(Bio)polymeric Hydrogels as Therapeutic Agents

Hydrogels derived from both natural and synthetic polymers have gained significant scientific attention in recent years for their potential use as biomedical materials to treat human diseases. While a great deal of research efforts have been directed towards investigating polymeric hydrogels as matrices for drug delivery systems, examples of such hydrogels exhibiting intrinsic therapeutic properties are relatively less common. Characteristics of synthetic and natural polymers such as high molecular weight, diverse molecular architecture, chemical compositions, and modulated molecular weight distribution are unique to polymers. These characteristics of polymers can be utilized to discover a new generation of drugs and medical devices. For example, polymeric hydrogels can be restricted to the gastrointestinal tract, where they can selectively recognize, bind, and remove the targeted disease-causing substances from the body without causing any systemic toxicity that are associated with traditional small molecule drugs. Similarly hydrogels can be implanted at specific locations (such as knee and abdomen) to impart localized therapeutic benefits. The present article provides an overview of certain recent developments in the design and synthesis of functional hydrogels that have led to several polymer derived drugs and biomedical devices. Some of these examples include FDA-approved marketed products.     

Improvement of Fibre-Matrix-Adhesion of Natural Fibres by Chemical Treatment

Plastics, also called synthetic polymers, are playing an important role in daily living. To raise more applications it is necessary to modify known polymeric systems to reach improved materials/material systems. A possibility to create new optimised materials out of neat polymers is offered by compounding them with different filling material. Besides chemical modification of polymers, mixing, combining or use of different fillers, one possibility is given by the composite technique, whereas the combination of the polymeric matrix and the embedded reinforcement (e.g. fibre) are yielding in optimised materials adjusted to the required properties. Concerning the polymeric matrix, either thermoplastic or thermoset material can be used. In case of the reinforcement, either synthetic (carbon-, glass- or polymeric fibres) or natural fibres are introduced to composites. To obtain an appropriate adhesion of the matrix to the reinforcement system, synthetic fibres are equipped with an avivage. For natural fibres, there are no such materials available and the hydrophilic property of this system surface prevents an adhesion to hydrophobic polymers, as well as to sizings. In this paper, ways are shown to modify the natural fibres via chemical treatment to yield higher physical properties at better adhesion. Also we will explain activities on the use of natural fibres as reaction systems and processing tools as well as the attempt to isolate the different compounds of the neat fibre via selective work-up.     

Ion exchange membranes from poly(2,6-dimethyl-1,4-phenylene oxide) and related applications

Ion exchange membranes (IEMs) play a significant role in fields of energy and environment, for instance fuel cells, diffusion dialysis, electrodialysis, etc. The limited choice of commercially available IEMs has produced a strong demand of fabricating IEMs with improved properties via facile synthetic strategies over the past two decades. Poly(phenylene oxide) (PPO) is considered as a promising polymeric material for constructing practical IEMs, due to its advantages of good physicochemical properties, low manufacturing cost and easy post functionalization. In this review, we present the accumulated efforts in synthetic strategies towards diverse types of PPO-based IEMs. Relation between polymer structures and the resulted features is discussed in detail. Besides, applying IEMs from PPO and its derivatives in fuel cell, diffusion dialysis and electrodialysis is summarized and commented.     

Recycling of waste from polymer materials: An overview of the recent works

Polymer recycling is a way to reduce environmental problems caused by polymeric waste accumulation generated from day-to-day applications of polymer materials such packaging and construction. The recycling of polymeric waste helps to conserve natural resource because the most of polymer materials are made from oil and gas. This paper reviews the recent progress on recycling of polymeric waste form some traditional polymers and their systems (blends and composites) such as polyethylene (PE), polypropylene (PP), and polystyrene (PS), and introduces the mechanical and chemical recycling concepts. In addition, the effect of mechanical recycling on properties including the mechanical, thermal, rheological and processing properties of the recycled materials is highlighted in the present paper.     

Changes in electronic properties of polymeric one-dimensional {[M(CN)2]-}n (M = Au, Ag) chains due to neighboring closed-shell Zn(II) or open-shell Cu(II) ions

A series of d(10) dicyanometallate polymeric compounds were studied by electronic spectroscopy and density functional theory (DFT) calculations. In these materials, the negatively charged one-dimensional (1D) polymeric chains are linked together by [M(en)(2)](2+) (M = Cu(II) and Zn(II); en = ethylenediamine). More than innocent building blocks, the [M(en)(2)](2+) units offer a possible synthetic way to modify electronic properties of the materials. Through its low energy d-d excited state, the d(9) copper(II) ions offer deactivation pathways for the normally emissive dicyanometallate polymer. Deactivation was shown to be specific to the excited state energy.     

Recent progress in conductive polymeric materials for biomedical applications

Advanced polymeric materials undoubtedly constitute one of the most promising classes of new materials due to their intriguing electronic, optical, and redox properties. The incredible progress in this area has been driven by the development of novel synthetic procedures owing to the emergence of nanotechnology and by the large array of applications. In particular, hybridization of polymeric materials with nanomaterials has allowed the production of promising functional materials with tailored properties and functionalities for targeted biomedical applications. Consequently, sufficient researchers have carried out imperative studies on these advanced polymeric materials over the last decade. Beyond scientific and fundamental interest, such advanced materials are conspicuous from technological perspectives as well. In this review, we accentuate the proliferation of advanced polymeric materials in diverse biomedical applications.     

Design, synthesis and photo-cross-linking of a new photosensitive macromonomer from tetra-branched poly(ethylene oxide)s

A general procedure to increase the amount of photoreactive chromophore groups per oligoether chain is presented. In this work, a photoreactive macromonomer with four functionalities was synthesized by a four-step synthetic pathway with high yield. The photochemical behavior of this compound was studied with a view to obtaining polymeric networks. The significant advantage in this strategy is that the preparation of this material has as last operation, the obtaining and processing of polymer as thin film. In this way, the synthetic strategy based on assembling: (i) the polyether chains, (ii) a film forming backbone, and (iii) a photoactive moiety to be used for cross-linking, seems a viable solution to the problem of the continuous processing of materials.     

Covalent Organic Frameworks and Cage Compounds: Design and Applications of Polymeric and Discrete Organic Scaffolds

Porous organic materials are an emerging class of functional nanostructures with unprecedented properties. Dynamic covalent assembly of small organic building blocks under thermodynamic control is utilized for the intriguingly simple formation of complex molecular architectures in one‐pot procedures. In this Review, we aim to analyze the basic design principles that govern the formation of either covalent organic frameworks as crystalline porous polymers or covalent organic cage compounds as shape‐persistent molecular objects. Common synthetic procedures and characterization techniques will be discussed as well as more advanced strategies such as postsynthetic modification or self‐sorting. When appropriate, comparisons are drawn between polymeric frameworks and discrete organic cages in terms of their underlying properties. Furthermore, we highlight the potential of these materials for applications ranging from gas storage to catalysis and organic electronics.     

Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis,Assembly, and Applications

Organically modified cubic polyhedral oligomeric silsesquioxanes (POSS) have attracted increasing attention in the design of novel functional hybrid materials for applications such as porous materials, liquid crystals, semiconductors, high‐temperature lubricants, fuel cells, and lithium batteries. The nanosized POSS moiety can be conveniently modified on the periphery with a variety of functional groups to lead to hybrid materials with desired functions. In addition, suitable mono‐functionalized POSS derivatives can be incorporated into polymers as side chains via various synthetic strategies to offer a wide class of functional polymeric materials with tunable physical properties for targeted applications. In this Focus Review, we aim to summarize the recent developments on the chemistry and applications of POSS‐based molecules and polymers. Moreover, the properties as well as assembly behavior of the POSS‐based functional hybrid materials will be reviewed, and the relationship of the performance of the hybrid materials with the intrinsic nature of the POSS unit will be addressed.     

Organic semiconductors for solution-processable field-effect transistors (OFETs)

The cost-effective production of flexible electronic components will profit considerably from the development of solution-processable, organic semiconductor materials. Particular attention is focused on soluble semiconductors for organic field-effect transistors (OFETs). The hitherto differentiation between "small molecules" and polymeric materials no longer plays a role, rather more the ability to process materials from solution to homogeneous semiconducting films with optimal electronic properties (high charge-carrier mobility, low threshold voltage, high on/off ratio) is pivotal. Key classes of materials for this purpose are soluble oligoacenes, soluble oligo- and polythiophenes and their respective copolymers, and oligo- and polytriarylamines. In this context, micro- or nanocrystalline materials have the general advantage of somewhat higher charge-carrier mobilities, which, however, could be offset in the case of amorphous, glassy materials by simpler and more reproducible processing.     

Synthetic,layered nanoparticles for polymeric nanocomposites (PNCs)

This review discusses preparation and use of the synthetic layered nanoparticles in polymer matrices, i.e., in the polymeric nanocomposites (PNCs). Several types of synthetic or semi‐synthetic layered materials are considered, namely the phyllosilicates (clays), silicic acid (magadiite), layered double hydroxides (LDHs), zirconium phosphates (ZrPs), and di‐chalcogenides. The main advantage of synthetic clays is their chemical purity (e.g. absence of amorphous and gritty contaminants, as well as arsenic, iron, and other heavy metals), white to transparent color that assures reproducibly of brightly colored products, as well as a wide range of aspect ratios, p = 20 to ≤6000. Several large scale production facilities have been established. The synthetic clay and LDH industries are oriented toward big volume markets: catalysis, foodstuff, cosmetics, pharmaceuticals, toiletry, etc. The use of these materials in PNCs is limited to synthetic clays and LDHs, mainly for reinforcement, permeability control, reduction of flammability, and stabilization, e.g. during dehydrohalogenation of chlorinated macromolecules. The use of lamellar ZrPs and di‐chalcogenides is at the laboratory stage of functional polymeric systems development, e.g. for electrically conductive materials, catalysts or support for catalysts, in photochemistry, molecular and chiral recognition, or in fuel cell technologies, etc. Copyright © 2007 John Wiley & Sons, Ltd.     

Nonlinear chemical dynamics in synthetic polymeric systems: motivations and strategies for success

Two motivations for studying nonlinear chemical dynamics with polymeric systems are considered: observing new nonlinear phenomena and developing new materials because of nonlinearities in polymerization processing. Examples from frontal polymerization are given. Three strategies are considered: coupling polymerizations to nonlinear systems such as oscillating reactions, using inherent nonlinearities in polymerization reactions and investigating the effects of polydispersity on known instabilities.     

Synthesis and Sterochemical Studies of Some New Chelate Polymers

The polychelates of bivalent metal ions such as copper, nickel, cobalt, manganese, and zinc have been synthesized from polymeric ligands derived from 4,4′ -dihydroxy-3,3′ -diacetyl biphenyl and 4,4′-diamino diphenyl methane. Elemental, magnetic susceptibility, visible and IR spectra, and thermal properties have been studied. The analytical data suggest the general formula (ML)_n for the polychelates. The polychelates are quite stable but insoluble in common organic solvents.     

Synthesis and Study of Second-order Nonlinear Optical Properties of 3-Substituted-6- (substituted-phenylazo) coumarins

It has attracted a lot of attentions to synthesize and investigate the behaviors of organic second-order nonlinear optical (NLO) materials. [1,2] We have ever reported that acridine derivatives ,[3] 4-substituted-benzylideneoxazol-5(4H)-one[4] and 4,4′-di-styryl-biphenyl derivatives[5] possess good second-order NLO properties. Coumarin derivatives are good organic optical materials and azobenzene derivatives possess a higher second-order nonlinear polarization values, however, there are few reports about the study on the synthetic method, optical behavior, especially,second-order NLO properties of 3-substitued-6-(substituted-phenylazo) coumarin derivatives. Therefore, a series of the following compounds were prepared in order to investigate their NLO behavior.     

Inorganic semiconductors-graphene composites in photo(electro)catalysis: Synthetic strategies,interaction mechanisms and applications

The remarkable physicochemical properties of graphene (GR) and derivatives can be leveraged in the photocatalytic activity of GR-semiconductor photocatalysts. The hitherto state of knowledge on the role of GR in these composite materials is insufficient and leaves many questions unanswered, thus it is imperative to fully understand the interaction mechanisms between GR and inorganic semiconductors. Detailed study and optimization of the features related to the interface are still very much sought to efficiently design photocatalysts targeting their eventual commercialization. This review shows that photocatalytic activity of such composites depends not only on high GR electron mobility and charge transfer, but also on the properties of the interface (such as interface morphology, size, crystal phases and facet, dimensionality of composites, etc.). Focusing on the last advancements in this field, this review analyses the challenges involved in the synthetic strategies of GR-semiconductor photo(electro)catalysts in various applications including pollutant degradation, organic synthesis, hydrogen evolution and photoreduction of carbon dioxide (CO₂). Mechanism of interaction between GR and semiconductors are thoroughly discussed by examining the proposed mechanism in the diverse areas where the composite materials are employed in photo(electro)catalytic processes. In addition, various synthetic and characterization technique available hitherto are presented, since they are pivotal to the understanding of the composites properties (such as morphology, crystal phases and exposed facets, degree of crystallinity, dimensionality etc.), and even to shed more light on interaction mechanisms of the photocatalyst constituents. As a future outlook, it is envisaged that research will not only focus on optimizing GR electrical and chemical properties, yet in the synthesis of GR-semiconductor photocatalysts attention needs also be placed on the properties of the resulting composites, using suitable synthetic methods and proper characterizations to assess their performance.     

Synthesis of highly sulfonated poly(arylene ether sulfone) random (statistical) copolymers via direct polymerization

Novel biphenol‐based wholly aromatic poly (arylene ether sulfones) containing pendant sulfonate groups were prepared by direct aromatic nucleophilic substitution polycondensation of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenyl sulfone (SDCDPS), 4,4′‐dichlorodiphenylsulfone (DCDPS) and biphenol. Copolymerization proceeded quantitatively to high molecular weight in N‐methyl‐2‐pyrrolidinone at 190°C in the presence of anhydrous potassium carbonate. Tough membranes were successfully cast from the control and the copolymers, which had a SDCDPS/DCDPS mole ratio of either 40:60 or 60:40 using N,N‐dimethylactamide; the 100% SDCDPS homopolymer was water soluble. Short‐term aging (30 min) indicates that the desired acid form membranes are stable to 220°C in air and conductivity values at 25°C of 0.110 (40%) and 0.170 S/cm (60%) were measured, which are comparable to or higher than the state‐of‐the art fluorinated copolymer Nafion 1135 control. The new copolymers, which contain ion conductivity sites on deactivated rings, are candidates as new polymeric electrolyte materials for proton exchange membrane (PEM) fuel cells. Further research comparing their membrane behavior to post‐sulfonated systems is in progress.     

New fluorinated aromatic poly(ether-amide)s derived from 2,2′-bis(3,4,5-trifluorophenyl)-4,4′-diaminodiphenyl ether and various dicarboxylic acids

A new class of highly fluorinated aromatic poly(ether-amide)s was prepared through triphenyl phosphite-activated polycondensation of 2,2′-bis(3,4,5-trifluorophenyl)-4,4′-diaminodiphenyl ether (FPAPE) and four dicarboxylic acid comonomers. All the resulting polymers were thoroughly characterized by FT-IR, UV, and NMR spectroscopic methods. The effects of the fluorine atoms directly linked to the lateral phenyl rings as well as fluoro-containing phenyl groups attached to the macromolecular chains on some properties of the polymers were investigated by comparing with poly(ether-amide)s prepared from 4,4′-oxydianiline (4,4′-ODA) and 2,2′-diphenyl-4,4′-diaminodiphenyl ether (PAPE). The FPAPE-derived polymers exhibited excellent solubility in a variety of organic solvents. Results obtained from X-ray studies showed that the presence of the bulky fluoro-containing phenyl groups attached to the chains disrupts their structural order in a great amount, and leads to a decrease in crystallinity extent of the macromolecules. Furthermore, the highly fluorinated polymeric chains showed a significant enhancement in organo-solubility, heat-stability and T_g values when compared to their non-fluorinated counterparts.     

芳杂环聚西佛碱Fe~(2+)配合物的合成及磁性能

以 2 ,2′ 二氨基 4 ,4′ 联噻唑 (DABT) ,2 ,6 二乙酰基吡啶 (DAP)及苯二甲醛为原料合成了三个新型结构的芳杂环聚西佛碱 (PBTAP ,PBTMP ,PBTPP) ,并制备了其相应的Fe2 + 配合物 .利用FTIR确定了聚合物及其配合物的结构 ,借助多功能材料物理特性测量系统 (PPMS :PhysicalPropertyMeasurementSystem)测定配合物的磁性能 ,测试结果表明这三个聚合物的Fe2 + 配合物都是有机软磁体 ,具有相对较高的磁饱和强度 (Ms) ,其中PBTAP Fe2 + 的磁饱和强度为 6 2emu g ,顺磁居里温度 (Tp)达 88K ,且具有S型的磁滞回线 ,此结果表明此配合物在低温下是有机软铁磁体 .     

Smart polymeric materials: emerging biochemical applications

Smart polymeric materials respond with a considerable change in their properties to small changes in their environment. Environmental stimuli include temperature, pH, chemicals, and light. "Smart" stimuli-sensitive materials can be either synthetic or natural. This review discusses the application of smart materials as tools to solve biological problems such as bioseparation, drug delivery, biosensor design, tissue engineering, protein folding, and microfluidics. The goal for these endeavors is to mimic the "smartness" of biological systems and ultimately moderate complex systems such as immune responses at desired levels. The versatility and untapped potential of smart polymeric materials makes them one of the most exciting interfaces of chemistry and biology.     

Thermal degradation kinetics of structurally diverse poly(bispropargyl ethers-bismaleimide) blends

Structurally diverse bispropargyl ethers using resorcinol,quinol,4,4￠-dihydroxy biphenyl,bisphenol-A,4,4￠-dihydroxy diphenyl ketone,4,4￠-dihydroxy diphenylsulphone,trimethyl indane bisphenol and tetramethyl spirobiindane bisphenol were prepared by using phase transfer catalyst.Synthesized materials were separately blended with 4,4￠-bismaleimido diphenyl methane(BMIM)in mole ratios(0.5:0.5).The materials were thermally cured and the structural characterisation and the thermal properties of these cross-linked materials are investigated using Fourier-transform infrared(FTIR)spectrophotometer and thermogravimetric analyzer(TGA).Among the different materials investigated poly MRPE,poly MBPEBPA and poly MSPE show higher onset degradation temperature of 300°C indicating higher thermal stability.The degradation kinetics is investigated using Flynn-Wall-Ozawa(FWO),Vyazovkin(VYZ)and Friedman(FRD)methods.Amongst the various cured materials investigated,the activation energy(Ea-D)values obtained for poly MRPE and poly MKPE were observed to increase continuously froma=0.2 to 0.8 and the values range from 199 kJ/mol to 245 k J/mol and 153 k J/mol to 295 k J/mol respectively.The crosslinked materials resulting from these bispropargyl monomers definitely need more energy for bond cleavage due to the presence of more aromatic units.The volatile products obtained during the thermal degradation of the polymers were analyzed using thermogravimetric-Fourier transform infrared analyses(TG-FTIR).The phenols,substituted phenols,carbon monoxide,carbon dioxide and small amount of aniline were found to be the major products during thermal degradation of these cured blends.