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Inkjet-printed paper-based volatile organic compound (VOC) sensor strips imaged with polydiacetylenes (PDAs) are developed. A microemulsion ink containing bisurethane-substituted diacetylene (DA) monomers, 4BCMU, was inkjet printed onto paper using a conventional inkjet office printer. UV irradiation of the printed image allowed fabrication of blue-colored poly-4BCMU on the paper and the polymer was found to display colorimetric responses to VOCs. Interestingly, a blue-to-yellow color change was observed when the strip was exposed to chloroform vapor, which was accompanied by the generation of green fluorescence. The principal component analysis plot of the color and fluorescence images of the VOC-exposed polymers allowed a more precise discrimination of VOC vapors., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Biodegradation of polymers in composting conditions is an alternative end-of-life (EoL) scenario for contaminated materials collected through the municipal solid waste management system, mainly when mechanical or chemical methods cannot be used to recycle them. Compostability certification requirements are time-consuming and expensive. Therefore, approaches to accelerate the biodegradation of these polymers in simulated composting conditions can facilitate and speed up the evaluation and selection of potential compostable polymer alternatives and inform faster methods to biodegrade these polymers in real composting. This review highlights recent trends, challenges, and future strategies to accelerate biodegradation by modifying the polymer properties/structure and the compost environment. Both abiotic and biotic methods show potential for accelerating the biodegradation of biodegradable polymers. Abiotic methods, such as the incorporation of additives, reduction of molecular weight, reduction of size and reactive blending, are potentially the most straightforward, providing a level of technology that allows for easy adoption and adaptability. Novel methods, including the concept of self-immolative and triggering the scission of polymer chains in specific conditions, are increasingly sought. In terms of biotic methods, dispersion/encapsulation of enzymes during the processing step, biostimulation of the environment, and bioaugmentation with specific microbial strains during the biodegradation process are promising to accelerate biodegradation., (© 2023 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

To prepare biobased polymers, particular attention must be paid to the obtention of the monomers from which they are derived. (Meth)acrylates and their analogs constitute such a class of monomers that have been extensively studied due to the wide range of polymers accessible from them. This review therefore aims to highlight the progresses made in the production and polymerization of (meth)acrylates and their analogs. Acrylic acid production from biomass is close to commercialization, as three different high-potential intermediates are identified: glycerol, lactic acid, and 3-hydroxypropionic acid. Biobased methacrylic acid is less common, but several promising options are available, such as the decarboxylation of itaconic acid or the dehydration of 2-hydroxyisobutyric acid. Itaconic acid is also a vinylic monomer of great interest, and polymers derived from it have already found commercial applications. Methylene butyrolactones are promising monomers, obtained from bioresources via three different intermediates: levulinic, succinic, or itaconic acid. Although expensive, methylene butyrolactones have a strong potential for the production of high-performance polymers. Finally, β-substituted acrylic monomers, such as cinnamic, fumaric, muconic, or crotonic acid, are also examined, as they provide an original access to biobased materials from various renewable raw materials, such as protein waste, lignin, or wastewater., (© 2021 Wiley-VCH GmbH.)

Singlet fission (SF) is a spin-allowed process in which a higher-energy singlet exciton is converted into two lower-energy triplet excitons via a triplet pair intermediate state. Implementing SF in photovoltaic devices holds the potential to exceed the Shockley-Queisser limit of conventional single-junction solar cells. Although great progress has been made in exploiting the underlying mechanism of SF over the past decades, the scope of materials capable of SF, particularly polymeric materials, remains poor. SF-capable polymer is one of the most potential candidates in the implementation of SF into devices due to their distinct superiorities in flexibility, solution processability and self-assembly behavior. Notably, recent advancements have demonstrated high-performance SF in isolated donor-acceptor (D-A) copolymer chains. This review provides an overview of recent progress in the development of SF-capable polymeric materials, with a significant focus on elucidating the mechanisms of SF in polymers and optimizing the design strategies for SF-capable polymers. Additionally, the paper discusses the challenges encountered in this field and presents future perspectives. It is expected that this comprehensive review will offer valuable insights into the design of novel SF-capable polymeric materials, further advancing the potential for SF implementation in photovoltaic devices., (© 2023 Wiley-VCH GmbH.)

Circularly polarized luminescence (CPL) materials with clustering-triggered emission (CTE) characteristic have gradually attracted attention for their unique photophysical properties. However, the majority of reported clusteroluminogens lack chirality and exhibit heterogeneity, making it challenging to achieve a well-defined helical structure necessary for efficient CPL with high dissymmetry factor (g lum ). In this paper, chiral liquid crystals are constructed to obtain CTE-based CPL materials with high g lum values. Side chain liquid crystal polymer PM6Chol bearing cholesterol clusteroluminogens are designed and synthesized. PM6Chol-coated film and PM6Chol thermal-treated film are also successfully prepared by different film-forming methods. Both the films inherit the CTE characteristic of cholesterol and show excitation wavelength-dependent luminescent behavior. However, the two polymer films exhibit different liquid crystal phase structures, with PM6Chol-coated film being a chiral bilayer smectic C phase and PM6Chol thermal-treated film being an achiral bilayer smectic A phase. Attributed to helical arrangement of cholesterol, PM6Chol-coated film emits efficient CPL with g lum values up to 1.0 × 10 -1 . For PM6Chol thermal-treated film, no CPL signal is detected due to the absence of helical structure. However, it shows obvious room-temperature phosphorescence with 2.0 s afterglow and 23.9 ms lifetime., (© 2023 Wiley-VCH GmbH.)

The development of peptidomimetics to modulate the conformational profile of peptides has been extensively studied in the fields of biological and medicinal chemistry. However, large‐scale synthesis of peptidomimetics with both an ordered sequence and a controlled secondary structure is highly challenging. In this paper, the framework of peptidomimetics has been designed to be alternating an achiral α,α‐disubstituted α‐amino acid unit and a chiral α‐methylphenylalanine unit. The polymers are synthesized via invented Ugi reaction‐based polycondensation technique. The chiral higher‐order structures of the alternating peptides are evaluated mainly through circular dichroism (CD) spectroscopy. The UV–Vis and CD spectra of the polymers in three solvents are systematically measured at various temperatures. The anisotropic factors of CD (gCD) values are calculated to know the chiroptical response. The results indicate the characteristic conformational behaviors. In a polar solvent, the hydrogen bonds between the N‐H group of MePhe unit and the C=O of α,α‐diphenylglycine unit outweigh the intraresidue hydrogen bonds in α,α‐diphenylglycine unit, leading to the formation of a prevailing preferred‐handed 310‐helical conformation. On the other hand, in a less polar solvent, the intrachain hydrogen bonds switch to intraresidue hydrogen bonds in α,α‐diphenylglycine unit, which make the polymer adopting a prevailing extended planar C5‐conformation. [ABSTRACT FROM AUTHOR]

The development of bio-based polymer materials, such as polylactic acid (PLA) -based polymers, is an effective strategy to reduce dependence on petrochemical-based polymers. However, the preparation of bio-based polymers with high barrier properties is a major challenge. To overcome this challenge, a nacreous layer structure with a ' brick and mud ' pattern is mimicked to improve the overall performance of the material. In this paper, Poly ( L -lactic acid) (PLLA) and Polypropylene Glycol (PPG) was combined to prepare bio-based polyurethane (PU-PLLA), which is used as the slurry structure of nacreous layer. The bio-based biomimetic composite membrane (PU-PLLA/BN) is then obtained by adding boron nitride (BN, brick structure of pearl layer) to it. The water vapor permeability test results show that the permeability of PU-PLLA material can be reduced by more than 50% by 5 wt.% BN, which is because the addition of BN can increase the length and tortuosity of the gas molecular diffusion path in the composite. Therefore, this pearl-inspired PU-PLLA/BN film has excellent moisture resistance, which opens up a broad road for the practical application of PLLA in flexible laminated packaging., (© 2023 Wiley-VCH GmbH.)

The charge carrier mobility of organic field-effect transistors (OFETs) has been remarkably improved through several engineering approaches and techniques by targeting pivotal parts. Herein, an ultrathin perovskite channel layer that boosts the field-effect mobility of conjugated polymer OFETs by forming perovskite-conjugated polymer hybrid semiconducting channel is introduced. The optimized lead-iodide-based perovskite-conjugated polymer hybrid channel transistors show enhanced hole mobility of over 4 cm 2  V -1  s -1 (average = 2.10 cm 2  V -1  s -1 ) with high reproducibility using a benchmark poly(3-hexylthiophene) (P3HT) polymer and employing high-k fluorinated polymer dielectrics. A significant hole carrier mobility enhancement of ≈200-400% in benzo[1,2-b:4,5:b']dithiophene (BDT)-based conjugated polymers is also demonstrated by exploring certain interactive groups with perovskite. This significant enhancement in the transistor performance is attributed to the increased charge carrier density in the hybrid semiconducting channel and the perovskite-polymer interactions. The findings of this paper demonstrate an exceptional engineering approach for carrier mobility enhancement in hybrid perovskite-conjugated-polymer-based electronic devices., (© 2023 Wiley-VCH GmbH.)

The pursuit of innovative organic materials and the examination of the “structure‐function” correlation in lithium‐ion batteries (LIBs) are crucial and highly desirable. Current research focuses on the creation of novel conjugated organic polymers with polycarbonyl groups and examining the impact of electrode structure on the function of lithium‐ion batteries. In this paper, two novel cyanovinylene‐based conjugated organic polymers, NBA‐TFB and NBA‐TFPB, are synthesized using a Knoevenagel condensation reaction with naphthalene diimide as the integral unit. The performance of NBA‐TFB and NBA‐TFPB as cathodes in lithium‐ion batteries is investigated. Improved conductivity and increased active site density in NBA‐TFPB resulted in superior electrochemistry compared to NBA‐TFB. Specifically, NBA‐TFPB exhibited a larger reversible capacity (87.58 mAh g−1 at 0.2C and 88.34% retention after 100 cycles), exceptional rate capability (66.13 mAh g−1 at 5C), and robust cycling stability (99.58% coulombic efficiency at 1C and 60.71% retention after 2000 cycles). This study expands the family of diimide‐based naphthalene polymers and provides a strategy for enhancing the performance of organic electrode materials containing polycarbonyl structure. [ABSTRACT FROM AUTHOR]

The search for materials with better performance, longer service life, lower environmental impact, and lower overall cost is at the forefront of polymer science and material engineering. This has led to the development of self-healing polymers with a range of healing mechanisms including capsular-based, vascular, and intrinsic self-healing polymers. The development of self-healable systems has been inspired by the healing of biological systems such as skin wound healing and broken bone reconstruction. The goal of using self-healing polymers in various applications is to extend the service life of polymers without the need for replacement or human intervention especially in restricted access areas such as underwater/underground piping where inspection, intervention, and maintenance are very difficult. Through an industrial and scholarly lens, this paper provides: a) an overview of self-healing polymers; b) classification of different self-healing polymers and polymer-based composites; c) mechanical, thermal, and electrical analysis characterization; d) applications in coating, composites, and electronics; e) modeling and simulation; and f) recent development in the past 20 years. This review highlights the importance of healable polymers for an economically and environmentally sustainable future, the most recent advances in the field, and current limitations in fabrication, manufacturing, and performance., (© 2022 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

The macroscopic modeling of gas transport in mixed-matrix membranes (MMMs) made of a Polymer of Intrinsic Microporosity (PIM-1) and silicalite1 (MFI) is compared to the experimental results presented in a previous paper, which shows unexpectedly large gas separation factors, although the silicalite-1 filler is practically nonselective. The mismatch between the predictions of the Maxwell model and the experiments is zeroed by the recognition of nonideal effects, the extent of which is evaluated. The good performance of the PIM-1 MMM is explained by non-covalent cross-linking of the PIM-1 matrix. Cross-linking results from π-π stacking interactions between the 2-phenylethyl grafts on the outer surface of the MFI crystals and the aromatic ladder segments of PIM-1, in agreement with the current explanation of the good transport performance of PIM-1 MMMs containing porous aromatic fillers (e.g., PAF-1)., (© 2022 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

In recent years, transdermal drug delivery based on microneedles (MNs) technology has received extensive attention, which offers a safer and painless alternative to hypodermic needle injections. They can pierce the stratum corneum and deliver drugs to the epidermis and dermis-structures of skin, showing prominent properties such as minimally invasiveness, bypassing first-pass metabolism, and can be self-administered. A range of materials has been used to fabricate MNs, such as silicon, metal, glass, and polymers. Among them, polymer MNs have gained increasing attention from pharmaceutical and cosmetic companies as one of the promising drug delivery methods. MN products have recently become available on the market, and some of them are under evaluation for efficacy and safety. This paper focuses on the current state of polymer MNs in drug transdermal delivery. The materials and methods for the fabrication of polymer MNs and their drug administration are described. The recent progress of polymer MNs for treatment of cancer, vaccine delivery, blood glucose regulation, androgenetic alopecia, obesity, tissue healing, myocardial infarction, and gout are reviewed. The challenges of MNs technology are summarized and the future development trend of MNs is also prospected., (© 2022 Wiley-VCH GmbH.)

Singlet fission (SF) is a spin–allowed process in which a higher–energy singlet exciton is converted into two lower‐energy triplet excitons via a triplet pair intermediate state. Implementing SF in photovoltaic devices holds the potential to exceed the Shockley–Queisser limit of conventional single‐junction solar cells. Although great progress has been made in exploiting the underlying mechanism of SF over the past decades, the scope of materials capable of SF, particularly polymeric materials, remains poor. SF–capable polymer is one of the most potential candidates in the implementation of SF into devices due to their distinct superiorities in flexibility, solution processability and self‐assembly behavior. Notably, recent advancements have demonstrated high‐performance SF in isolated donor‐acceptor (D‐A) copolymer chains. This review provides an overview of recent progress in the development of SF‐capable polymeric materials, with a significant focus on elucidating the mechanisms of SF in polymers and optimizing the design strategies for SF‐capable polymers. Additionally, the paper discusses the challenges encountered in this field and presents future perspectives. It is expected that this comprehensive review will offer valuable insights into the design of novel SF‐capable polymeric materials, further advancing the potential for SF implementation in photovoltaic devices. [ABSTRACT FROM AUTHOR]

SNIPS stands for a membrane fabrication technique that combines the evaporation induced self-assembly of the block copolymers and the classical nonsolvent induced phase separation. It is a one-step readily scalable technique to fabricate integral asymmetric isoporous membranes. The prominent developments in the last decade have carved out a niche for SNIPS as a potential technique to fabricate next generation isoporous membranes. In the last decade, a rich polymer library and variety of membrane postmodification routes have been successfully implemented to fabricate SNIPS membranes having the desired pore functionality. Some of these membranes form soft nanochannels in hydrated state due to swelling of the pore wall, i.e., the pore forming block of the block copolymer. These membranes having soft nanochannels have demonstrated the potential to perform several challenging separation tasks in ultrafiltration and nanofiltration. This paper highlights the currently accessible pore functionality, the strategies to tune the swelling of the soft nanochannels, the potential applications, and future perspectives of these membranes., (© 2021 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

Tailor-made polymers are needed to fully exploit the possibilities of additive manufacturing, constructing complex, and functional devices in areas such as bioelectronics. In this paper, the synthesis of a conducting and biocompatible graft copolymer which can be 3D printed using direct melting extrusion methods is shown. For this purpose, graft copolymers composed by conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and a biocompatible polymer polylactide (PLA) are designed. The PEDOT-g-PLA copolymers are synthesized by chemical oxidative polymerization between 3,4-ethylenedioxythiophene and PLA macromonomers. PEDOT-g-PLA copolymers with different compositions are obtained and fully characterized. The rheological characterization indicates that copolymers containing below 20 wt% of PEDOT show the right complex viscosity values suitable for direct ink writing (DIW). The 3D printing tests using the DIW methodology allows printing different parts with different shapes with high resolution (200 µm). The conductive and biocompatible printed patterns of PEDOT-g-PLA show excellent cell growth and maturation of neonatal cardiac myocytes cocultured with fibroblasts., (© 2021 Wiley-VCH GmbH.)

With the rapid development on 3D printing technology, more and more works have been devoted to 3D display. 3D display will really come true by using circularly polarized luminescence (CPL)-active materials with both high quantum yield and dissymmetry factor (g em ) in organic light-emitting diode or liquid crystals (LCs). But so far most of these CPL materials cannot meet the real application requirement because of the low g em values in the range of 10 -5 -10 -2 . In this paper, ternary chiral emissive LCs (P-N*-LCs) is designed by doping chiral binaphthyl-based enantiomers as chiral dopant (Guest 1) and achiral conjugated polymer as induced CPL emitter (Guest 2) into nematic liquid crystal (N-LCs) Host 5CB. Both Guest 1 and Guest 2 show excellent compatibility with Host 5CB. The obtained ternary P-N*-LCs can emit strong-induced CPL signal with g em up to 1.12 and Ф FL up to 66.1%. This work first develops a new strategy for the smart design of excellent CPL materials from versatile achiral conjugation fluorescence polymers., (© 2020 Wiley-VCH GmbH.)

Flexible electronics require its substrate to have adequate thermal stability, but current thermally stable polymer substrates are difficult to be disintegrated and recycled; hence, generate enormous electronic solid waste. Here, a thermally stable and green solvent-disintegrable polymer substrate is developed for flexible electronics to promote their recyclability and reduce solid waste generation. Thanks to the proper design of rigid backbones and rational adjustments of polar and bulky side groups, the polymer substrate exhibits excellent thermal and mechanical properties with thermal decomposition temperature (T d,5% ) of 430 °C, upper operating temperature of over 300 °C, coefficient of thermal expansion of 48 ppm K -1 , tensile strength of 103 MPa, and elastic modulus of 2.49 GPa. Furthermore, the substrate illustrates outstanding optical and dielectric properties with high transmittance of 91% and a low dielectric constant of 2.30. Additionally, it demonstrates remarkable chemical and flame resistance. A proof-of-concept flexible printed circuit device is fabricated with this substrate, which demonstrates outstanding mechanical-electrical stability. Most importantly, the substrate can be quickly disintegrated and recycled with alcohol. With outstanding thermally stable properties, accompanied by excellent recyclability, the substrate is particularly attractive for a wide range of electronics to reduce solid waste generation, and head toward flexible and "green" electronics., (© 2020 Wiley-VCH GmbH.)

Advanced synthetic materials are needed to produce nano- and mesoscale structures that function autonomously, catalyze reactions, and convert chemical energy into motion. This paper describes supracolloidal fiber-like structures that are composed of self-adhering, or "sticky," oil-in-water emulsion droplets. Polymer zwitterion surfactants serve as the key interfacial components of these materials, enabling multiple functions simultaneously, including acting as droplet-stabilizing surfactants, interdroplet adhesives, and building blocks of the fibers. This fiber motion, a surprising additional feature of these supracolloidal structures, is observed at the air-water interface and hinged on the chemistry of the polymer surfactant. The origin of this motion is hypothesized to involve transport of polymer from the oil-water interface to the air-water interface, which generates a Marangoni (interfacial) stress. Harnessing this fiber motion with functional polymer surfactants, and selection of the oil phase, produced worm-like objects capable of rotation, oscillation, and/or response to external fields. Overall, these supracolloidal fibers fill a design gap between self-propelled nano/microscale particles and macroscale motors, and have the potential to serve as new components of soft, responsive materials structures., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The research on multiple hydrogen bonds (H-bonds) hydrogels have gradually aroused wide interest. In this paper, a multiple H-bonds-reinforced poly(acrylamide-co-2-vinyl-4,6-diamino-2-vinyl-1,3,5-triazine)/tannic acid (P(Am-co-VDT)/TA) hydrogels are prepared. The results suggest that the prepared hydrogel has two types of H-bonds crosslinking regions: A "soft" region of H-bonds between the diaminotriazine (DAT) moieties on the polymer chains and the TA pyrogallol/catechol groups, and a "hard" region of H-bonds forming by DAT moieties with itself. The hard crosslinking region exhibits significantly higher activation energy than the soft region. Such soft and hard dual physically crosslinked networks dramatically enhance the mechanical properties of P(Am-co-VDT)/TA hydrogels in a synergistic manner (tensile strength is 2.34 MPa, elongation at break is 410%). Due to the multiple hydrogen bonds, the hydrogel has good pH sensitivity and rapid response to shape memory within a few minutes. In addition, the hydrogels have the capacity of physical adsorption of the anti-inflammatory drug diclofenac sodium and other molecules with a specific spatially arranged chemical composition. These hydrogels with high mechanical strength, excellent shape memory behavior, and capacity of adsorption of anti-inflammatory drug could be attractive candidates for applications in the fields of biomedicine, tissue engineering, and medical materials., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The integration of porous thin films using microelectronic compatible processes sometimes requires the protection of the interior of the pores during the critical integration steps. In this paper, the polymerization of neo-pentyl methacrylate (npMA) is performed via initiated chemical vapor deposition (iCVD) on a porous organosilicate (SiOCH) and on a dense SiOCH. The characterizations by Fourier-transform infrared spectroscopy, spectroscopic ellipsometry, and time-of-flight secondary ion mass spectrometry of the different stacks show that iCVD is a powerful technique to polymerize npMA in the nanometric pores and thus totally fill them with a polymer. The study of the pore filling for very short iCVD durations shows that the polymerization in the pores is complete in less than ten seconds and is uniform in depth. Then, the poly(npMA) film growth continues on top of the filled SiOCH layer. These characteristics make iCVD a straightforward and very promising alternative to other infiltration techniques in order to fill the porosity of microporous thin films., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This review focuses on the attachment of polymer brushes to polymeric biomaterial substrates by chemical surface modification methods for biomedical applications. In the first part of this paper, a general introduction to the synthesis of polymer brushes is given. Thereafter, a comprehensive overview of recent work on the chemical surface modification of polymeric biomaterials, with a focus on "grafting-to," "grafting-from," and "grafting-through" strategies, is provided. Finally, some representative cutting-edge biomedical applications of modified polymeric biomaterials, mainly including antifouling materials and biocompatible materials, are highlighted. On the basis of this literature study, a perspective on future trends in this field is provided., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Supramolecular chemistry has provided versatile and affordable solutions for the design of tough, flexible polymers. However, application of supramolecular chemistry has been limited to the production of rigid, high-performance polymers due to weak segment mobility. This paper describes a new method of toughening rigid high-performance polymers using the synergistic effect between dual Cu 2+ -coordination bonds as a crosslink. These dual Cu 2+ -coordination cross-linked high-performance polymers are a class of rigid polymers with an outstanding combination of strength and toughness. The distinct lifetimes and binding strengths of the dual Cu 2+ -coordination bonds in a rigid polymer network elicit different dynamic behaviors to improve its energy dissipation and mechanical properties. Moreover, the reformation and removal of Cu 2+ -coordination bonds by pyrophosphoric acid endows these cross-linked high-performance polymers with recyclability., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel capability built upon secondary electron (SE) spectroscopy provides an enhanced cross-linking characterization toolset for polymeric biomaterials, with cross-linking density and variation captured at a multiscale level. The potential of SE spectroscopy for material characterization has been investigated since 1947. The absence of suitable instrumentation and signal processing proved insurmountable barriers to applying SE spectroscopy to biomaterials, and consequently, capturing SE spectra containing cross-linking information is a new concept. To date, cross-linking extent is inferred from analytical techniques such as nuclear magnetic resonance (NMR), differential scanning calorimetry, and Raman spectroscopy (RS). NMR provides extremely localized information on the atomic scale and molecular scale, while RS information volume is on the microscale. Other methods for the indirect study of cross-linking are bulk mechanical averaging methods, such as tensile and compression modulus testing. However, these established averaging methods for the estimation of polymer cross-linking density are incomplete because they fail to provide information of spatial distributions within the biomaterial morphology across all relevant length scales. The efficacy of the SE spectroscopy capability is demonstrated in this paper by the analysis of poly(glycerol sebacate)-methacrylate (PGS-M) at different degrees of methacrylation delivering new insights into PGS-M morphology., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This article discusses the importance of understanding the relationship between macromolecular structures and their functions in (opto)electronic and energy storage applications. The article highlights the need for comprehensive knowledge in order to achieve high-performance materials and explores various aspects of this relationship, including polymer synthesis, processing, controlled degradation, and application-driven investigations. The article also features research papers and review articles that delve into specific topics such as direct arylation polymerization, conjugated polyelectrolytes, non-conjugated pendant electroactive polymers, and the use of macromolecular structures in photovoltaics, energy storage, and wearable electronics. The authors emphasize the potential for multi-functionality in advanced organic electronic devices and discuss emerging areas such as 3D printing of conjugated polymers and sustainable solutions for end-of-life management. Overall, the article provides a comprehensive overview of the current research and advancements in the field of macromolecular structures for electronics, optoelectronics, and energy storage. [Extracted from the article]

A highly multitasking 3D polycarbazole based microporous organic polymer (ACzMOP) is rationally prepared via a low‐cost FeCl3 catalyzed polymerization route utilizing a newly developed Td ‐symmetric adamantane core tetracarbazolic monomer. The nitrogen‐rich ACzMOP integrated with photo‐redox active electron‐rich π‐conjugated polycarbazole modules featuring large BET surface area of 1568 m 2 g −1, pore volume of 1.58 cc g −1, excellent physicochemical stability, and strong fluorescence in both aqueous and solid phases. Aqueous suspension including ACzMOP coated paper strip is highly responsive to the aqueous solution of nitroaromatics especially 2,4‐dinitrotoluene, an unavoidable intermediate of 2,4,6‐trinitrotoluene contamination, with ultra‐trace level detection capability (up to 0.32 ppb). The thin layer of solid polymer is capable of detecting nitroaromatic vapors, especially nitrotoluenes in a very sensitive manner. Moreover, the polymer exhibit record uptake of nitrotoluenes and nitrophenols with maximum uptake capability up to 510 mg g −1 setting a new benchmark among known porous materials. The polymer efficiently degrades toxic 4‐nitrophenol to the value‐added 4‐aminophenol precursor (TOF = 0.143 h −1) via photocatalytic pathway. For the very first time, ACzMOP as a single material system is capable of efficiently sensing and removing all sorts of nitroaromatic contaminations with regenerability under mild washing/vacuum conditions. [ABSTRACT FROM AUTHOR]

The covalent cross-linked rubber has outstanding mechanical properties and chemical resistance, making it possible for a wide range of applications. Towards efforts to resource waste and environmental pollution, rubber recycling is a concerning problem. However, it is a big challenge to endow the most widely used commercial rubber systems with recyclability. In this paper, a novel reprocessable and recyclable acrylonitrile-butadiene rubber (NBR) is developed by introducing oxime-carbamate bonds into the raw NBR. Amidoxime NBR is prepared by a nucleophilic addition reaction of hydroxylamine hydrochloride and raw NBR, and then cross-linked amidoxime NBR using different amounts of toluene diisocynate (TDI). Results show that the obtained material exhibits good reprocessable property; the repairing efficiency exceeds 90% after two remoldings. In addition, it also has better mechanical properties: A tensile strength reaching a maximum value of 4.85 MPa when TDI cross-linker is 15.36 wt%, which is superior to vulcanized NBR (3.18 MPa)., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tandem mass spectrometry is a powerful technique for investigating polymer architecture. However, in-depth studies of the technique for polymers is relatively lacking when compared to other areas of mass spectrometry (MS). This paper examines the use laser-induced dissociation and collision-induced dissociation (CID) in MALDI-LIFT-ToF/ToF experiments to compare the usage of the two techniques on a range of polymeric analytes. It is demonstrated that for samples with an energetically preferable fragmentation pathway, such as those with a functional group in the backbone or a labile end group, post source decay (PSD) provides a simplified spectra with an increased pathway selectivity due to its utilization of metastable decay. This makes PSD a preferable technique for polymer sequencing, especially in low-resolution time-of-flight techniques. Conversely, CID fragments less selectively, leading to higher intensity peaks from less favorable fragmentations. This makes CID more preferred for exact structural determination, such as finding the repeat unit structure., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nitroxide-mediated polymerization (NMP) is employed to graft synthetic polymers from polysaccharides. This work demonstrates the first successful polymer grafting from starch nanoparticles (SNPs) via NMP. To graft synthetic polymers from the SNPs' surface, the SNPs are first functionalized with 4-vinylbenzyl chloride prior to reaction with BlocBuilder MA yielding a macroinitiator. Methyl methacrylate with styrene, acrylic acid, or methyl acrylate are then grafted from the SNPs. The polymerizations exhibited linear reaction kinetics, indicating that they are well controlled. Thermal gravimetric analysis and spectroscopic techniques confirmed the synthesis of the precursors materials and the success of the grafting from polymerizations. The incorporation of hydrophobic synthetic polymers on hydrophilic SNPs yields new hybrid materials that could find use in several industrial applications including paper coatings, adhesives, and paints., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Contact lenses are medical devices commonly used to correct refractive errors and to maintain ocular health. Microorganisms such as bacteria that grow on the lens surface cause irritation to the eyes and can even cause loss of vision. In this paper, two different coating strategies are employed to form an efficient antimicrobial coating on contact lenses. In the first method, a presynthesized copolymer of polyethyleneimine‐graft‐polyethylene glycol methacrylate (PEI‐PEGMA) is used and the coated lenses show antimicrobial activity (in vitro) against methicillin‐resistant Staphylococcus aureus (MRSA) bacteria with killing efficacy >99.99% and log reduction of 5.1 and proxy host cell viability of 79%. In the second method, commercially available monomers/polymers such as glycidyl methacrylate (GMA), sulfobetaine methacrylate, and polyethyleneimine are used. A typical formulation consisting of 1% GMA shows antibacterial activity against MRSA with killing efficacy >99.99% and log reduction of 6.3. Proxy host cell viability for the coated lenses is found to be 90% indicating that the coating is nontoxic. Antibacterial coating reported here is very effective in killing gram‐positive bacteria such as MRSA and S. aureus. The second method using commercially available monomers/polymers involving a simple coating procedure is also easily scalable. [ABSTRACT FROM AUTHOR]

Light and electrothermal responsive polymer photonic crystals (PCs) modified with 1′‐acryloyl chloride‐3′,3′‐dimethyl‐6‐nitro‐spiro(2H‐1‐benzopyran‐2,2′‐indoline) (SPMA) are proposed, and their dynamic display patterns are achieved through the combination of the SPMA‐modified PCs and a patterned graphite layer. These PCs exhibit fluorescence under UV light irradiation because of the isomerization of the SPMA, which is restricted in the shell of the polymer colloidal spheres. After a voltage is applied to the patterned graphite layer, the fluorescence of PCs in the specific area disappears, and dynamic display patterns are obtained. Under UV light irradiation, the PCs change from the "partial‐fluorescence" state to the initial "fluorescence" state, and the patterns disappear. Using this technique, the PC pattern "M L N" on the glass substrate and PC patterns from "0" to "9" on the paper substrate are fabricated. Thus, these dual‐responsive PCs have potential applications in information recording, anticounterfeiting, dynamic display, and photoelectric devices. 1′‐Acryloyl chloride‐3′,3′‐dimethyl‐6‐nitro‐spiro(2H‐1‐benzopyran‐2,2′‐indoline) (SPMA)‐modified photonic crystals (PCs) with light and electrothermal response and their dynamic display patterns are prepared. With UV irradiation, the PCs exhibit fluorescence due to the isomerization of PS@P(MMA‐co‐SPMA). After a voltage is applied, increasing temperature of the graphite layer causes the disappearance of fluorescence. Thus, the PC patterns "M L N" and "0" to "9" on different substrates are fabricated. [ABSTRACT FROM AUTHOR]

In this paper, preparation method and actuation properties of an innovative composite membrane composed of thermo- and pH-responsive poly(N-isopropylacrylamide-co-acrylic acid) fibers (average diameter ≈ 905 nm) embedded within a passive thermoplastic polyurethane (TPU) matrix at different angles with degree of alignment as high as 98% are presented. The composite membrane has a gradient of TPU along the thickness. It has the capability of temperature- and pH-dependent direction-, and size-controlled actuation in few minutes. The stresses generated at the responsive fiber and nonresponsive matrix provide actuation, whereas the angle at which fibers are embedded in the matrix controls the actuation direction and size. The temperature has no effect on actuation and actuated forms at pH 7 and above, whereas the size of the actuated forms can be controlled by the temperature at lower pH. The membranes are strong enough to reversibly lift and release ≈426 times weight of their own mass (2.47 g metal ring is lifted by a 5.8 mg membrane). Soft actuators are of interest as smart scaffolds, robotics, catalysis, drug release, energy storage, electrodes, and metamaterials., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this paper, the facile synthesis of hybrid Fe 3 O 4 magnetic nanoparticles carrying helical poly(phenyl isocyanide) (PPI) arms via both "grafting from" and "grafting onto" strategies is reported. First, alkyne-Pd(II) catalysts are anchored onto the surface of the Fe 3 O 4 magnetic nanoparticle, which promote the polymerization of enantiopure phenyl isocyanide, affording the expected hybrid magnetic nanoparticle with Fe 3 O 4 in core and helical PPI as arms. The nanoparticle also exhibits highly optical activity due to the excess of one-handed helicity of the PPI arms. Moreover, the hybrid magnetic nanoparticle can be alternatively synthesized via "grafting onto" strategy. A triethoxysilanyl-terminated single handed helical PPI bearing l-alanine ester pendants is prepared and grafted onto the surface of Fe 3 O 4 nanoparticle. The generated hybrid magnetic nanoparticles show both magnetic character and optical activity. Taking advantage of these properties, they can be used in enantioselective crystallization of racemic threonine. The enantiomeric excess (ee) of the induced crystals is up to 93%. Moreover, the nanoparticles can be facilely recovered and recycle used for at least four times in enantioselective crystallization without significantly loss of its enantioselectivity., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

For polymer solar cells (PSCs), efficient polymer electron acceptors are always based on strong electron-withdrawing imide unit or boron-nitrogen coordinative bond (B←N). In this paper, a new polymer electron acceptor based on thiophene-S,S-dioxide (TDO) unit is reported. The polymer electron acceptor, PBDT-TDO, consists of alternating TDO unit and 4,8-bis(alkylthienyl)-2-yl]benzo[1,2-b:4,5-b']dithiophene (BDT) unit. For comparison, a control polymer with alternating BDT unit and thiophene unit has also been synthesized. Replacing thiophene unit with TDO unit in the polymer backbone leads to large downshift of lowest unoccupied molecular orbital/highest occupied molecular orbital energy levels by 0.9 eV/0.4 eV, which is attributed to the dearomatization and electron deficiency of TDO unit. The replacement also leads to redshift of absorption spectra by ≈110 nm. PSC device with PBDT-TDO as the electron acceptor shows photovoltaic response with the preliminary power conversion efficiency of 0.64%. This work suggests a new approach to design polymer electron acceptors using the TDO unit., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Over the last century, polymers are everywhere we look, have transformed our daily lives, and gained global acceptance. All of these have heavily impacted the direction of polymer science over the last ten years with a five-fold increase in papers with the concepts of "polymer" and "sustainability". Bexis, Coulombier, Dove, and co-workers report on the ring-opening polymerisation of a propargyl-functionalised cyclic carbonate to yield a versatile system for telechelic and block copolymer synthesis (2000378). [Extracted from the article]

Developing mechano‐responsive fluorescent polymers that exhibit distinct responses to distinct mechanical stresses requires a careful design of the fluorophore in order to tune its interactions with the polymer. A series of mechanofluorochromic (MFC) polymer composites are prepared by dispersing difluoroboron diketonates complexes with various alkyl side‐chain lengths (DFB‐alkyl) in linear low‐density polyethylene. Observation of the resulting polymer composites under a microscope reveals different aggregate sizes of the three DFB‐alkyls, thus confirming the functionalization by alkyl side chains as a powerful approach to control the aggregation process in a polymer. Besides, the three polymer composite samples are shown to be sensitive to both stretching and scratching, thereby consisting in the first reported example of MFC polymer responding to these two distinct mechanical stimuli. To establish a structure–property relationship, the strategy consisted in applying controlled tensile or friction forces while simultaneously monitoring fluorescence changes. Interestingly, the intensity of the MFC response to both stretching and scratching depends on the alkyl chain length and thus on the aggregation properties of the fluorophore. According to a time‐resolved fluorescence study, the emission is found to originate from different species following the type of applied stress (tensile or friction force). [ABSTRACT FROM AUTHOR]

Functional polymer composites have gained extensive interest due to their wide range of applications. Various functionalities are mainly provided by functional fillers and their networks in polymer matrix. Therefore, morphology control on filler network has important influence on the final functionalities. The confinement, assembly, and relaxation of inorganic functional fillers in polymers are thought as the basic issues related to such control. Processing as the means to achieve the desired shape and properties for materials often involves strong temperature and shear field, among other factors-not to mention the complex interaction between polymer and filler. These processing fields and interactions during processing are reported to have profound influence on the confinement, assembly, and relaxation of inorganic fillers in polymer matrix. Therefore, various functionalities could be significantly affected by processing. This paper is a review of recent developments in this area., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The preparation of well-defined block copolymers using controlled radical polymerization depends on the proper order of monomer addition. The reversed order of monomer addition results in a mixture of block copolymer and homopolymer and thus has typically been avoided. In this paper, the low blocking efficiency of reversed monomer addition order is utilized in combination with surface initiated reversible addition-fragmentation chain-transfer polymerization to establish a facile procedure toward mixed polymer brush grafted nanoparticles SiO 2 -g-(PS (polystyrene), PS-b-PMAA (polymethacrylic acid)). The SiO 2 -g-(PS, PS-b-PMAA) nanoparticles are analyzed by gel permeation chromatography deconvolution, and the fraction of each polymer component is calculated. Additionally, the SiO 2 -g-(PS, PS-b-PMAA) are amphiphilic in nature and show unique self-assembly behavior in water., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

There is a common phenomenon that the heterogeneity of natural oligosaccharides contains various sugar units, which can be used to enhance affinity and selectivity toward a specific receptor, so the synthesis of heterogeneous glycopolymers is always an important issue in the glycopolymer field. Herein, this study conducts a one-pot method to prepare polyrotaxane-based heteroglycopolymers anchored with different sugar units and fluorescent moieties via the combination of host-guest interaction, thiol-ene, and copper-catalyzed click chemistry in water. Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, X-ray diffraction, and Ellman's assay test are used in the paper to characterize the compounds. Quartz crystal microbalance-dissipation (QCD-D) experiments and bacterial adhesion assay are utilized to study the interactions of polyrotaxane-based heteroglycopolymers with Con A and Escherichia coli. The results reveal that polyrotaxanes (PRs) with mannose and glucose present better specificity toward Con A and E. coli than PRs with glucose due to synergistic effects., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Quantification of the stimuli-responsive phase transition in polymers is topical and important for the understanding and development of novel stimuli-responsive materials. The temperature-induced phase transition of poly(N-isopropylacrylamide) (PNIPAm) with one thiol end group depends on the confinement-free polymer or polymer brush-on the molecular weight and on the nature of the second end. This paper describes the synthesis of heterotelechelic PNIPAm of different molecular weights with a thiol end group-that specifically binds to gold nanorods and a hydrophilic NIPAm end group by reversible addition-fragmentation chain-transfer polymerization. Proton high-resolution magic angle sample spinning NMR spectra are used as an indicator of the polymer chain conformations. The characteristics of phase transition given by the transition temperature, entropy, and width of transition are obtained by a two-state model. The dependence of thermodynamic parameters on molecular weight is compared for hydrophilic and hydrophobic end functional-free polymers and brushes., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The current state-of-the-art mixing strategies of nanoparticles with insulating polymeric components have only partially utilized the unique electrical conductivity of graphene in nanocomposite systems. Herein, this paper reports a nonmixing method of direct creation of polymer/graphene nanocomposites from polymer blends via laser irradiation. Polycarbonate-laser-induced graphene (PC-LIG) nanocomposite is produced from a PC/polyetherimide (PC/PEI) blend after exposure to commercially available laser scribing with a power of ≈6 W and a speed of ≈2 cm s -1 . Extremely high electrical conductivities are obtained for the PC-LIG nanocomposites, ranging from 26 to 400 S m -1 , depending on the vol% of the starting PEI phase in the blend. To the authors' knowledge, these conductivity values are at least one order of magnitude higher than the values that are previously reported for conductive polymer/graphene nanocomposites prepared via mixing strategies. The comprehensive microscopy and spectroscopy characterizations reveal a complete graphitization of the PEI phase with columnar microstructure embedded in the PC phase., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This paper reports the efficient synthesis of the first class of polyisobutylene(PIB)-supported palladium-PEPPSI precatalyst (PEPPSI = pyridine-enhanced precatalyst preparation, stabilization, and initiation). The new complexes are employed in Buchwald-Hartwig amination of aryl chlorides and are found to be reasonably active in the titled cross-coupling reaction. The supported catalysts are tested in polar (1,4-dioxane and 1,2-dimethoxyethane) as well as in aliphatic reaction media (toluene and n-heptane) and display superior activity in the highly lipophilic solvent (n-heptane). The catalytic efficacy of PIB-Pd-PEPPSI precatalyst is measured to be comparable to its nonsupported analog. Pd-leaching is determined by inductively coupled plasma mass spectrometry (ICP-MS) after a simple liquid/liquid extraction and is found to be 2 ppb in the product phase, translating into a recovery of ≈99.8% of the palladium., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photochromic materials are an important class of "smart materials" and are broadly utilized in technological devices. However, most photochromic materials reported so far are composed of inorganic compounds that are challenging to process and suffer from poor mechanical performance, severely limiting their applications in various markets. In this paper, inorganic photochromic tungsten trioxide (WO 3 ) nanocrystals are conveniently grafted with polymers to hurdle the deficiency in processability and mechanical properties. This new type of photochromic material can be thermally processed into desired geometries like disks and dog-bone specimens. Fully reversible photochromic response under UV light is also achieved for WO 3 -graft polymers, exhibiting tunable response rate, outperforming the pristine WO 3 nanocrystals. Notably, the resulted graft polymers show extraordinary mechanical performance with excellent ductility (≈800% breaking strain) and relatively high breaking strength (≈2 MPa). These discoveries elucidate an effective pathway to design smart inorganic/organic hybrid thermoplastic elastomers endowed with outstanding photochromic and mechanical properties as well as exceptional processability., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Highly conductive anion exchange membranes (AEMs), along with the ability to suppress swelling, are critical but challenging requirements for alkaline fuel cell applications. To achieve this criterion, a series of poly(ether sulfone)s (PESFs) with flexible alkyl imidazolium pendants attached directly on large planar 6,12-bis(4-hydroxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (DCP) units is reported. The planar DCP units stabilize the hydrophobic phase through strong π-π interactions and also facilitate the formation of ionic conducting channels through self assembly of hydrophilic pendants. The AEM prepared here, based on rational design, has a relatively low ion exchange capacity (IEC) of 1.86 × 10 -3 mol g -1 and exhibits high hydroxide ion (OH - ) conductivity of 101 × 10 -3 S cm -1 , a low swelling ratio of 9.3% and a water uptake of 39.6%. Furthermore, the AEMs reported in this paper have excellent stability in 1 m NaOH solution at 80 °C over 500 h. Therefore, the synthesized polymers offer a new insight into the design of high performance materials for AEMs., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Enzymatic catalysis and control over macromolecular architectures from reversible addition-fragmentation chain transfer polymerization (RAFT) are combined to give a new method of making polymers. Horseradish peroxidase (HRP) is used to catalytically generate radicals using hydrogen peroxide and acetylacetone as a mediator. RAFT is used to control the polymer structure. HRP catalyzed RAFT polymerization gives acrylate and acrylamide polymers with relatively narrow molecular weight distributions. The polymerization is rapid, typically exceeding 90% monomer conversion in 30 min. Complex macromolecular architectures including a block copolymer and a protein-polymer conjugate are synthesized using HRP to catalytically initiate RAFT polymerization., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this paper, a novel synthesis of polyethylene glycol (PEG)-modified polypyrrole (PPy) nanomaterials is demonstrated by combining reversible addition-fragmentation chain transfer polymerization and oxidative polymerization. Dye molecules with a heat-labile linker are used as a model drug and covalently anchored onto the PEGlated PPy nanomaterials via "click chemistry." The strong absorption of such PPy nanomaterials in the near-infrared region endows the system excellent photothermal effect, which can be used not only as efficient photothermal agents for photothermal therapy but also good controllers of a drug-release system by retro D-A reaction., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This paper describes a simple system for multi-agent delivery. The system consists of a biodegradable polymer particle with a hollow interior, together with a hole on its surface that can be completely or partially sealed via thermal annealing. A hydrophobic dye, Nile-red, entrapped within the shell of hollow particles presents a sustained release behavior while methylene blue, a hydrophilic model agent, encapsulated in the hollow interior shows a fast release manner. The release profiles of the probes can be further independently controlled by encapsulating methylene blue-loaded polymer nanoparticles, instead of free dye, in the hollow particle with a small hole on its surface., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this paper, the surface modification of CdSe- and CdZnS-based quantum dots (QDs) with a functional silica shell is reported. Functionalized silica shells are prepared by two routes: either by ligand exchange and a modified Stöber process or by a miniemulsion process with amphiphilic poly(oxyethylene) nonylphenylether also know as Igepal CO-520 (IG) as oligomeric amphiphile and modified silica precursors. The polymerizable groups on the functionalized silica shell allow covalent bonding to a polymer matrix and prevent demixing during polymerization and crosslinking. This allows the homogeneous incorporation of QDs in a crosslinked polymer matrix. This paper furthermore demonstrates that the resulting QDs, which are i) shielded with a proper silica shell and ii) functionalized with crosslinkable groups, can be used in two-photon-initiated polymerization processes in combination with different photoresists to obtain highly luminescent 3D structures. The resulting luminescent structures are attractive candidates for photonics and metamaterials research., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polyethers-polymers with the structural element (R'-O-R)n in their backbone--are an old class of polymers which were already used at the time of the ancient Egyptians. However, still today these materials are highly important with applications in all areas of our life, reaching from the automotive and paper industry to cosmetics and biomedical applications. In this Review, different aliphatic polyethers like poly(epoxide)s, poly(oxetane)s, and poly(tetrahydrofuran) are discussed. Special emphasis is placed on the history, the polymerization techniques (industrially and in academia), the properties, the applications as well as recent developments of these materials., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)