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Covalently immobilized gelatin gradients within three-dimensional porous scaffolds

Chinese Science Bulletin 2009年第18期54卷 3174-3180页

作者： WU JinDan TAN HuaPing LI LinHui GAO ChangYou Key Laboratory of Macromolecular Synthesis and Functionalization Ministry of Education and Department of Science and Engineering Zhejiang University Hangzhou 310027 China

A stable gelatin gradient providing continuous increment of signaling for cell adhesion and proliferation was fabricated within 3D poly(L-lactic acid) (PLLA) scaffolds. The porous PLLA scaffold fabricated by NaCl particle leaching was vertically fixed on a glass vial. 1,6-Hexanediamine/propanol solution was continuously injected into the vial by a micropump to aminolyze the PLLA scaffold. As a result of reaction time difference, the introduced -NH2 groups increased continuously along with the longitude of the PLLA scaffold in the z-direction. After covalent immobilization of gelatin by glutaraldehyde coupling, the gelatin gradient scaffold was thus obtained. In vitro chondrocyte culture showed that the cells had higher viability and more extending morphology in the gelatin gradient scaffold than that in the uniform gelatin control.

关键词：多孔支架共价固定明胶梯度三维细胞粘附聚乳酸金属制品

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One Pot synthesis of Amphiphilic Hyperbranched Poly-(amino ester)and Its Dynamic Surface Activity

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中国化学（英文版） 2010年第10期28卷 2049-2054页

作者： Gong,Zhangshui Ni,Xufeng Liang,Zhenhua Shen,Zhiquan Key Laboratory of Macromolecular Synthesis and Functionalization of Ministry of Education Department of Polymer Science and EngineeringZhejiang UniversityHangzhouZhejiang 310027China

Amphiphilic hyperbranched poly(amino ester)s with hydrophilic multi-ethoxylated triacrylate backbone and hydrophobic long alkyl side chain were firstly synthesized via one pot Michael addition *** poly-(amino ester)could dissolve in cold water and self-assemble into loose *** 50-1000 ms bubble,the dynamic surface tension(DST)of the poly(amino ester)aqueous solution(0.5 wt%)still maintained in the range of32-28 mN/*** aqueous solutions of poly(amino ester)s with different molecular weights showed the lower critical solution temperature(LCST)in the range of 8-50℃,which could also be tuned by its *** with hydrophobic groups on the terminal units and partially neutralized with acid,the poly(amino ester)s still kept their stable dynamic surfactant behaviors,indicating promising application.

关键词： amphiphilic hyperbranched polymer Michael addition polymerization dynamic surface tension amphiphile surfactant

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Polymerization of n-Octylallene with Rare Earth Catalyst Composed of Ln(P204)3/Al(i-Bu)3

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中国化学（英文版） 2010年第10期28卷 2055-2058页

作者： Ni,Xufeng Zhu,Weiwei Shen,Zhiquan MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhouZhejiang 310027China

Polymerization of n-octylallene was successfully carried out using a conventional binary rare earth catalytic system composed of rare earth tris(2-ethylhexylphosphonate)(Ln(P204)3)and tri-isobutyl aluminum(Al(i-Bu)3)for the first *** effects of catalyst,solvent,reaction time and temperature on the polymerization of n-octylallene were *** resulting poly(n-octylallene)has weight-average molecular weight of 11000,molecular weight distribution of 1.4 and 96% yield under the moderate reaction conditions:[Al]/[Y]=50(molar ratio),[n-octylallene]/[Y]=100(molar ratio),polymerized at 80 ℃ for 20 h in *** poly(n-octylallene)obtained consisted of 1,2-and 2,3-polymerized units,and was characterized by FT-IR,1H NMR and *** investigation shows that the polymerization of n-octylallene has some living polymerization characteristics,preparing the polymer with controlled molecular weight and narrower molecular weight distribution.

关键词： n-octylallene polymerization rare earths

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Donor-acceptor(D-A)terpolymers based on alkyl-DPP and t-BocDPP moieties for polymer solar cells

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Chinese Chemical Letters 2017年第12期28卷 2223-2226页

作者： Fateh Ullah Sun Qian Weitao Yang Muhammad Naeem Shah Zhongqiang Zhang Hongzheng Chen Chang-Zhi Li MOE Key Laboratory of Macromolecular Synthesis and Functionalization State Key Laboratory of Silicon MaterialsDepartment of Polymer Science andEngineeringZhejiang UniversityHangzhou 310027China

A series of low band gap terpolymers based on 4,8-bis（5-（2-ethylhexyl）thiophen-2-yl）benzo[l,2-b：4,5- b＇]dithiophene （BDTr） and diketopyrrolopyrrole （DPP） with varied solubilizing groups （i.e., tert- butoxycarbonyl, t-Boc and 2-octyldodecyl） are developed as electron donors for bulk heterojunction （BHJ） polymer solar cells （PSCs）. The results reveal that the one with 50% t-Boc concentration （P3） performs better than the other terpolymers used in this study in conventional PSC devices with a power conversion efficiency of 2.92%.

关键词： Conjugated polymerOrganic semiconductorPolymer solar cellsBulk heterojunctionDiketopyrrolopyrrole

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Anionic Copolymerization of Carbonyl Sulfide with Epoxides via Alkali Metal Alkoxides

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Chinese Journal of Chemistry 2018年第7期36卷 625-629页

作者： Cheng-Jian Zhang Jia-Liang Yang Lan-Fang Hu Xing-Hong Zhang MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Zhejiang University Hangzhou Zhejiang 310027 China

Carbonyl sulfide （COS）, an analogue of carbon dioxide （CO2）, can be converted to CO2 via the carbonic anhydride enzymes widely existing in nature. COS is an ideal monomer for making poly（monothiocarbonate）s, which are difficult to synthesize by traditional methods. Herein, for the first time, we describe an anionic copolymerization of COS with epoxides using alkali metal alkoxides as the catalysts （initiators）, affording poly（monothiocarbonate）s with 100% alternating degree, 〉99% tail-to-head （T-H） content, high number-average molecular weights （Mns, up to 90.3 kg/mol） with narrow molecular weight distributions （D=Mw/Mn, 1.05-1.31 for COS/propylene oxide copolymers） under solvent-free and mild conditions. Oxygen-sulfur exchange reaction （O/S ER）, which can result in the production of contaminated dithiocarbonate and carbonate units in the main chain, was nearly completely depressed at 0 ℃. In addition, in contrast to previously reported salen chromium （iron） complexes that required multiple synthetic steps, this work provides simple, low-cost, and effective catalysts for making colorless sulfur-containing polymers.

关键词： carbonyl sulfide copolyrnerization alkali metal alkoxides sulfur-containing polymer

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Dual inhibition of PD-1 and LAG-3:uncovering mechanisms to reverse T cell exhaustion and enhance anti-tumor immunity

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Science Bulletin 2025年第5期70卷 624-626页

作者： Xiaoxue Zhou Fangfang Zhou Long Zhang School of Medicine Hangzhou City UniversityHangzhou 310015China MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou 310058China The First Affiliated Hospital the Institutes of Biology and Medical SciencesSuzhou Medical CollegeSoochow UniversitySuzhou 215031China MOE Laboratory of Biosystems Homeostasis and Protection and Innovation Center for Cell Signaling Network Life Sciences InstituteZhejiang UniversityHangzhou 310058China The MOE Basic Research and Innovation Center for the Targeted Therapeutics of Solid Tumors The First Affiliated HospitalJiangxi Medical CollegeNanchang UniversityNanchang 330031China Cancer Center Zhejiang UniversityHangzhou 310058China

Recent studies published in Cell have elucidated the collaborative roles of LAG-3 and PD-1 in driving T cell exhaustion,revealing how targeting both immune checkpoints could enhance immune responses[1],[2],[3].Among these,two studies were led by Dario ***'s team at the University of Pittsburgh School of Medicine,while the third was conducted by *** Wherry's team at the University of Pennsylvania.

关键词： immunity driving exhaustion

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Fabrication and Performance of a Low Operating Pressure Nanofiltration Poly(vinyl chloride) Hollow Fiber Membrane

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Chinese Journal of Polymer Science 2014年第3期32卷 377-384页

作者： Jian-hua Wang Yue-li Wu Yong-hua Zhang 朱宝库 You-yi Xu MOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment TechnologyDepartment of Polymer Science and EngineeringZhejiang University

A low operating pressure nanofiltration membrane is prepared by interfacial polymerization between m-phenylenediamine （MPDA） and trimesoyl chloride （TMC） using PVC hollow fiber membrane as supporting. A series of PVC nanofiltration membranes with different molecular weight cutoff （MWCO） can be obtained by controlling preparation conditions. Chemical and morphological characterization of the membrane surface was carried out by FTIR-ATR and SEM. MWCO was characterized by filtration experiments. The preparation conditions were investigated in detail. At the optimized conditions （40 min air-dried time, aqueous phase containing 0.5% MPDA, 0.05% SDS and 0.6% acid absorbent, oil phase containing 0.3% TMC, and 1 min reaction time）, under 0.3 MPa, water flux of the gained nanofiltration membrane reaches 17.8 L/m2-h, and the rejection rates of methyl orange and MgSO4 are more than 90% and 60%, respectively.

关键词： PVC Interracial polymerization Nanofiltration membrane Hollow fiber membrane.

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Light-induced dynamic RGD pattern for sequential modulation of macrophage phenotypes

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Bioactive Materials 2021年第11期6卷 4065-4072页

作者： Yilun Luo Xiaowen Zheng Peiqi Yuan Xingyao Ye Lie Ma MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou310027China

Due to the critical roles of macrophage in immune response and tissue repair,harnessing macrophage phenotypes dynamically to match the tissue healing process on demand attracted many *** there have developed many advanced platforms with dynamic features for cell manipulation,few studies have designed a dynamic chemical pattern to sequentially polarize macrophage phenotypes and meet the immune requirements at various tissue repair ***,we propose a novel strategy for spatiotemporal manipulation of macrophage phenotypes by a UV-induced dynamic Arg-Gly-Asp(RGD)*** employing a photo-patterning technique and the specific interaction between cyclodextrin(CD)and azobenzene-RGD(Azo-RGD),we prepared a polyethylene glycol-dithiol/polyethylene glycol-norbornene(PEG-SH/PEG-Nor)hydrogel with dynamic RGD-patterned *** irradiation with 365-nm UV light,the homogeneous RGD surface was transformed to the RGD-patterned surface which induced morphological transformation of macrophages from round to elongated and subsequent phenotypic transition from pro-inflammation to *** mechanism of phenotypic polarization induced by RGD pattern was proved to be related to Rho-associated protein kinase 2(ROCK2).Sequential modulation of macrophage phenotypes by the dynamic RGD-patterned surface provides a remote and non-invasive strategy to manipulate immune reactions and achieve optimized healing outcomes.

关键词： Light-responsive Dynamic RGD pattern Macrophage phenotype Immune response Tissue repair

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Miktoarms hyperbranched polymer brushes:One-step fast synthesis by parallel click chemistry and hierarchical self-assembly

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Science China Chemistry 2010年第12期53卷 2461-2471页

作者： HAN Yi & GAO Chao MOE key laboratory of macromolecular synthesis and functionalization Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 310027,China 1. MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China

Spherical molecular brushes with amphiphilic heteroarms were facilely synthesized by grafting the arms of hydrophobic 2-azidoethyle palmitate and hydrophilic monoazide-terminated poly(ethylene glycol) onto the core of alkyne-modified hyperbranched polyglycerol (HPG) with high molecular weight (Mn=122 kDa) via one-pot parallel click *** parallel click grafting strategy was demonstrated to be highly efficient (～100%),very fast (～ 2 h) and well controllable to the amphilicity of molecular *** adjusting the feeding ratio of hydrophobic and hydrophilic arms,a series of brushes with different arm ratios were readily *** resulting miktoarms hyperbranched polymer brushes (HPG-g-C16/PEG350) were characterized by hydrogen-nuclear magnetic resonance (1H NMR),Fourier transform infrared (FT-IR) spectroscopy,gel permeation chromatography (GPC),and differential scanning calorimetry (DSC) *** spherical molecular brushes showed high molecular weights up to 230 kDa,and thus could be visualized by atomic force microscopy (AFM).AFM and dynamic laser light scattering (DLS) were employed to investigate the self-assembly properties of amphiphilic molecular brushes with closed proportion of hydrophobic and hydrophilic *** brushes could self-assemble hierarchically into spherical micelles,and network-like fibre structures,and again spherical micelles by addition of n-hexane into the dichloromethane or chloroform solution of *** addition,this kind of miktoarms polymer brush also showed the ability of dye loading via host-guest encapsulation,which promises the potential application of spherical molecular brushes in supramolecular chemistry.

关键词： miktoarms molecular brushes hyperbranched polyglycerol amphiphilic self-assembly

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Thermo-responsive stick-slip behavior of advancing water contact angle on the surfaces of poly(N-isopropylacrylamide)-grafted polypropylene membranes

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Science China Chemistry 2010年第1期53卷 183-189,289页

作者： WAN LingShu,MENG XiangLin,YANG YunFeng,TIAN Jing & XU ZhiKang key laboratory of macromolecular synthesis and functionalization,Ministry of Education Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 310027,China 1. Key Laboratory of Macromolecular Synthesis and Functionalization Ministry of Education Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China

Wettability of a solid surface is highly important to its practical application,especially for the surface that shows thermoresponsive *** this paper,we describe a thermo-responsive stick-slip behavior of water droplets on the surfaces of poly(N-isopropylacrylamide)(PNIPAM)-grafted polypropylene *** emission scanning electron microscope(FESEM) images elucidate that the morphology of PNIPAM-grafted membrane surface is thermo-responsive,i.e.,the surface becomes rougher above the lower critical solution temperature(LCST) of *** the surface of nascent polypropylene membranes,the water droplet shows a smooth motion resulting in advancing and receding water contact angles of 111° and ～65°,*** the PNIPAM-grafted membrane surfaces,the water droplet shows a stick-slip pattern above the LCST,whereas it advances smoothly below the *** phenomenon is reproducible and can be ascribed to the energy barriers enhanced by the shrink of PNIPAM chains above the *** also find that the slip contact angle decreases from 102° to 92° after several stick-slip *** decrease is attributed to the water adsorption on the grafted PNIPAM layer,which is confirmed by the continuous decrease of the receding water contact angle.

关键词： stick-slip behavior water contact angle thermo-responsive surface poly(N-isopropylacrylamide) polypropylene membrane

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