嵌段聚合物修饰的金纳米粒子的制备及表征

通过RAFT合成聚(甲基丙烯酸缩水甘油酯)-b-聚(乙二醇甲基丙烯酸酯)嵌段共聚物(PGMA-bPMAPEG),再用半胱氨酸(Cys)使PGMA中的环氧基团开环,制备含有巯基的两亲水嵌段聚合物PMAPEG-bP(GMA-Cys)。并以其作为修饰剂,通过原位还原法使HAuCl4在NaBH4的还原下制备金/聚合物纳米复合粒子(Au@PMAPEG-b-P(GMA-Cys)NPs)。经FT-IR、UV-vis、TG、XRD、TEM和DLS表征,发现金纳米复合粒子呈均匀分散的球形,平均粒径约为10nm,在527nm处出现了金纳米粒子的表面等离子共振吸收峰,金约占总重量的49%。由于外层嵌段共聚物的修饰作用,金纳米复合粒子在室温下放置6个月未发生粒子间的聚集。     

两亲性聚合物修饰的大粒径金纳米粒子的相转移

通过对线性聚乙烯亚胺（linear polyethylenimineLPEI）的棕榈酸改性和季铵化制备了具有两亲性结构的线性聚合物。两亲性线性聚合物在没有诸如硫醇、四正辛基溴化铵（TOAB）等其它化学物质的协助下,通过氨基和柠檬酸钠负离子之间的离子键或氢键相互作用,成功将粒径为18nm柠檬酸钠保护的金纳米粒子（AuNP...     

水溶性铁硫簇纳米粒子的制备及表征

铁硫簇是普遍存在于生物体内的最古老的生命物质之一[1,2]。1960年人们对固氮细菌、亚线粒体片段及哺乳动物的起源进行研究时发现了一种具有高效氧化还原能力的蛋白质,后来被证明是铁硫蛋白,此后对铁硫簇的研究才得以迅速展开。铁硫蛋白结构中包含有铁与巯基丙氨酸中的硫结合成的具有一定构型的铁硫簇合物,基本结构单元主要以Fe2S2、Fe3S4、Fe4S4这3种簇合物的形式而存在。铁硫簇的一个重要结构特征,就是铁原子由无机硫原子以桥的方式联接,同时,蛋白质肽链中半胱胺酸的巯基作为配体与铁原子相结合。这些铁原子以高自旋Fe!或Fe"形式存在…     

结构可控的聚合物长短刷接枝纳米粒子

通过RAFT聚合制备了一系列窄分子量分布的聚(γ-甲基丙烯酰氧基丙基三乙氧基硅烷)(PTEPM)-b-聚甲基丙烯酸甲酯(PMMA)嵌段共聚物和PTEPM、PMMA低聚物.将具有不同PMMA分子量的2种PTEPM-b-PMMA共聚物与低聚物PMMA或PTEPM进行共组装(微相分离),形成片、柱、球等不同PTEPM相区结构.采用盐酸气氛处理,PTEPM相区水解交联形成倍半硅氧烷SiO1.5内核,分离纯化得到聚合物长短刷接枝纳米粒子.使用这种相分离-交联-分散制备方法,调节嵌段共聚物分子结构和三组分比例,可实现聚合物接枝纳米粒子内核形状和尺寸、接枝密度、长短刷比例、长刷长度的精确调控.这些纳米粒子是研究聚合物纳米复合材料结构-性能关系的理想模型体系.     

聚合物/无机纳米粒子自组装复合膜的制备与应用

对聚合物/无机纳米粒子二维自组装复合膜的制备方法进行了系统地分类阐述,在详细介绍各种方法的特点的基础上比较了它们各自的优缺点.并简述了这类复合膜在应用方面的最新研究成果.     

由嵌段共聚物制备有形状的核壳结构聚合物纳米颗粒

嵌段共聚物可自发组装形成形貌丰富的纳米粒子和有序纳米结构的材料,为纳米材料和纳米技术领域提供了很重要的新材料和新手段.该领域的进一步发展提出了对嵌段共聚物的自组装体赋予功能性的要求,即需要通过可控聚合反应合成反应性嵌段共聚物,并且对其自组装的纳米粒子进行结构、形状及功能性的调控.本文针对以上研究目标,结合本课题组在该领...     

嵌段共聚物调控纳米粒子自组装的研究进展

嵌段共聚物和纳米粒子复合纳米材料具有优异的性能,在生物医药、光电材料、催化材料等领域具有很大的应用价值,已成为备受关注的研究热点.利用嵌段共聚物自组装能够形成特定形态的纳米结构聚集体,将纳米粒子选择性的分布和定位于嵌段共聚物聚集体中,可以改善纳米粒子的性能及其应用.本文综述了近年来实验上利用自组装制备嵌段共聚物-纳米粒子复合纳米材料的方法,并总结分析了影响纳米粒子在嵌段共聚物聚集体中的分布和定位的各种因素,包括纳米粒子的大小、形状及其表面化学.最后总结了嵌段共聚物-纳米粒子的自组装在理论模拟方面的研究.     

两亲性三嵌段共聚物PHB-PEG-PHB的合成及其纳米粒子的制备与表征

基于聚(β-丁内酯)(PHB)和聚乙二醇(PEG)的两亲性三嵌段共聚物聚(β-丁内酯)-聚乙二醇-聚(β-丁内酯)(PHB-PEG-PHB)可在聚乙二醇钾盐大分子引发剂的作用下、以四氢呋喃为溶剂,通过β-丁内酯(BL)的阴离子开环聚合进行制备,调节BL与聚乙二醇钾盐的配比,可制备分子量不同的共聚物.产物可通过1H-NMR、13C-NMR、FTIR、DSC、GPC等测试进行表征,DSC结果表明无定形的PHB阻碍了PEG的结晶,且随着PHB链段长度的增加,阻碍作用更加明显.PHB-PEG-PHB可在水中通过沉淀/溶剂蒸发技术进行自组装形成具有核壳结构的纳米粒子,并通过SEM、DLS手段对其表征,发现粒子尺寸在纳米级,形态为球形或方形.聚合物的初始浓度对纳米粒子的形态和尺寸有明显影响,随着聚合物初始浓度的降低,纳米粒子的尺寸降低.     

以胶体粒子为模板制备核壳纳米复合粒子

核壳纳米复合粒子具有许多不同于单组分胶体粒子的独特的光、电、磁、催化等物理与化学性质,是构筑新型功能复合材料的重要组元,在光子带隙材料、微波吸收材料、电磁流变液、催化剂和生物等领域有重要应用.本文从控制核壳复合粒子的微观结构及壳层均匀性与厚度的角度,详细评述了目前以胶体粒子为模板制备粒径从纳米到微米尺度的核壳复合粒子的方法.指出利用胶体粒子模板表面与壳层物质或其前驱物间的特殊相互作用(包括静电和化学相互作用),是完善现有制备方法和发展新方法来制备具有设定组成、结构和性能的核壳复合粒子的关键,同时也是将来的粒子表面纳米工程和获取有序的、先进纳米复合材料的主要方向。     

以PAMAM树形分子为模板制备Pd纳米簇合物

以酯端基聚酰胺-胺树形分子(PAMAM)为模板在甲醇溶剂中制备了Pd纳米簇合物. 采用紫外-可见分光光度法和红外光谱法研究了Pd²⁺与树形分子的作用机理, 结果表明, Pd²⁺与树形分子内部胺基基团(主要为叔胺基)产生了络合作用. 采用硼氢化钠还原法制备了树形分子包裹的、粒径为2 nm的球形面心立方Pd纳米簇合物. 紫外-可见吸收光谱研究结果表明, Pd²⁺与树形分子的摩尔比越小, 生成的纳米簇合物尺寸越小; 由于高代数树形分子具有封闭结构, 且其内部配体数目较多, 采用较高代数的树形分子(5.5代)比低代数(3.5代)更有利于得到尺寸小、分散性较好的Pd纳米簇合物.     

Photoredox-Catalyzed Reduction of Halogenated Arenes in Water by Amphiphilic Polymeric Nanoparticles

The use of organic photoredox catalysts provides new ways to perform metal-free reactions controlled by light. While these reactions are usually performed in organic media, the application of these catalysts at ambient temperatures in aqueous media is of considerable interest. We here compare the activity of two established organic photoredox catalysts, one based on 10-phenylphenothiazine (PTH) and one based on an acridinium dye (ACR), in the light-activated dehalogenation of aromatic halides in pure water. Both PTH and ACR were covalently attached to amphiphilic polymers that are designed to form polymeric nanoparticles with hydrodynamic diameter D_H ranging between 5 and 11 nm in aqueous solution. Due to the hydrophobic side groups that furnish the interior of these nanoparticles after hydrophobic collapse, water-insoluble reagents can gather within the nanoparticles at high local catalyst and substrate concentrations. We evaluated six different amphiphilic polymeric nanoparticles to assess the effect of polymer length, catalyst loading and nature of the catalyst (PTH or ACR) in the dechlorination of a range of aromatic chlorides. In addition, we investigate the selectivity of both catalysts for reducing different types of aryl-halogen bonds present in one molecule, as well as the activity of the catalysts for C-C cross-coupling reactions. We find that all polymer-based catalysts show high activity for the reduction of electron-poor aromatic compounds. For electron-rich compounds, the ACR-based catalyst is more effective than PTH. In the selective dehalogenation reactions, the order of bond stability is C-Cl > C-Br > C-I irrespective of the catalyst applied. All in all, both water-compatible systems show good activity in water, with ACR-based catalysts being slightly more efficient for more resilient substrates.     

Synthesis of Amphiphilic ABCBA-Type Pentablock Copolymer from Consecutive ATRPs and Self-Assembly in Aqueous Solution

Summary: A novel amphiphilic ABCBA-type pentablock copolymer with properties that are sensitive to temperature and pH, poly(2-dimethylaminoethyl methacrylate)-block-poly(2,2,2-trifluoroethyl methacrylate)-block-poly(ε-caprolactone)-block-poly(2,2,2- trifluoroethyl methacrylate)-block-poly(2-dimethylaminoethyl methacrylate) (PDMAEMA- b-PTFEMA-b-PCL-b-PTFEMA-b-PDMAEMA), was synthesized via consecutive atom transfer radical polymerizations (ATRPs). The copolymers obtained were characterized by gel permeation chromatography (GPC) and ¹H nuclear magnetic resonance (NMR) spectroscopy, respectively. The aggregation behaviors of the pentablock copolymers in aqueous solution with different pH (pH = 4.0, 7.0 and 8.5) were studied. Transmission electron microscopic images revealed that spherical micelles from self-assembly of the pentablock copolymer were prevalent in all cases. The mean diameters of these micelles increased from 34, 46, to 119 nm when the pH of the aqueous solution decreased from 8.5, 7.0, to 4.0, respectively.     

Amphiphilic diblock copolymers bearing pendant aromatic acetal groups: Synthesis and tunable pH‐triggered assembly/disassembly transition behavior

A novel aromatic acetal‐based acid‐labile monomer 2‐phenyl‐5‐ethyl‐5‐acryloxymethyl‐1,3‐dioxacyclohexane (HEDPA) was synthesized and polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization using alkynyl functional chain transfer agent (CTA‐Alk). Afterward, a series of amphiphilic diblock copolymers composed of fixed hydrophobic poly(2‐phenyl‐5‐ethyl‐5‐acryloxymethyl‐1,3‐dioxacyclohexane) (PDAEP) segments and various lengths of hydrophilic mPEG segments were prepared through click reaction between alkynyl‐terminated PDAEP and azido‐terminated mPEG. The self‐assembly behaviors of the diblock copolymers were investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), fluorescence spectroscopy, and ¹H NMR. These results indicated that the diblock copolymers could self‐assemble into nano‐sized micelles with PDAEP cores and PEG coronas in aqueous solution. DLS, fluorescence spectroscopy and UV–vis spectroscopy were used to monitor the pH‐triggered assembly/disassembly transition of the micelles. These results showed that the assembly/disassembly transition behaviors of the diblock copolymers micelles can be adjusted by changing the lengths of the mPEG segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1537–1547     

基于蛋白和多肽为模板的贵金属纳米簇合成研究

贵金属(Au, Ag, Pt等)纳米簇通常指的是由几个到约一百个原子组成的分子聚集体, 具有生物相容性好、超小尺寸(<2 nm)以及优异的物理化学性质, 尤其是能发出较强荧光等特点引起了人们的广泛关注. 目前多种贵金属纳米簇的合成方法已相继被报道, 且已应用于生物荧光成像、电化学发光、生物传感器以及细胞标记等多个领域. 本文共分为五部分, 首先重点介绍近几年兴起的以蛋白和多肽为模板来合成纳米簇的方法及优点, 并随后总结列举了文献中所采用的蛋白以及自主设计的多肽组分序列的类别, 随后探索了蛋白和多肽中的特定氨基酸与合成的贵金属纳米簇的荧光波长、量子产率、粒径之间的联系. 本文最后总结阐述了蛋白和多肽为模板成功合成贵金属纳米簇的先决条件并对其生物医学应用前景进行了展望.     

两亲性嵌段共聚物PAA-b-PS的合成及胶束形态

通过丙烯酸叔丁酯的自由基调聚和苯乙烯的原子转移自由基聚合（ATRP）法合成了聚丙烯酸叔丁酯-聚苯乙烯（PtBA-b-PS）嵌段共聚物,然后在三氟乙酸作用下进行选择性水解得到了两亲性聚丙烯酸-聚苯乙烯（PAA-b-PS）嵌段共聚物。利用1H-NMR、FT-IR和GPC对产物的结构进行了表征。采用透析法制备了PAA-b-P...     

Poly(vinyl alcohol)-based Amphiphilic Copolymer Aggregates as Drug Carrying Nanoparticles

A series of amphiphilic polyisobutylene-block-poly(vinyl alcohol) (PIB-b-PVA) copolymers of constant PIB and varying PVA block length was synthesized by living carbocationic polymerization and their solution behavior was studied. The synthesis involved the preparation of polyisobutylene-b-poly(tert.-butyl vinyl ether) followed by hydrolysis with hydrogen bromide. The copolymers were characterized by gel permeation chromatography, ¹H-NMR, and MALDI-TOF MS methods. The micellization behavior of the copolymers was investigated in aqueous media by direct dissolution and dialysis using static and dynamic light scattering. The critical micelle concentration, micelle size, aggregation number, and micelle shape were determined. The ability of the aggregates as drug carrying nanodevices was also investigated by doping them with indomethacin. UV-Vis measurements showed that the solubility of indomethacine increased significantly. Our findings suggest that the solubility is largely dependent upon the block segment ratios.     

两亲性嵌段共聚物的合成及其在离子液体中的自组装行为

采用阴离子开环聚合法合成了两亲性嵌段共聚物PLA-PEG-PLA.用FT-IR,1H NMR和GPC等手段对嵌段共聚物的结构组成进行了表征.两亲性嵌段共聚物在离子液体1-丁基-3-甲基咪唑六氟磷酸盐中能自组装成胶束,用透射电子显微镜观察了聚合物在离子液体中形成胶束的纳米结构.当疏水链长固定时,胶束的自组装形状主要依赖于亲水链的长度.两亲性共聚物在离子液体中可自组装成可控制结构的纳米胶束,这种纳米结构胶束在很多领域具有广泛的应用前景.     

On the Roles of Electron Transfer in Catalysis by Nanoclusters and Nanoparticles

Electron transfer plays a major role in chemical reactions and processes, and this is particularly true of catalysis by nanomaterials. The advent of metal nanoparticle (NP) catalysts, recently including atomically precise nanoclusters (NCs) as parts of nanocatalyst devices has brought increased control of the relationship between NP and NC structures and their catalytic functions. Consequently, the molecular definition of these new nanocatalysts has allowed a better understanding and management of various kinds of electron transfer involved in the catalytic processes. This Minireview brings a chemist‘s view of several major aspects of electron-transfer functions concerning NPs and NCs in catalytic processes. Particular focus concerns the role of NPs and NCs as electron reservoirs and light-induced antenna in catalytic processes from H₂ generation to more complex reactions and sustainable energy production.     

含氟两亲性嵌段聚合物乳液的合成

以聚乙二醇单甲醚(MPEG)为原料,与2-溴异丁酰溴经酯化反应合成了端基为溴原子的MPEG-Br;以MPEG-Br为大分子引发剂,甲基丙烯酸十二氟庚酯经电子活化再生原子转移自由基乳液聚合法合成了新型的含氟两亲性嵌段聚合物(1)乳液,其结构经1H NMR,IR和X-射线光电子能谱(XPS)表征。接触角测量结果表明:1可改变岩心的润湿性,由强液湿转变为气湿。     

Synthesis and Characterization of Amphiphilic Block Copolymer by Block Copolymerization of Butadiene and Acrylamide using Macroazoinitiator

Abstract

Macroazoinitiator (MAI) was prepared from hydroxyl‐terminated polybutadiene (HTPB) and 4,4′‐azobis‐4‐cyanopentanoic acid by direct polycondensation in the presence of 1‐methyl‐2‐chloropyridinium iodide at room temperature. This MAI used for block copolymerization of AAm at 60°C gave the best results in chloroform but the formation of a crosslinked product could not be ruled out in dioxane. It was inferred that for production of a linear block copolymer, homogeneous reaction mixture was required.

The resulting products were characterized by spectral studies IR and NMR, viscosity measurements. Distinct phase segregation of hydrophobic and hydrophilic blocks was evident through DSC analysis.