基于贻贝启发的水下仿生胶黏剂

海洋中的贻贝依靠丝足(Byssus)与足盘(Plaque)可以在潮湿及水下环境中快速而牢固地黏附于各种固体表面。贻贝强健的足部具有沟渠状的生理结构,通过类似于“注塑生产”的生理过程,它们可以生成丝足与足盘。贻贝将液态的蛋白质挤压到沟渠里,只需几秒钟时间,这些蛋白质就能形成一条条发丝一样纤细的丝足。每条丝足的末端都有一个黏性足盘,足盘可以牢牢地黏附在岩石及固体表面。丝足及足盘由多种黏附蛋白(Mfps)组成,且几乎每种黏附蛋白都含有L-3,4-二羟基苯丙氨酸(DOPA)成分。在过去的数十年间,科研人员基本揭示了贻贝黏附蛋白的结构及其黏附机理。DOPA的儿茶酚基团,通过氧化交联、金属螯合、氢键、静电作用、疏水作用、π-π作用、阳离子-π作用等各种共价和非共价相互作用,实现强大的界面黏接。基于贻贝黏附蛋白的结构及其黏附机理,通过使用DOPA及其类似物修饰的聚合物体系,人们得到了多种具有优秀机械性能和功能化的新型仿生多巴类水下胶黏剂。本综述首先介绍了贻贝黏附蛋白的组成特点及其黏附机理;随后分别介绍了凝聚层类胶黏剂、水凝胶类胶黏剂、智能型水下胶黏剂的结构特点及黏附机理;最后讨论了目前仿生水下胶黏剂存在的问题及未来发展前景。     

含多巴胺的贻贝仿生聚氨酯

将具有神奇黏附效果的贻贝黏附蛋白中的功能元——儿茶酚(catechol)与具有结构可设计、简单易得、低成本的聚氨酯相结合,制备新型高性能的贻贝仿生聚氨酯黏附材料.首先,通过异氰酸酯化学合成了含羧基的聚氨酯,接着通过碳二亚胺化学将含有儿茶酚功能团的多巴胺(dopamine)和含羧基的聚氨酯相结合制备了含多巴胺的聚氨酯.经过傅立叶转换红外光谱(FTIR)、核磁共振(NMR)和紫外-可见分光光度仪(UV-Vis)等分析测试研究结果表明,多巴胺确实已被引入到聚氨酯中;同时,通过测试搭接剪切强度研究了其粘接性能,结果表明含多巴胺的聚氨酯相对于含羧基的聚氨酯的粘接性能得到大幅提高,其对金属基材的粘接强度提高了30%左右,达到5.2MPa,可以与贻贝黏附蛋白相媲美.     

仿贻贝粘附蛋白聚合物的研究及动态

贻贝粘附蛋白以其对不同基材表面及在水下都具备高强的粘附能力而闻名。根据仿生学原理,通过将贻贝粘附蛋白功能元即邻苯二酚基团与合成高分子相结合制备仿贻贝粘附蛋白聚合物,达到复制重现甚至超越天然贻贝粘附蛋白粘附效力的目的,是目前贻贝仿生领域研究热点之一。本文综述了近年来国内外仿贻贝粘附蛋白聚合物的研究进展。我们按照主链结构的种类进行了分类,对仿贻贝粘附蛋白聚合物材料的发展过程、材料的设计思路以及应用领域进行了系统的归纳总结。通过研究分子结构与仿生材料功能特性之间的相互关系,希望为以后设计合成新型的功能化的贻贝仿生材料提供有益的借鉴和参考。     

仿壁虎和贻贝黏附材料

自然界中的动物和植物经过45亿年长期的进化使其结构与功能达到近乎完美的程度,实现了结构与功能的统一。黏附材料在生物医学、建筑等领域都具有重要的应用价值。受自然界中具有优异黏附特性的生物材料启发(如壁虎、贻贝等),国内外许多课题组相继开展了仿生黏附材料的研究。根据黏附机理的不同,黏附材料大致可分为可逆黏附和永久黏附两大类。壁虎的可逆黏附是基于其脚趾多尺度微纳结构与接触面间的范德华力,贻贝的永久黏附则源自其分泌的黏附蛋白。本文就壁虎、贻贝及其他生物黏附材料的黏附机理及其相应仿生黏附材料的国内外研究现状进行简要的综述,并对该领域未来的发展方向作了展望。     

聚多巴胺在生物材料表面改性中的应用

海洋生物贻贝通过其足腺分泌的具有超强黏附性能的蛋白,可在海水等潮湿环境中牢固黏附在各种材料的表面。受此黏附蛋白的启发,研究发现聚多巴胺(PDA)具有类似于贻贝黏附蛋白的结构和超强黏附性能。在碱性条件下,PDA可在各种材料的表面迅速成膜,其中含有大量亲水的羟基和氨基官能团,可提高材料表面的亲水性和化学多功能性;PDA可作为中间层,在基底材料表面强力结合功能分子。由于PDA的形成过程简单且不需要有机溶剂,近年来常被应用于材料的表面改性。此外,由于PDA可促进细胞的黏附,具有良好的生物相容性,在生物材料表面改性中也有较多的应用。本文将综述PDA的黏附机理及其在生物材料表面改性中的应用,并提出PDA在生物材料表面改性应用中的展望及研究过程中存在的问题,为PDA在生物材料和组织工程中的应用提供参考。     

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...     

基于贻贝仿生化学的分离功能材料

贻贝仿生的表面化学是近年来材料学、化学、生物医学等领域的交叉研究热点。多巴胺可以作为贻贝足丝蛋白(Mfp)超强黏附特性的模型分子,通过复杂的氧化-自聚和组装,形成多种功能的聚多巴胺(PDA)纳米涂层和纳米粒子,在分离膜、吸附材料、生物医用材料、生物黏结剂等领域有着广阔的应用前景。本研究小组近年来持续开展了基于贻贝仿生化学的分离功能材料制备与结构调控的研究工作,率先将多巴胺表面沉积方法应用于多孔分离膜表面的构建与功能化,提出了多巴胺的自聚-沉积过程模型,进而验证了PDA沉积层的纳滤分离特性,建立了一条简单方便的膜表面功能化与纳滤膜制备新途径。本文主要对基于贻贝仿生化学的分离功能材料,特别是分离膜的研究进展进行综述,并对将来的发展趋势进行展望。     

仿贻贝粘性高分子的应用进展

海洋贻贝类生物的足丝分泌蛋白几乎能够在所有基底材料上实现高强度、高韧性的粘附,且不受水或者潮湿环境影响。这种环境友好、条件温和的高效生物粘附剂引起了研究人员的兴趣,尤其在粘附机理和应用前景方面更是研究人员关注的重点。大量研究表明,贻贝超强的粘附能力与其分泌的粘附蛋白中高含量的3,4-二羟基苯丙氨酸(多巴,DOPA)单元相关。受贻贝粘附蛋白的启发,人们研究发现,多巴胺(DA)分子具有与之相似的官能团,聚合后有相似分子结构,使用聚多巴胺替代聚多巴,可以在基体表面达到相似的粘附性能。本文简单介绍了仿贻贝粘性物质中的代表多巴胺自聚合形成聚多巴胺(PDA)与粘附机理,并重点介绍了近年来DOPA衍生物在表面改性、催化、生物防污及生物医学领域的应用和前景。     

基于多巴胺表面改性技术研究现状

海洋贻贝类生物通过足丝分泌的黏附蛋白,在潮湿环境中可以短时间固化,并紧固黏附在基质表面.研究表明,3,4-二羟基-L-苯基丙氨酸(多巴,DOPA)是这种黏附蛋白中的重要组成部分.多巴胺(DA)作为DOPA的一种衍生物,拥有同样的强黏附性.且多巴胺的自聚合产物聚多巴胺(PDA)存在许多官能团,如邻苯二酚、胺、亚胺,这些官...     

Maps强力黏附单元DOPA二联体与HClO反应的理论研究

应用量子化学从头算HF/3-21G方法,在全局优化中确定贻贝黏附蛋白的强力粘附单元DOPA二联体的几何构型、各原子电荷分布及热力学参数.计算表明:DOPA二联体易与HClO发生亲电取代反应生成2-氯-4-酮-5羟基-苯丙氨酸,破坏了贻贝内超强黏附单元DOPA二联体的结构,降低粘附蛋白内粘性;热力学性质的ΔH放热为88.712 kJ/mol,吉布斯自由能变ΔG恒小于0,较易自发正向进行.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.