Co-reporter:Fengshou Wu, Hongbo Tong, Kai Wang, Zheng Wang, Zaoying Li, Xunjin Zhu, Wai-Yeung Wong, Wai-Kwok Wong
Journal of Photochemistry and Photobiology A: Chemistry 2016 Volume 318() pp:97-103
Publication Date(Web):1 March 2016
DOI:10.1016/j.jphotochem.2015.12.003
•A series of new Cu(I) complexes, namely [Cu(dpa)X(PPh3)] and [Cu(dpa)(PPh3)2](BF4) were prepared and characterized.•Crystal structures of the Cu(I) heteroleptic complexes were presented.•The Cu(I) complexes are luminescence-tunable depending on the electronic characteristics of the corresponding auxiliary ligands.Neutral mononuclear Cu(I) complexes based on 2,2′-dipyridylamine (dpa), formulated as [Cu(dpa)X(PPh3)] (X = Cl (A4), Br (A5), I (A6)), monocationic mononuclear Cu(I) complexes with counterion BF4−, i.e. [Cu(dpa)(PPh3)2](BF4) (A1), Cu(dpa)(DPEphos)(BF4) (A2) and [Cu(dpa)(Binap)](BF4) (A3), where DPEphos = bis [2-(diphenylphosphino) phenyl] ether, Binap = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, have been prepared and characterized by 1H NMR, mass spectroscopy and single-crystal X-ray analyses. Their photophysical properties in both CH2Cl2 solution and PMMA (poly(methyl methacrylate)) film have been investigated. All the complexes display a typical metal-to-ligand charge transfer absorption band in the region of 350–400 nm, and a broad and featureless luminescence at room temperature. Specifically, their emission maxima vary from 494 to 562 nm in the PMMA films due to the different electronic characteristics of the auxiliary ligands. Additionally, the thermogravimetric analysis shows that those complexes chelated with diphosphine ligands have a higher thermal stability than those with triphenylphosphine or halides ligands.
Co-reporter:Fengshou Wu, Jie Li, Hongbo Tong, Zaoying Li, Chihaya Adachi, Adam Langlois, Pierre D. Harvey, Li Liu, Wai-Yeung Wong, Wai-Kwok Wong and Xunjin Zhu
Journal of Materials Chemistry A 2015 vol. 3(Issue 1) pp:138-146
Publication Date(Web):23 Oct 2014
DOI:10.1039/C4TC01885K
Mononuclear Cu(I) complexes based on bis(pyrazol-1-yl-methyl)-pyridine derivatives and ancillary triphenylphosphine have been prepared and characterized by 1H NMR, mass spectroscopy and single-crystal X-ray analysis. The thermogravimetric analysis shows that the complexes exhibit high thermal stability. The electronic absorption spectra display two features in the regions of 230–260 and 290–350 nm attributable to mixed ligand-to-ligand (LLCT) and metal-to-ligand-charge-transfer (MLCT) excited states, which is supported by the results of density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on these Cu(I) complexes. These complexes are strongly emissive in the solid state at ambient temperature. Intense blue or green emission in the poly(methyl methacrylate) film is observed in the region of 475–518 nm for these complexes with the emission lifetimes in the microsecond time scale (12–20 μs), indicating that the emission may be phosphorescence emission. Increasing the steric hindrance of the substituents on the pyrazole unit results in a blue-shift of the emission bands and enhanced emission quantum efficiency in PMMA films. The two most emissive complexes have been used for the fabrication of phosphorescent organic light-emitting diodes (POLEDs).
Co-reporter:Sizhe Zhu, Fengshou Wu, Kai Wang, Yunman Zheng, Zaoying Li, Xiulan Zhang, Wai-Kwok Wong
Bioorganic & Medicinal Chemistry Letters 2015 Volume 25(Issue 20) pp:4513-4517
Publication Date(Web):15 October 2015
DOI:10.1016/j.bmcl.2015.08.072
The cell-based studies of 5, 10, 15, 20-Tetrakis (4-amidinophenyl) porphyrin (Por1), its Zn complex (Por2) and amidinophenyl bisporphyrin (Por3) were carried out to examine their photocytotoxicity, cellular uptake and sub-cellular localization with human nasopharyngeal carcinoma cell (HK-1), using 5, 10, 15, 20-Tetrakis (N-methyl-4-pyridyl) porphyrin (H2TMPyP) as a reference. These porphyrins showed low dark-cytotoxicity and high photo-cytotoxicity against HK-1. The amphiphilic amidinophenyl bisporphyrin (Por3) displayed better cellular uptake than the single hydrophilic Por1, Por2 and H2TMPyP. As seen from the extent of overlapping of the fluorescence profiles, lysosomal localization of amidinophenylporphyrin Por1–Por3 and mito/lyso localization of the H2TMPyP occurred in the cells. The results suggest these porphyrins with amidine group could be used as potential agents in photodynamic therapy.The photocytotoxicity, cellular uptake and subcellular localization tests of Por1, Por2 and Por3 against the tumor cells were investigated. The results showed that bisporphyrin compound (Por3) with good hydrophobic/hydrophilic balance shows a better cellular uptake in HK-1 than that of other porphyrins with a single hydrophilic substituent. The confocal microscopy study shows that Por1, Por2 and Por3 were only localized with different density in lysosomal, while H2TMPyP was found both in lysosomal and mitochondria of HK-1.
Co-reporter:Fengshou Wu, Hongbo Tong, Zaoying Li, Wang Lei, Li Liu, Wai-Yeung Wong, Wai-Kwok Wong and Xunjin Zhu
Dalton Transactions 2014 vol. 43(Issue 33) pp:12463-12466
Publication Date(Web):13 May 2014
DOI:10.1039/C4DT01070A
A new approach has been illustrated for the development of stable, efficient, and environmentally “friendly” white phosphorescent materials. Under mild conditions, a new one-dimensional coordination polymer has been prepared from benzo-18-crown-6 with CuI in the presence of KI, which is capable of emitting direct white light in the solid state.
Co-reporter:Kai Wang, Shuai-Hua Song, Yun-Man Zheng, Zao-Ying Li
Chinese Chemical Letters 2013 Volume 24(Issue 11) pp:1011-1013
Publication Date(Web):November 2013
DOI:10.1016/j.cclet.2013.07.018
5,10,15,20-Tetrakis(4-amidinophenyl)porphyrin (Por 1), its Zn complex (Por 2) and amidinophenyl bispophyrin (Por 3) interacting with calf thymus DNA were investigated by scanning electron microscopy (SEM) and the shape and size of the porphyrin–DNA complexes were observed after photo irradiation. The results showed that the shape and size of DNA had significant differences with blank group by virtue of the interaction between the porphyrins and ct-DNA. This suggests the morphological characterization could be used to study the interaction and judge DNA photocleavage activity indirectly through the photo irradiation of porphyrins.Morphological images, such as shape and size of porphyrins–DNA, were observed using scanning electron microscopy (SEM).
Co-reporter:Zuxi Jin;Hai Zhong;Shixi Li;Zaoying Li
Journal of Applied Electrochemistry 2013 Volume 43( Issue 8) pp:783-788
Publication Date(Web):2013 August
DOI:10.1007/s10800-013-0576-8
A novel phenylethynyl-containing conjugative organodisulfide compound 9-trimethylsilane ethynyl-5,8-dihydro-lH,4H-2,3,6,7-tetrathia-anthracene (TMSEDTTA) was synthesized by a facile preparation method, characterized by elemental analysis, Fourier transform infrared spectroscopy (FT-IR), Raman spectrum, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA), and was tested as cathode active material in rechargeable lithium batteries. The electrochemical properties of S–S bonds redox behavior in the organodisulfides were investigated in 1.0 M LiClO4/EC/DMC (1:1, v/v) solution. The system has many advantages, such as high theoretical charge density (ca. 365 mAh g−1), fast redox process and enhanced reversibility. The fast redox process and enhanced reversibility are due to the intramolecular cleavage-recombination of the S–S bond, and the intramolecular electrocatalytic effect of phenylethynyl chain. The cyclic voltammogram of TMSEDTTA shows multiple redox peaks. The separation of the anodic and cathodic peak potentials for disulfide bond in TMSEDTTA is 0.4 V. The charge–discharge tests show an initial capacity of 330 mAh g−1 and the coulomb efficiency of more than 80 % after the electrochemical activation.
Co-reporter:Jianlin Hu, Zuxi Jin, Hai Zhong, Hui Zhan, Yunhong Zhou, Zaoying Li
Journal of Power Sources 2012 Volume 197() pp:297-300
Publication Date(Web):1 January 2012
DOI:10.1016/j.jpowsour.2011.09.012
A new phosphonamidate, bis(N,N-diethyl)(2-methoxyethoxy)methylphosphonamidate (DEMEMPA) has been synthesized as N-P collaborative flame retardant additive in electrolytes for lithium ion batteries (LIBs). It is found that adding 10 vol.% of DEMEMPA to 0.9 M LiPF6/EC/DMC can significantly inhibit the burning of electrolytes and provide a wide electrochemical window. Further studies indicate that the electrolytes with and without DEMEMPA have similar electrochemical behavior with natural graphite and LiFePO4 electrodes. These support the feasibility of using DEMEMPA as a flame retardant additive for LIBs.Highlights► We synthesized a new N-P collaborative flame retardant additive for lithium ion batteries (LIBs). ► The additive can provide a wide electrochemical stability window. ► The electrolytes with and without DEMEMPA have similar electrochemical behavior with natural graphite and LiFePO4 electrodes. ► The additive acts as a Lewis base, which enhances the stability of the electrolyte.
Co-reporter:Qian-ni Guo;Cheng Zhong;Yun-guo Lu
Journal of Inclusion Phenomena and Macrocyclic Chemistry 2012 Volume 72( Issue 1-2) pp:79-88
Publication Date(Web):2012 February
DOI:10.1007/s10847-011-9941-6
Novel 2,3-bis(1H-pyrrol-2-yl)quinoxaline-functionalized hydrazones were prepared and characterized as new chemosensors for copper(II) ion. The binding properties of the compounds 4, 5, 6 and 7 for cations were examined by UV–vis, fluorescence spectroscopy, and linear sweep voltammetric experiments (LSV). The results indicate that a 1:1 stoichiometric complex is formed between compound 4 (or 5, 6, 7) and copper(II) ion, and the association constant is 1.3 × 105 M−1 for 4, 2.1 × 106 M−1 for 5, 4.1 × 105 M−1 for 6 and 8.0 × 105 M−1 for 7, respectively. The recognition mechanism between compound 4 (or 5, 6, 7) and metal ion was discussed based on their electrochemical properties, absorbance changes, and the fluorescence quenching effect when they interact with each other. Control experiments revealed that compound 4 (or 5, 6, 7) has a highly selective response to copper (II) ion.
Co-reporter:Yuan Hu, Qian-qian Li, Hua Li, Qian-ni Guo, Yun-guo Lu and Zao-ying Li
Dalton Transactions 2010 vol. 39(Issue 47) pp:11344-11352
Publication Date(Web):01 Nov 2010
DOI:10.1039/C0DT00737D
N,N′-((5,5′-(Quinoxaline-2,3-diyl)bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))bis(4-methoxyaniline) 4 and N,N′-((5,5′-(quinoxaline-2,3-diyl)-bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))dianiline 5 have been prepared and structurally characterized. The X-ray crystal structures of compounds 4 and 4a have been determined. These compounds displayed good sensitivity toward transition metal ions with Cd(II), Zn(II) turn-on and Cu(II), Hg(II) turn-off in fluorescence. It is an elegant example of on/off behavior like a lamp. When Cd(II) or Zn(II) is added into compounds 4 or 5, the lamp will switch on, and then when Cu(II) or Hg(II) is added into the mixture, the lamp will switch off. The binding properties of 4 and 5 for cations were examined by fluorescence spectroscopy. The fluorescence data and crystal structure indicate that a 1:1 stoichiometry complex is formed between compound 4 (or 5) and metal ions, and the binding affinity is very high. The recognition mechanism between compound 4 (or 5) and metal ion was discussed based on the their chemical constructions and the CHEF/CHEQ effect when they interacted with each other.
Co-reporter:Lei Wu, Zhiping Song, Lishan Liu, Xiangfeng Guo, Lingbo Kong, Hui Zhan, Yunhong Zhou, Zaoying Li
Journal of Power Sources 2009 Volume 188(Issue 2) pp:570-573
Publication Date(Web):15 March 2009
DOI:10.1016/j.jpowsour.2008.12.070
A new fire-retardant—dimethyl(2-methoxyethoxy)methylphosphonate (DMMEMP) has been synthesized and evaluated as a high safe electrolyte solvent for lithium-ion batteries. This report summarizes the physical and electrochemical properties of the new compound. It is found that, this nonflammable phosphonate has a moderate viscosity, a high dielectric constant and a good thermal stability. It can provide a wide electrochemical stability window of 0–5.5 V (vs. Li+/Li), a high conductivity of 2.0 mS cm−1 at 20 °C with 1 M LiTFSI. The electrochemical performance investigated with the Li/LiFePO4 half-cells shows a good capacity of 148.1 mAh g−1 and a coulombic efficiency close to 100% at the 10th cycle.
Co-reporter:Kai Wang;Chun-Ting Poon;Wai-Kwok Wong;Wai-Yeung Wong;Chun Y. Choi;Daniel W. J. Kwong;Heng Zhang
European Journal of Inorganic Chemistry 2009 Volume 2009( Issue 7) pp:922-928
Publication Date(Web):
DOI:10.1002/ejic.200801047
Abstract
A series of (4-cyanophenyl)porphyrins have been prepared and structurally characterized by 1H NMR, IR and UV/Vis spectroscopy, mass spectrometry, and elemental analysis. The relative singlet-oxygen quantum yields, two-photon absorption cross-sections and DNA photocleavage activities of these porphyrins were measured. The results show that (4-cyanophenyl)porphyrins with a properly designed hydrophobic/hydrophilic balance for better cellular uptake have potential application in two-photon-absorption photodynamic therapy. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Co-reporter:Zhi Zhang, Rui He, Kun Yan, Qian-ni Guo, Yun-guo Lu, Xu-xia Wang, Hao Lei, Zao-ying Li
Bioorganic & Medicinal Chemistry Letters 2009 Volume 19(Issue 23) pp:6675-6678
Publication Date(Web):1 December 2009
DOI:10.1016/j.bmcl.2009.10.003
5-(4-Aminophenyl)-10,15,20-tris(4-sulfonatophenyl) manganese(III) porphyrin conjugated with dextran was synthesized. Its potential of being used as a tumor-targeting magnetic resonance imaging contrast agent was evaluated in vitro and in vivo. The results demonstrated that the compound has a longitudinal relaxivity (R1) higher than Gd-DTPA, low cytotoxicity and binding specificity to tumor cell membrane.The synthesis and evaluation of Mn porphyrin–dextran as MRI contrast agents are reported.
Co-reporter:Kai Wang;Zhi Zhang;Qianni Guo;Xiaoping Bao
Frontiers of Chemistry in China 2008 Volume 3( Issue 4) pp:406-412
Publication Date(Web):2008 December
DOI:10.1007/s11458-008-0073-5
A water-soluble porphyrin dimer (Por Dimer) containing eight positive charges, bridged by 4,4′-dicarboxy-2,2′-bipyridine, has been synthesized. With Meso-tetrakis(N-methyl-pyridium-4-yl)porphyrin (H2TMPyP) as the reference compound, the water-soluble porphyrin dimer was investigated for its interaction with DNA by absorption, fluorescence, and circular dichroism (CD) spectroscopy. The apparent affinity binding constant (Kapp = 1.2 × 106) of Por Dimer binding to CT DNA was measured by a competition method with ethidium bromide (EB) (that of H2TMPyP was 6.9 × 106). The cleavage ability of Por Dimer to pBR322 plasmid DNA was studied by gel electrophoresis. The results suggest that the binding modes of Por Dimer were complex and involve both intercalation and outside binding.
Co-reporter:Chuan-Qi Yin;Bao-Jiang He;Shao-Hua Huang;Jun-Yi Zhang;Zheng-Wu Bai
Chirality 2008 Volume 20( Issue 7) pp:
Publication Date(Web):
DOI:10.1002/chir.20555
Abstract
Four dendrimers were synthesized on aminopropyl-modified silica gel using methyl acrylate and ethylene diamine as building blocks by divergent method. Four generations of chiral stationary phases (CSPs) were prepared by coupling of L-2-(p-toluenesulfonamido)-3-phenylpropionyl chloride to corresponding dendrimers. The derivatives prepared on silica gel were characterized by FT-IR, 1H NMR, and elemental analysis. The selector loadings of these four generations of CSPs generally showed a decrease tendency with the increase of generation numbers of dendrimers. The enantioseparation properties of these CSPs were preliminarily investigated by high-performance liquid chromatography. The CSP derived from the three-generation dendrimer exhibited the best enantioseparation capability. Effects of the mobile phase composition and molecular structures of racemic mixtures on enantioseparation were further studied. Chirality, 2008. © 2008 Wiley-Liss, Inc.
Co-reporter:Kai Wang, Lei Wu, Xiu Lan Zhang, Zao Ying Li
Chinese Chemical Letters 2007 Volume 18(Issue 12) pp:1455-1459
Publication Date(Web):December 2007
DOI:10.1016/j.cclet.2007.09.013
The porphyrins tailed with acetylsalicylic acid (ASA) and Zn (or Cu) complexes were prepared. Meanwhile, morphological images, such as shape and size of porphyrins–BSA congeries were observed by using atomic force microscopy (AFM). The result showed the interaction of BSA and prepared porphyrins led to obvious change of shape and size of BSA congeries.
Co-reporter:Kai Wang;Zhi Zhang;Lei Wu
Chemistry & Biodiversity 2007 Volume 4(Issue 3) pp:514-522
Publication Date(Web):19 MAR 2007
DOI:10.1002/cbdv.200790044
Four new cationic porphyrins, compounds 1–4, with five to seven positive charges, were synthesized, characterized, and investigated for their binding properties towards calf-thymus DNA (CT-DNA). UV/VIS and fluorescence-titration data indicated strong binding, the apparent binding constants (Kapp; (1.3–10)×10−6M) increasing with increasing number of charges, as determined by competitive fluorescence titration using ethidium bromide (EB) as molecular probe. These results were qualitatively confirmed by the observed photocleavage efficiency of the porphyrins towards plasmid pBR322 DNA.
Co-reporter:Shi-Ren Deng, Ling-Bo Kong, Gao-Qiang Hu, Tao Wu, Dan Li, Yun-Hong Zhou, Zao-Ying Li
Electrochimica Acta 2006 Volume 51(Issue 13) pp:2589-2593
Publication Date(Web):5 March 2006
DOI:10.1016/j.electacta.2005.07.045
A novel kind of benzene-based organodisulfide, 5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracene (DTTA) and its homopolymer, poly(5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracene) (PDTTA) were designed, synthesized and presented as a cathode material for high-energy secondary lithium batteries. The polyorganodisulfides were characterized by FT-IR, XPS and elemental analysis. The designed system has many advantages, such as high theoretical charge density (ca. 471 mAh/g), fast redox process and enhanced cycling stability, which are due to the intramolecular electrocatalytic effect of polyphenyl chain and the intramolecular cleavage–recombination of the SS bond, respectively. The cyclic voltammetry test results proved the effect of this kind of electrocatalysis, and the charge–discharge experimental results showed that the polymer has the specific capacity of 422 mAh/g at 2nd cycle and 170 mAh/g at the 44th cycle.
Co-reporter:Tao Jia, Zhong-Xing Jiang, Kai Wang, Zao-Ying Li
Biophysical Chemistry 2006 Volume 119(Issue 3) pp:295-302
Publication Date(Web):1 February 2006
DOI:10.1016/j.bpc.2005.09.025
The binding properties of cationic porphyrin–phenylpiperazine hybrids to calf thymus (CT) DNA were investigated by using absorption, fluorescence and circular dichroism (CD) spectra, and the apparent affinity binding constants (Kapp) of the porphyrins for CT DNA were determined by using a competition method with ethidium bromide (EB). Intercalation of porphyrin into CT DNA occurred when two phenylpiperazines were introduced at cis position onto the periphery of cationic porphyrin. The photocleavages of pBR322 plasmid DNA by the porphyrins were consistent with the values of Kapp. With [porphyrin] / [DNA base pairs] ratio increased, the binding mode tended to be outside binding, and the cleavage abilities of the porphyrins varied. In the presence of sodium azide, a quencher of 1O2, the cleavage of DNA by the porphyrin of intercalation was less inhibited.
Co-reporter:Fengshou Wu, Jie Li, Hongbo Tong, Zaoying Li, Chihaya Adachi, Adam Langlois, Pierre D. Harvey, Li Liu, Wai-Yeung Wong, Wai-Kwok Wong and Xunjin Zhu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 1) pp:NaN146-146
Publication Date(Web):2014/10/23
DOI:10.1039/C4TC01885K
Mononuclear Cu(I) complexes based on bis(pyrazol-1-yl-methyl)-pyridine derivatives and ancillary triphenylphosphine have been prepared and characterized by 1H NMR, mass spectroscopy and single-crystal X-ray analysis. The thermogravimetric analysis shows that the complexes exhibit high thermal stability. The electronic absorption spectra display two features in the regions of 230–260 and 290–350 nm attributable to mixed ligand-to-ligand (LLCT) and metal-to-ligand-charge-transfer (MLCT) excited states, which is supported by the results of density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on these Cu(I) complexes. These complexes are strongly emissive in the solid state at ambient temperature. Intense blue or green emission in the poly(methyl methacrylate) film is observed in the region of 475–518 nm for these complexes with the emission lifetimes in the microsecond time scale (12–20 μs), indicating that the emission may be phosphorescence emission. Increasing the steric hindrance of the substituents on the pyrazole unit results in a blue-shift of the emission bands and enhanced emission quantum efficiency in PMMA films. The two most emissive complexes have been used for the fabrication of phosphorescent organic light-emitting diodes (POLEDs).
Co-reporter:Fengshou Wu, Hongbo Tong, Zaoying Li, Wang Lei, Li Liu, Wai-Yeung Wong, Wai-Kwok Wong and Xunjin Zhu
Dalton Transactions 2014 - vol. 43(Issue 33) pp:NaN12466-12466
Publication Date(Web):2014/05/13
DOI:10.1039/C4DT01070A
A new approach has been illustrated for the development of stable, efficient, and environmentally “friendly” white phosphorescent materials. Under mild conditions, a new one-dimensional coordination polymer has been prepared from benzo-18-crown-6 with CuI in the presence of KI, which is capable of emitting direct white light in the solid state.
Co-reporter:Yuan Hu, Qian-qian Li, Hua Li, Qian-ni Guo, Yun-guo Lu and Zao-ying Li
Dalton Transactions 2010 - vol. 39(Issue 47) pp:NaN11352-11352
Publication Date(Web):2010/11/01
DOI:10.1039/C0DT00737D
N,N′-((5,5′-(Quinoxaline-2,3-diyl)bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))bis(4-methoxyaniline) 4 and N,N′-((5,5′-(quinoxaline-2,3-diyl)-bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))dianiline 5 have been prepared and structurally characterized. The X-ray crystal structures of compounds 4 and 4a have been determined. These compounds displayed good sensitivity toward transition metal ions with Cd(II), Zn(II) turn-on and Cu(II), Hg(II) turn-off in fluorescence. It is an elegant example of on/off behavior like a lamp. When Cd(II) or Zn(II) is added into compounds 4 or 5, the lamp will switch on, and then when Cu(II) or Hg(II) is added into the mixture, the lamp will switch off. The binding properties of 4 and 5 for cations were examined by fluorescence spectroscopy. The fluorescence data and crystal structure indicate that a 1:1 stoichiometry complex is formed between compound 4 (or 5) and metal ions, and the binding affinity is very high. The recognition mechanism between compound 4 (or 5) and metal ion was discussed based on the their chemical constructions and the CHEF/CHEQ effect when they interacted with each other.
