Stress memory polymers

Like shape memory polymers, a novel phenomenon of stress memory was shown in which the stress of a material can respond to an external stimulus. This concept was further enlightened by a switch‐spring‐frame model that would eliminate the limitation of existing models which overlooked the stimulus responsive nature of such polymers. The discovery being reported in this article was stemmed from a real case study into shape memory polymer fibers in compression stocking for varicose veins. The breakthrough of stress memory enabled researchers to develop applications needing stimuli‐responsive forces, which can broaden the horizon of such smart polymers in emerging smart products in many multidisciplinary fields such as sensors, stress garments, and massage devices, electronic skins, and artificial muscles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 893–898     

刺激响应纳米碳杂化材料

碳纳米管和石墨烯是碳纳米材料的典型代表,其纳米尺度赋予了其优异的光、电、热以及机械性能。然而,这些碳纳米材料间存在较强的范德华力,导致其溶解性差,后续加工处理困难。为提高碳纳米材料的溶解性,通常利用聚合物或其它小分子物质对其进行修饰。而利用刺激响应性聚合物或化合物功能化碳纳米材料,不仅可以提高其溶解性,还可以赋予其环境刺激响应功能。本文主要综述了近年来利用温度、pH、光以及CO2响应聚合物或小分子化合物对碳纳米管和石墨烯进行共价键、非共价键修饰并赋予其环境刺激响应特性的方法、功能和相关应用,展望了修饰得到的纳米碳杂化材料的应用前景及下一步发展方向。     

Water-soluble supramolecular polymers constructed by macrocycle-based host-guest interactions

Water soluble supramolecular polymers are especially important due to their superior biocompatibility and environmental adaptation, which determined they have wide applications in various areas, such as drug delivery, self-healing, shape memory. On the other hand, macrocyclic compounds are the most used building blocks in the preparation of supramolecular polymers. Macrocycle-based supramolecular polymers, which introduce the host-guest interaction in the system, endow these polymers with interesting and smart physicalchemical properties. In this review, we summarized recent studies about supramolecular polymers in aqueous solution based on macrocyclic compounds.     

Detection and amplification of chirality by helical polymers

A unique feature of synthetic helical polymers for the detection and amplification of chirality is briefly described in this article. In sharp contrast to host-guest and supramolecular systems that use small synthetic receptor molecules, chirality can be significantly amplified in a helical polymer, such as poly(phenylacetylene)s with functional pendants, which enable the detection of a tiny imbalance in biologically important chiral molecules through a noncovalent bonding interaction with high cooperativity. The rational design of polymeric receptors can be possible by using chromophoric helical polymers combined with functional groups as the pendants, which target particular chiral guest molecules for developing a highly efficient chirality-sensing system. The chirality sensing of other small molecular and supramolecular systems is also briefly described for comparison.     

Radiation chemistry of smart polymers (A Review)

Radiation chemistry methods used to prepare smart polymers are surveyed. The properties of these polymeric materials are considered. The benefits of radiation-chemical procedures for manufacturing smart polymers are discussed. The areas of their practical use are outlined     

Stimuli-responsive hydrogels based on polysaccharides incorporated with thermo-responsive polymers as novel biomaterials

In recent years, intelligent hydrogels which can change their swelling behavior and other properties in response to environmental stimuli such as temperature, pH, solvent composition and electric fields, have attracted great interest. The hydrogels based on polysaccharides incorporated with thermo-responsive polymers have shown unique properties such as biocompatibility, biodegradability, and biological functions in addition to the stimuli-responsive characters. These "smart" hydrogels exhibit single or multiple stimuli-responsive characters which could be used in biomedical applications, including controlled drug delivery, bioengineering or tissue engineering. This review focuses on the recent developments and future trends dealing with stimuli-responsive hydrogels based on grafting/blending of polysaccharides such as chitosan, alginate, cellulose, dextran and their derivatives with thermo-sensitive polymers. This review also screens the current applications of these hydrogels in the fields of drug delivery, tissue engineering and wound healing.     

Robust and smart hydrogels based on natural polymers

This review summarizes recent progress of the robust and smart hydrogels prepared from natural polymers including polysaccharides,proteins,etc.These hydrogels exhibit outstanding mechanical properties due to their nanofibrous aggregated microstructures and special crosslinking networks.Furthermore,these hydrogels show some smart stimuliresponsive behaviors triggered by pH,temperature,light,electricity and magnetism.Hopefully,these hydrogels derived from natural polymers with inherent biodegradation and biocompatibility have great application potential in the fields of biomedicine,tissue engineering,soft robots and bio-machine.     

Structural optimization of highly branched thermally responsive polymers as a means of controlling transition temperature

Highly branched “smart” polymers have emerged as a unique class of polymers with wide‐ranging applications. Poly(N‐isopropylacrylamide) (pNIPAAm) is at the forefront of stimuli‐responsive polymers; however, few transition temperature‐modification methods of linear pNIPAAm have been explored in highly branched systems. In this study, the three primary techniques of transition temperature modification of linear pNIPAAm are investigated for their efficacy on highly branched polymers. Of these techniques, cosolvent‐mediated tacticity control demonstrates an effect opposite of that which is expected. Temperature transition control via end‐group modification shows a marked decrease in efficacy in highly branched systems, despite highly branched systems having more end groups per polymer. Copolymerization with hydrophilic comonomers exhibits varying changes in efficacy compared to linear analogs, lending insights into the specific effects on the structured water surrounding the copolymer. While copolymerization proved to be most versatile in changing the transition temperature, all of the techniques showed interesting secondary effects. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

New approach for chiral separation: from polysaccharide-based materials to chirality-responsive polymers

Chiral separation that is closely related to daily life is a meaningful research. Polysaccharide-(e.g., cellulose, amylose derivatives) based chiral packing materials afford powerful chiral stationary phases(CSPs) toward a broad range of racemic compounds. However, considering the explosive growth of specific chiral drugs, the separation efficiencies of these CSPs need further improvement, which calls for new approaches and strategies. Smart polymers can change their physical or chemical properties dynamically and reversibly according to the external stimuli(e.g., thermo-, pH, solvent, ion, light, critical parameters for chromatographic separation) exerted on them, subsequently resulting in tunable changes in the macroscopic properties of materials. In addition to their excellent controllability, the introduction of chiral characteristics into the backbones or side-chains of smart polymers provides a promising route to realize reversibly conformational transition in response to the chiral analytes. This dramatic transition may significantly improve the performance of materials in chiral separation through modulating the enantioselective interactions between materials and analytes. With the help of chirality-responsive polymers, intelligent and switchable CSPs could be developed and applied in column-liquid chromatography. In these systems, the elution order or enantioselectivity of chiral drugs can be precisely modulated, which will help to solve many challenging problems that involve complicated enantiomers. In this paper we introduce some typical examples of smart polymers that serve as the basis for a discussion of emerging developments of CPSs, and then briefly outline the recent CSPs based on natural and certain synthetic polymers.     

Hybridization of inorganic nanoparticles and polymers to create regular and reversible self-assembly architectures

Inorganic nanoparticles (NPs) with diversified functionalities are promising candidates in future optoelectronic and biomedical applications, which greatly depend on the capability to arrange NPs into higher-order architectures in a controllable way. This issue is considered to be solved by means of self-assembly. NPs can participate in self-assembly in different manners, such as smart self-organization with blended molecules, as the carriers of host molecules for assembly and disassembly with guest molecules, as netpoints to endow the architectures specific functionalities, and so forth. To enhance the structural stability of the as-prepared assembly architectures, polymers have been utilized to create NP-polymer composites. Meanwhile, such a strategy also demonstrates the possibility of integrating the functionalities of NPs and/or polymers by forming regular architectures. The emerging interest in the current optoelectronic and biological areas strongly demands intelligent nanocomposites, which are produced by combination of the excellent functionalities of NPs and the responsiveness of polymers. On the basis of the recent progress in fabricating NP-polymer composites, this critical review summarizes the development of new methods for fabricating regular self-assembly architectures, highlights the reversible assembly and disassembly behavior, and indicates the potential applications.     

Stimulus responsive fluorescent hyperbranched polymers and their applications

Fluorescent hyperbranched polymers (FHBPs), which combine the versatile fluorescent property with unique characteristics of hyperbranched architecture, are desirable candidates for stimulus responsive materials. This review demonstrates the structure and environment-dependent emission behaviors of a series of FHBPs. AEE active FHBPs showing opposite performance to ACQ effect are used to sensitively detect explosives and a superamplification effect is found. Specially designed FHBPs can complex with metal ions, leading to fluorescence turn-off due to complex quenching effect. The protonation of amino-containing FHBPs exhibits pH-dependent fluorescence responses to solution acidity. Some FHBPs containing responsive moieties are photo- and thermo-sensitive, and show potential applications as smart materials.     

Responsive polymers for analytical applications: A review

Stimuli-responsive polymers are capable of translating changes in their local environment to changes in their chemical and/or physical properties. This ability allows stimuli-responsive polymers to be used for a wide range of applications. In this review, we highlight the analytical applications of stimuli-responsive polymers that have been published over the past few years with a focus on their applications in sensing/biosensing and separations. From this review, we hope to make clear that while the history of using stimuli-responsive polymers for analytical applications is rich, there are still a number of directions to explore and exciting advancements to be made in this flourishing field of research.     

The magic of integration:Exploring the construction of dithienylethene-based infinite coordination polymers and their synergistic effect for gaseous ammonia probe applications

Infinite coordination polymers are recognized as excellent platform for functionalization.Dithienylethene motifs,which are one of the most attractive functional moieties,were incorporated into an infinite coordination polymer,to deliver a‘‘smart’’porous material that can response to external stimuli.The obtained dithienylethene-based infinite coordination polymers(named Cu-DTEDBA)share the advantages of both infinite coordination polymers(porosity and stability)and dithienylethene motifs(photochromism).The physical and chemical properties of Cu-DTEDBA were characterized by FTIR,TEM,SEM,XRD,TGA,UV–vis,EDX and BET.Moreover,the combination of dithienylethene and infinite coordination polymers gives rise to a synergistic effect,which induces functional behaviors of ammonia sensor applications.Both open and closed forms of Cu-DTEDBA exhibit distinct colorimetric change upon exposure to gaseous ammonia,which is not observed in dithienylethene free molecules.     

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。     

智能高分子表面的设计及其在生物医学中的应用

一般高分子材料表面对外界刺激反应性较弱,但利用一些化学或物理方法可提高其响应性,使其智能化。本文介绍了近年来智能高分子表面的几种设计思路、响应机理及其在生物医用材料方面的应用,并且提出了今后的发展趋势。     

Novel pH‐sensitive polymers containing sulfonamide groups

Novel pH‐sensitive polymers were synthesized by copolymerizing a monomer derivatized from 4‐amino‐N‐[4,6‐dimethyl‐2‐pyrimidinyl]benzene sulfonamide with N,N‐dimethylacrylamide. The linear copolymers showed pH‐sensitive solubility, while chemically crosslinked hydrogels exhibit a relatively sharp transition in swelling around physiological pH. These changes were found to be reversible. By varying the type of sulfonamide and the copolymer composition, a new class of pH‐sensitive polymers with a broad range of transition pH can be synthesized.     

Structural phenomena in polymers arising at low temperatures and by the action of high forces

New structural phenomena which can be produced in polymers at low temperatures or by the action of high forces are described and discussed. Experimental evidence supports the argument that the deformation of polymers can develop not only as a result of conformational changes of the macromolecules proper but also by transformation of more complex structural formations. The consequence of this phenomenon is the possibility of large deformations far below the glass-transition temperature in a crystalline polymer with well-developed supermolecular structure. This type of deformation takes place without molecular orientation. Another phenomenon discussed is the sharp change of supermolecular structure in crystalline polymers caused by the action of a shock wave. These effects ought to be connected with an energetic rather than entropic deformation mechanism because the transformations occur at a supermolecular level. Thus, there can be two extreme types of deformation processes: the well-known conformation changes that occur at a molecular level, and the deformation of supermolecular structures. Examples of the pure form of the latter type of mechanism obtained under extreme conditions are given.     

Water-soluble polymers for hostile environment enhanced oil recovery applications

This paper describes polymerization and properties of a number of water-soluble polymers suitable for enhanced oil recovery applications. The polymers described here can tolerate long-term exposure to hostile environment conditions of elevated temperatures and high salinity and hardness levels encountered in deeper petroleum reservoirs. The stable polymers reported here, in principle contain two or more of the following monomers: acrylamide, N-vinyl-2-pyrrolidone, sodium 2-acrylamido-2-methylpropanesulfonate and N,N-dimethylacrylamide in proper ratios. The polymers reported here can be used directly to increase the viscosity of the injected water and consequently reducing its mobility to recover additional oil from petroleum reservoirs. Alternatively, these polymers can be used in combination with a suitable crosslinker to produce gels in-situ to block high permeability channels or fractures under hostile environment applications.     

Self-immolative polymers

Smart polymers are special kinds of polymeric molecules that respond to external stimuli. We have developed a novel smart polymer designed to sequentially disassemble into its building blocks upon initiation by a triggering event at the polymer head. The polymer structure is based on a polyurethane backbone that disassembles through a domino-like, 1,6-elimination and decarboxylation reactions. We synthesized a self-immolative polymer that amplifies a single cleavage reaction into multiple release of fluorogenic molecules and confirmed the head-to-tail disassembly concept. These polymers can be used to prepare highly sensitive molecular sensors with large signal-to-noise ratios. The sensors should be useful for the detection of a wide range of biological and chemical activities through use of the appropriate trigger at the polymer head.