动态硼酸酯键管控邻苯二酚基团与功能黏附性高分子设计

“黏附”是一种普遍存在的多尺度相互作用,其实质是界面处化学键、氢键或范德华力等的形成.近年来,在贻贝仿生的基础上将黏性因子邻苯二酚基团嵌入到动态硼酸酯聚合物中,成为了功能黏附性高分子的重要发展方向.本专论从分子黏附、微/纳表面黏附和宏观表面黏附3个尺度,介绍硼酸酯键管控邻苯二酚基团在高分子材料功能化方面的研究进展.分子黏附,主要讨论硼酸酯聚合物中邻苯二酚基团与分子或离子相互作用规律及其对材料形貌和刺激响应性能的调控;微/纳表面黏附,论述硼酸酯聚合物体系超分子驱动力和组装机制,介绍其在微/纳材料功能化改性方面的研究进展;宏观表面黏附,讨论硼酸酯键管控邻苯二酚基团与黏附性能调控的关联规律,介绍硼酸酯聚合物功能黏附材料在宏观组装、攀爬机器人领域的应用.最后,从新型硼酸酯聚合物设计、动态键精准管控和器件化应用的角度,对该领域未来前景和发展趋势做出了展望.     

含有邻苯二酚基团的材料在抗菌防污领域的研究进展

贻贝是海洋污损生物中最为常见的一类生物,它可以粘附在几乎所有材料的表面,这是由于贻贝能够分泌具有优异粘附性能的贻贝粘附蛋白.贻贝粘附蛋白结构中具有邻苯二酚基团,并已被证明是一种有效的表面改性锚定剂,几乎可以粘附在任何材料表面.本文针对含有邻苯二酚基团的材料,结合近五年的国内外研究报道,介绍了含有邻苯二酚基团材料的制备方...     

表面富集季胺盐的交联聚苯乙烯微球合成与表征及其溶胀行为研究

在聚合物微球表面引入不同的基团 (如亲水性的羟基或羧基 ) ,可以改善聚合物微球的稳定性甚至生物相容性[1～ 4] ;利用表面基团可以把无机半导体微粒和功能有机分子以及生物分子引入聚合物微球[5～ 8] ,赋予聚合物微球特殊的性能 ,使其广泛应用于涂料、光电功能材料和生物医用材料等领域[9～ 15] .其中 ,表面带有阳离子的聚合物微球在絮凝剂、胶粘剂、水性涂料等方面已经得到广泛研究[16～ 2 0 ] .通常阳离子聚合物微球可以根据不同的需要利用常规乳液聚合、核壳乳液聚合等方法来合成 .亲水性和疏水性单体进行的无皂乳液聚合[2 1] ,因其能在…     

多巴及其衍生物黏附性的研究与应用进展

多巴(DOPA)是海洋贻贝等生物分泌黏液的重要组成部分,它具有很强的黏附性,不仅可以黏附在无机材料表面,也可以黏附在有机材料表面。进一步的研究表明,含邻苯二酚基团的多巴类衍生物同样具有与多巴相类似的强黏附性,由此发展起来的聚多巴胺涂层在诸多领域已得到应用。基于上述研究成果,科学家们将多巴及其衍生物引入高分子中,得到了一系列黏附性能强的仿生高分子,在各领域也已得到应用。本文综述了多巴及其衍生物黏附机理的研究和它们在各领域的应用现状。     

贻贝仿生胶粘剂研究进展

海洋贻贝因其分泌的含邻苯二酚结构的多巴粘附蛋白而拥有在潮湿或者水下环境对不同固体表面快速而牢固的粘附能力.通过模仿贻贝中大量丰富的多巴粘附蛋白结构的仿生胶粘剂能在干燥和水下环境中实现对各种基材的有效粘接.最近十余年来,学术界一直致力于合成含邻苯二酚结构的仿生聚合物胶粘剂,探究聚合物本体和外界环境对胶粘剂粘接性能的影响....     

新型氟硅高分子材料的研究进展

在聚合物体系中以共价键的形式同时引入硅氧烷结构和含氟基团所得到的氟硅高分子材料是近年来研究较多的一类含杂原子的新型材料。该材料不但具有硅氧烷突出的热稳定性与有机氟聚合物优良的表面自洁性能,还兼备有机硅聚合物良好的加工性能,成为新型材料研究领域的一个研究热点,无论是在自组装方面还是防污、超疏水、耐高温等材料的制备方面都有很大的应用潜力。本文归纳总结了这一类材料最新的研究进展,针对其性能方面进行了简要的概述,并对这类新型的功能性氟硅材料的研究领域和方向进行了展望。     

生物医用材料表面仿细胞膜结构改性

细胞膜因其固有的生物相容性,可以作为体内植入材料及器件表面生物相容化改性的范例。大量研究结果表明,用细胞外层膜的亲水官能团－磷酰胆碱基团修饰材料表面,可显著提高材料的生物相容性,具有广阔的应用前景。本文综述了用含磷酰胆碱基团小分子及聚合物进行仿细胞膜结构改性的各种方法及其代表性工作;讨论了不同方法得到的仿细胞膜结构表面的性能;总结了几种有影响的生物相容性机理;对仿细胞膜结构表面改性研究及应用的前景做了展望。     

低表面能侧基含氟聚合物*

含氟聚合物材料具有优异的热稳定性、极低的表面能、强化学稳定性和生物相容性等,在功能涂料、织物整理、微电子、汽车以及航空航天等领域具有很好的应用前景。本文综述了侧基含氟聚合物的主链、全氟烷基链、主链与全氟烷基链段间连接基团的结构对聚合物表面性能的影响,并总结了环境友好型低表面能侧基含氟聚合物的研究进展。     

组织工程中生物可降解高分子的功能化及生物学修饰

可生物降解高分子在组织工程中有十分重要的作用。本文从组织工程对支架材料的生物学要求出发,对可生物吸收高分子的本体改性引入功能基团,进而通过化学键合促进细胞特异性黏附的短肽序列(ROD)、含功能性基团的水凝胶通过化学键合或物理包覆固定RGD以及聚合物表面修饰固定RGD三个方面进行了综述。     

含吡啶基金属-超分子聚合物研究进展

金属-超分子聚合物是由金属离子与配体之间的相互作用形成的,是一类具有多样化几何构造和拓扑结构的新型功能高分子,它包括线型、接枝、交联、树枝等多种骨架结构.金属-超分子聚合物具有光、电、磁等特性,因此潜在的应用前景非常广阔,不仅可以在生物医用、分子器件、纳米材料,还可以在催化化学反应及吸附储氢等领域获得应用.由于吡啶基团为常用配体,且近年含吡啶基团的金属-超分子聚合物研究最为广泛,最为代表性,因此,本文以聚合物结构分类对近几年含吡啶基团的金属-超分子聚合物的研究进展作了简要综述.     

Polymer composition and substrate influences on the adhesive bonding of a biomimetic, cross-linking polymer

Hierarchical biological materials such as bone, sea shells, and marine bioadhesives are providing inspiration for the assembly of synthetic molecules into complex structures. The adhesive system of marine mussels has been the focus of much attention in recent years. Several catechol-containing polymers are being developed to mimic the cross-linking of proteins containing 3,4-dihydroxyphenylalanine (DOPA) used by shellfish for sticking to rocks. Many of these biomimetic polymer systems have been shown to form surface coatings or hydrogels; however, bulk adhesion is demonstrated less often. Developing adhesives requires addressing design issues including finding a good balance between cohesive and adhesive bonding interactions. Despite the growing number of mussel-mimicking polymers, there has been little effort to generate structure-property relations and gain insights on what chemical traits give rise to the best glues. In this report, we examine the simplest of these biomimetic polymers, poly[(3,4-dihydroxystyrene)-co-styrene]. Pendant catechol groups (i.e., 3,4-dihydroxystyrene) are distributed throughout a polystyrene backbone. Several polymer derivatives were prepared, each with a different 3,4-dihyroxystyrene content. Bulk adhesion testing showed where the optimal middle ground of cohesive and adhesive bonding resides. Adhesive performance was benchmarked against commercial glues as well as the genuine material produced by live mussels. In the best case, bonding was similar to that obtained with cyanoacrylate "Krazy Glue". Performance was also examined using low- (e.g., plastics) and high-energy (e.g., metals, wood) surfaces. The adhesive bonding of poly[(3,4-dihydroxystyrene)-co-styrene] may be the strongest of reported mussel protein mimics. These insights should help us to design future biomimetic systems, thereby bringing us closer to development of bone cements, dental composites, and surgical glues.     

Synthesis and studies of catechol-containing mycobactin S and T analogs

The syntheses of catechol-containing mycobactin S and T analogs are described. These analogs incorporate a catechol-glycine moiety in place of the phenol-oxazoline of the naturally occurring mycobactins S and T. Studies indicated that the new siderophore analogs bind iron, and promote the growth of a number of microbes, especially strains of mycobacteria, as expected.     

Preparation of macroreticular redox resins with hydroquinone and catechol units as pendant groups and their properties

Macroreticular redox resins with hydroquinone and catechol units as pendant groups were prepared by the Friedel-Crafts reaction of macroreticular styrene/divinylbenzene copolymer with 2,5- and 3,4-dimethoxybenzyl chlorides, followed by removal of the methyl groups with hydrobromic acid. The redox capacity of the macroreticular resins was determined by oxidation of hydrazobenzene with resins in oxidized form. Resins with 1,4-benzoquinone units were capable of oxidizing hydrazobenzene, whereas those with 1,2-benzoquinone (catechol quinone) units exhibited no apparent oxidative ability; this seems to be due to a complex formation between azobenzene and the catechol units in the reduced resins. Adsorption of metallic ions onto catechol-containing resins showed a high selectivity for Hg²⁺ ion. The effects of pH, reaction time, and ion concentration on the adsorption were also studied.     

Total synthesis of petrobactin and its homologues as potential growth stimuli for Marinobacter hydrocarbonoclasticus, an oil-degrading bacteria

A modular synthesis was developed to access petrobactin, a catechol-containing siderophore isolated from Marinobacter hydrocarbonoclasticus. A range of petrobactin homologues with differing dihydroxybenzamide motifs and in one case an increased number of carbons in the polyamine backbone were also synthesized. As such, these systems represent new isomeric probes to study iron transport properties in M. hydrocarbonoclasticus. The synthesis of petrobactin and its homologues and the first biological study of how these agents influence the growth of Mycobacterhydrocarbonoclasticus are reported. New synthetic methods were developed to overcome issues (imide formation) encountered in earlier syntheses. Both the (1)H and (13)C NMR of petrobactin were consistent with the recently revised structure showing that petrobactin in fact contains a 3,4-dihydroxybenzene motif rather than a 2,3-dihydroxybenzene motif. The preliminary biological studies suggested that using the native petrobactin 1b for M. hydrocarbonoclasticus-specific growth stimulation may be a poor strategy for oil-spill cleanup.     

Catechol-Containing Schiff Bases on Thiacalixarene: Synthesis,Copper (II) Recognition,and Formation of Organic-Inorganic Copper-Based Materials

For the first time, a series of catechol-containing Schiff bases, tetrasubstituted at the lower rim thiacalix[4]arene derivatives in three stereoisomeric forms, cone, partial cone, and 1,3-alternate, were synthesized. The structure of the obtained compounds was proved by modern physical methods, such as NMR, IR spectroscopy, and HRMS. Selective recognition (K_b difference by three orders of magnitude) of copper (II) cation in the series of d-metal cations (Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺) was shown by UV-vis spectroscopy. Copper (II) ions are coordinated at the nitrogen atom of the imine group and the nearest oxygen atom of the catechol fragment in the thiacalixarene derivatives. High thermal stable organic-inorganic copper-based materials were obtained on the base of 1,3-alternate + Cu (II) complexes.     

Colorimetric metal ion binding of catechol-based coatings inspired by melanin and molecular imprinting

Catechol-containing biomolecules and related synthetic materials are of interest for a broad range of applications. Our group has been interested in the potential of eumelanin, a catechol-containing biomaterial and the black-to-brown pigment in humans, and synthetic eumelanin analogues for water purification applications. In an attempt to apply the strategy of molecular imprinting towards lead-binding synthetic eumelanin coatings, we developed a PbO₂-mediated synthesis that was subsequently tested with a number of catechols in addition to the eumelanin and polydopamine monomers l-dopa and dopamine. Although this strategy did not provide significant improvements in affinity or selectivity, we found that the PbO₂-mediated oxidative polymerisation of 1,2-dihydroxybenzene generates a coating that darkens visibly upon binding Pb²⁺ and other metal ions. Oxidative polymerisation of catechol with sodium periodate also yields a coating with this colorimetric response. Of eight metal ions tested, the coatings are most responsive to Pb²⁺ and Cu²⁺, as analysed by quantitative colorimetry. With further optimisation, these coatings could prove useful for the colorimetric sensing of metal ions.     

ARCHITECTURE OF LADDER,TUBULAR AND SIEVE-PLATE POLYMERS PREPARED BY STEPWISE COUPLING POLYMERIZATION

"Stepwise-coupling polymerization" (SCP) is a very useful approach for preparing microstructure-controllableordered network polymers, including soluble one-dimensional ladderlike polymers (LP) and tubular polymers (TP), and two-dimensional sieve-plate polymers. The novel reactive LPs are important precursors of micro-structure controllable polymerssuch as "fishbone-" or "rowboat-"like mesomorphic polymers and their metal complexes as well as tubular polymers (TPs).They are full of great potential for use as advanced materials.     

荧光聚合物研究进展

本文总结了近年来荧光聚合物的研究进展,主要介绍了荧光聚合物的分类：按其溶解性能可分为非水溶性、水溶性和两亲荧光聚合物三大类;荧光聚合物的合成：荧光化合物为引发剂、荧光化合物为链转移剂、荧光功能单体聚合、荧光化合物与聚合物的化学键合、非荧光功能单体聚合等五种制备荧光聚合物的设计合成方法;荧光聚合物的应用：荧光聚合物在荧光化学传感器、荧光分子温度计、荧光造影、药物载体、荧光探针等方面的应用研究。     

温度敏感树形聚合物

温度敏感树形聚合物结合了温敏聚合物对温度具有响应行为的特点以及树形聚合物非线形构造的方式、大尺度、结构易于调节和功能化等特征,在智能材料和生物医药等领域有着重要的研究价值和应用前景。此类聚合物可以通过在树形聚合物表面引入温敏基元、控制聚合物结构的亲疏水比例以及采用温敏基元直接构筑聚合物等方式形成,其温敏性可以通过调控聚合物内部或外部基团的亲疏水性、树枝化基元代数、树形构造方式等得以实现与控制。此外,树形聚合物独特的拓扑结构赋予其与线形聚合物不同的温敏行为及脱水机理。本文综述了包括温敏树枝状大分子、温敏树枝化聚合物、温敏超支化聚合物等不同类型温敏树形聚合物近年来的研究进展,重点介绍这些聚合物的合成方法、温敏行为和拓扑结构对温敏行为的影响,以及在纳米材料、生物医用、分子传感器等方面的应用研究。