液相组合合成研究进展

综述了近年来液相组合合成的研究进展,主要包括液相组合合成法(LPCS),氟合成,树状载体组合合成及高分子辅助试剂在液相组合合成中的应用等。     

Modular synthesis of functional polymer nanoparticles from a versatile platform based on poly(pentafluorophenylmethacrylate)

Control of functionalities in polymer nanoparticles (PNPs) is important for their application. Thus, there is an interest for well‐defined nanoparticle platforms to which desired functions could readily, and in modular fashion, be imparted. Herein, we report an amine‐reactive PNP platform for the modular synthesis of functional PNPs from poly(pentafluorophenylmethacrylate) (poly(PFPMA)) through a simple substitution/nanoprecipitation/photo‐crosslinking strategy. Substitution of amine containing coumarin into poly(PFPMA) allows for the achievement of structural stability of nanoprecipitated particles through photo‐crosslinking after nanoprecipitation, making it possible to carry out subsequent chemical transformations in organic solvents if needed. We demonstrate that various small molecules and an amine‐terminated polymer could be used to modify the crosslinked PNPs to endow them with various functions including fluorescence and responsiveness to temperature changes. The functional PNPs were characterized with variable temperature dynamic light scattering (DLS), UV–vis, and photoluminescence (PL) spectroscopy, and transmission electron microscopy (TEM). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1895–1901     

Epoxy polymer coating to prevent the corrosion of aluminum nanoparticles

Aluminum nanoparticles were coated by epoxy polymer in order to prevent the corrosion reaction. The coverage of the epoxy polymer film was controlled from 0% to 100%, which changed the corrosion rate of nanoparticles quantitatively. The surface of the polymer coating was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM), and the corrosion resistance of these nanoparticles was estimated by the wet/dry corrosion test on platinum (Pt) plate with a NaCl solution. From a TEM analysis, 10 mass% polymer‐coated Al particles in the synthesis were almost 100% covered on the surface by a polymer film of 10 nm thick. On the other hand, 3 mass% polymer‐coated Al was partially covered by a film. In the AFM–Kelvin force microscopy, the potential around the Al particles had a relatively low value by the polymer coating, which indicated that the conductivity of the Al was isolated from Pt plate by the polymer. Both the corrosion and H₂ evolution reaction rates were quantitatively reduced by the mass% of polymer coating. In the case of 10 mass% coated sample, there was very little corrosion of Al nanoparticles. This fact suggested that the electrochemical reaction was suppressed by the polymer coating. Thus, it was found that the corrosion reaction rate of Al nanoparticles could be quantitatively suppressed by the mass% of epoxy coating. Copyright © 2015 John Wiley & Sons, Ltd.     

Orthogonal synthesis and modification of polymer materials

In this review, we detail the progress throughout the years toward developing truly orthogonal polymerization mechanisms and modification procedures en route to complex macromolecular structures built from synthetic polymer materials. The orthogonal modifications of polymer side-chains and end-groups via sequential click reactions is described providing post-polymerization routes to functional materials and unique polymer topologies. Further, historical and modern orthogonal polymerization methodologies are thoroughly reviewed showing the evolution of the field through the decades long study of selective polymerization mechanisms that provide unique copolymer structures that are typically difficult to achieve. These include the combinations of reversible deactivation radical polymerization mechanisms with a variety of polymerization mechanisms including ring opening polymerizations, ring opening metathesis polymerizations, and cationic polymerizations, to name a few.     

Tailoring block copolymer and polymer blend morphology using nanoparticle surfactants

Combining the functionality of nanoparticles (NPs) with the processability of polymers offers great promise for designing novel materials. In particular, NPs with tailored surface properties can effectively modify the interface between two distinct fluids and/or different polymer matrices which allows them to function as efficient surfactants. The efficiency of NP surfactants is strongly affected by their size and shape, which influences their adsorption energy to the interface, and the entropic contribution to the system. In this review, the assembly of size- and shape-controlled inorganic NPs at the interface of block copolymers (BCPs) and polymer blends has been focused. First, we discuss the design of size- and shape-controlled NP surfactants and we review the examples of NP surfactant-driven BCPs and polymer blend morphologies. In addition, we review the recent investigations of the morphological transition of BCP emulsion particles induced by NP surfactants. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 228–237     

Fabrication and characterization of gold/acrylic polymer nanocomposites

We report the method of incorporation of preformed gold nanoparticles (AuNPs) into the acrylic polymer (AP) matrices and optical, TEM characterization of AuNP/AP bulk and film composite. It was shown that incorporation of dodecanethiol-covered AuNP can be enhanced in the presence of SiO₂ nanoparticles, enabling at the same time a wider range of tailoring of composite properties for optical processing.     

共轭聚合物荧光纳米粒子研究进展

近年来,共轭聚合物荧光纳米粒子因其优异的光学性能,在化学、医学和环境科学等研究领域显示了极其广阔的应用前景.相比于传统无机半导体荧光纳米材料,共轭聚合物荧光纳米粒子具有结构多样性、功能可设计性、生物相容性好等显著优势.本文从共轭聚合物荧光粒子的制备方法、光学性能、表面功能化修饰出发,重点讨论了近年来共轭聚合物纳米粒子作为荧光探针在细胞成像及生物化学检测方面的研究进展,阐述了当前研究的主要发展方向和仍需解决的问题.     

Digging into the Sequential Space of Thiolactone Precision Polymers: A Combinatorial Strategy to Identify Functional Domains

Functional sequences of precision polymers based on thiolactone/Michael chemistry are identified from a large one‐bead one‐compound library. Single‐bead readout by MALDI‐TOF MS/MS identifies sequences that host m‐THPC that is a second generation photo‐sensitizer drug. The corresponding Tla/Michael‐PEG conjugates make m‐THPC available in solution and drug payload as well as drug release kinetics can be fine‐tuned by the precision segment.     

Antimicrobial polymer nanostructures: Synthetic route,mechanism of action and perspective

Protection against bacterial infections is an important research field in modern society. Antimicrobial polymers have received considerable attention as next-generation biocides because they represent an ecologically friendly approach that does not promote resistance. In the last decade, many authors have reported the development of nano-sized antimicrobial polymers with enhanced bactericidal performance by increasing the active-area of biocides. This review presents several suitable methods of synthesis of antimicrobial polymer nanomaterials with various shapes, including a nanosphere and fibrous and tubular structures. We also discuss the antimicrobial mechanisms of these polymers. In addition, antimicrobial polymer thin films, which can inhibit bacterial adhesion, are introduced briefly with examples. Our aim is to present synthetic routes and formation mechanisms of various antimicrobial polymer nanostructures.     

Investigation of segmental reorganization within amphiphilic block polymer nanoparticles derived from shell crosslinked micelle templates: Shell crosslinked knedel-like inversion

The construction of nanoscopic materials by synthetic methodologies that iterate covalent and supramolecular interactions has been developed over the past three decades as a powerful method to afford complex functional materials. Indeed, the present study was nearly lost in the archives of dissertation research completed in 2001, which revealed nanoscale conformational dynamics in the segmental reorganization, and partial inversion, of topologically shell crosslinked knedel-like (SCK) nanoparticles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 204–214     

Tailored polymer-supported templates in dynamic combinatorial libraries: simultaneous selection, amplification and isolation of synthetic receptors

The thermodynamically controlled synthesis and isolation of macrocyclic receptors from dynamic combinatorial libraries has been achieved in a single step using a polymer-supported template. The templates were cinchona alkaloids which show interesting enantio- and diastereoselective molecular recognition events in libraries based on pseudo-dipeptide building blocks. The synthetic routes used to derivatise the alkaloids and attach them to polymer supports minimised any influence of the tethering linkage on the templating activity. Systematic studies have been carried out to probe how the polymer morphology and the template loading affect the selectivity and isolation yield of the macrocyclic receptors. Molecular recognition between solid-phase bound templates and selected receptors also enabled their affinity-type chromatographic separation.     

PEG化的聚合物载体树脂研究进展

组合化学已成为发现和优化新药、亲和配体和催化过程中的重要组成部分.高分子载体树脂在组合化学中起着关键的作用,各种类型的聚合物树脂在有机合成中已被广泛开发为载体、反应物和催化剂.与传统的Merrifield树脂相比较,聚乙二醇(PEG)化的聚合物树脂具有与极性溶剂更好的相容性、更高的溶剂吸收和溶胀性能.本文主要综述与PEG相关联的聚合物树脂在有机合成载体领域中的最新成果.     

Orthogonal multiple click reactions in synthetic polymer chemistry

This review highlights the concept of multiple click reaction strategy which is utilized for design and synthesis of well‐defined complex macromolecular structures as well as multifunctionalization of well‐defined polymers. This review examines the click combinations mainly from double to quadruple and additionally from the most frequently used to the least. The present review may also be regarded as an update for recent reviews dealing with specifically double and triple click reaction combinations in synthetic polymer chemistry. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3147–3165     

CombiDOCK: Structure-based combinatorial docking and library design

We have developed a strategy for efficiently docking a large combinatorial library into a target receptor. For each scaffold orientation, all potential fragments are attached to the scaffold, their interactions with the receptor are individually scored and factorial combinations of fragments are constructed. To test its effectiveness, this approach is compared to two simple control algorithms. Our method is more efficient than the controls at selecting best scoring molecules and at selecting fragments for the construction of an exhaustive combinatorial library. We also carried out a retrospective analysis of the experimental results of a 10×10×10 exhaustive combinatorial library. An enrichment factor of approximately 4 was found for identifying the compounds in the library that are active at 330 nM.     

聚合物纳米材料研究进展——Ⅱ.聚合物/无机纳米复合材料

复合物纳米材料包括纳米聚合物和聚合物／无机纳米复合材料。本文综述了聚合物／无机纳米复合材料的研究进展，重点介绍了溶胶－凝胶法，原位生成法，模板法，插层复合，沉积法，机械粉碎，分子平壤 ，溶液或融混合法的研究进展。     

The coating of conducting copolymer on coordination polymer nanorod: A visible light active p-n heterojunction photocatalyst for H2 production

A visible light active p-n heterojunction photocatalyst was synthesized successfully through in-situ chemical oxidation copolymerization of aniline (ANI) and diphenylamine-4-sulfonate (DPAS) with the existence of coordination polymer nanorod (CPNR) under initiation of ammonium persulfate (APS). Compared with neat coordination polymer nanorod, the resulted p-n heterojunction photocatalyst exhibits higher H₂ generationrate under visible light irradiation. In this heterojunction photocatalyst, as a p-type semiconductor possessing suitable energy levels with coordination polymer nanorod, poly-(aniline-co-N-(4-sulfophenyl)-aniline) (PAPSA) forms p-n heterojunction with n-type coordination polymer nanorod, the inner electric field of p-n heterojunction accelerates the separation of electrons and holes, which enhances H₂ production performance. Furthermore, the influence of concentration ratio between DPAS and ANI on photocatalytic property of the p-n heterojunction photocatalyst was discussed and a reasonable condition to fabricate photocatalyst with high H₂ generationrate had been obtained. During photocatalytic water splitting H₂ generation, the p-n heterojunction photocatalyst exhibited outstanding stability.