A green chemoenzymatic pathway for the synthesis of conducting polyaniline (PANI) composites is presented. Laccase-catalyzed polymerization in combination with anionic polysaccharides is used to produce polysaccharide/PANI composites, which can be processed into flexible films or coated onto cellulose surfaces. Different polysaccharide templates are assessed, including κ-carrageenan, native spruce O-acetyl galactoglucomannan (GGM), and TEMPO-oxidized cellulose and GGM. The resulted conducting biocomposites derived from natural materials provide a broad range of potential applications, such as in biosensors, electronic devices, and tissue engineering.

Polysaccharide/polyaniline biocomposites are synthesized using a green, chemoenzymatic procedure. Anionic polysaccharides, for example, naturally occurring κ-carrageenan, and TEMPO-oxidized cellulose, are used as templates in laccase-catalyzed polymerization of aniline.

A simple and efficient polymer grafting onto hydrothermal carbonization (HTC)-derived materials is described. The method pertains to the Diels–Alder cycloaddition reaction of furan moieties present on the surface of a HTC material with the maleimide groups stemming from a maleimide protected poly(ethylene glycol) (Me-PEG-MI) by a retro Diels-Alder reaction. The precursor polymer, HTC material, and final product are characterized. Successful grafting is confirmed by elemental analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and dispersion studies.

Facile “graft-to” cycloaddition-mediated polymer functionalization of hydrothermal carbonization (HTC)-derived materials is carried out by use of a dienophile-functionalized polymer. Masked maleimide terminated poly(ethylene glycol) (PEG) is used as a model dienophile containing polymer to graft onto the surface of the HTC material. Analysis of PEGylated carbons (Fourier transform infrared, elemental analysis, X-ray photoelectron spectroscopy, and dispersion studies) all indicate the successful surface modification.

It is known that Polyamide 6 absorbs water in its amorphous phase. The exact composition of the amorphous phase will determine the uptake process. The heterogeneity in the amorphous phase with respect to plasticization by water uptake is quantified in this paper using NMR relaxometry. It is shown that water occupies and plasticizes only a small part (∼6%) of the nylon matrix. This part is located in between the crystalline domains where polymer chain mobility is higher. At low moisture content (<4%) water molecules are tightly bound to the polymer and have the same dynamics. A highly mobile pool of guest-hydrogen nuclei is detected starting at a moisture content of 4%. Here, water is absorbed in clusters and the interaction between the polymer chains and water molecules decreases, leading to decoupling of the dynamics of water and polymer.

How much of the amorphous phase of a nylon-6 film is affected by water at room temperature far below the glass transition temperature and will take part in water transport? In this study nylon films are saturated with H₂O/D₂O and investigated with NMR relaxometry. Furthermore, the relaxation curves reveal that above a moisture content of 4% a mobile type of water molecules is present in the nylon matrix.

Self-assembly of poly(2-vinylpyridine)-block-poly(ϵ-caprolactone) (P2VP-b-PCL) diblock copolymer in the presence of a selective solvent is investigated by transmission electron microscopy and atomic force microscopy. Addition of water into a P2VP-b-PCL solution in N,N-dimethylformamide at 20 °C produces elongated truncated lozenge shaped single crystals of uniform size and shape in large quantities. The single crystals are composed of PCL single-crystal layer sandwiched between two P2VP layers tethered on the top and bottom basal surfaces. The formation of the single crystals is found to depend on the temperature. These findings provide a facile approach to the preparation of uniform single crystals in large quantities.

Single crystals of uniform shape and size in large quantities can be obtained via self-assembly of a coil-crystalline block copolymer by simply adding a selective solvent into the copolymer solution.

The nucleophilic living ring-opening polymerization of N-substituted glycine N-carboxyanhydrides using solid-phase synthesis resins is reported. By variation of experimental parameters, products with near Poisson distributions are obtained. As opposed to reversible deactivation radical polymerization, the living polymerization is demonstrated to be viable to high monomer conversion and through multiple monomer addition steps. Successful preparation of a multiblock copolypeptoid is proof for a highly living and robust character of the solid-phase peptoid polymerization.

Nucleophilic living ring-opening polymerization from solid-phase synthesis resins allows for the synthesis of highly defined polypeptoids. Multi-block copolymers are accessible via the successive monomer addition due to the stable propagating species. This new approach represents the missing link between solid-phase peptoid synthesis and solution-phase living nucleophilic polymerization of polypeptoids.

Polymer hydrogels that are capable of spontaneously healing injury are being developed at a rapid pace because of their great potential in biomedical applications. Here, the self-healing property of tough graphene nanocomposite hydrogels fabricated by using graphene peroxide as polyfunctional initiating and cross-linking centers is reported. The hydrogels show excellent self-healing ability at ambient temperature or even lower temperatures for a short time and very high recovery degrees (up to 88% tensile strength) can be achieved at a prolonged healing time. The healed gels exhibit very high tensile strengths (up to 0.35 MPa) and extremely high elongations (up to 4900%). The strong interactions between the polyacrylamide chains and the graphene oxide sheets are essential to the mechanical strengths of the healed gels.

Graphene oxide composite hydrogels fabricated by using graphene peroxide as polyfunctional initiating and cross-linking centers exhibit excellent self-healing behavior. The healed gels exhibit very high tensile strength (up to 0.35 MPa) and extremely high elongations (up to 4900%).

Utilizing the colorimetric and fluorogenic changes, a system based on polydiacetylenes (PDAs) is developed for the detection of neomycin. The PDA supramolecules polymerized from the mixed liposome composed of N-(3-hydroxyphenyl)pentacosa-10,12-diynamide (PCDA-AP) and pentacosa-10,12-diynoic acid (PCDA) at an optimized ratio of 1:9 display a unique colorimetric change (blue to red) and fluorescent enhancement in the presence of neomycin. The detection limit for neomycin is estimated to be 2.55 × 10⁻⁷ M by the fluorogenic method. The optical changes induced by neomycin can be attributed to the disruption of the hydrogen bonding between phenol and carboxylic acid from PCDA-AP and PCDA.

The polydiacetylene supramolecules polymerized from the mixed liposome composed of N-(3-hydroxyphenyl)pentacosa-10,12-diynamide and pentacosa-10,12-diynoic acid at an optimal ratio of 1:9 display a unique colorimetric change (blue to red) and fluorescent enhancement in the presence of neomycin.

Two emerging material classes are combined in this work, namely polymeric carbon nitrides and microporous polymer networks. The former, polymeric carbon nitrides, are composed of amine-bridged heptazine moieties and showed interesting performance as a metal-free photocatalyst. These materials have, however, to be prepared at high temperatures, making control of their chemical structure difficult. The latter, microporous polymer networks have received increasing interest due to their high surface area, giving rise to interesting applications in gas storage or catalysis. Here, the central building block of carbon nitrides, a functionalized heptazine as monomer, and tecton are used to create microporous polymer networks. The resulting heptazine-based microporous polymers show high porosity, while their chemical structure resembles the ones of carbon nitrides. The polymers show activity for the photocatalytic production of hydrogen from water, even under visible light illumination.

Heptazine-based microporous polymer networks (HMPs) are synthesized by room temperature polycondensation of cyameluric chloride with aromatic diamines. Polymer networks with significant surface area and pore volume are obtained. HMPs are active and stable photocatalysts for the production of hydrogen from water, even under visible light irradiation.

Click chemistry has had a significant impact in the field of materials science over the last 10 years, as it has enabled the design of new hybrid building blocks, leading to multifunctional and responsive materials. One key application for such materials is in the biomedical field, such as gene or drug delivery. However, to meet the functional requirements of such applications, tailored degradability of these materials under biological conditions is critical. There has been an increasing interest in combining click chemistry techniques with a range of degradable or responsive building blocks as well as investigating new or milder chemistries to design click delivery systems that are capable of physiologically relevant degradation. This Feature Article will cover some of the different approaches to synthesize degradable click delivery systems and their investigation for therapeutic release.

The development of click chemistry has provided a versatile toolbox of building blocks for materials assembly, allowing the design of next-generation materials for applications in biomedicine. However, for the effective design of materials for therapeutic applications, it is critical to achieve controlled and/or triggered degradation. This Feature Article highlights the development of degradable click carriers and their investigation in biological conditions.

The straightforward synthesis of a series of poly(thioether)s by photoinduced thiol-ene click polyaddition of α,ω-alkylene thiols is reported. It is found that linear and telechelic poly(thioether)s can be directly obtained from α,ω-alkylene thiols with, for example, alkyl chain length of m = 1,2,3, and 9. The reaction proceeds without additives such as (radical) initiators or metal compounds and can simply be carried out by UV-irradiation of the bulk monomer or monomer solution. Ex situ kinetic studies reveal that the reaction proceeds by a typical a step-growth polyaddition mechanism. As the homologue series of poly(thioether)s are now synthetically accessible, new direct pathways to tailored poly(alkyl sulphoxide)s and poly(alkyl sulfone)s are now possible.

Thiol-ene click polyaddition. α,ω-Alkylene thiols are polymerized to telechelic poly(thioether)s by photoinduced thiol-ene click polyaddition. The poly(thioether)s are found to be linear and semicrystalline. The melting points increase systematically with the count of the main chain methylene groups.

Atom transfer radical polymerization (ATRP) catalyzed by high oxidation state metal salts of FeX₃ is developed for the first time in the absence of both external initiator and reducing agent. Methyl methacrylate (MMA) and styrene are polymerized successfully using FeX₃/Phosphorous ligands with well-controlled molecular weight distributions (<1.5). The molecular weight of the polymers increases with monomer consumption with the progress of time and the polymerization behaviors show a decent ATRP trend. Activators and initiators are suggested to generate in situ by the addition reaction of MMA and one equivalent of FeX₃. The PMMA synthesized from without-initiator system is characterized by ¹H, ¹³C and DEPT (distortionless enhancement by polarization transfer nuclear magnetic resonance) nuclear magnetic resonance spectroscopy. Chain extension and copolymerization experiments prove the livingness of the obtained polymer.

Methyl methacrylate (MMA) is polymerized successfully using FeX₃/Phosphorous ligands in the absence of external alkyl halide initiators and reducing agents. The study shows that the radical could be formed by an addition of MMA with one equivalent of FeX₃, which may help to initiate the polymerization. The molecular weight of the polymer increases with monomer consumption with a decent atom transfer radical polymerization trend.

This review deals with nanoporous materials made from the self-assembly of block copolymers with a special interest in the chemical functions covering the surface of their nanopores. A detailed overview of the existing methods and strategies to generate well-defined organic functional groups covering the surface of the pore walls is provided. This further enables to finely tune the affinity of the pore walls and to perform well-defined chemical reactions onto them, which is essential for further dedicated applications.

The different strategies to prepare nanoporous materials with well-defined chemical functionalities at the pore walls from block copolymers are discussed in this Feature Article.

A facile method for the synthesis of polyaniline–polypyrrole composite materials with network morphology is developed based on polyaniline nanofibers covered by a thin layer of polypyrrole via vapor phase polymerization. The hydrogen storage capacity of the composites is evaluated at room temperature exhibits a twofold increase in hydrogen storage capacity. The HCl-doped polyaniline nanofibers exhibit a storage capacity of 0.46 wt%, whereas the polyaniline–polypyrrole composites could store 0.91 wt% of hydrogen gas. In addition, the effect of the dopant type, counteranion size, and the doping with palladium nanoparticles on the storage properties are also investigated.

Entangled polyaniline nanofibers are shown to be a good support for the synthesis of conducting polyaniline–polypyrrole composites with network morphology. The thin layer of polymerized polypyrrole covering the nanofibers improves the hydrogen storage capacity of the novel polymer composites.

The use of the molecular imprinting technique to produce polymers with high specificity for a given “molecular template” has undergone a rapid and expansive evolution since the inception of the idea over half a century ago. It was only a matter of time before the seemingly inevitable “marriage” of this concept with another modern research obsession, the generation of “smart” polymers, capable of reacting quickly, accurately and reproducibly to changes in their environment. Many advances have since been made, concerning the quality and diversity of these systems and polymers responsive to temperature, pH and a host of other environmental cues now exist. This article provides a succinct overview of the process and outcomes of “smart” molecular imprinting, followed by a detailed assessment of recent developments and applications in such field.

The field of molecularly imprinted polymers (MIPs) is rapidly evolving and of increasing importance to our society. The “smart” MIPs are the intellectual MIP systems that show tunable response(s) to external stimuli, such as temperature, pH, light, ionic strength, biomolecule, and magnetic fields, having considerable potentials and applications across a wide range of fields.

1-Vinyl-2-(hydroxymethyl)imidazole (2) is synthesized by a procedure described in the literature. Corresponding copolymers with upper critical solution temperature (UCST)-type transitions in water and high-glass transition temperatures (T_g) are prepared by free radical copolymerization with N-vinylimidazole (1). Depending on the copolymer composition, the cloud point can be varied between 19 and 41 °C. As the copolymer composition is identical with the monomer feed ratio, the cloud point can be easily tuned in the desired range. Furthermore, a distinctive pH-dependence and salt effect can be observed.

Copolymers (3a–f) of 1-vinyl-2-(hydroxymethyl) imidazole (2) and N-vinylimidazole (1) are synthesized. The copolymers show upper critical solution temperatures from a certain ratio of monomer 2. The cloud point depends on the copolymer composition and is easily tunable. In addition, the cloud point is measured at different pH values to emphasize the assumption that hydrogen bonding is responsible for the critical solution behavior.

An unprecedented strategy for the high-efficiency preparation of the cyclic polymers is developed. In this strategy, the atom transfer radical polymerization, the substitution of chain-end halide by azide group and Cu-catalyzed alkyne–azide cyclization, i.e., the frequently used three separated steps for the preparation of cyclic polymers, are integrated into a one-pot reaction by the introduction of a “regulator”. The kernel of this novel strategy is the utilization of the different rates between the competitive ATRP propagation and S_N2 substitution of a tertiary-carbon halogen and secondary-carbon halogen. 0.55 g (yield = 59%) cyclic poly(methyl methacrylate) is obtained from 3.0 mL reaction solution. This work proposed a high-efficiency and bright promising strategy for the preparation of cyclic polymer, which would evoke more research interests on cyclic polymer.

A strategy of one-pot ATRP/substitution/CuAAC cyclization for the synthesis of cyclic polymers of methacrylates is developed by the introduction of a regulator. 0.55 g of cyclic poly(methyl methacrylate) (yield = 59%) is obtained from 3.0 mL of reaction solution. This high efficiency and promising strategy for the preparation of cyclic polymers of methacrylates would evoke more research interests on cyclic polymer.

A combination of high internal phase emulsion (HIPE) templating and additive manufacturing technology (AMT) is applied for creating hierarchical porosity within an acrylate and acrylate/thiol-based polymer network. The photopolymerizable formulation is optimized to produce emulsions with a volume fraction of droplet phase greater than 80 vol%. Kinetic stability of the emulsions is sufficient enough to withstand in-mold curing or computer-controlled layer-by-layer stereolithography without phase separation. By including macroscale cellular cavities within the build file, a level of controlled porosity is created simultaneous to the formation of the porous microstructure of the polyHIPE. The hybrid HIPE–AMT technique thus provides hierarchically porous materials with mechanical properties tailored by the addition of thiol chain transfer agent.

A combination of high internal phase emulsion (HIPE) templating and layer-by-layer photopolymerization within computer-guided manufacturing technology is applied for the preparation of hierarchically porous polymeric structures with four levels of porosity. Objects with predetermined macroscopical structure and internal polyHIPE architecture are formed, exhibiting pores from micro- to macroscopic in size.

Biotinylated polymers with side-chain aldehydes were prepared for use as multifunctional scaffolds. Two different biotin-containing chain transfer agents (CTAs) and an aldehyde-containing monomer, 6-oxohexyl acrylate (6OHA), are synthesized. Poly(ethylene glycol) methyl ether acrylate (PEGA) and 6OHA are copolymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of the biotinylated CTAs. The resulting polymers are analyzed by GPC and¹H NMR spectroscopy. The polymer end groups contained a disulfide bond, which could be readily reduced in solution to remove the biotin. Reactivity of the aldehyde side chains is demonstrated by oxime and hydrazone formation at the polymer side chains, and conjugate formation of fluorescently labeled polymers with streptavidin is investigated by gel electrophoresis.

Cleavable aldehyde side chain, biotin end-group polymers are prepared by reversible addition–fragmentation chain transfer polymerization. The synthesis of short and extended linker disulfide-containing biotin chain transfer agents and aldehyde-functionalized monomers is described. Additionally, the cleavability of streptavidin polymer conjugates with fluorescent reporters conjugated through the aldehyde bond is shown.

Near-infrared (NIR) polymer light-emitting diodes (PLEDs) based on a fluorene–dioctyloxyphenylene wide-gap host material copolymerized with a low-gap emitter are presented. Various loadings (1, 2.5, 10, 20 mol%) of the low-gap emitter are studied, with higher loadings leading to decreased efficiencies likely due to aggregation effects. While the 10 mol% loading resulted in almost pure NIR emission (>99.6%), the 1 mol% loading yielded optimum device performance, which is among the best reported to date for a unblended single-layer pure polymer emitter, with an external quantum efficiencies of 0.04% emitting at 909 nm. The high spectral purity of the PLEDs combined with their performance support the methodology of copolymerization as an effective strategy for developing NIR PLEDs.

Polymer light-emitting diodes are fabricated by copolymerizing a low-bandgap donor–acceptor–donor segment in various loadings with a high-gap fluorene dialkoxybenzene host. By controlling the loadings, emission wavelength and efficiency could be controlled, resulting in an emission at ≈909 nm with an external quantum efficiencies of almost 0.04%, which is one of the best at this wavelength for a single-layer pure polymer emitter.

Intrinsically glucoside-based microspheres are prepared in olive oil via a water in oil inverse suspension polymerization. The microspheres are characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) microscopy, and X-ray photoelectron spectroscopy (XPS), evidencing the intrinsic glucose character of the spheres. A novel boronic acid fluorescent molecule was subsequently conjugated to the microspheres in an aqueous environment, exhibiting the spatial and uniform distribution of glucoside as well as the affinity of the microspheres to bind with boron, evidenced via fluorescence spectroscopy measurements.

Intrinsically glucoside-based microspheres are prepared in olive oil via a water in oil inverse suspension polymerization. The microspheres are characterized by scanning electron microscopy, Fourier transform infrared microscopy, and X-ray photoelectron spectroscopy. A novel boronic acid fluorescent molecule is subsequently conjugated to the microspheres exhibiting the spatial distribution of glucoside as well as the affinity of the microspheres to bind with boron.

Metallo-supramolecular core cross-linked (CCL) micelles are fabricated from terpyridine-functionalized double hydrophilic block copolymers, poly(2-(2-methoxyethoxy)ethyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate-co-4′-(6-methacryloxyhexyloxy)-2,2′:6′,2″-terpyridine) [PMEO₂MA-b-P(DEA-co-TPHMA)] via the formation of bis(terpyridine)ruthenium(II) complexes. These metallo-supramolecular CCL micelles exhibit not only high structural integrity under different pH values and temperatures in aqueous solution, but multistimuli responsiveness including pH-responsive cores, thermo-responsive shells, and reversible dissociation of bis(terpyridine)ruthenium(II) complexes upon addition of competitive metal ion chelator, which allows for precisely controlled release of the encapsulated hydrophobic guest molecules via the combination of different stimuli.

Metallo-supramolecular core cross-linked (CCL) micelles are fabricated from the terpyridine-functionalized double hydrophilic block copolymers via the formation of bis(terpyridine)ruthenium(II) complexes. The stable CCL micelles exhibit not only structural integrity under different pH and temperatures but multistimuli responsiveness in aqueous solution, including pH-responsive cores, thermo-responsive shells, and dissociable cross-linker.

Front Cover: A redox-induced shape-memory polymer is prepared by cross-linking β-cyclodextrin modified chitosan and ferrocene modified poly(ethylene imine). The reversible redox-sensitive β-CD/Fc inclusion complexes and covalent cross-links serve as reversible phases and fi xing phases, respectively. This material can be processed into a desired temporary shape upon reduction and recovers to its initial shape after oxidation. The shape memory behavior also occurs when glucose is introduced with glucose oxidase entrapped in the system. Further details can be found in the article by Z.-Q. Dong, Y. Cao, Q.-J. Yuan, Y.-F. Wang, J.-H. Li, B.-J. Li,* and S. Zhang- on page 867.

The establishment of advanced living/controlled polymerization protocols allows for engineering synthetic polymers in a precise fashion. Combining advanced living/controlled polymerization techniques with highly efficient coupling chemistries facilitates quantitative, modular, and orthogonal functionalization of synthetic polymer strands at their chain termini as well as side-chain functionalization. The review highlights the current status of selected post-functionalization techniques of polymers via orthogonal ligation chemistries, major characteristics of the specific transformation chemistry, as well as the characterization of the products.

The current status of selected post-functionalization techniques of polymers via orthogonal ligation chemistry is highlighted. Combining advanced living/controlled polymerization techniques with highly efficient coupling chemistries facilitates quantitative, modular, and orthogonal functionalization of synthetic polymer strands at their chain termini as well as side-chain functionalization.

The carbon nitride poly(triazine imide) with intercalated bromide ions is a layered, graphitic material of 2D covalently bonded molecular sheets with an exceptionally large gallery height of 3.52 Å due to the intercalated bromide anions. The material can be cleaved both mechanically and chemically into thin sheets and scrolls analogous to the carbon-only systems graphite and graphene.

The carbon nitride poly(triazine imide) with intercalated bromide ions—a graphitic material of 2D covalently bonded molecular layers—can be cleaved both mechanically and chemically into thin sheets and scrolls analogous to the carbon-only systems graphite and graphene. Cleaved sheets of this layered C, N material can be deposited via the Scotch tape technique or via spin-coating.

Mixing a bis-hydrophilic, cationic miktoarm star polymer with a linear polyanion leads to the formation of unilamellar polymersomes, which consist of an interpolyelectrolyte complex (IPEC) wall sandwiched between poly(ethylene oxide) brushes. The experimental finding of this rare IPEC morphology is rationalized theoretically: the star architecture forces the assembly into a vesicular shape due to the high entropic penalty for stretching of the insoluble arms in non-planar morphologies. The transmission electron microscopy of vitrified samples (cryogenic TEM) is compared with the samples at ambient conditions (in situ TEM), giving one of the first TEM reports on soft matter in its pristine environment.

“Live” observation of soft matter by transmission electron microscopy (TEM) in liquid water: a star-shaped bis- hydrophilic cationic copolymer co-assembles with linear anionic polyelectrolytes into polymersomes as evidenced by cryo-TEM and in situ TEM in a native environment. Conditions for the formation of vesicular interpolyelectrolyte complexes are derived theoretically: the star-shaped architecture widens the range of the vesicular morphology.

Heck coupling reactions are introduced as an efficient method to prepare porous polymers. Novel inorganic-organic hybrid porous polymers (HPPs) were constructed via Heck coupling reactions from cubic functional polyhedral oligomeric silsesquioxanes (POSS), iodinated octaphenylsilsesquioxanes (OPS) and octavinylsilsesquioxanes (OVS) using Pd(OAc)₂/PPh₃ as the catalyst. Here, two iodinated OPS were used, IOPS and p-I₈OPS. IOPS was a mixture with 90% octasubstituted OPS (I₈) and some nonasubstituted OPS (I₉), while p-I₈OPS was a nearly pure compound with ≥99% I₈ and ≥93% para-substitution. IOPS and p-I₈OPS reacted with OVS to produce the porous materials HPP-1 and HPP-2, which exhibited comparable specific surface areas with S_BET of 418 ± 20 m² g⁻¹ and 382 ± 20 m² g⁻¹, respectively, with total pore volumes of 0.28 ± 0.01 cm³ g⁻¹ and 0.23 ± 0.01 cm³ g⁻¹, respectively. HPP-1 showed a broader pore size distribution and possessed a more significant contribution from the mesopores, when compared with HPP-2, thereby indicating that IOPS may induce more disorder because of the geometrical asymmetry. HPP-1 and HPP-2 possessed moderate carbon dioxide uptakes of 134 and 124 cm³ g⁻¹ at 1 bar at 195 K, making them promising candidates for CO₂ capture and storage. The synthesized porous polymers may be easily post-functionalized using the retained ethenylene groups.

Heck coupling reactions are introduced as an efficient method to prepare novel hybrid porous polymers from cubic functional polyhedral oligomeric silsesquioxanes, iodinated octaphenylsilsesquioxanes, and octavinylsilsesquioxanes. Using the retained ethenylene groups, the resulting porous materials may be easily post-functionalized.

A novel redox-induced shape-memory polymer (SMP) is prepared by crosslinking β-cyclodextrin modified chitosan (β-CD-CS) and ferrocene modified branched ethylene imine polymer (Fc-PEI). The resulting β-CD-CS/Fc-PEI contains two crosslinks: reversible redox-sensitive β-CD-Fc inclusion complexes serving as reversible phases, and covalent crosslinks serving as fixing phases. It is shown that this material can be processed into temporary shapes as needed in the reduced state and recovers its initial shape after oxidation. The recovery ratio and the fixity ratio are both above 70%. Furthermore, after entrapping glucose oxidase (GOD) in the system, the material shows a shape memory effect in response to glucose. The recovery ratio and the fixity ratio are also above 70%.

A redox-induced shape-memory polymer is prepared by crosslinking β-cyclodextrin modified chitosan and ferrocene modified branched poly(ethylene imine). The reversible redox-sensitive β-CD/Fc inclusion complexes and covalent crosslinks serve as reversible phases and fixing phases, respectively. The shape memory behavior also happens when glucose is introduced with glucose oxidase entrapped in the system. The recovery ratio and fixity ratio are above 70%.

Poly(para-phenylene vinylene) (PPV) and its derivatives are important semiconducting polymers for organic electronics. Herein, an alkene metathesis approach to obtain PPVs is reported. Tri(iso propyl)silyl-substituted norbornadienes are employed as solubilizing agents. As PPV precursors divinylbenzene is used for acyclic diene metathesis and paracyclophane diene for a ring-opening metathesis polymerization-type approach. The resulting polymers are analyzed by gel permeation chromatography (GPC), UV-vis, fluorescence, and nuclear magnetic resonance (NMR) spectroscopy. All of the polymers show good solubility in common solvents.

Copolymerization of tri(iso propyl)silyl-substituted norbornadiene with different poly(para-phenylene vinylene) (PPV) precursors in a combined acyclic diene metathesis and/or ring-opening metathesis polymerization process gives novel rod-coil block copolymers. The resulting polymers show increased solubility compared with pure PPV and are examined by gel permeation chromatography, NMR, UV-vis, and fluorescence spectroscopy.

The synthesis of cationic mono-(6-O-(1-vinylimidazolium))-ß-cyclodextrin with toluenesulfonate as the corresponding anion is described. Free-radical copolymerization of the resulting host–guest complex with N-isopropylacrylamide or N,N-diethylacrylamide yielded copolymers showing a temperature-controlled solubility window in water. The impact of different anionic guests and salt concentrations on solubility behavior was investigated via turbidity measurements.

A monomeric pseudo-betaine based on a cationic host for an anionic guest is synthesized. Polymerization of the complex with thermosensitive comonomers yields copolymers showing a thermally controlled solubility window in water. The obtained poly(pseudo-betaines) are insoluble below a certain temperature, soluble above it and finally insoluble when a second critical temperature is reached (ISI transition).

A Dissipative particle dynamics (DPD) simulations are performed to study the cooperative self-assembly of coil–rod–coil triblock copolymers and nanoparticles in solution. The results show that, when the nanoparticle concentration exceeds a given value, the ternary systems can form a novel nanocage composed of two-end coil-caps and middle rod-linkers. The novel nanocage is very similar to the real bird cage and the captured nanoparticles like the bird. It is the first nanocage from the self-assembly of coil–rod–coil triblock copolymers. This may be used for the release of drugs and fertilizers, or as nanoreactors.

This novel “nanocage” formed by the cooperative self-assembly of coil–rod–coil triblock copolymers enriches the material source of the nanocage. The novel structure is may be used to the release of drug and fertilizer, or the nanoreactors.