Chiral Recognition and Resolution Based on Helical Polymers

Helical polymers have attracted a great deal of attention and been extensively investigated due to their various applications.One of the most important applications of helical polymers is chiral recognition and resolution of enantiomers for the reason that a pair of enantiomers is commonly with different physiological and toxicological behaviors in biological systems.Helical polymers usually present unexpected high chiral recognition ability to a variety of racemic compounds.What's more,the chiral recognition and resolution abilities of the system are dependent on the highly ordered helical structures of the helical polymers.This mini review mainly focuses on the recent progress in chiral recognition and resolution based on helical polymers.The synthetic methodology for helical polymers is firstly discussed briefly.Then recent advances of chiral recognition and resolution systems based on helical polymers,especially polyacetylenes and polyisocyanides,are described.We hope this mini review will inspire more interest in developing helical polymers and encourage further advances in chiral-related disciplines.     

PAMAM-containing semiconducting polymers: Effect of dendritic side chains on optoelectronic and solid-state properties

Dendronized polymers are a particularly interesting platform for the preparation of advanced semiconductors given their high degree of functionalization, monodispersity, and bulkiness. Despite advantageous features, the incorporation of dendritic moieties in semiconducting polymers is still relatively underexplored, and the impact on the optoelectronic, thermomechanical, and solid-state properties are difficult to predict. This work focuses on the incorporation of polyamidoamine (PAMAM) dendritic side chains to semicrystalline polymers based on diketopyrrolopyrrole. Using a versatile synthetic strategy based on the azide-alkyne Huisgen 1,3-dipolar cycloaddition, dendronized semiconducting polymers were prepared and the effect of the dendritic side chains on different properties were carefully characterized using different techniques. The dendritic side chains were found to reduce aggregation and crystallinity of the polymers in thin films. PAMAM-containing semiconducting polymers were also shown to have good charge transport properties in organic field-effect transistors, within the same order of magnitude to that of diketopyrrolopyrrole-based polymers bearing branched alkyl chains. This new design approach is particularly interesting to develop advanced semiconducting polymers given its synthetic versatility and the structural diversity of the dendronized moieties. Furthermore, the utilization of dendritic moieties in semiconducting polymers is a promising approach to fine-tune the thermomechanical properties toward semiconducting polymers for next-generation organic electronics.     

高分子立构复合结晶的研究进展

立构复合结晶是高分子结晶中的一种普遍现象,也是不同高分子之间共结晶的特殊形式.互为立体异构高分子在共混物和立体嵌段共聚物中可形成立构复合结晶.由于这种独特的链凝聚结构,立构复合结晶材料与相应的同质结晶材料的性能显著不同,立构复合结晶通常可提高高分子材料的熔点、耐热性、结晶能力、结晶度、机械力学性能、耐溶剂性能等.通过立构复合结晶,可使一些非晶或难结晶的高分子转变为可结晶或高结晶度的状态,从而实现材料性能的转变.因此,互为立体异构高分子之间的立构复合结晶为聚合物材料的性能优化和调控提供了有效的途径.文献已报道了多类可立构复合结晶的聚合物体系,包括脂肪族聚酯、脂肪族聚碳酸酯、聚甲基丙烯酸酯、聚酰胺和聚酮等.本文根据聚合物化学结构的不同,针对文献已报道的可立构复合结晶的高分子体系,综述了其立构复合结晶的形成条件、结构特征与物理性质.     

非晶态与晶态的压电热电铁电高聚物

本文综述了晶态与非晶态两类高聚物的压电性,热释电性和铁电性。这些现象近年来研究得愈来愈广泛。文中以聚氯乙烯作为非晶态高聚物的例子;以PVDF及其共聚物,还有尼龙11作为晶态高聚物的例子。按照偶极子模型,高聚物一般假定需具备四个条件,就可显示出较大的压电性,热释电性和铁电性。本文探讨了上述高聚物的结构与性能,这些对识别材料是很重要的。最后,列举了PVDF及其它材料的压电常数,热释电系数和介电常数,以供读者参考。     

Opportunities In Interfacial Area Between Organic and Materials Chemistry

It is well recognized that the current trend in organic chemistry is diverged into two frontiers: biochemistry and materials chemistry. This talk presents our recent research effort in the interfacial area between organic and materials chemistry. The major theme of our research is focused upon the rational design, synthesis and characterization of novel functional and multifunctional polymers and molecules. Typical examples of current projects are: 1). Development of polymerization methodologies: a). exploration of palladium catalyzed reactions for polycondensations, b). living ring-opening polymerization of cyclic lactone to form thioester-functionalized polyesters for chemo-ligation, 2). Design, synthesis and physical studies of photorefractive polymers, 3). Second order nonlinear optical polymers, 4). Conjugated diblock polymers for the formation of self-assembled, nano-sized electroactive materials, 5). High-performance light emitting diodes from new conjugated polymers, 6). Conjugated liquid crystalline polymers, 7). Architectural controls of polymer microstructures, including synthesis of dendritic polyphenylenevinylenes, 8). Metal-containing functional polymers. 9) Biocompatible polymers.     

Synthetic Uniform Polymers and Their Use for Understanding Fundamental Problems in Polymer Chemistry

Summary: A uniform polymer is a polymer composed of molecules that are uniform with respect to molecular weight and constitution. Besides natural uniform polymers such as nucleic acids and polypeptide, synthetic uniform polymers have been obtained by a variety of approaches. In particular, a combination of living polymerization and supercritical fluid chromatography (SFC) separation is one of the promising ways for the preparation of uniform polymers. End‐functionalized uniform polymers enabled us to prepare uniform polymer architectures such as block, graft, comb, and star polymers. Their use for understanding the fundamental problems in polymer chemistry is discussed; topics include crystallization of polymers, chain conformation in solution, and association of stereoregular polymers in solution.

SFC traces of isotactic PMMA containing an authentic sample of the 45‐mer (a) and of the isolated uniform PMMA of 100‐mer (b).     

Thermal conductivity behaviour of polymers around glass transition and crystalline melting temperatures

The thermal conductivity of five semi-crystalline and four amorphous polymers was determined within a wide range of temperature, starting at room temperature and going up to temperatures above the polymer melting point (Tm) for semi-crystalline polymers or above the glass transition temperature (Tg) for amorphous polymers. Two transient techniques were employed in the experimental investigation: the hot wire technique for the group of amorphous polymers, and the laser flash technique for the semicrystalline polymers. As expected, the experimental results show that Tg exerts a measureable influence on the thermal conductivity of amorphous polymers. In the case of semi-crystalline polymers, a singular behaviour of the thermal conductivity is observed within the Tm range. In order to explain the anomalous behaviour, the influence of these transition temperatures on the thermal conductivity behaviour with temperature has been analysed in terms of a phonon conduction process and temperature variations of specific heat and modulus of elasticity of the analyzed polymers.     

Preparation and characterization of molecularly imprinted polymers based on β‐cyclodextrin‐stabilized Pickering emulsion polymerization for selective recognition of erythromycin from river water and milk

Molecularly imprinted polymers were prepared via β‐cyclodextrin‐stabilized oil‐in‐water Pickering emulsion polymerization for selective recognition and adsorption of erythromycin. The synthesized molecularly imprinted polymers were spherical in shape, with diameters ranging from 20 to 40 µm. The molecularly imprinted polymers showed high adsorption capacity (87.08 mg/g) and adsorption isotherm data fitted well with Langmuir model. Adsorption kinetics study demonstrated that the molecularly imprinted polymers acted in a fast adsorption kinetic pattern and the adsorption features of molecularly imprinted polymers followed a pseudo‐first‐order model. Adsorption selectivity analysis revealed that molecularly imprinted polymers had a much better specificity for erythromycin than that for spiramycin or amoxicillin, and the relative selectivity coefficient values on the bases of spiramycin and amoxicillin were 3.97 and 3.86, respectively. The Molecularly imprinted polymers also showed a satisfactory reusability after four times of regeneration. In addition, molecularly imprinted polymers exhibited good adsorption capacities for erythromycin under complicated environment, that is, river water and milk. These results proved that the as‐prepared molecularly imprinted polymers is a potent absorbent for selective recognition of erythromycin, and therefore it may be a promising candidate for practical applications, such as wastewater treatment and detection of erythromycin residues in food.     

Surface Lewis acid-base properties of polymers measured by inverse gas chromatography

Surface Lewis acid-base properties are significant for polymers materials. The acid constant, K(a) and base constant, K(b) of many polymers were characterized by some researchers with inverse gas chromatography (IGC) in recent years. In this paper, the surface acid-base constants, K(a) and K(b) of 20 kinds of polymers measured by IGC in recent years are summarized and discussed, including seven polymers characterized in this work. After plotting K(b) versus K(a), it is found that the polymers can be encircled by a triangle. They scatter in two regions of the triangle. Four polymers exist in region I. K(b)/K(a) of the polymers in region I are 1.4-2.1. The other polymers exist in region II. Most of the polymers are relative basic materials.     

Preparation of bio-based polymers for materials applications

A new technology developed by us for the synthesis of well defined, tailored cellulose-synthetic polymer graft polymers and crosslinked cellulose graft polymers with control over the molecular weight of the synthetic polymer graft, a high degree of graft substitution, and knowledge of the backbone-graft linkage is reviewed. The potential of bio-based polymers using these new tailored cellulosic graft polymers for use in plastics, resins, and composite applications is discussed. The new graft polymers can function as compatibilizers/interfacial agents in the preparation of biopolymer-synthetic polymer composites and blends with the desirable properties of the constitutent polymers incorporated into the new material system.     

Advanced Materials: Trends and Possibilities in Liquid Crystalline Polymers

During the past ten years there has been a sharp increase in interest in the opportunities afforded by R & D in the field of specialty polymers. Interest is mainly being shown in two distinct categories of polymers, namely, (a) polymers which are used in very small quantities to fulfill critical needs as a part of device system, and (b) high-performance engineering polymers which significantly extend their mechanical and thermal properties for structural applications. The first category ranges from advanced resists and insulating layers for microelectronic devices to membranes for filtration systems. The second category encompasses improved matrices for advanced composites as well as liquid crystalline polymers. In the present paper an overview is first given of the emerging opportunities for advanced materials and particularly specialty polymers. The status of work on liquid crystalline copolyesters is then discussed with special emphasis on one of the major problems confronting this field, namely interpreting the microstructure of the copolyesters.     

Recent advances and future trends in molecularly imprinted polymers-based sample preparation

Molecular imprinting technology is a well-established technique for the obtainment of tailor-made polymers, so-called molecularly imprinted polymers, with a predetermined selectivity towards a target analyte or structurally related compounds. Accordingly, molecularly imprinted polymers are considered excellent materials for sample preparation providing unprecedented selectivity to analytical methods. However, the use of molecularly imprinted polymers in sample preparation still presents some shortcomings derived from the synthesis procedure itself limiting its general applicability. In this regard, molecularly imprinted polymers use to display binding sites heterogeneity and slow diffusion mass transfer of analytes to the imprinted sites affecting their overall performance. Besides, the performance of molecularly imprinted polymers in organic solvents is excellent, but their selective binding ability in aqueous media is considerably reduced. Accordingly, the present review pretends to provide an updated overview of the recent advances and trends of molecularly imprinted polymers-based extraction, focusing on those strategies proposed for the improvement of mass transfer and selective recognition in aqueous media. Besides, with the progressive implementation of Green Chemistry principles, the different steps and strategies for the preparation of molecularly imprinted polymers are reviewed from a green perspective.     

Dynamics of star branched polymers in a matrix of linear chains — a Monte Carlo study

A simple cubic lattice model of the melt of 3-arm star-branched polymers of various length dissolved in a matrix of long linear chains (n₁ = 800 beads) is studied using a dynamic Monte Carlo method. The total polymer volume fraction is equal to 0,5, while the volume fraction of the star polymers is about ten times smaller. The static and dynamic properties of these systems are compared with the corresponding model systems of isolated star-branched polymers and with the melt of linear chains. It has been found that the number of dynamic entanglements for the star polymers with arm length up to 400 segments is too small for the onset of the arm retraction mechanism of polymer relaxation. In this regime dynamics of star-branched polymers is close to the dynamics of linear polymers at corresponding concentration and with equivalent chain length. The entanglement length for star polymers appears to be somewhat larger compared with linear chains.     

Zwitterionic polymers: Addressing the barriers for drug delivery

Nanocarriers play an important role in drug delivery for disease treatment. However, nanocarriers face a series of physiological barriers after administration such as blood clearance, nonspecific tissue/cell localization, poor cellular uptake, and endosome trapping. These physiological barriers seriously reduce the accumulation of drugs in target action site, which results in poor therapeutic efficiency. Although polyethylene glycol (PEG) can increase the blood circulation time of nanocarriers, its application is limited due to the “PEG dilemma”. Zwitterionic polymers have been emerging as an appealing alternative to PEG owing to their excellent performance in resisting nonspecific protein adsorption. Importantly, the diverse structures bring functional versatility to zwitterionic polymers beyond nonfouling. This review focuses on the structures and characters of zwitterionic polymers, and will discuss and summarize the application of zwitterionic polymers for drug delivery. We will highlight the strategies of zwitterionic polymers to address the physiological barriers during drug delivery. Finally, we will give some suggestions that can be utilized for the development of zwitterionic polymers for drug delivery. This review will also provide an outlook for this field. Our aim is to provide a comprehensive and systemic review on the application of zwitterionic polymers for drug delivery and promote the development of zwitterionic polymers.     

The effect of inhomogeneous stickiness on polymer aggregation

The aggregation of polymers is important in the formation of marine aggregates and the vertical transport of material in the ocean. A polymer may be inhomogeneous along its length, with associating groups at some points along its length where bonds are more likely to form. In this paper we investigate the effects of inhomogeneous 'stickiness' along the polymer length. We describe the results of three-dimensional off-lattice simulations of polymer-polymer aggregation for four different types of polymer: polymers which are sticky along their entire length, polymers which are sticky at the ends only and two types of polymer which are slightly sticky along their entire length. We examine the mean radius of gyration and the fractal dimension of the resulting aggregates and the dynamics of aggregation. The slightly sticky polymers and the polymers which are sticky only at the ends form aggregates with a higher fractal dimension than the polymers which are sticky along their entire length. However, the mean radius of gyration of the aggregates formed by polymers which are sticky only at the ends is significantly larger than that of the aggregates formed from slightly sticky polymers. The aggregation dynamics are also different for the polymers which are sticky only at the ends compared to the slightly sticky polymers. A single 'stickiness value' is therefore likely to be inadequate to describe a polymer. We also examine the effect of polymer rigidity; it seems that the effect of inhomogeneous stickiness is greater for almost-straight polymers than for coiled chains.     

Thermoanalytical studies on specialty polymers in Japan

Thermoanalytical studies on specialty polymers in Japan are reviewed. The basic and applied researches for the developments of new specialty polymers such as high-performance polymers, liquid crystalline polymers, and biodegradable polymers during the 1990's are introduced from the standpoint of thermal analysis. Many studies were performed for the improvements of durability and thermal stability of engineering polymers, biodegradable polymers and so on. A special topic of researches on the thermal behavior of polymers by high-pressure differential thermal analysis is included in this review. This revised version was published online in July 2006 with corrections to the Cover Date.     

Adapting semiconducting polymer doping techniques to create new types of click postfunctionalization

After the historical development from the insoluble polyacetylene film to soluble and processible aromatic polymers, donor-acceptor-type aromatic polymers have recently emerged as a new class of semiconducting polymers. The polymer energy levels and band gaps can be tuned by the appropriate selection of the donor and acceptor moieties, and some of these polymers showed good optoelectronic or photovoltaic performances. The conventional synthetic method for achieving donor-acceptor-type aromatic polymers is based on the metal-catalyzed polycondensation between donor-type monomers and acceptor-type co-monomers. In this tutorial review, a new methodology for introducing donor-acceptor chromophores into semiconducting polymers is described. The donor-acceptor structures are constructed in the main chains and side chains of semiconducting polymers using a polymer reaction based on high-yielding addition reactions between the electron-rich alkynes and strong acceptor molecules, such as tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ). Considering the p-type doping features of TCNE and TCNQ, the experimental procedure is the same as the conventional doping technique for semiconducting polymers. However, the resulting donor-acceptor type polymers are chemically stable due to the absence of unstable unpaired electrons (polarons). The donor-acceptor alternating polymers were achieved in one step from the precursor poly(aryleneethynylene)s and poly(arylenebutadiynylene)s. When the side chain alkynes were post-functionalized, the polymer energy levels were controlled by the species and amount of the employed acceptor molecules. These atom-economic acceptor additions satisfy most of the requirements of the "click chemistry" concept. In contrast to the conventional click chemistry reactions, the reactions between electron-rich alkynes and acceptor molecules provide a wide variety of polymers with promising optoelectronic applications.     

New comb-like polymers: Synthesis,structures and reactivity

Comb-like polymers have been widely investigated mainly to correlate their structures with the thermal behaviour. Our interests are directed on the synthesis of new types of comb-like polymers bearing reactive groups in the side chains, main chain or as end groups. One part of the investigations deals with the behaviour of photosensible polymers containing azobenzene, cinnamic acid and mesoionic moieties. The use of enzymes as catalysts for the synthesis of new methacrylic derivatives and for the modification of polymers illustrates a fascinating contribution to polymer chemistry. The classical Diels-Alder addition was also used for the synthesis and modification of polymers. Finally, the construction of polymers containing rotaxanes in the side chains is presented.     

Functionalized liquid-crystalline polymers towards NLO-applications and piezo-sensors

A systematic synthesis of functionalized 1c polymers is possible starting from precursor polymers with phenolic groups. The esterification of these precursor polymers with chiral acids proceeds nearly quantitatively and produces polymers with cholesteric and chiral smectic C* phases. A further functionalization of these polymers with “NLO-chromophores” produces polymers, which are suitable for second harmonic generation; a functionalization with crosslinkable groups leads to polymers, which act as piezoelements.     

Functionalization of living polymers – results and problems

In spite of intensive research, work during the last 20–30 years, even today, the reaction products of living polymers are produced only in small quantities on industrial scale. The expected production of tyres from telechelic polymers was not reached, The difficulty is that the functionalization of living polymers does not result in only one type of functionalized polymer chain but always in a mixture of non-, mono-, di- and polyfunctionalized compounds. During the last years different technologies for functionalizing living polymers were developed in Buna. The results of these investigations are discussed. Likewise, we show that the functionalized living polymers of ∝-methylstyrene are of great interest for different industrial uses. A complete technological scheme for the production of telechelic polymers has been developed, which is attached herewith.