Hydrogels of Thermoreversible Comb‐Polymers Exhibit Increased Resistance for Dissolution

The N‐isopropylacrylamide (NiPAM) polymers exhibit thermoreversible properties in aqueous solutions. The resiliency of NiPAM hydrogels is believed to influence the outcome when the polymers are utilized in biomedical applications. To determine the influence of polymer architecture on hydrogel resiliency, polymers of NiPAM, methyl methacrylate (MMA) and acrylic acid were synthesized as random polymers and as comb polymers, where MMA was incorporated as side‐chains. Random polymers exhibited a Lower Critical Solution Temperature (LCST) that decreased in proportion to MMA content in polymers. The LCST of comb polymers was not dependent on MMA content or the length of MMA side‐chain (between 3.0 and 10.1 kD). Whereas low molecular weight (～100 kD) random polymers did not form intact gels, comb‐polymers of equivalent molecular weight were capable of forming intact gels. Gel resiliency, as determined by propensity of hydrogels to dissolve upon cooling, was improved when the molecular weight of comb‐polymers was increased but the length of the MMA side‐branch did not influence the gel resiliency. We conclude that hydrogel dissolution was dependent on polymer architecture as well as the polymer molecular weight.     

Progress with Light‐Emitting Polymers

Light‐emitting polymers have been studied intensively as materials for light‐emitting diodes (LEDs). Here research efforts toward developing these materials for commercial applications are reviewed. The Figure shows the preferred two‐layer device structure for commercial polymer LEDs as well as polyfluorene, one of the polymers discussed.     

Dendritic Gels—Many Arms Make Light Work

Dendrimers and dendrons are a unique class of molecular‐scale building blocks for the construction of nanostructured materials. This article provides an accessible overview of the ways in which the unique architectural feature of molecular‐scale branching can endow gel‐phase materials with tunability and a high density of functionality. This makes these structures ideal for the construction of multiply crosslinked covalent gels, and also for the self‐assembly of multiply bound non‐covalent (supramolecular) gels. The unique properties and potential applications of these types of material are discussed.     

Hydrophobic Hydrogels with Fruit‐Like Structure and Functions

Normally, a polymer network swells in a good solvent to form a gel but the gel shrinks in a poor solvent. Here, an abnormal phenomenon is reported: some hydrophobic gels significantly swell in water, reaching water content as high as 99.6 wt%. Such abnormal swelling behaviors in the nonsolvent water are observed universally for various hydrophobic organogels containing omniphilic organic solvents that have a higher affinity to water than to the hydrophobic polymers. The formation of a semipermeable skin layer due to rapid phase separation, and the asymmetric diffusion of water molecules into the gel driven by the high osmotic pressure of the organic solvent–water mixing, are found to be the reasons. As a result, the hydrophobic hydrogels have a fruit‐like structure, consisting of hydrophobic skin and water‐trapped micropores, to display various unique properties, such as significantly enhanced strength, surface hydrophobicity, and antidrying, despite their extremely high water content. Furthermore, the hydrophobic hydrogels exhibit selective water absorption from concentrated saline solutions and rapid water release at a small pressure like squeezing juices from fruits. These novel functions of hydrophobic hydrogels will find promising applications, e.g., as materials that can automatically take the fresh water from seawater.     

Cyclodextrin Insulation Prevents Static Quenching of Conjugated Polymer Fluorescence at the Single Molecule Level

Conjugated polymers (CPs) are promising materials for fluorescence imaging application. However, a significant problem in this field is the unexplained abnormally low fluorescence brightness (or number of fluorescence photons detected per one excitation photon) exhibited by most of CP single chains in solid polymer hosts. Here it is shown that this detrimental effect can be fully avoided for short chains of polyfluorene‐bis‐vinylphenylene (PFBV) embedded in a host polymer matrix of PMMA, if the conjugated backbone is insulated by cyclodextrin rings to form a polyrotaxane (PFBV‐Rtx). Fluorescence kinetics and quantum yields are measured for the polymers in liquid solutions, pristine films, and solid PMMA blends. The fluorescence brightness of PFBV‐Rtx single chains dispersed in a solid PMMA is very close to that expected for a chain with 100% fluorescence quantum yield, while the unprotected PFBV chains of the same length possess 4 times lower brightness. Despite this, the fluorescence decay kinetics are the same for both polymers, suggesting the presence of static or ultrafast fluorescence quenching in the unprotected polymer. About 80% of an unprotected PFBV chain is estimated to be completely quenched. The hypothesis is that the cyclodextrin rings prevent the quenching by working as ‘bumpers’ reducing the mechanical forces applied by the host polymer to the conjugated backbone and help retaining its conformational freedom. While providing a recipe for making CP fluorescence bright at the single‐molecule level, these results identify a lack of fundamental understanding in the community of the influence of the environment on excited states in conjugated materials.     

Some Remarks on the Viscometric Behaviour of the Systems Couplers-Gelatin and Couplers-Synthetic Polymers

Some aspects of the mechanism of the interactions between nondiffusing couplers and gelatin or hydrophilic synthetic polymers were investigated by viscometry, studying (a) the role played by the polymer; (b) the effect of the solvent; (c) the influence of operative factors.

The interactions between the polymers and the couplers examined depended on the type, molecular size and structure of the polymer and on the chemical structure of the coupler. In most cases a threshold polymer concentration was found, above which the interactions began to be evident.

Polar surface active solvents seem to interact with the coupler aliphatic side chain, hindering the coiling up of the polymer- coupler aggregates, while pre-warming of the samples hinders the building up of intermolecular aggregates.

An ageing effect of the polymer-coupler solutions was detected, which probably means that the aggregates undergo some structural and configurational changes during the storage time.     

Polymerization in sodium silicate solutions: a fundamental process in geopolymerization technology

Geopolymerization is an innovative technology that can transform several solid aluminosilicate materials into useful products called geopolymers or inorganic polymers. Although the geopolymerization mechanism is not well understood, the most proposed mechanism includes four parallel stages: (a) dissolution of solid aluminosilicate materials in alkaline sodium silicate solution, (b) oligomerization of Si and/or Si–Al in aqueous phase, (c) polymerization of the oligomeric species, and (d) bonding of undissolved solid particles in the polymer. It is obvious that polymerization in sodium silicate solutions comprises a fundamental process in geopolymerization technology. Therefore, this article aims at studying experimentally the polymerization stage in synthetic pure sodium silicate solutions. The structure of sodium silicate gels as a function of the SiO₂/Na₂O molar ratio is examined and their hardness as well as hydrolytic stability are determined. In addition, the effect of aluminum incorporation in the hydrolytic stability of these gels is also examined. Finally, the structure of sodium silicate and aluminosilicate gels is correlated to the measured properties drawing very useful conclusions that could be applied on geopolymerization technology.     

Hydrogels with the ordered structures

A water-swollen hydrogel with a molecularly-ordered structure was prepared by copolymerizing acrylic acid and acrylic monomer containing hydrophobic long alkyl or mesogenic moiety. The gels with a long alkyl side chain formed the crystalline structure and undergo the reversible order–disorder transition with change in temperature or solvent composition which accompanied a dramatic change in Young’s modulus. These gels exhibited such chemomechanical behaviors as the shape memory and the rotational motility on the water surface. On the other hand, the gels with the mesogenic side chain formed the liquid crystalline structure with polymorphism in water, and mesophase diagram was established by changing copolymer composition and water content. Mechanism of these structural and chemomechanical behaviors has been explained in terms of order–disorder transition.     

Hydrogels with the ordered structures

A water-swollen hydrogel with a molecularly-ordered structure was prepared by copolymerizing acrylic acid and acrylic monomer containing hydrophobic long alkyl or mesogenic moiety. The gels with a long alkyl side chain formed the crystalline structure and undergo the reversible order–disorder transition with change in temperature or solvent composition which accompanied a dramatic change in Young's modulus. These gels exhibited such chemomechanical behaviors as the shape memory and the rotational motility on the water surface. On the other hand, the gels with the mesogenic side chain formed the liquid crystalline structure with polymorphism in water, and mesophase diagram was established by changing copolymer composition and water content. Mechanism of these structural and chemomechanical behaviors has been explained in terms of order–disorder transition.     

Photoaddressable Polymers for Optical Data Storage

Photoaddressable polymers (PAPs) are side‐chain copolymer systems functionalized with azobenzene chromophores and mesogenic side groups. They show very large birefringence values after illumination with polarized light. The molecular mechanisms involved are photoinduced isomerization cycles of the azo side groups, which induce strong molecular reorientations (cooperative motion of light‐absorbing azobenzene chromophores and non‐absorbing mesogenic groups). Due to the long‐term and high‐temperature stability of their light‐induced birefringence, PAPs are very promising recording materials for optical data storage applications such as high‐capacity DVDs and holographic memory.     

Self‐Assembly of Hyperbranched Polymers and Its Biomedical Applications

Hyperbranched polymers (HBPs) are highly branched macromolecules with a three‐dimensional dendritic architecture. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. In this paper, the recent developments in HBP self‐assembly and their biomedical applications have been comprehensively reviewed. Many delicate supramolecular structures from zero‐dimension (0D) to three‐dimension (3D), such as micelles, fibers, tubes, vesicles, membranes, large compound vesicles and physical gels, have been prepared through the solution or interfacial self‐assembly of amphiphilic HBPs. In addition, these supramolecular structures have shown promising applications in the biomedical areas including drug delivery, protein purification/detection/delivery, gene transfection, antibacterial/antifouling materials and cytomimetic chemistry. Such developments promote the interdiscipline researches among surpramolecular chemistry, biomedical chemistry, nano­technology and functional materials.     

Time-resolved electrostatic force microscopy of polymer solar cells

Blends of conjugated polymers with fullerenes, polymers, or nanocrystals make promising materials for low-cost photovoltaic applications. Different processing conditions affect the efficiencies of these solar cells by creating a variety of nanostructured morphologies, however, the relationship between film structure and device efficiency is not fully understood. We introduce time-resolved electrostatic force microscopy (EFM) as a means to measure photoexcited charge in polymer films with a resolution of 100 nm and 100 micros. These EFM measurements correlate well with the external quantum efficiencies measured for a series of polymer photodiodes, providing a direct link between local morphology, local optoelectronic properties and device performance. The data show that the domain centres account for the majority of the photoinduced charge collected in polyfluorene blend devices. These results underscore the importance of controlling not only the length scale of phase separation, but also the composition of the domains when optimizing nanostructured solar cells.     

Mechanochromic Photonic Gels

Polymer gels are remarkable materials with physical structures that can adapt significantly and quite rapidly with changes in the local environment, such as temperature, light intensity, electrochemistry, and mechanical force. An interesting phenomenon observed in certain polymer gel systems is mechanochromism – a change in color due to a mechanical deformation. Mechanochromic photonic gels are periodically structured gels engineered with a photonic stopband that can be tuned by mechanical forces to reflect specific colors. These materials have potential as mechanochromic sensors because both the mechanical and optical properties are highly tailorable via incorporation of diluents, solvents, nanoparticles, or polymers, or the application of stimuli such as temperature, pH, or electric or strain fields. Recent advances in photonic gels that display strain‐dependent optical properties are discussed. In particular, this discussion focuses primarily on polymer‐based photonic gels that are directly or indirectly fabricated via self‐assembly, as these materials are promising soft material platforms for scalable mechanochromic sensors.     

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self‐Assemblies

Self‐assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self‐assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self‐assemblies made from a water‐soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer‐embedded self‐assembled architectures are investigated by combining small‐angle neutron and X‐ray scattering, coarse‐grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar‐to‐lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. This study shows promise for enabling more flexibility in processing and utilizing water‐soluble conjugated polymers in aqueous solutions for self‐assembly based fabrication of stimuli‐responsive nanostructures and sensory materials.     

具有光学活性高性能高分子材料的研究进展

旋光性聚合物可以使通过它的偏振光发生偏转,在手性识别和对映体拆分、手性催化剂、液晶、生物医药、光学开关和非线性光学等领域展现出良好的应用前景。本文综述了几种利用旋光性单体缩聚合成具有光学活性高分子材料的方法,对所得聚合物的热稳定性、可溶性、旋光性等主要性能进行分析比较,得到一系列重要的结论,并对其影响机理进行讨论。在此...     

Recent Advances in Conjugated Polymer Materials for Disease Diagnosis

The extraordinary optical amplification and light‐harvesting properties of conjugated polymers impart sensing systems with higher sensitivity, which meets the primary demands of early cancer diagnosis. Recent advances in the detection of DNA methylation and mutation with polyfluorene derivatives based fluorescence resonance energy transfer (FRET) as a means to modulate fluorescent responses attest to the great promise of conjugated polymers as powerful tools for the clinical diagnosis of diseases. To facilitate the ever‐changing needs of diagnosis, the development of detection approaches and FRET signal analysis are highlighted in this review. Due to their exceptional brightness, excellent photostability, and low or absent toxicity, conjugated polymers are verified as superior materials for in‐vivo imaging, and provide feasibility for future clinical molecular‐imaging applications. The integration of conjugated polymers with clinical research has shown profound effects on diagnosis for the early detection of disease‐related biomarkers, as well as in‐vivo imaging, which leads to a multidisciplinary scientific field with perspectives in both basic research and application issues.     

Light‐Emitting Polythiophenes

Polythiophenes are one of the most important classes of conjugated polymers, with a wide range of applications, such as conducting films, electrochromics, and field‐effect transistors, which have been the subject of a number of older and more recent reviews. Much less attention has been paid to the light‐emitting properties of this class of materials, although their unique properties present a number of opportunities unavailable from more popular polymeric light emitters such as polyfluorene or poly(p‐phenylene vinylene). This article reviews achievements to date in applications of thiophene‐based polymers and oligomers as electroluminescent materials. We demonstrate the basic principles of controlling the optical properties of polythiophenes through structural modifications and review the most important light‐emitting materials created from thiophene derivatives. Special attention is paid to consequences of structural variations on the performance of light‐emitting diodes fabricated with these materials.     

Self‐Assembled Peptide–Polyfluorene Nanocomposites for Biodegradable Organic Electronics

Based on self‐assembly and mimicking strategies occurring in nature, peptide nanomaterials play a unique role in a new generation of hybrid materials for the electronics of the 21st century. This report describes the functionalization of diphenylalanine (FF)‐based micro/nanostructures with blue‐emitting conducting polymers of the polyfluorene (PF) family. The FF:PF polymer nanocomposites are synthesized by a liquid‐vapor phase method. Electron microscopy images reveal di‐octyl‐substituted PF (PF8) to bind better to the FF micro/nanotubes in comparison with ethyl‐hexyl PF (PF2/6), which influences its optical properties. Molecular dynamics simulations of FF nanotubes with monomeric units of PFs show that PF8 favors greater proximity to the grooves on the surface of the nanotubes due to a higher van der Waals interaction energy compared to PF2/6. The FF:PF nanocomposites are further utilized in light‐emitting diodes. Biodegradability tests from FF:PF8 nanocomposite films show more than 80% weight loss in 2 h by enzymatic action compared to PF8 pristine films, which do not degrade. Self‐assembly of FF nanostructures with organic semiconductors opens up a new generation of biocompatible and biodegradable materials in organic electronics.     

Hybrid Nanocomposite Materials—between inorganic glasses and organic polymers

The sol–gel process, with its associated mild conditions, offers a new approach to the synthesis of composite materials with domain sizes approaching the molecular level. Transparent organic–inorganic composites can be prepared by dissolving preformed polymers into sot–gel precursor solutions, and then allowing the tetraalkyl orthosilicates to hydrolyze and condense to form glassy SiO₂ phases of different morphological structures. Alternatively, both the organic and inorganic phases can be simultaneously formed through the synchronous polymerization of the organic monomer and the sol–gel precursors. Depending upon such factors as the structures of the organic and inorganic components, the phase morphology, the degree of interpenetration, and the presence of covalent bonds between the phases, the properties of these composites can vary greatly and range from elastomeric rubbers to high–modulus materials.     

非线性光学聚合物材料的研究进展

非线性光学聚合物是新型的具有很高实用价值的功能材料，在光电子信息领域具有广阔的应用前景。文中简要介绍了非线性光学理论和极化原理，综述了非线性光学聚合物材料的研究现状及进展，首重阐述了掺杂型、侧主链型、交联型及共轭型等非线性光学聚合物的结构与性能，展望了今后的研究方向。