•A series of POSS-containing polymeric microspheres were designed and prepared.•The microspheres exhibit strong emission with stability against photobleaching.•The microspheres were nearly monodisperse with an average size of 1.4 μm.•The solid-state quantum yield of the microspheres is as high as 68%.A series of novel fluorescent poly(methyl methacrylate) microbeads with narrow size distribution and intense solid state emission were designed and prepared by dispersion polymerization. The featured polyhedral oligosilsesquioxane was introduced into the perylene bisimides fluorophore system to fabricate polymeric microspheres. With poly (12-hydroxystearic acid) chains grafted to poly(methyl methacrylate) backbone as stabilizer, the obtained microspheres were narrow distributed as well as easily dispersed which are shown in the dynamic light scattering and scanning electron microscope measurement. Fluorescence microscope images of petroleum-ether dispersion of the sample exhibited strong orange emission with stability against photobleaching. More importantly, due to the steric hindrance of bulky polyhedral oligosilsesquioxane moieties, the aggregation-induced fluorescence quenching of perylene bisimides can be suppressed significantly, thus the solid-state quantum yield of the microspheres can be boosted to 68%, which is the highest record for perylene bisimide along polymeric microspheres. The excellent luminescent property, in combination with the monodisperse nature and the high stability against photobleaching of the polyhedral-oligosilsesquioxane containing microspheres, makes them a kind of promising material for fabrication of luminescent devices.

•A novel perylene diimide material was prepared by ionic self-assembly method.•The complex possesses supramolecular structure with liquid crystallinity.•The sequential phase transformations are sensitive to peripheral chain motions.•The complex can be aligned by simple shearing and shows anisotropic property.A novel perylene diimide material was prepared by ionic self-assembly (ISA) method. The phase behavior and aggregated structures of the complex were then elucidated via a combination of different experimental techniques such as differential scanning calorimetry, one- and two-dimensional X-ray diffraction, UV/Vis absorption spectra, and Fourier transform infrared spectroscopy. The experimental results reveal that the ISA complex possesses multiple thermally-induced phase structures which are sensitive to peripheral chain motions. At room temperature, it can self-assemble into a monoclinic crystalline structure with dimensions of a = 4.10 nm, b = 3.70 nm, c = 0.34 nm, α = β = 90°, γ = 98.94°. During heating, the complex enters a hexagonal columnar liquid crystalline phase before developing into another monoclinic liquid crystalline phase. Notably, the complex can be well aligned by simple shearing, which shows anisotropic properties in UV/Vis absorption spectra. This property, in combination with the supramolecular structure, makes the complex a promising material for use in polarized optoelectronic devices.Download high-res image (426KB)Download full-size image

A novel S-heterocyclic annulated perylene diimide (SPDI) derivative connected to two polyhedral oligosilsesquioxane (POSS) nanoparticles was designed and synthesized to reveal the effect of bulky substituent groups on its self-assembly behavior and photoluminescence properties. This featured organic–inorganic hybrid can easily self-assemble into crystalline microbelts with a length of several hundred micrometers. The phase behavior and crystal structure of the compound was then elucidated via a combination of different experimental techniques such as differential scanning calorimetry (DSC), one- and two-dimensional (1D and 2D) X-ray diffraction (XRD), UV/Vis and fluorescence spectra, and tandem mass spectrometry with traveling wave ion mobility separation. The experimental results reveal that the compound has a strong propensity to form a dimer in solution and possesses unique molecular packing of discrete dimeric motifs in the solid state. Moreover, due to this discrete molecular packing behavior, the compound exhibits enhanced photoluminescence properties both in solution and in the solid state compared to the reference compound SPDI without a pendant POSS cage. In addition, based on the dual reactions of electron transfer and fluoride-triggered Si–O bond cleavage, the POSS containing SPDI exhibits higher selectivity and sensitivity to fluoride anions, and a quicker response against the reference SPDI without a pendant POSS cage. The enhanced luminescence properties, and the ability to form ultralong crystalline microbelts, in combination with the rapid selective response for F− make this compound a promising material for the fabrication of luminescent devices and colorimetric chemosensors.

A novel tetraphenylethylene material with liquid crystalline (LC) helical structure and aggregation-induced emission (AIE) property was prepared by ionic self-assembly (ISA). The AIE activity, phase behavior, self-assembly structure, and molecular packing behavior of the complex were then elucidated via a combination of different experimental techniques such as UV–vis absorption spectra, photoluminescence spectra, differential scanning calorimetry, polarized optical microscopy, one- and two-dimensional X-ray diffraction, and Fourier transform infrared spectroscopy. The experimental results reveal that the ISA complex possesses high-efficiency luminescent property with quantum yield as high as 46% in solid state. Meanwhile, the complex could self-assemble into different interesting structures which are sensitive to peripheral chain motions. During heating, the complex takes a low-ordered helical supramolecular structure at ambient temperature and then forms another LC phase with high-ordered helical molecular stacking. These ordered hierarchical structures, in combination with the liquid crystallinity and excellent AIE property of the ISA complex, make it a promising material for fabrication of luminescent devices.

Herein, we demonstrate that the REDV peptide modified nanoparticles (NPs) can serve as a kind of active targeting gene carrier to condensate pZNF580 for specific promotion of the proliferation of endothelial cells (ECs). First, we synthesized a series of biodegradable amphiphilic copolymers by ring-opening polymerization reaction and graft modification with REDV peptide. Second, we prepared active targeting NPs via self-assembly of the amphiphilic copolymers using nanoprecipitation technology. After condensation with negatively charged pZNF580, the REDV peptide modified NPs/pZNF580 complexes were formed finally. Due to the binding affinity toward ECs of the specific peptide, these REDV peptide modified NPs/pZNF580 complexes could be recognized and adhered specifically by ECs in the coculture system of ECs and human artery smooth muscle cells (SMCs) in vitro. After expression of ZNF580, as the key protein to promote the proliferation of ECs, the relative ZNF580 protein level increased from 15.7% to 34.8%. The specificity in actively targeting ECs of the REDV peptide conjugated NPs/pZNF580 complexes was still retained in the coculture system. These findings in the present study could facilitate the development of actively targeting gene carriers for the endothelialization of artificial blood vessels.Keywords: actively targeting; endothelial cells; gene carriers; nanoparticles; proliferation; REDV peptide

A novel S-heterocyclic annulated perylene diimide (SPDI) derivative connected to two polyhedral oligosilsesquioxane (POSS) nanoparticles was designed and synthesized to reveal the effect of bulky substituent groups on its self-assembly behavior and photoluminescence properties. This featured organic–inorganic hybrid can easily self-assemble into crystalline microbelts with a length of several hundred micrometers. The phase behavior and crystal structure of the compound was then elucidated via a combination of different experimental techniques such as differential scanning calorimetry (DSC), one- and two-dimensional (1D and 2D) X-ray diffraction (XRD), UV/Vis and fluorescence spectra, and tandem mass spectrometry with traveling wave ion mobility separation. The experimental results reveal that the compound has a strong propensity to form a dimer in solution and possesses unique molecular packing of discrete dimeric motifs in the solid state. Moreover, due to this discrete molecular packing behavior, the compound exhibits enhanced photoluminescence properties both in solution and in the solid state compared to the reference compound SPDI without a pendant POSS cage. In addition, based on the dual reactions of electron transfer and fluoride-triggered Si–O bond cleavage, the POSS containing SPDI exhibits higher selectivity and sensitivity to fluoride anions, and a quicker response against the reference SPDI without a pendant POSS cage. The enhanced luminescence properties, and the ability to form ultralong crystalline microbelts, in combination with the rapid selective response for F− make this compound a promising material for the fabrication of luminescent devices and colorimetric chemosensors.