层层组装微胶囊的制备及其智能响应与物质包埋释放性能

在胶体微粒模板上进行聚合物间或聚合物和小分子间的交替层层(LBL)组装, 得到核壳微粒, 然后去除胶体微粒得到层层组装微胶囊. 综述了层层组装微胶囊在组装驱动力、智能响应性能和物质包埋与释放等方面的最新研究进展. 首先从组装驱动力和微胶囊结构调控出发, 简述了基于静电和氢键作用的LBL微胶囊的交联方法及交联所引起的微胶囊结构和性能的变化, 介绍了基于新驱动力如共价键作用、 碱基对作用和主客体作用制备LBL微胶囊的技术. 讨论了LBL微胶囊的智能响应性, 包括pH、 温度、 电荷、 光电磁和化学物质响应等. 详细介绍了LBL微胶囊包埋与释放功能物质尤其是药物、 蛋白和酶的方法及其特色, 包括LBL直接包埋与释放、 预吸附或共沉淀包埋与释放、 电荷选择性自沉积包埋与释放及爆释等. 最后, 着眼于微胶囊的靶向传递和功能器件, 介绍了采用静电作用和生物识别作用制备得到的微胶囊阵列.     

有机分子在基底上的自组装及其在仿生材料合成中的应用

基底对有机分子的自组装有着重要的影响作用，有机分子不同的自组装方式在仿生材料合成，生物膜等方面有重要用途，本文综述了有机分子在不同基底上的自组装方式及其在仿生材料合成中的应用，并对有机分子的自组装方式的发展趋势及广阔应用前景作了进一步的展望。     

含乳糖聚电解质靶向微胶囊的层层自组装构筑

设计合成了己二酸乳糖乙烯酯/对苯乙烯磺酸钠共聚物（PLESS）,通过层层自组装技术构筑聚烯丙基胺盐酸盐（PAH）与含乳糖聚电解质PLESS的靶向微胶囊。以紫外-可见吸收光谱监测了PAH与PLESS在平面的石英片进行层层自组装过程,研究了不同实验条件（聚电解质浓度、溶液盐度、盐种类）对PAH/PLESS多层膜自组装的影响;PAH与PLESS在球形碳酸钙微球模板上层层自组装,去除模板后得到层状结构的微胶囊,用透射电镜（TEM）等方法观察其形态形貌;通过花生凝集素识别考察其潜在靶向性;通过细胞MTT活性试验评价其生物相容性。     

刺激响应型微胶囊的可控释放研究进展

刺激响应型微胶囊由于具有独有的高稳定性、多功能性、膜结构的可调性、以及对不同芯材的运送能力,在药物封装和释放、人造细胞、催化、化学传感器等领域具有广阔的应用前景.本文综述了近年来不同刺激响应型复合微胶囊的可控释放的研究进展,包括温敏型、pH响应型、磁响应型、生物响应型、电响应型,以及光响应型微胶囊,根据释放机理的不同着重对光响应型微胶囊的释放过程进行了总结,并对微胶囊可控释放在未来的发展趋势进行了展望.     

寡肽组装体及其肿瘤光热免疫治疗应用

光热治疗与免疫治疗功能上的互补以及协同效应使得光热免疫治疗在抑制实体瘤及转移瘤方面具有非常优异的表现,然而当前使用的光热免疫制剂的局限性限制了其临床应用转化,对于这种复合疗法的开发和优化已经成为肿瘤治疗领域的研究热点.其中,基于寡肽分子设计的功能组装体获得了越来越多的关注,这类组装体不仅可以通过氨基酸编码设计组装结构,而且可以通过生物活性肽的引入实现优异的抗肿瘤治疗性能.本专论中将根据寡肽分子参与抗肿瘤体系构建的不同作用,结合本团队的研究进展,对近期寡肽组装体在肿瘤光热免疫治疗的研究进行总结.首先探讨了寡肽参与光热免疫体系组装调控的思路,阐述了组装调控过程中寡肽在强化体系稳定性、优化光热转化效率及诱导免疫应答的机理.此外,还结合国内外研究现状,对不同功能肽在肿瘤光热免疫治疗中的作用进行了总结,并分析了寡肽组装体在肿瘤治疗领域的应用前景,最后对该领域的发展方向进行了展望.     

光电功能配合物及其组装

从分子水平上研究具有光电功能特性的分子材料是当前化学的一个重要领域。本文以一些实例简短的介绍了我们近年来在光电功能配合物及其组装研究中的部分进展，强调了从超分子相互作用及分子识别在分子设计兼具无视和有机优点的功能配合物材料中的作用。     

LbL层层纳米自组装法制备新型微胶囊*

本文介绍了一种新颖、灵活的制备纳米或微米胶囊方法--层层纳米自组装法(LbL)。LbL法制备微胶囊的显著优越性在于能够在纳米尺度上对胶囊的大小、组成、结构、形态和囊壁厚度进行精确的控制.这种新型的微胶囊在生化、制药、药物控释、化妆品和催化等领域具有潜在的应用前景。     

分子识别在纳米材料组装中的应用

分子识别应用于纳米材料组装中的研究正受到人们的广泛关注,并逐渐成为超分子化学研究领域中的一个热点。本文对近年来利用分子识别实现纳米材料的组装及可控组装的研究工作进行了综述,并对该领域的研究前景进行了展望。     

自组装单分子膜及其表征方法

自组装单分子膜的研究是近年来十分活跃的研究领域. 随着膜的应用领域的拓展 ,对膜的表征方法不断提出新的要求.本文综述了自组装单分子膜体系的类型和基底表面的 处理方法,着重从电化学、谱学、显微学以及表面润湿性等方面综述了近几年来自组装单分子膜的表征方法研究进展, 并对其发展前景作了展望.     

Assembling and releasing performance of supramolecular hydrogels formed from simple drug molecule as the hydrogelator

A simple drug compound, 4-oxo-4-（2-pyridinylamino） butanoic acid （defined as AP）, was able to gel water at 4 wt% concentration under various conditions. In the superstructure, AP molecules assembled into fibrous aggregates driving by hydrogen bonds and π-π stacking interaction. The gels with different backbone structures released drug molecules in different speeds.     

Synthesis,self‐assembly and recognition properties of biomimetic star‐shaped poly(ε‐caprolactone)‐b‐glycopolymer block copolymers

Biomimetic star‐shaped poly(ε‐caprolactone)‐b‐poly(gluconamidoethyl methacrylate) block copolymers (SPCL‐PGAMA) were synthesized from the atom transfer radical polymerization (ATRP) of unprotected GAMA glycomonomer using a tetra(2‐bromo‐2‐methylpropionyl)‐terminated star‐shaped poly(ε‐caprolactone) (SPCL‐Br) as a macroinitiator in NMP solution at room temperature. The block length of PGAMA glycopolymer within as‐synthesized SPCL‐PGAMA copolymers could be adjusted linearly by controlling the molar ratio of GAMA glycomonomer to SPCL‐Br macroinitiator, and the molecular weight distribution was reasonably narrow. The degree of crystallization of PCL block within copolymers decreased with the increasing block length ratio of outer PGAMA to inner PCL. Moreover, the self‐assembly properties of the SPCL‐PGAMA copolymers were investigated by NMR, UV‐vis, DLS, and TEM, respectively. The self‐assembled glucose‐installed aggregates changed from spherical micelles to worm‐like aggregates, then to vesicles with the decreasing weight fraction of hydrophilic PGAMA block. Furthermore, the biomolecular binding of SPCL‐PGAMA with Concanavalin A (Con A) was studied by means of UV‐vis, fluorescence spectroscopy, and DLS, which demonstrated that these SPCL‐PGAMA copolymers had specific recognition with Con A. Consequently, this will not only provide biomimetic star‐shaped SPCL‐PGAMA block copolymers for targeted drug delivery, but also improve the compatibility and drug release properties of PCL‐based biomaterials for hydrophilic peptide drugs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 817–829, 2008     

葫芦脲：分子识别与组装

综述了葫芦脲这一类合成受体的最新研究进展，包括葫芦脲的分子设计与合成 ，离子和分子识别，键合的热力学性质，分子组装及其功能的最新研究概况。     

环三藜芦烃的分子识别与组装

环三藜芦烃是一类基于藜芦醚与甲醛缩聚物的大环主体分子,其具有独特的C3对称结构和刚性的富电子空腔,在超分子化学、材料科学等方面具有潜在的应用价值,受到人们越来越多的重视.本文主要概述了近年来环三藜芦烃及其衍生物在分子识别与超分子组装方面的一些研究进展.     

Synthesis and self‐assembly of novel amphiphilic copolymers poly(lactic acid)‐block‐poly(ascorbyl acrylate)

In this study, a novel type of amphiphilic block copolymers poly(lactic acid)‐block‐poly(ascorbyl acrylate) (PLA‐block‐PAAA) with biodegradable poly(lactic acid) as hydrophobic block and poly(ascorbyl acrylate) (PAAA) as hydrophilic block was successfully developed by a combination of ring‐opening polymerization and atom transfer radical polymerization, followed by hydrogenation under normal pressure. The chemical structures of the desired copolymers were characterized by ¹H NMR and gel permeation chromatography. The thermal physical properties and crystallinity were investigated by thermogravimetric analysis, differential scanning calorimetry, and wide angle X‐ray diffraction, respectively. Their self‐assembly behavior was monitored by fluorescence‐probe technique and turbidity change using UV–vis spectrometer, and the morphology and size of the nanocarriers via self‐assembly were detected by cryo‐transmission electron microscopy and dynamic light scattering. These polymeric micelles with PAAA shell extending into the aqueous solution have potential abilities to act as promising nanovehicles for targeting drug delivery. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Modular design in natural and biomimetic soft materials

Under eons of evolutionary and environmental pressure, biological systems have developed strong and lightweight peptide-based polymeric materials by using the 20 naturally occurring amino acids as principal monomeric units. These materials outperform their man-made counterparts in the following ways: 1) multifunctionality/tunability, 2) adaptability/stimuli-responsiveness, 3) synthesis and processing under ambient and aqueous conditions, and 4) recyclability and biodegradability. The universal design strategy that affords these advanced properties involves "bottom-up" synthesis and modular, hierarchical organization both within and across multiple length-scales. The field of "biomimicry"-elucidating and co-opting nature's basic material design principles and molecular building blocks-is rapidly evolving. This Review describes what has been discovered about the structure and molecular mechanisms of natural polymeric materials, as well as the progress towards synthetic "mimics" of these remarkable systems.     

仿生制备有机-无机复合微囊固定化葡萄糖氧化酶

将层层自组装技术与仿生矿化技术相结合,由聚苯乙烯磺酸钠、聚二甲基二烯丙基氯化铵和二氧化硅成功制备(聚苯乙烯磺酸钠-聚二甲基二烯丙基氯化铵)₂-二氧化硅复合微囊.采用扫描电子显微镜、红外光谱和热重对微囊的形貌和化学结构进行了表征.以该复合微囊作为理想载体固定化葡萄糖氧化酶.结果表明,固定于复合微囊中的葡萄糖氧化酶的热稳定性、pH稳定性、操作稳定性得到了提高;在最适条件下,复合微囊固定化葡萄糖氧化酶的酶活回收率为72.85%,米氏常数是游离葡萄糖氧化酶的2.21倍.复合微囊在化学/生物催化、药物/基因传递系统和生物传感器应用方面具有一定的潜能.     

Self-assembling viral mimetics: one long journey with short steps

Recently, the Foresight Institute has pronounced six economic challenges that can be addressed through the progress of nanotechnology. One of these is the health and longevity of human life. Amongst applications anticipated to provide a solution to this challenge, gene therapy appears to be particularly promising. In theory, many diseases that result from genetic disorders can be cured by correcting defective genes. In practice, finding efficient and safe delivery vectors remains the stumbling point on the path of genetic therapies to the clinic. Viruses, otherwise the most efficient transfectors, pose safety concerns over immune reactions, whereas synthetic gene packages greatly lack the structural integrity of viruses. An ideal vector is therefore seen as a compromise between the two: a nanoscale device, which would mimic a virus and act as a virus, but would do this at the designer's whim. A strategy to achieve this is offered by the virus architecture itself, the principles of which are translated into the function via exquisitely reproducible self-assembly mechanisms. Thus, to mimic a virus is to mimic the way it is built, i.e., self-assembly. With just a few attempts made so far, the journey to an artificial virus has had a short lifetime, but the promise it holds is not expected to reduce any time soon.     

Boronate-containing copolymers: polyelectrolyte properties and sugar-specific interaction with agarose gel

Copolymers of N-acryloyl-m-aminophenylboronic acid (NAAPBA) with acryamide (AA), N,N-dimethylacrylamide (DMAA), and N-isopropylacrylamide (NIPAM) were found to adsorb on cross-linked agarose gel (Sepharose CL-6B) in the pH range from 7.5-9.2, due to specific boronate-sugar interactions. The molar percentages of phenylboronic acid (PBA) groups in the boronate-containing copolymers (BCCs), as estimated by 1H NMR spectroscopy, were 13, 10, and 16%, respectively, whereas the apparent ionization constants, the pKa values, of the copolymers were similar and equal to 9.0 +/- 0.2 at 20 degrees C. The copolymers adsorption capacities were in the range of 15-30 mg x ml(-1) gel (14-36 micromol pendant PBA ml(-1) gel) at pH 9.2 and decreased with decreasing pH value. The interaction of monomeric NAAPBA with Sepharose CL-6B was characterized by an equilibrium association constant of 53 +/- 17 M(-1), the chromatographic capacity factor k' = 1.8, and a total content of binding sites of 27 +/- 10 micromol x ml(-1) gel at pH 9.2. The weak reversible binding of monomeric NAAPBA and almost irreversible binding of NAAPBA copolymers to the gel at pH 9.2 suggested a multivalent character of the copolymer adsorption. At pH 7.5, the maximal adsorption capacity was displayed by the AA-NAAPBA copolymer (15 mg x ml(-1) gel). All the BCCs could be completely desorbed from the gel by 0.1 M fructose in aqueous buffered media with pH values from 7.5-9.2. The strong adsorption of AA-NAAPBA on agarose gel probably relates to the conformation of the copolymer in aqueous solution and provides opportunities for biomedical applications of the copolymer under physiological conditions. Multivalent, weak-affinity adsorption of BCCs to the agarose gel seems to be a tentative model for the copolymers' binding to oligo- and polysaccharides of cell membranes and mucosal surfaces.     

Novel biomimetic surfactant: synthesis and micellar characteristics

Novel biomimetic surfactants based on cholesterol as the hydrophobic segment and poly[2-(methacryloyloxy)ethyl phosphorylcholine] (pMPC) as the hydrophilic segment were synthesized in the present study by atom transfer radical polymerization (ATRP) of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) using a cholesterol-based macroinitiator. The association behavior of cholesterol-block-poly[2-(methacryloyloxy)ethyl phosphorylcholine] (Chol-pMPCs) in aqueous solution was studied by (1)H NMR spectroscopy, fluorescence probe technique, and atomic force microscopy (AFM). The (1)H NMR spectrum of the polymer in CD(3)OD showed both the cholesterol group and the phosphorylcholine group while the cholesterol group did not appeared in the (1)H NMR spectrum of the polymer in D(2)O, which implied the formation of a micelle structure. Fluorescence excitation spectra of a pyrene probe solubilized in the aggregates of Chol-pMPCs suggested the presence of a critical micelle concentration (cmc) in water. The critical micelle concentrations of the polymers CMPC10, CMPC20 and CMPC40 were determined to be 7.27 x 10(-3), 13.47 x 10(-3), and 20.77 x 10(-3) mg . mL(-1), respectively. AFM images of the aggregates on mica suggested that the pMPC block formed the biocompatible micelle coronas and the cholesterol block formed the hydrophobic micelle cores. These new biomimetic diblock copolymers were evaluated as "stealthy" nanocapsules for the delivery of hydrophobic drugs. The anti-cancer drug adriamycin (ADR) was chosen as a hydrophobic drug to be incorporated into the inner core of the micelles and the morphology of the drug-loaded micelles were observed by AFM.     

PEG‐b‐PtBA‐b‐PHEMA well‐defined amphiphilic triblock copolymer: Synthesis,self‐assembly,and application in drug delivery

A series of well‐defined amphiphilic triblock copolymers, poly(ethylene glycol)‐b‐poly(tert‐butyl acrylate)‐b‐poly(2‐hydroxyethyl methacrylate) (PEG‐b‐PtBA‐b‐PHEMA), were synthesized via successive atom transfer radical polymerization (ATRP). ATRP of tBA was first initiated by PEG‐Br macroinitiator using CuBr/N,N,N′,N″,N′″‐pentamethyldiethylenetriamine as catalytic system to give PEG‐b‐PtBA diblock copolymer. This copolymer was then used as macroinitiator to initiate ATRP of HEMA, which afforded the target triblock copolymer, PEG‐b‐PtBA‐b‐PHEMA. The critical micelle concentrations of obtained amphiphilic triblock copolymers were determined by fluorescence spectroscopy using N‐phenyl‐1‐naphthylamine as probe. The morphology and size of formed aggregates were investigated by transmission electron microscopy and dynamic light scattering, respectively. Finally, an acid‐sensitive PEG‐b‐PtBA‐b‐P(HEMA‐CAD) prodrug via cis‐aconityl linkage between doxorubicin and hydroxyls of triblock copolymers with a high drug loading content up to 38%, was prepared to preliminarily explore the application of triblock copolymer in drug delivery. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012