胆甾基功能高分子研究进展

简要评述了胆甾基功能高分子的分子设计与合成研究进展,着重对侧基型高分子胆甾进行论述.     

A Modular Synthesis of Teraryl‐Based α‐Helix Mimetics,Part 1: Synthesis of Core Fragments with Two Electronically Differentiated Leaving Groups

Teraryl‐based α‐helix mimetics have proven to be useful compounds for the inhibition of protein–protein interactions (PPI). We have developed a modular and flexible approach for the synthesis of teraryl‐based α‐helix mimetics. Central to our strategy is the use of a benzene core unit featuring two leaving groups of differentiated reactivity in the Pd‐catalyzed cross‐coupling used for terphenyl assembly. With the halogen/diazonium route and the halogen/triflate route, two strategies have successfully been established. The synthesis of core building blocks with aliphatic (Ala, Val, Leu, Ile), aromatic (Phe), polar (Cys, Lys), hydrophilic (Ser, Gln), and acidic (Glu) amino acid side chains are reported.     

废弃天然高分子基功能材料

从废弃高分子角度对废弃生物质的高附加值再利用进行综述,阐述了废弃生物质中天然高分子的类型以及废弃生物质中包含的大量天然高分子具有官能团丰富、可降解、生物相容、无毒无害等优异的性能,归纳了废弃生物质的传统处理方法及作为材料使用的再利用途径,介绍了废弃天然高分子用作复合材料、吸附材料、载体材料、能源材料、医用高分子材料、智能高分子材料等的研究进展,并对废弃天然高分子的资源化利用进行了展望。     

学科大概念统领下基于真实情境的“合成高分子”单元教学

通过新旧课标与教材的对比分析,在大概念的统领下,确定“合成高分子”的教学目标以及认识方式。以“结构决定性质,性质决定用途”大概念统领单元教学,围绕教学目标选择新冠疫情下的“防病毒口罩”为情境,在真实问题的解决过程中发展学生认识合成高分子的基本思路,促进学生化学学科核心素养的发展。     

Enzymatic Synthesis of Sequence‐Defined Synthetic Nucleic Acid Polymers with Diverse Functional Groups

The development and in‐depth analysis of T4 DNA ligase‐catalyzed DNA templated oligonucleotide polymerization toward the generation of diversely functionalized nucleic acid polymers is described. The NNNNT codon set enables low codon bias, high fidelity, and high efficiency for the polymerization of ANNNN libraries comprising various functional groups. The robustness of the method was highlighted in the copolymerization of a 256‐membered ANNNN library comprising 16 sub‐libraries modified with different functional groups. This enabled the generation of diversely functionalized synthetic nucleic acid polymer libraries with 93.8 % fidelity. This process should find ready application in DNA nanotechnology, DNA computing, and in vitro evolution of functional nucleic acid polymers.     

Functional Zwitterionic Polymers on Surface: Structures and Applications

Zwitterionic polymers are important in a wide range of industrial, biological and medical fields. Their chemical structures include an equal amount of anion and cation groups, and such structures give rise to many unique functionalities, such as temperature response, anti‐polyelectrolyte effect, and strong hydration properties. In this review, we focus on the structures and applications of functional zwitterionic polymers on surfaces. We review three areas of applications according to the architecture of the polymeric systems: surface coating, complex solutions, and hydrogel. We review the simulation and theory work and highlight some outlooks for further development.     

合成高分子基温敏水凝胶在眼病治疗中的研究进展

由于眼部存在角膜/结膜屏障、血-房水屏障和血-视网膜屏障等,有效的眼部给药依然面临巨大挑战.近年来,温敏水凝胶在眼部给药领域受到了广泛关注.在室温下,温敏水凝胶材料呈液态,便于以局部滴加或玻璃体内注射的方式给药;当与眼部接触升温并超过其临界成胶温度时,能以物理交联的方式快速凝胶化,从而实现原位缓释给药,提高药物生物利用度.在众多温敏水凝胶材料中,合成高分子具有材料和功能多样化等优势,其中较常见的为泊洛沙姆、聚乙二醇/聚酯和聚(N-异丙基丙烯酰胺).本综述首先介绍了以上3类合成高分子基温敏水凝胶材料的制备方法和成胶特性.然后,围绕眼部给药存在的难点,探讨这些温敏水凝胶在治疗角膜病、干眼症、青光眼和眼部炎症等各种眼病中的相关研究进展.最后,我们比较了这3种水凝胶在使用性能上的优缺点,并对未来眼科温敏水凝胶的材料设计提出了设想和展望.     

Synthetic Adrenaline Receptors Based on Bisphosphonates

Synthetic models of the natural adrenergic receptors are presented, and their binding properties to several biologically important amines and amino alcohols in dimethylsulfoxide and methanol are discussed. NMR titrations have been carried out to determine their binding constants.     

基于环糊精的分子印迹技术

基于环糊精的分子印迹技术综合了超分子化学、高分子化学、分析化学等多学科优势,对人为可控的大型超分子主体化合物的合成有着指导意义,对具有多位点识别人工酶的实现也有巨大的推动作用。本文综述了近年来基于环糊精的分子印迹技术的研究进展：首先介绍了不同种类的基于环糊精的分子印迹产物的合成,包括合成思路、步骤、方法以及识别机理探讨;然后着重叙述了该体系的应用研究进展,包括其在分子识别、色谱分离、电化学传感器以及生物学控制等领域的应用;最后指出目前研究工作存在的不足,并对其发展前景进行了展望。     

Pd-Catalyzed Asymmetric N-Allylation of Amino Acid Esters with Exceptional Levels of Catalyst Control: Stereo-Divergent Synthesis of ProM-15 and Related Bicyclic Dipeptide Mimetics

A general and powerful method for the stereo-controlled Pd-catalyzed N-allylation of amino acid esters is reported, as a previously largely unsolved synthetic challenge. Employing a new class of tartaric acid-derived C₂-symmetric chiral diphosphane ligands the developed asymmetric amination protocol allows the conversion of various amino acid esters to the N-allylated products with highest levels of enantio- or diastereoselectivity in a fully catalyst-controlled fashion and predictable configuration. Remarkably, the in situ generated catalysts also exhibit outstanding levels of activity (ligand acceleration). The usefulness of the method was demonstrated in the stereo-divergent synthesis of a set of new conformationally defined dipeptide mimetics, which represent new modular building blocks for the development of peptide-inspired bioactive compounds.     

基于硅材料的分子印迹聚合物的制备及应用

分子印迹聚合物因制备简单、稳定性好、且具有分子识别功能使其在色谱分离、固相萃取、化学传感、模拟酶催化等方面有了广泛的应用。近年来,基于硅的分子印迹聚合物发展较为快速。本文主要介绍了以硅为母体材料和以硅为基质材料的分子印迹聚合物的制备及分子识别性质研究,并对其应用进行了分类,在此基础上对其将来的发展进行了展望。     

由不同功能单体合成的对羟基苯甲酸分子印迹聚合物识别特性的实验和理论研究

以对羟基苯甲酸(p—HB)为模板分子,以4-乙烯吡啶(4-Vpy)、丙烯酰胺(AM)或二者等摩尔比的混合物为功能单体制备了相应的分子印迹聚合物(Molecularly imprinted polymer,MIP),考察了MIP作为高效液相色谱柱固定相时模板分子及其类似物的保留行为,同时也考察了在乙腈流动相中添加剂乙酸或水对色谱保留的影响．三种MIPs的保留大小顺序为：当功能单体为4-Vpy时,MIP对模板及其类似物的保留最强;当以4-Vpy和AM作为混合单体时,保留次之;而功能单体为AM时,保留最差．以H2O作为添加剂时MIP的识别效果要优于以CH3CO2H为添加剂的情况．使用半经验量化法之一,PM3方法,借助Gaussian94软件对以p—HB与相应的功能单体体系进行了计算模拟．结果表明,聚合前单体与模板复合物结合能量的大小与实验所得的容量因子间具有正相关性．即结合能越高,容量因子k′值越大．     

基于MCM-41分子筛表面的镱离子印迹聚合物的制备及其性能

运用离子印迹技术,以3-氯丙基三乙氧基硅烷为锚定剂,将功能单体直链聚乙烯亚胺(PEI)接枝在MCM-41分子筛表面,选择镱离子作为模板离子,以环氧氯丙烷交联制备出基于MCM-41表面的镱离子印迹聚合物Yb(Ⅲ)-IIP-PEI/MCM-41,并以同样的方法制备非离子印迹聚合物(NIP-PEI/MCM-41)。 利用傅里叶变换红外光谱仪和扫描电子显微镜等技术手段对Yb³⁺印迹聚合物进行表征,采用静态吸附法确定了Yb(Ⅲ)-IIP-PEI/MCM-41对Yb³⁺的最佳吸附条件及选择性吸附性能。 结果表明,Yb(Ⅲ)-IIP-PEI/MCM-41和NIP-PEI/MCM-41的最大吸附量分别为229.93和99.27 mg/g;印迹材料对Yb³⁺的吸附符合Langmuir模型;吸附平衡在40 min的时候基本可以达到,可以利用准二级动力学模型来描述其吸附过程;Yb(Ⅲ)-IIP-PEI/MCM-41对Yb³⁺具有较强的选择性,同时也具有很好的重复使用性能。 成功地将MCM-41和离子印迹聚合物的优点结合起来,制备出一种对稀土Yb离子既有高吸附量又有高选择性的吸附材料,为进一步将其应用在处理实际废水,分离回收低浓度稀土废水中的稀土元素等方面打下了基础。     

Synthetic Receptors Based on Abiotic Cyclo(pseudo)peptides

Work on the use of cyclic peptides or pseudopeptides as synthetic receptors started even before the field of supramolecular chemistry was firmly established. Research initially focused on the development of synthetic ionophores and involved the use of macrocycles with a repeating sequence of subunits along the ring to facilitate the correlation between structure, conformation, and binding properties. Later, nonnatural amino acids as building blocks were also considered. With growing research in this area, cyclopeptides and related macrocycles developed into an important and structurally diverse receptor family. This review provides an overview of these developments, starting from the early years. The presented systems are classified according to characteristic structural elements present along the ring. Wherever possible, structural aspects are correlated with binding properties to illustrate how natural or nonnatural amino acids affect binding properties.     

Molecularly imprinted polymers with assistant recognition polymer chains for bovine serum albumin

A new protein molecularly imprinted polymer (MIP) was prepared with grafting polyvinyl alcohol as assistant recognition polymer chains (ARPCs). The ARPCs and acrylamide monomers were interpenetrated and then polymerized on the surface of macroporous acrylate adsorbent spheres. The template BSA was removed by treatment with 2.00 mol L-1 potassium chloride (KCl) solution and the adsorbed proteins were detected with sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). 0.150, 0.500, and 2.00 mo...