarized, including (1) doping level control; (2) cationic substitution; (3) anionic substitution; (4) cationic–anionic substitution; (5) the crystal-site engineering approach; (6) mixing of nanophases.
Co-reporter:Guogang Li, Chun Che Lin, Yi Wei, Zewei Quan, Ying Tian, Yun Zhao, Ting-Shan Chan and Jun Lin
Chemical Communications 2016 - vol. 52(Issue 46) pp:NaN7379-7379
Publication Date(Web):2016/05/04
DOI:10.1039/C6CC01969B
By cosubstituting [Ca2+–P5+] for [La3+–Si4+] in the Eu-doped Ca(2→8)La(8→2)(SiO4)6−x(PO4)xO2 (0 ≤ x ≤ 6) system, Eu3+ ions are controllably and gradually transformed to Eu2+. Thus, the emission colors consecutively changed from red to blue/green light. Furthermore, excellent warm-white lights with the low correlated color temperature (CCT) range of 3500–3800 K and a high color rendering index (Ra) (88.4–93.2) have been achieved by mixing the as-prepared phosphors at different cation cosubstitution ratios.
Co-reporter:Guogang Li, Yun Zhao, Yi Wei, Ying Tian, Zewei Quan and Jun Lin
Chemical Communications 2016 - vol. 52(Issue 16) pp:NaN3379-3379
Publication Date(Web):2016/01/18
DOI:10.1039/C5CC09782G
Here we report a novel Ca10(PO4)6O:Ce3+ phosphate phosphor, consisting of an apatite structure, whose emission peaks under excitation with near-ultra violet light were found to shift from 410 nm (blue light) to 510 nm (yellowish-green light) with an increasing Ce3+ doping level due to the Ce3+ at the different concentrations preferentially occupying different crystallographic sites.