Biomolecular Densely Grafted Brush Polymers: Oligonucleotides,Oligosaccharides and Oligopeptides

In this Minireview, we describe synthetic polymers densely functionalized with sequence-defined biomolecular sidechains. We focus on synthetic brush polymers of oligonucleotides, oligosaccharides, and oligopeptides, prepared via graft-through polymerization from biomolecule functionalized monomers. The resulting structures are brush polymers wherein a biomolecular graft is positioned at each monomer backbone unit. We describe key synthetic milestones, identify synthetic opportunities, and highlight recent advances in the field, including biological applications.     

Synthesis of Liquid Crystalline Polymers with Side Chains

The present paper covers the synthesis and characterization of several intermediate products, monomer, and polymers. 3-{ 2-[ 4-( 4-Nitrophenylazo ) phenoxy] ethyloxycarbonyl} propanoyloxy (2-hydroxy) propyl acrylate (4) was prepared by the ring-opening reaction of glycidyl acrylate with the monoester of succinic acid (3). The polymers (5) with different molecular weights were prepared by the free-radical polymerization. The polymers (5) had liquid crystalline behavior without decomposition as revealed by DSC, optical microscope.     

In Situ Synthesis and Copolymerization of Oligonucleotides on Conducting Polymers

 Two strategies of DNA biochip construction on conducting polymers are investigated. The first involves a direct electro-copolymerization of pyrrole–oligonucleotides (oligonucleotides tethered to a pyrrole group) with the pyrrole leading to a polypyrrole film bearing the oligonucleotides. Successive copolymerizations allow the transformation of a microelectrode array into a DNA array. The second methodology involves a direct in situ synthesis of oligonucleotides on a conducting polymer used as an organic electrode. In this way a 5′ electrolabile protecting group, p-nitrobenzoyl, was used. In order to construct short oligonucleotide sequences, the other protecting groups of the bases have also to be modified. Preliminary results based on this technology are shown. Received July 28, 1998. Revision October 19, 1998.     

疏水缔合型水溶性高分子的合成与表征

本文综述了疏水缔合型水溶性高分子的合成与表征方法，６文中介绿了在合成过程中提高油溶性单体和水溶性单体的混溶性以及疏水基团均匀分布的方法，并了用核磁共振，上光谱等方法测定疏水物含量的方法。     

疏水缔合水溶性聚合物的合成研究进展

综述了疏水缔合水溶性聚合物的合成的最新研究进展。主要合成方法有非均相共聚、均相共聚、胶束共聚、反相微乳液聚合、无皂乳液聚合、活性阴离子聚合以及超临界二氧化碳介质等。     

含吡啶环大环多胺的合成及其与Cu(Ⅱ)的络合行为

本文以2,6-二溴甲基吡啶和对甲苯磺酰胺钠盐合成含吡啶环大环多胺,得到了尚未见文献报道的含四个吡啶环的三十二环胺. 2,6-二溴甲基-吡啶与甲苯磺酰胺钠盐在无水乙醇回流温度下得到1,9,17,25-四甲苯磺酰基大环多胺.用浓硫酸脱去N-甲苯磺酰基化合物的甲苯磺酰基, 生成标题大环多胺化合物. 配体与Cu(Ⅱ)的络合由紫外吸收光谱测定. 实验结果表明配体确与Cu^2^+以1:2络合成为双核络合物.     

Bioinspired Thermoresponsive Photonic Polymers with Hierarchical Structures and Their Unique Properties

Thermoresponsive photonic materials having hierarchical structures are created by combining a template of Morpho butterfly wings with poly(N‐isopropylacrylamide) (PNIPAM) through a chemical bonding and polymerization route. These materials show temperature‐induced color tunability. Through reacting with both NIPAM monomers and the amino groups of chitosan in wing scales, glutaraldehyde workes as a bridge by creating chemical bonding between the biotemplate and the PNIPAM. The corresponding reflection peaks red‐shift with increase in temperature—an opposite phenomenon to previous studies, demonstrating a thermoresponsive photonic property. This unique phenomenon is caused by the refractive index change due to the volume change of PNIPAM during the temperature rising. This work sets up an efficient strategy for the fabrication of stimuli‐responsive photonic materials with hierarchical structures toward extensive applications in science and technology.

     

Conjugated Oligomers and Polymers Sheathed with Designer Side Chains

Conjugated polymers (CPs) are often referred to as molecular wires because of their quasi one‐dimensional electronic wavefunctions delocalized along the polymer chains. However, in the solid state, CPs tend to self‐assemble through π‐stacking, which greatly attenuates the one‐dimensional nature. By molecular design, CPs can be molecularly insulated just like electric power cords, resulting in so‐called “insulated” molecular wires (IMWs). In this Focus Review, we will discuss their unique photophysical, electronic, and mechanical properties which originate from the absence of π‐stacking.     

Conformational Changes in Polymers with Interactive Side Chains

It is privilege and a pleasure for me to present a lecture in this symposium honoring the awarding of an Honorary Doctor of Science Degree to Professor Carl S. Marvel of the University of Arizona, by the Polytechnic Institute of New York. It was my privilege to work under the direction of Professor Marvel for my PhD degree, and then for two additional years as a research associate or postdoctoral fellow.     

三次采油用水溶性聚合物:进展及挑战

三次采油是我国主要的原油增产方式,但目前所用聚合物存在溶解时间长、耐温抗盐性差等缺陷,无法满足越来越复杂的油藏环境的要求。本文综述了作者所在团队通过改进聚合工艺、"剪裁"聚合物分子结构、设计智能自组装体系等手段研究新型聚合物驱油剂的工作,并展望了未来的发展趋势。     

自由基官能化聚合合成主链桂嘧啶碱基的聚合物

以合成的三种嘧啶衍生物为单体,通过加入能在自由基作用下开环异构的乙烯酮缩醛类进行了酯基封端、酯基嵌入的官能化聚合反应,对所得聚合物的生物降解性进行了一定程度的探查。     

Synthesis and Properties of Polymers Containing Phosphatidylcholine Analogues in the Main Chains and Long Alkyl Groups in the Side Chains

Abstract

Several new polymers containing hydrophilic phosphatidylcholine analogues in the main chains and hydrophobic docosyl or stearyl groups in the side chains have been synthesized. The polymers exhibit thermotropic liquid crystalline behaviors from 65°C up to ca. 280°C as determined by polarizing microscopy. One of the polymers shows slight crystallinity as evidenced by wide-angle x-ray diffraction. The viscosity measurements show that some of the polymers have properties similar to usual polyelectrolytes. However, one polymer shows a linear increase of reduced viscosity.     

Polymers with macrocyclic architectures: Synthesis and properties

The preparation by living polymerization and the investigation of the properties of polymers with cyclic chain architectures have been recently undertaken. The cyclization involves a unimolecular end-to-end reaction of a heterodifunctional linear precursor. The elementary steps of the cyclization mechanism are examined in the light of matrix-assisted laser desorption/ ionization mass spectrometry (MALDI-MS) data obtained on linear polystyrene precursors and cyclized products. The synthetic procedures developed to prepare macrocyclic polymers of various structures, as well as macrocyclic random and block copolymers are then reviewed and discussed. The main characteristics of the cyclic (co)polymers are compared to the corresponding linear chains and some of the original properties that are induced by the cyclic chain architecture are presented.     

Selective Interpolymer Complexation between Acrylic Copolymers and Nonionic Polymers

Abstract

Selective interpolymer complexation has been studied between methacrylic acid-methacrylamide copolymer and some complementary polymers such as poly(methacrylamide), poly(vinyl pyrrolidone), and poly(ethylene oxide). The relative order of complexation ability of the various nonionic polymers has been interpreted on the basis of the nature of interactions between different units of polymers. Configurational environment and neighboring group influences seem to affect interpolymer complex formation.     

Water-Soluble Polymers with Appending Porphyrins as Bioinspired Catalysts for the Hydrogen Evolution Reaction

Molecular design to improve catalyst performance is significant but challenging. In enzymes, residue groups that are close to reaction centers play critical roles in regulating activities. Using this bioinspired strategy, three water-soluble polymers were designed with appending Co porphyrins and different side-chain groups to mimic enzyme reaction centers and activity-controlling residue groups, respectively. With these polymers, high hydrogen evolution efficiency was achieved in neutral aqueous media for electro- (turnover frequency >2.3×10⁴ s⁻¹) and photocatalysis (turnover number >2.7×10⁴). Porphyrin units are surrounded and protected by polymer chains, and more importantly, the activity can be tuned with different side-chain groups. Therefore, instead of revising molecular structures that is difficult from both design and synthesis points of view, polymers can be used to improve molecular solubility and stability and simultaneously regulate activity by using side-chain groups.     

Complexation of Terbium Ion with the Copolymer of Acrylic Acid and Acrylamide Grafted onto Polyethylene

Acrylic acid (AA) and acrylamide (AAm) were graft copolymerized onto polyethylene powder by the preirradiation method. The PE powder grafted with both AA and AAm (PE-g-(AA-co-AAm)) rapidly adsorbed Tb ion with an efficiency higher than did PE powder grafted with AA (PE-g-AA). The complex formation constant of Tb ion with PE-g-(AA-co-AAm) was larger than that with PE-g-AA because the introduction of the acrylamide part decreased the steric hindrance for complexation between Tb and the carboxyl group of the graft chains. Tb ion was efficiently separated from transition metal ions, such as Co, upon passage of a solution through a column packed with PE-g-(AA-co-AAm).     

Chimeric RNA Oligonucleotides with Triazole and Phosphate Linkages: Synthesis and RNA Interference

Chimeric RNA oligonucleotides with an artificial triazole linker were synthesized using solution‐phase click chemistry and solid‐phase automated synthesis. Scalable synthesis methods for jointing units for the chimeric structure have been developed, and after click‐coupling of the jointing units with triazole linkers, a series of chimeric oligonucleotides was prepared by utilizing the well‐established phosphoramidite method for the elongation. The series of chimeric 21‐mer oligonucleotides that possessed the triazole linker at different strands and positions allowed for a screening study of the RNA interference to clarify the preference of the triazole modifications in small‐interfering RNA molecules.     

侧链含自由基单元的1,4-吡咯并吡咯二酮共轭聚合物的合成和半导体性质研究

合成了两个侧链含有2,2,6,6-四甲基哌啶-1-氧自由基单元(TEMPO)的1,4-吡咯并吡咯二酮(DPP)共轭聚合物PDPP4T-1和PDPP4T-2,并开展了其半导体性质研究。薄膜场效应晶体管器件测试结果显示,相对于不含TEMPO的聚合物PDPP4T,PDPP4T-1和PDPP4T-2的场效应器件性能有所降低,不过,含TEMPO的聚合物器件性能最高仍达到了2.12cm²·V^-1·s^-1。进一步通过原子力显微镜和X射线衍射对TEMPO引入后导致性能降低的可能原因进行了研究。