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Room temperature polymerization of alkyl isocyanates catalyzed by rare earth Schiff base complexes

Science China Chemistry 2009年第11期52卷 1843-1850页

作者： XiongFa Yang XuFeng Ni ZhiQuan Shen Key Laboratory of Macromolecular Synthesis and Functionalization Ministry of Education Institute of Polymer Science Zhejiang University Hangzhou 310027 China

The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H2salen)2Cl3·2C2H7OH/Al(i-Bu)3) at room temperature was investigated. The influences of ligand str... 详细信息

The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H₂salen)₂Cl₃·2C₂H₇OH/Al(i-Bu)₃) at room temperature was investigated. The influences of ligand structure, catalyst composition, polymerization temperature, polymerization time, the concentration of catalyst and monomer, and the polymerization solvent on the polymerization of isocyanates were studied. It was found that under the polymerization conditions, examined La(H₂salen_A)₂Cl₃·2C₂-H₇OH/Al(i-Bu)₃ (H₂salen_A= N,N′-disalicylideneethylene diamine) is a fairly high efficient catalyst for the polymerization of n-hexyl isocyanate (n-HexNCO) to prepare high molecular weight poly(n-hexyl isocyanate) (PHNCO) with narrower molecular weight distribution at room temperature. PHNCO could be prepared with yield of 74.0%, number-average molecular weight (M _n) of 40.20×10⁴ and MWD of 1.79 under the following optimum conditions: [Al]/[La] = 30 (molar ratio), [n-HexNCO]/[La] = 100 (molar ratio), [n-HexNCO] = 3.43 mol/L polymerization at 20°C for 12 h in toluene. In the same polymerization conditions, poly (n-octyl isocyanate) (PONCO) with yield of 67.3%, and poly(n-butyl isocyanate) (PBNCO) with yield of 45.5%, could be prepared respectively. The kinetics of the polymerization of n-HexNCO was also investigated and found to be first-order with respect to both monomer and catalyst concentrations.

关键词： rare earth catalyst Schiff base complex polymerization alkyl isocyanate

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Induced migration of endothelial cells into 3D scaffolds by chemoattractants secreted by pro-inflammatory macrophages in situ

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Regenerative Biomaterials 2017年第3期4卷 139-148页

作者： Xuguang Li Yuankun Dai Tao Shen Changyou Gao MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou 310027China

Cell migration in scaffolds plays a crucial role in tissue regeneration,which can better mimic cell behaviors in *** this study,a novel model has been proposed on controlling 3D cell migration in porous collagen-chitosan scaffolds with various pore structures under the stimulation of inflammatory cells to mimic the angiogenesis *** cells(ECs)cultured atop the scaffolds in the Transwell molds which were placed into a well of a 24-well culture plate were promoted to migrate into the scaffolds by chemoattractants such as vascular endothelial growth factor(VEGF)and tumor necrosis factor-alpha(TNF-α)secreted by the pro-inflammatory macrophages incubated in the well culture *** phenotype of macrophages was mediated by 50 ng/ml interferongamma(IFN-c)and different concentrations of lipopolysaccharide(LPS,150–300 ng/ml).The cell migration depth had a positive correlation with LPS concentration,and thereby the TNF-a *** ECs migrated easier to a deeper zone of the scaffolds prepared at10C(187 lm in pore diameter)than that at20C(108 lm in pore diameter)as *** method provides a useful strategy to study the 3D cell migration,and is helpful to reveal the vascularization process during wound healing in the long run.

关键词： cell migration chemoattractants endothelial cells macrophages scaffolds

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Surface glycosylation of polymeric membranes

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Science China Chemistry 2008年第10期51卷 901-910页

作者： DAI ZhengWei WAN LingShu XU ZhiKang Key Laboratory of Macromolecular Synthesis and Functionalization of Ministry of Education Institute of Polymer ScienceZhejiang UniversityHangzhou 310027China

Surface glycosylation of polymeric membranes has been inspired by the structure of natural biomem-branes. It refers to that glycosyl groups are introduced onto the membrane surface by various strate-gies, which combine the separation function of the membrane with the biological function of the sac-charides in one system. In this review, progress in the surface glycosylation of polymeric membranes is highlighted in two aspects, i.e. the glycosylation methods and the potential applications of the sur-face-glycosylated membranes.

关键词： membrane surface glycosylation enzyme immobilization protein recognition

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Assessing the synergy effect of additive and matrix on single-crystal growth: Morphological revolution resulted from gel-mediated enhancement on CIT-calcite interaction

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Chinese Chemical Letters 2018年第8期29卷 1296-1300页

作者： Yujing Liu Ying Tan Jie Ren Hongzheng Chen Hanying Li MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering State Key Laboratory of Silicon Materials Zhejiang University

It is well known that in biomineralization, the inorganic solids crystallized in the presence of organic phases, which are generally recognized as additives and matrix, leading to the crystal morphology modification. However, the synergy effects of both soluble additive and insoluble matrix on regulating the morphology of synthetic single-crystals are less studied. Here, we examine the morphological revolution of calcite single crystals induced by the additive, citrate（CIT）, or/and the matrix, agarose gel network. The agarose gel matrix is inert to the crystal morphology in the sense that the agarose gelgrown calcite crystals maintain in characteristic rhombohedra. In contrast, CIT additives are active in crystal morphology modification and crystals begin to exhibit curved rough surfaces when grown in solution with the concentration of CIT coated Au nanoparticles（[CIT-Au NPs]） of more than 2.25 mg/***, once agarose gel and CIT-Au NPs are simultaneously introduced, the curved morphological feature emerges at a much lower [CIT-Au NPs] of around 0.2 mg/mL. Increasing the gel concentrations further reduce the [CIT-Au NPs] needed to trigger calcite morphological modification, suggesting that the gel networks reduce the CIT diffusion and thereby enhance the kinetic effects of CIT on crystallization. As such, this work may have implications for understanding the mechanism of hierarchical biominerals construction and provide rational strategy to control single-crystal morphologies.

关键词： Biomineralization Synergy effect Additive CIT Gel matrix Calcite single-crystal Morphology

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Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

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Chinese Journal of Polymer Science 2015年第8期33卷 1186-1195页

作者： Ce Tian 凌君 You-qing Shen MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang University Department of Chemical and Biological Engineering Zhejiang University

Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copolymers, i.e. random copolymers of L-glutamic acid （Glu） with L-leucine （Leu） [poly（Glu-r-Leu）s], as well as their block copolymers with polysarcosine （polySar）. Well-defined poly（Glu-r-Leu）s with predictable compositions and molecular weights were synthesized by ring opening polymerization of corresponding N-carboxyanhydride monomers. We investigated the relationship between hydrophilicity-hydrophobicity transition and copolymer composition. With increasing Leu fraction, both the pH value of cloud point and the micellar size increased. Poly（Glu-r-Leu） with 60% Leu exhibited a cloud point at the pH of 5.0 to 6.0 the same as that in endosome and lysosome. Poly（Glu-r-Leu）-b-polySars assembled in phosphate buffer and performed pH-responsive morphology change from orbicular micelles at high pH to worm-like micelles at low pH. They were potential pH-responsive carriers for drug and gene delivery to enhance cargo release in cellules.

关键词： α-Amino acid NCA Random/block copolypeptide pH-Responsive Hydrophilicity-hydrophobicity transition.

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Migration of endothelial cells into photo-responsive hydrogels with tunable modulus under the presence of pro-inflammatory macrophages

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Regenerative Biomaterials 2019年第5期6卷 259-267页

作者： Wangbei Cao Xuguang Li Xingang Zuo Changyou Gao MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou 310027China

Cell migration in three-dimensional environment is extremely important for tissue regeneration and other biological *** this work,a model system was developed to study how endothelial cells(ECs)migrate into photo-responsive hydrogels under the presence of pro-inflammatory *** hydrogel was synthesized from hyaluronic acid grafted with coumarin and methacrylate moieties by both carbon–carbon covalent linking and coumarin dimerization under UV irradiation at 365 *** structure of the hydrogel was conveniently modulated by UV irradiation at 254nm to decompose the coumarin dimers,leading to the significant decrease of modulus and increase of swelling ratio and mesh *** the presence of M1 macrophages,ECs were induced to migrate into the hydrogels with a different degree.A significant larger net displacement of ECs was found in the softer hydrogel obtained by irradiation with UV at 254nm than in the stiffer original one at day 7.

关键词： 3D cell migration immune-response hydrogel photo-responsive hyaluronic acid

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Enhance efferocytosis capacity of dendritic cells for diabetic wound healing by nanozyme-loaded nanofiber dressings

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Nano Today 2025年 64卷

作者： Jian, Danfeng Ye, Kai Wang, Limo Jin, Lulu Yang, Huang Ma, Lie Yi, Chenggang Mao, Zhengwei Wu, Jindan MOE Key Laboratory of Advanced Textile Materials & Manufacturing Technology Zhejiang Sci-Tech University Hangzhou310018 China Department of Plastic Surgery The Second Affiliated Hospital School of Medicine Zhejiang University Hangzhou310003 China MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Zhejiang University Hangzhou310003 China Department of Hepatobiliary and Pancreatic Surgery The Second Affiliated Hospital School of Medicine Zhejiang University Hangzhou310003 China Key Laboratory of Precision Diagnosis and Treatment for Hepatobiliary and Pancreatic Tumor of Zhejiang Province Zhejiang Hangzhou310009 China

Improving efferocytosis of dendritic cells (DCs) by inhibiting membrane transporter protein SLC7A11 has been explored for healing diabetes wounds. However, the administration of SLC7A11 inhibitors has been linked to the generation of reactive oxygen species (ROS), which may compromise the viability and functionality of DCs. To mitigate this adverse effect, a nanozyme-loaded nanofiber dressing, termed GIPH, was developed. This dressing encapsulates a specific SLC7A11 inhibitor (HG106) in the core layer and incorporates an efficient nanozyme, Ir NPs-PVP, in the shell layer. The Ir NPs-PVP nanozyme effectively neutralizes ROS produced by HG106, thereby enhancing the viability of DCs and further promoting their efferocytosis. Our in vitro experiment results demonstrated that GIPH-treated Bone Marrow-Derived Dendritic Cells (BMDCs) exhibited a 1.68-fold increase in survival and a 1.52-fold enhancement in efferocytosis rate compared to those treated with HG106 alone. Furthermore, in a diabetic mouse wound model, the GIPH group showed superior healing outcomes, with wound nearly achieving complete recovery by day 12 (97.5 %). This research highlights the therapeutic potential of nanozyme-loaded nanofiber dressings while providing valuable insights for future investigations into the DCs-mediated wound healing process. © 2025 Elsevier Ltd

关键词： Nanofibers

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Graphene nanosheets decorated with Pd,Pt,Au,and Ag nanoparticles:synthesis,characterization,and catalysis applications

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Science China Chemistry 2011年第2期54卷 397-404页

作者： HE HongKun GAO Chao MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou 310027China

We report that noble metal nanopartcles (Pd, Pt, Au, and Ag) decorated-graphene nanosheets can be synthesized with the template of graphene oxide by a one-pot solution-based method. The resulting hybrid materials are characterized by transmission electronic microscopy, energy dispersive X-ray spectroscopy, scanning electronic microscopy, atomic force microscopy, X-ray diffraction, and Raman spectroscopy, which demonstrate that the metal nanoparticles have been uniformly deposited on the surfaces of graphene nanosheets. Our results in turn verify that the carboxylic groups of graphene oxide are statistically distributed on its whole sheet surface rather than just at its edges. The graphene-metal nanohybrids can be used as catalysts in the reduction of potassium hexacyanoferrate(Ⅲ) with NaBH4 in aqueous solution. Our results suggest that graphene is a superior substrate to support metals for applications in the heterogeneous catalysis.

关键词： graphene graphene oxide noble metal nanoparticles hybrids catalyst

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A facile approach to construct hybrid multi-shell calcium phosphate gene particles

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Journal of Zhejiang University-Science B(Biomedicine & Biotechnology) 2010年第4期11卷 292-297页

作者： Zhi-xue XU Ran ZHANG You-xiang WANG Qiao-ling HU MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Zhejiang University Hangzhou 31002 7 China

The calcium phosphate (CaP) particles have attracted much attention in gene therapy. How to construct stable gene particles was the determining factor. In this study,hybrid multi-shell CaP gene particles were successfully constructed. First,CaP nanoparticles served as a core and were coated with DNA for colloidal stabilization. The ξ-potential of DNA-coated CaP nanoparticles was -15 mV. Then polyethylenimine (PEI) was added and adsorbed outside of the DNA layer due to the electrostatic attraction. The ξ-potential of hybrid multi-shell CaP particles was slightly positive. With addition of PEI,the hybrid multi-shell particles could condense DNA effectively,which was de-termined by ethidium bromide (EtBr) exclusion assay. The hybrid particles were spherical and uniform with diameters of about 150 nm at proper conditions. By simple modification of PEI,the hybrid multi-shell CaP gene particles were successfully constructed. They may have great potential in gene therapy.

关键词： Calcium phosphate Polyethylenimine （PEI） Hybrid Gene

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A Near-Infrared Aie-Active Ir(Iii) Complex with a Super-Large Stokes Shift and Efficient Singlet Oxygen Generation

SSRN

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SSRN 2025年

作者： Wang, Lei Guan, Yuge Zhang, Haoke Liu, Chun Cancer Hospital of Dalian University of Technology State Key Laboratory of Fine Chemicals Dalian University of Technology Linggong Road 2 Dalian116024 China MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Zhejiang University Hangzhou310058 China Zhejiang-Israel Joint Laboratory of Self-Assembling Functional Materials ZJU-Hangzhou Global Scientific and Technological Innovation Center Zhejiang University Hangzhou311215 China School of Food and Health Zhejiang Agricultural and Forestry University Hangzhou311300 China

Iridium complexes have demonstrated wide applicability across various fields, particularly in bioimaging and photodynamic therapy due to their exceptional photophysical properties. However, their effectiveness in biological treatments is often limited by aggregation-caused quenching (ACQ), which reduces luminescence efficiency, hinders precise targeting, and lower singlet oxygen generation. Herein, we report the design and synthesis of a novel trifluoromethylated cationic cyclometalated Ir(III) complex incorporating diphenylamino (DPA) and trifluoromethyl groups, which exhibits desirable AIE characteristics, a super-large Stokes shift, and near-infrared (NIR) emission. Comprehensive structural and photophysical analyses, including single-crystal X-ray diffraction and transmission electron microscopy, reveal that these Ir(III) complexes show robust aggregation behavior, significant π-π and C-H-F interactions, and exceptional oxygen sensitivity in EC films ( = 0.05586 Torr⁻¹). Notably, the DPA-modified complex Ir3 demonstrates enhanced singlet oxygen generation within intracellular environments, exhibiting distinct phototoxicity and minimal dark toxicity against HeLa cells. This work advances the design strategy of AIE-active Ir(III) complexes for photodynamic therapy (PDT) and oxygen sensing, offering insights into developing functional materials with enhanced NIR emission, substantial stokes shifts, and selective bioimaging capabilities. These findings provide a promising foundation for further applications of Ir(III) complexes in cancer phototherapy and other biomedical fields. © 2025, The Authors. All rights reserved.

关键词： Single crystals

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