新颖表面结构的脲醛树脂-聚丙烯酰胺复合微球的制备研究

将高分子微凝胶模板法应用于制备脲醛树脂[Urea-formaldehyde resin (UF Resin)]-聚丙烯酰胺[Polyacrylamide (PAM)]有机-有机复合微球材料. 以PAM高分子微凝胶为模板, 通过控制甲醛和尿素的缩聚反应在反相悬浮体系中进行, 制备得到了具有新颖表面形貌的脲醛树脂-聚丙烯酰胺[UF Resin/PAM]有机-有机复合微球, 利用扫描电子显微镜(SEM)、热重分析(TGA)、红外(FT-IR)等手段对复合微球进行了表征. 实验结果表明, 复合微球的表面形貌与甲醛和尿素溶液的pH值、甲醛和尿素溶液的浓度、甲醛和尿素的摩尔比、模板的组成等因素有关. 可以预期, 本研究方法将为制备具有特异表面形貌的有机-有机复合微球材料提供了一条有效的途径.     

有机无机杂化膜材料的制备技术

有机无机杂化膜兼有机膜韧性和无机膜耐高温性能,具有优良的气体渗透选择性,成为高分子化学和材料科学等领域的研究热点.本文综述了近年来有机无机杂化膜材料的制备技术进展,着重探讨了溶胶-凝胶法制备聚酰亚胺类杂化膜材料的研究状况,并作了简要述评。     

不同结构形态二氧化硅/高分子复合微凝胶材料制备研究

敏感性二氧化硅/高分子微凝胶复合材料既具有二氧化硅良好的化学稳定性、低毒性和易于功能性,又具有敏感性高分子微凝胶对外界环境(如温度、pH等)的刺激响应特性,因而广泛应用于药物控释、吸附分离、载体和微反应器等重要领域。本文根据二氧化硅和敏感性高分子复合结构的不同,对二氧化硅/高分子核-壳型复合微凝胶、高分子/二氧化硅核-壳型复合微凝胶及杂化网络结构二氧化硅-高分子复合微凝胶等三类复合材料的制备研究进展进行较为详尽地阐述和分析。     

模板法制备无机纳米材料的研究进展

模板法在无机纳米材料的制备过程中能够有效地控制形貌、粒径和结构,已成为合成无机纳米材料的前沿方法。综述了模板法制备无机纳米材料的研究进展,主要介绍了硬模板剂(多孔阳极氧化铝、介孔碳)和软模板剂(高分子聚合物、生物高分子)的制备及其应用,结合模板法的作用机制,重点论述了不同种类的模板剂在无机纳米材料制备过程中对于形貌的影响。并对模板法制备无机纳米材料的前景和现存问题进行了总结。参考文献35篇。     

有机-无机杂化一维纳米材料的合成及其二次转化

近十年来,随着纳米科技的发展,有机．无机杂化一维纳米材料的设计合成与应用成为了自然科学领域的研究热点．本文综述了由有机小分子与无机组分杂化而成的一维纳米材料的合成方法,包括水热／溶剂热法、共沉淀法、非水相溶胶凝胶法、模板法、后嵌入法等．并对有机一无机杂化一维纳米材料的二次转化,如通过二次转化获得功能性一维氧化物、碳氮化物、硫属化合物及高分子杂化纳米材料,进行了讨论与展望．     

无机材料/天然高分子复合微球的制备研究进展

微球是一种新型药物载体,具有很大的开发与应用潜力.天然高分子具有良好的生物相容性、可降解性,易在生物体内分散,可制备成微球.无机材料(主要为无机矿物)力学性能优良,且价廉易得.通过天然高分子与无机材料两者耦合杂化作用,可优势互补、协同增效,进而产生许多优异的理化性能.使用无机材料改性天然高分子,通过乳化交联法、溶液混合法、原位合成法、挤出法等多种方法可制备得到无机材料/天然高分子复合微球.将无机材料/天然高分子复合微球应用于药物传递系统中,缓释效果明显,安全无毒害,且载体材料价格相对低廉,对于开发新型药物载体具有一定的意义.本文综述了近年无机材料/天然高分子复合微球的制备、载药与释药性能的相关研究,分析了常用制备方法的利弊,展望了复合微球的发展方向.     

介孔纳米 MoPO-AlPO4 的制备及其对异丁烯选择氧化的催化性能

 分别采用溶胶-凝胶法和等体积浸渍法制备了 MoPO-AlPO4 催化剂, 考察了钼物种存在状态对催化剂晶格氧活性以及异丁烯选择氧化反应性能的影响. N2 吸附-脱附、X 射线衍射、高分辨透射电镜、X 射线光电子能谱、傅里叶变换红外光谱、程序升温还原和微反实验结果表明, 与浸渍法制备的催化剂相比, 溶胶-凝胶法制备的 MoPO-AlPO4 催化剂为介孔纳米材料, 其比表面积和孔数量均有较大程度的提高. 在浸渍法制备的催化剂中, 钼物种以四面体 MoO42− 和八表面体 MoO66− 形式存在; 而在溶胶-凝胶法制备的催化剂中钼物种主要以四面体 MoO42− 的形式存在, 并有部分钼物种嵌入到了 AlPO4 骨架中. 钼物种的种类对异丁烯选择氧化反应的活性和选择性有较大影响, 溶胶-凝胶法制备的催化剂由于嵌入 AlPO4 骨架中钼物种的存在, 异丁烯选择氧化反应性能得到较大提高.     

硫化物-高分子复合微球表面形貌与模板组成关系的研究

以N-异丙基丙烯酰胺(NIPAM)和甲基丙烯酸(MAA)为单体, 通过反相悬浮聚合法制备了多种MAA含量不同的阴离子型P(NIPAM-co-MAA)共聚微凝胶. 以这些共聚微凝胶为模板, 在不同表面活性剂存在下, 合成了一系列CuS(CdS、ZnS)-P(NIPAM-co-MAA)无机-有机复合微球材料, 研究了表面活性剂种类, 模板组成等因素对上述硫化物-高分子复合微球表面形貌的影响. 结果表明, 实验条件下所得复合微球表面均具有图案化结构, 该结构明显依赖于表面活性剂的种类和模板微凝胶的组成. 就模型体系而言, 随表面活性剂Span-20、Span-80和Span-85的HLB(亲水亲油平衡)值降低, 微球表面形貌趋于粗糙, 但仍然十分规整; 就模板组成而言, 模板中MAA含量增加使得复合微球的表面形貌变得更加精细. 据此, 认为通过选用合适的表面活性剂和微凝胶模板可以在一定范围内调控这些无机-有机复合微球的表面形貌, 从而为后续应用研究奠定基础.     

水热微乳法合成La(OH)3纳米棒的形貌控制研究

自1991年Iijima发现碳纳米管以来,一维纳米材料如纳米管、纳米线、纳米棒和纳米纤维等由于其具有独特的光、电、磁等性质及其潜在的应用前景而引起全世界的广泛关注,一维纳米材料的制备方法有化学气相沉积法、溶胶一凝胶法、催化剂辅助法、固相化学反应法、模板法、溶剂热法、微乳法和水热,微乳法等,其中水热,微乳法是近年来兴起的一种很有发展前途的制备一维纳米材料的方法。     

SiO2-HA/PNIPAm核壳温敏微凝胶的合成及其溶胀性能

以SiO₂纳米颗粒为核,以透明质酸（HA）和聚异丙基丙烯酰胺（PNIPAm）的杂化凝胶（HA/PNIPAm）为壳制备了一系列无机-有机杂化核壳结构单分散微凝胶.该微凝胶具有很好的温度敏感性,其最低临界转变温度（LCST）在34 ℃附近;该微凝胶具有负触变性,且温度高于LCST时负触变性更明显.用动态光散射（DLS）测定了微凝胶颗粒的水动力学粒径随温度的变化关系,实验数据可以用我们早前建立的硬核高分子凝胶分子热力学模型进行关联计算,结果表明只需较少的模型参数就可较好地描述温度响应的核壳结构高分子凝胶的溶胀行为.     

Exploring Microfluidic Routes to Microgels of Biological Polymers

Polymer microgels in the size range from several micrometers to hundreds of micrometers are used in the pharmaceutical, cosmetics, nutrition, pesticide, and food industries, as well as in the encapsulation of cells. To date, a broad range of strategies for the generation of polymer microgels exist, however, these methods involve multistage processes, do not utilize biocompatible components or do not allow precise control of the dimensions and internal structure of the microgels. Recently, microfluidic strategies for the production of polymer particles have offered precise control over the shapes, morphologies, and size distributions of polymer colloids. This paper discusses the most recent results obtained by the authors in the area of the microfluidic production of biopolymer microgels. It provides a brief review of the microfluidic methods for the continuous synthesis and fabrication of microgels, sets the criteria for the successful microfluidic generation of biomicrogels, and describes two methods for the preparation of microgels by microfluidic means. The article concludes with a summary and an outlook.

     

Sensitive microgels as model colloids and microcapsules

Polymer microgels consist of swollen networks of crosslinked macromolecules with particulate dimensions. If these networks exhibit a delicate interplay with their environment that allows them to be swollen and deswollen or to be crosslinked and decrosslinked upon external stimulation, they can serve for a variety of applications in sensing and actuation. Such environmental sensitivity can be realized either by the use of covalently crosslinked polymer networks that exhibit critical miscibility with their swelling medium or by the use of transient and reversible, supramolecular chain crosslinking. This article highlights some achievements in the synthesis and application of sensitive microgels. In one area of focus, the article discusses the use of sensitive microgels as model colloids to study relations between structure, dynamics, and properties of soft matter. In another area of focus, the paper discusses the use of these microgels to encapsulate, host, and release functional additives. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 435–449     

Strong and tough hydrogels crosslinked by multi-functional polymer colloids

Tough polymer hydrogels have great potential applications in soft actuators, artificial muscles, tissue engineering, and so forth. To improve the strength and toughness of hydrogels, numerous strategies have been developed to integrate efficient energy dissipation mechanisms into the hydrophilic networks. Among them, the use of macro-crosslinkers to replace conventional chemical ones has become promising to develop tough hydrogels. Polymer colloids—including nano-/microparticles, nano-/microgels, hydrophobic associates, and block copolymer assemblies—have been employed in literature as multi-functional macro-crosslinkers that link polymer chains through covalent bonds or noncovalent interactions. The dislocation, deformation, desociation, and rupture of polymer colloids upon loadings are the major mechanisms to dissipate energy. This article provides a comprehensive account of most recent progresses on tough hydrogels crosslinked by polymer colloids, and explores the toughening mechanisms. It aims to inspire novel designs of tough hydrogels with multi-functionalities. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1336–1350     

反应性聚合物微凝胶的合成及应用

反应性聚合物微凝胶是一种具有反应活性,分子内交联的高分子。它具有优良的加工性能,涂膜的力学性能及耐久性也十分优异,主要应用于制备高档涂料或对涂料进行改性,本文着重介绍了反应性聚合物微凝胶的合成方法及其在涂料改性方面的应用。     

Gel-induced selective crystallization of polymorphs

Although nanoporous materials have been explored for controlling crystallization of polymorphs in recent years, polymorphism in confined environments is still poorly understood, particularly from a kinetic perspective, and the role of the local structure of the substrate has largely been neglected. Herein, we report the use of a novel material, polymer microgels with tunable microstructure, for controlling polymorph crystallization from solution and for investigating systematically the effects of nanoconfinement and interfacial interactions on polymorphic outcomes. We show that the polymer microgels can improve polymorph selectivity significantly. The polymorphic outcomes correlate strongly with the gel-induced nucleation kinetics and are very sensitive to both the polymer microstructure and the chemical composition. Further mechanistic investigations suggest that the nucleation-templating effect and the spatial confinement imposed by the polymer network may be central to achieving polymorph selectivity. We demonstrate polymer microgels as promising materials for controlling crystal polymorphism. Moreover, our results help advance the fundamental understanding of polymorph crystallization at complex interfaces, particularly in confined environments.     

Microgels as drug carriers for sonopharmacology

The ultrasound-induced cleavage of covalent and non-covalent bonds to activate drugs (sonopharmacology) is a promising concept to gain control over the action of active pharmaceutical ingredients by an external trigger. Previously, linear polymer architectures bearing drug payloads were exploited for drug release by using the principles of polymer mechanochemistry. In this work, the carrier design is altered by the polymer topology to improve the ultrasound-triggered release of covalently anchored drugs from polymer scaffolds. We use microgels crosslinked by mechanoresponsive disulfides and copolymerized with Diels-Alder adducts of furylated payload molecules and acetylenedicarboxylate. Force-induced thiol formation induces a Michael-type addition liberating the payload from the microgels. The use of microgels significantly reduces sonication times compared to linear polymer chains and shields the cargo efficiently from non-triggered activation using ultrasound that produces inertial cavitation at a frequency of 20 kHz as model condition.     

pH-Sensitive microgels functionalized with folic acid

One of the most promising strategies in anticancer therapies is the targeted delivery through malignancy-associated cellular markers. The design of new synthetic devices with enhanced stimuli-responsive sensitivity and targeting ligands is a promising field for the development of cancer-specific delivery systems. One of the pathways to achieve this aim is the chemical functionalization of nanodevices such as microgels. The p-nitrophenyl acrylate (NPA) is an active ester molecule with a group that can be easily cleavaged by the nucleophilic attack of species such as amines. This modification consists of an easy chemical reaction that leads to several types of functionalized microgels, which are originally made up of NPA as one of their constituent monomers.

Here is reported the chemical functionalization of NPA-based microgels by incorporating pH-sensitive functional groups and folic acid as a tumor targeting ligand into the same initial polymer network. For this purpose, microgels of p-nitrophenyl acrylate (NPA)-co-methacrylamide (MeAM) synthesized by precipitation polymerization, were modified with two different pyridine derivatives: 2-aminomethylpyridine (2-AMP) and 2-aminopyridine (2-AP), thus pH-sensitive microgels with acid pH swelling capacity were obtained. The equilibrium swelling behaviour was studied as a function of pH, ionic strength, copolymer composition and type of pyridine derivative. In addition, the microgels were derivatized with ethylene diamine, to obtain amino-functionalized microgels to which the folic acid was subsequently attached as the targeting ligand. As final step, pH-sensitive groups and folic acid were equimolarly attached to the polymer chains to obtain the fully functionalized microgels.     

Effect of chemical composition on properties of pH-responsive poly(acrylamide-co-acrylic acid) microgels prepared by inverse microemulsion polymerization

In this research, a series of pH-responsive microgels based on acrylamide (AM), acrylic acid (AA) as the main monomers, and N,N′-methylenebisacrylamide as a divinyl cross-linking agent, have been prepared by inverse microemulsion polymerization. The effect of chemical composition of poly(acrylamide-co-acrylic acid) (P(AM-co-AA)) on hydrodynamic diameters, morphology, swelling ratios and pH-responsive behaviour and thermal properties of microgels were discussed. With an increase of the mole percentages of AA in the feed ratio, the microgels have higher swelling ratios. The TEM photographs show that the spherical morphology of the microgels are regular relatively. Comparing with PAM microgels, number-average diameters of P(AM-co-AA) microgels were larger because of the presence of AA chain segment in the polymer chain. Turbidities of microgels determined through UV–vis spectrophotometer indicate that the microgels exhibit favourable pH-responsive behaviour, and responsive pH value is related to the dissociation constant of AA. Moreover, thermal stable properties of microgels were confirmed by differential scanning calorimeter. It was observed that an increase in the mole percentages of AA in the feed ratio provided lower glass transition temperature and thermal decomposition temperature of pH-responsive microgels.     

Polymer microgels: reactors for semiconductor, metal, and magnetic nanoparticles

We report a strategy for the production of materials with structural hierarchy. The approach employs polymer microgels as templates for the synthesis of semiconductor, metal, or magnetic nanoparticles (NPs). We show that NPs with predetermined dimensions and size-dependent properties can be synthesized by using a very delicate balance between the reaction conditions, the composition and the structure of microgel templates, and the concentration of NPs in the microgel. Postheat treatment of microgels doped with semiconductor nanoparticles reduces NP polydispersity and allows control of their photoluminescence. Microgel templates are particularly beneficial in the synthesis of polymer microspheres heavily loaded with monodisperse superparamagnetic Fe(3)O(4) NPs. Hybrid submicrometer-size microgels have promising potential applications in photonics, catalysis, and separation technologies.     

Varying the Stiffness and Diffusivity of Rod-Shaped Microgels Independently through Their Molecular Building Blocks

Microgels are water-swollen, crosslinked polymers that are widely used as colloidal building blocks in scaffold materials for tissue engineering and regenerative medicine. Microgels can be controlled in their stiffness, degree of swelling, and mesh size depending on their polymer architecture, crosslink density, and fabrication method—all of which influence their function and interaction with the environment. Currently, there is a lack of understanding of how the polymer composition influences the internal structure of soft microgels and how this morphology affects specific biomedical applications. In this report, we systematically vary the architecture and molar mass of polyethylene glycol-acrylate (PEG-Ac) precursors, as well as their concentration and combination, to gain insight in the different parameters that affect the internal structure of rod-shaped microgels. We characterize the mechanical properties and diffusivity, as well as the conversion of acrylate groups during photopolymerization, in both bulk hydrogels and microgels produced from the PEG-Ac precursors. Furthermore, we investigate cell-microgel interaction, and we observe improved cell spreading on microgels with more accessible RGD peptide and with a stiffness in a range of 20 kPa to 50 kPa lead to better cell growth.