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Comprehensive Summary: Advanced functionalization‐decorated porous organic polymers (POPs) are emerging as a prominent research focus, spanning from their construction to applications in gas storage and separation, catalysis, energy storage, electrochemistry, and other areas. Furthermore, the inherent organic nature, tailored pore structures, and adjustable chemical components of POPs offer a versatile platform for the incorporation of various metal active sites. Meticulously designed molecular building blocks can serve as organic ligands uniformly distributed throughout POPs, leading to the effective isolation of inorganic metal active sites at the molecular level. In this manner, POPs containing active metal centers bridge the gap between organic and inorganic scaffolds. This review aims to provide an overview of recent research progress on metal‐decorated POPs, focusing on strategies for incorporating metal active sites into POPs and their applications in adsorption, separation, catalysis, and photoelectrochemistry. Finally, current challenges and future prospects are discussed for further research. Key Scientists: Advanced functionalized porous organic polymers have become a new research hotspot, ranging from their construction to their use in gas storage and separation, catalysis, energy storage, electrochemistry, and other applications. In 2002, the McKeown group was the first to report phthalocyanine‐based MPOPs with permanent porosity and a moderate surface area. In 2010, the Yu group prepared nanoporous polyporphyrin materials P(Fe‐TTPP) from the metallated porphyrin with functionalized thiophenyl groups by the FeCl3 catalyzed oxidation couple reaction showing the surface area of 1522 m2·g–1. Subsequently, in 2013, the Deng group was the first to use metalated salens as the original building blocks for preparing MPOPs. The Morin group was the first to produce a series of ferrocene‐based nanoporous frameworks via radical polymerization, with surface areas ranging from 385 to 899 m2·g–1. In 2016, the Han group synthesized two N‐pyridinylphenylcarbazole (PPC) ligands to produce a series of metalized polycarbazole networks. Recently, the Tan group reported a solvent‐knitting hyper‐cross‐linking reaction to produce HUST‐1, which contains a porphyrin unit. The porphyrin moiety provides a centered square‐planar metal post‐coordination site, resulting in the metalated HUST‐1‐Co, which exhibits high efficiency in the catalytic conversion of CO2. Additionally, the Kegnæs group combined the decomposition of the palladium complex with an in situ catalyzed polymerization reaction, enabling the confinement of nascent Pd particles in the developing polymer network. This review focuses on recent research progress in metal‐decorated POPs, emphasizing strategies for incorporating metal active sites into POPs and their applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • Modular bioengineered nanofibrils neutralize SARS-CoV-2 virus-like particles. • Recombinant protein subunits spontaneously assemble into functional fibrils. • The assembled amyloid-like nanofibrils are biocompatible. • Mesoscopic structure and activity of the protein assembly are easily modulated. • Surfaces coated with nanofibrils capture SARS-CoV-2 Spike in wet environments. The recent coronavirus disease 2019 (COVID-19) pandemic caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has spurred intense research efforts to develop new materials with antiviral activity. In this study, we genetically engineered amyloid-based nanofibrils for capturing and neutralizing SARS-CoV-2. Building upon the amyloid properties of a short Sup35 yeast prion sequence, we fused it to SARS-CoV-2 receptor-binding domain (RBD) capturing proteins, LCB1 and LCB3. By tuning the reaction conditions, we achieved the spontaneous self-assembly of the Sup35-LCB1 fusion protein into a highly homogeneous and well-dispersed amyloid-like fibrillar material. These nanofibrils exhibited high affinity for the SARS-CoV-2 RBD, effectively inhibiting its interaction with the angiotensin-converting enzyme 2 (ACE2) receptor, the primary entry point for the virus into host cells. We further demonstrate that this functional nanomaterial entraps and neutralizes SARS-CoV-2 virus-like particles (VLPs), with a potency comparable to that of therapeutic antibodies. As a proof of concept, we successfully fabricated patterned surfaces that selectively capture SARS-CoV-2 RBD protein on wet environments. Collectively, these findings suggest that these protein-only nanofibrils hold promise as disinfecting coatings endowed with selective SARS-CoV-2 neutralizing properties to combat viral spread or in the development of sensitive viral sampling and diagnostic tools. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Advanced functionalization‐decorated porous organic polymers (POPs) are emerging as a prominent research focus, spanning from their construction to applications in gas storage and separation, catalysis, energy storage, electrochemistry, and other areas. Furthermore, the inherent organic nature, tailored pore structures, and adjustable chemical components of POPs offer a versatile platform for the incorporation of various metal active sites. Meticulously designed molecular building blocks can serve as organic ligands uniformly distributed throughout POPs, leading to the effective isolation of inorganic metal active sites at the molecular level. In this manner, POPs containing active metal centers bridge the gap between organic and inorganic scaffolds. This review aims to provide an overview of recent research progress on metal‐decorated POPs, focusing on strategies for incorporating metal active sites into POPs and their applications in adsorption, separation, catalysis, and photoelectrochemistry. Finally, current challenges and future prospects are discussed for further research. Key Scientists: Advanced functionalized porous organic polymers have become a new research hotspot, ranging from their construction to their use in gas storage and separation, catalysis, energy storage, electrochemistry, and other applications. In 2002, the McKeown group was the first to report phthalocyanine‐based MPOPs with permanent porosity and a moderate surface area. In 2010, the Yu group prepared nanoporous polyporphyrin materials P(Fe‐TTPP) from the metallated porphyrin with functionalized thiophenyl groups by the FeCl3 catalyzed oxidation couple reaction showing the surface area of 1522 m2·g–1. Subsequently, in 2013, the Deng group was the first to use metalated salens as the original building blocks for preparing MPOPs. The Morin group was the first to produce a series of ferrocene‐based nanoporous frameworks via radical polymerization, with surface areas ranging from 385 to 899 m2·g–1. In 2016, the Han group synthesized two N‐pyridinylphenylcarbazole (PPC) ligands to produce a series of metalized polycarbazole networks. Recently, the Tan group reported a solvent‐knitting hyper‐cross‐linking reaction to produce HUST‐1, which contains a porphyrin unit. The porphyrin moiety provides a centered square‐planar metal post‐coordination site, resulting in the metalated HUST‐1‐Co, which exhibits high efficiency in the catalytic conversion of CO2. Additionally, the Kegnæs group combined the decomposition of the palladium complex with an in situ catalyzed polymerization reaction, enabling the confinement of nascent Pd particles in the developing polymer network. This review focuses on recent research progress in metal‐decorated POPs, emphasizing strategies for incorporating metal active sites into POPs and their applications. [ABSTRACT FROM AUTHOR]

The overuse and ineffective management of plastics have led to significant environmental pollution. Catalytic upcycling into value-added chemicals has emerged as a promising solution. This review provides a comprehensive overview of recent advances in catalytic upcycling, focusing on the cleavage of chemical bonds such as carbon-carbon (C-C), carbon-oxygen (C-O), and carbon-hydrogen (C-H) in plastics. It systematically discusses plastics conversion via electrocatalysis, thermal catalysis, and photocatalysis. Additionally, it explores the conversion of plastics into value-added chemicals and functional polymers. The review also addresses the challenges in this field and aims to offer insights for developing sustainable and effective plastics upcycling technologies. [ABSTRACT FROM AUTHOR]

AbstractThe depletion of petroleum-based fossil resources and ever-increasing environmental problems are serious issues in the production of polymeric materials. An increasingly important approach is to obtain the building blocks used in the production of these materials from renewable sources of natural origin. In the present study, bio-sourced tartaric acid-based tartarimides were evaluated as monomeric diol compounds to synthesize polyurethane polymers. Structurally diverse tartarimides were conveniently obtained from the condensation reactions of tartaric acid with various primary amine compounds. The diol structure of the generated tartarimides allowed to access polyurethanes along with the polymerizations of diisocyanate monomers. Copolymers in the range of 22.9 kDa to 29.3 kDa molecular weights were obtained with moderately high total monomer conversions (up to 96%). Depending on the tartarimide and diisocyanate monomers employed during polymerization, copolymers with different physical and thermal properties were generated. By utilizing tartarimides carrying furan and alkene functionalities, side chain reactive polyurethanes were synthesized. These reactive polymers were evaluated in post-polymerization modification and crosslinking processes by using radical thiol-ene and Diels-Alder based click reactions. The results obtained in this study demonstrated that the bio-sourced tartarimides could provide a convenient access to structurally tailorable polyurethane polymers that are important materials in various applications. [ABSTRACT FROM AUTHOR]

Exfoliated graphite (ExG) embedded in a polymeric matrix represents an accessible, cost-effective, and sustainable method for generating nanosized graphite-based polymer composites with multifunctional properties. This review article analyzes diverse methods currently used to exfoliate graphite into graphite nanoplatelets, few-layer graphene, and polymer-assisted graphene. It also explores engineered methods for small-scale pilot production of polymer nanocomposites. It highlights the chemistry involved during the graphite intercalation and exfoliation process, particularly emphasizing the interfacial interactions related to steric repulsion forces, van der Waals forces, hydrogen bonds, π-π stacking, and covalent bonds. These interactions promote the dispersion and stabilization of the graphite derivative structures in polymeric matrices. Finally, it compares the enhanced properties of nanocomposites, such as increased thermal and electrical conductivity and electromagnetic interference (EMI) shielding applications, with those of neat polymer materials. [ABSTRACT FROM AUTHOR]

Low‐cost and high‐performance electronics based on synthetically simple materials are required to fuel the deployment of smart packaging and wearable electronics. Metal phthalocyanines (MPcs) are promising semiconductors for use in n‐type organic thin film transistors (OTFTs) but often require high operating voltages. The first silicon phthalocyanine‐based OTFT with a polymer dielectric is reported as an alternative to traditional metal oxide dielectrics. Incorporating poly(methyl methacrylate) (PMMA) as the dielectric successfully reduces the threshold voltage (VT) of bispentafluorophenoxy SiPc (F10‐SiPc) from 14.9V to 7.3V while retaining high mobility. Further reduction in VT is obtained by using copolymers and blends of PMMA and dimethylamino ethyl methacrylate (DMAEMA)‐containing polymers, where a higher molar fraction of DMAEMA leads to a consistent drop in VT to ‐0.7 V. The electron‐donating groups of the tertiary amines in the DMAEMA show clear interfacial doping of the semiconductor, reducing the voltage required to populate the dielectric/semiconductor interface with charge carriers and turn on the device. Blending trace amounts of DMAEMA‐containing copolymers with PMMA proves to be an effective strategy for reducing the VT while keeping the charge mobility high, unlike when using pure copolymers with elevated DMAEMA content. Time of flight secondary ion mass spectroscopy (ToF‐SIMS) and X‐ray photoelectron spectroscopy (XPS) demonstrate that the DMAEMA‐containing copolymer is floating to the surface of the PMMA blend at the dielectric–semiconductor interface, which explains the reduced VT. Synchrotron scanning transmission X‐ray microscopy (STXM) demonstrates that PMMA promotes a more edge‐on orientation of F10‐SiPc films, compared to the more face‐on orientation when deposited on the DMAEMA containing copolymer. This study demonstrates a straightforward process for designing dielectric polymers and their blends for the reduction in VT for n‐type OTFTs. [ABSTRACT FROM AUTHOR]

Polymeric materials with antibacterial properties hold great promise for combating multidrug‐resistant bacteria, which pose a significant threat to public health. However, the synthesis of most antibacterial polymers typically involves complicated and time‐consuming procedures. In this study, we demonstrate a simple and efficient strategy for synthesizing functional poly(vinylpyridinium salt)s via pyridinium‐yne click polymerization. This click polymerization could proceed with high atom economy under mild conditions without any external catalyst, yielding soluble and thermally stable poly(vinylpyridinium salt)s with satisfactory molecular weights and well‐defined structures in excellent yields. Additionally, the incorporation of luminescent units such as fluorene, tetraphenylethylene, and triphenylamine into the polymer backbone confers excellent aggregation‐enhanced emission properties upon the resulting polymers, rendering them suitable for bacterial staining. Moreover, the existence of pyridinium salt imparts intrinsic antibacterial activity against multidrug‐resistant bacteria to the polymers, enabling them to effectively inhibit wound bacterial infection and significantly expedite the healing process. This work not only provides an efficient method to prepare antibacterial polymers, but also opens up the possibility of various applications of polymers in healthcare and other antibacterial fields. [ABSTRACT FROM AUTHOR]

The properties of polymer mixtures obtained by various methods in solid phase, solution and emulsion have been investigated. It has been shown that it is possible to obtain composite materials with different properties based on mixtures of polymers obtained in the solid phase as a result of thermal-mechanical effects. It has been determined that the addition of PVC of 5-10 k.h. leads to an increase in the unsaturation of the elastomers and the amount of chlorine combined in them. The increase in the reactivity of elastomers makes it possible to obtain compositions resistant to various effects based on them. Properties of mixtures obtained from separately diluted solutions with elastomers - SKEP-50 and SKEPT-60 and functional polymers - PVC and CAPP have been investigated. It has been shown that despite the absence of chemical bonding in such mixtures, physical bonding occurs in the resulting mixtures. As a result, it has been confirmed by various methods that there is combined chlorine in the mixtures and that a new structure is formed, different from the structure of the initial components. Emulsions of SKEP-50, SKEP-60 and PVC have been obtained and mixed. The physical-chemical properties of the mixture of emulsions and IR spectrum and stability of the polymer layer obtained from the mixtures have been investigated. It has been shown that, unlike emulsions of initial polymers, the emulsion mixture has high physical-chemical and durability properties and can be used as a protective coating. [ABSTRACT FROM AUTHOR]

Functional polymers play an important role in various biomedical applications. From many choices, poly(2-isopropenyl-2-oxazoline) (PIPOx) represents a promising reactive polymer with great potential in various biomedical applications. PIPOx, with pendant reactive 2-oxazoline groups, can be readily prepared in a controllable manner via several controlled/living polymerization methods, such as living anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition–fragmentation transfer (RAFT) or rare earth metal-mediated group transfer polymerization. The reactivity of pendant 2-oxazoline allows selective reactions with thiol and carboxylic group-containing compounds without the presence of any catalyst. Moreover, PIPOx has been demonstrated to be a non-cytotoxic polymer with immunomodulative properties. Post-polymerization functionalization of PIPOx has been used for the preparation of thermosensitive or cationic polymers, drug conjugates, hydrogels, brush-like materials, and polymer coatings available for drug and gene delivery, tissue engineering, blood-like materials, antimicrobial materials, and many others. This mini-review covers new achievements in PIPOx synthesis, reactivity, and use in biomedical applications. [ABSTRACT FROM AUTHOR]

The majority of bioactive polysaccharides are present in some marine creatures. These polysaccharides are considered as promising anti-obesity agents, their anti-obesity properties involve a number of mechanisms, including suppression of lipid metabolism and absorption, impact on satiety, and prevention of adipocyte diferentiation. Obesity is linked to type 2 diabetes, cardiovascular disease, and other metabolic syndromes. In this review various bioactive polysaccharides like chitin, chitosan, fucosylated chondroitin sulphate, chitooligosaccharides and glycosaminoglycans have been discussed for their anti-obesity efects through various pathways. Critical evaluation of observational studies and intervention trials on obesity, lipid hypertrophy, dyslipidemia, and type 2 diabetes was done with a primary focus on specifc marine fauna polysaccharide as a source of seafood that is consumed all over the world. It has been observed that consumption of individual seafood constituents was efective in reducing obesity. Thus, marine derived novel bioactive polysaccharides have potential applications in food and pharmaceutical industries. [ABSTRACT FROM AUTHOR]

Fabric‐reinforced shape memory polymer composites are lightweight, strong, formable, controllable, and suitable for various engineering and innovative applications. This study aims to fabricate and characterize electrothermal dual drive shape memory polymer composite fabrics (SMPCFs) of different densities with three‐dimensional (3D) angle‐interlock structures. The tensile properties, electrothermal properties, recovery forces (both tensile and bending), and shape recovery properties of SMPCFs were evaluated. The SMPCFs exhibited a tensile elongation of over 20% at the transition temperature. SMPCFs can reach transition temperatures when loaded with 2 V. The recovery forces are up to 225 N in tensile recovery force and 3.6 N in bending recovery force. In the shape recovery test, the recovery ratio exceeded 97%. Finally, the demonstration of recovery properties can stimulate the possibilities of SMPCFs in innovation and applications. Highlights: Core‐shell structured composite filaments were prepared.3D angle‐interlock composite fabrics: high strength, electrothermal drive.Tensile recovery force of composite fabrics can be up to 225 N.Elongation at transition temperatures was up to 20%. [ABSTRACT FROM AUTHOR]

Chiral materials with circularly polarized luminescence (CPL) have garnered significant attention owing to their distinctive luminescent properties and wide array of applications. CPL enables the selective emission of left and right circularly polarized light. The fluorescence quantum yield and dissymmetry factor play pivotal roles in the generation of CPL. Helical polymers exhibit immense promise as CPL materials due to their inherent chirality, structural versatility, modifiability, and capacity to incorporate diverse chromophores. This Review provides a brief review of the synthesis of CPL materials based on helical polymers. The CPL can be realized by aggregation‐induced CPL of non‐emissive helical polymers, and helices bearing chromophores on the pendants and on the chain end. Furthermore, future challenges and potential applications of CPL materials are summarized and discussed. [ABSTRACT FROM AUTHOR]

This work presents the use of natural rubber (NR) grafted with poly(vinyl propionate) (NR-g-PVP) as an alternative compatibilizer in silica-filled NR compounds. The effects of NR-g-PVP with 10, 20 and 30% grafting on the properties of NR compounds were studied and compared with a commercial coupling agent (bis[3-(triethoxysilyl)propyl] tetrasulfide, TESPT). NR-g-PVP was compatible with silica and NR. The NR-g-PVP reduced filler-filler interactions and increased fillerrubber interactions. The crosslink density decreased with the percentage of grafting due to the steric hindrance. The compatibilization affected the physical and mechanical properties. The interactions of NR-g-PVP with silica via hydrogen bonding and subsequent vulcanization prevented undesirable filler-filler interactions and reduced the absorption of accelerators or basic materials. It caused a good dispersion of silica in the NR matrix and improved physical and mechanical properties. A 10% grafting (G10) was suitable for the compatibilizer in a silica-filled NR compound, showing the largest improvements in tensile properties, tear strength, and hardness. However, TESPT provided better properties than G10. [ABSTRACT FROM AUTHOR]

Smart materials represent an emerging and highly exploited category, particularly in the creation of textiles that can sense and respond to various external stimuli, such as temperature or humidity. This study introduces for the first time the hygroscopic elongation and drying shrinkage properties of stimulus-responsive single-component polyamide (PA) fibers copolymerized with polyetherdiamine and diethylenetriamine (DETA). PA copolymers containing 5-15% polyetherdiamine were comprehensively characterized, including nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR), relative viscosity, and differential scanning calorimetry (DSC) analyses. Subsequently, these PA copolymers were successfully melt-spun into fibers and knitted into double-layered fabrics. PA fibers containing 15% polyetherdiamine showed significant results, with a moisture-absorbing elongation of 15.6% and a drying shrinkage of 94.9%. The Qmax and moisture regain of the PA fabric are 0.206 W·cm-2 and 4.4%, respectively. These moisture-driven, fiber-based smart textiles exhibit changes in breathability and shape retention at different humidity levels, thereby maintaining a more comfortable microclimate. Such textiles have great potential for widespread use in clothing, helping to improve comfort and adaptability. [ABSTRACT FROM AUTHOR]

Novel metastable intermixed composites (MICs) constructed by carbon nanomaterials are expected to achieve high energy content and high combustion efficiency, but traditional preparation technologies always bring barely improvement in performance. Herein, novel PVDF/CuO/Al@CNTs MICs with independent continuous carbon nanotubes (CNTs) conductive networks were prepared by thoroughly utilizing the conductivity and photothermal properties of CNTs. A conductive network can be constructed at the interface of each encapsulated PVDF/CuO/Al particle with the addition of >0.5 wt% CNTs. The great increase in electrical and thermal conductivity of PVDF/CuO/Al@CNTs MICs indicates excellent energy transfer efficiency across the sample. Significant enhancement of the combustion reaction has been achieved, with the minimum ignition energy and ignition delay time of PVDF/CuO/Al@CNTs3 reduced by ~31% and ~50%, respectively. This indicates that the CNTs with unique photothermal properties can be utilized as an effective igniter. Moreover, the optimal PVDF/CuO/Al@CNTs1 MICs enhanced the pressurization rate (~300%), energy output (~55%), and combustion velocity (~200%). The mechanism of the fast combustion reaction can also be discussed by the weak interface interaction and the energy conductive of the CNTs network throughout the sample. This work provides a modern strategy for strong combustion MICs that can be generalized and applied in the field of energetic materials. Highlights: An independent continuous CNTs conductive network was prepared with a small amount of CNTs.The electrical and heat conversion efficiency is greatly improved.CNTs with unique photothermal properties can be utilized as an effective igniter.The laser sensitivity is improved, and the reaction energy, pressure, and pressure rates are significantly increased.The combustion performance was significantly improved, and more intense, and the combustion speed was significantly increased. [ABSTRACT FROM AUTHOR]

This study introduces an efficient strategy for synthesizing polyhydroxyurethane-based multicomponent hydrogels with enhanced rheological properties. In a single-step process, 3D materials composed of Polymer 1 (PHU) and Polymer 2 (PVA or gelatin) were produced. Polymer 1, a crosslinked polyhydroxyurethane (PHU), grew within a colloidal solution of Polymer 2, forming an interconnected network. The synthesis of Polymer 1 utilized a Non-Isocyanate Polyurethane (NIPU) methodology based on the aminolysis of bis(cyclic carbonate) (bisCC) monomers derived from 1-thioglycerol and 1,2-dithioglycerol (monomers A and E, respectively). This method, applied for the first time in Semi-Interpenetrating Network (SIPN) formation, demonstrated exceptional orthogonality since the functional groups in Polymer 2 do not interfere with Polymer 1 formation. Optimizing PHU formation involved a 20-trial methodology, identifying influential variables such as polymer concentration, temperature, solvent (an aprotic and a protic solvent), and the organo-catalyst used [a thiourea derivative (TU) and 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU)]. The highest molecular weights were achieved under near-bulk polymerization conditions using TU-protic and DBU-aprotic as catalyst–solvent combinations. Monomer E-based PHU exhibited higher M w ¯ than monomer A-based PHU (34.1 kDa and 16.4 kDa, respectively). Applying the enhanced methodology to prepare 10 multicomponent hydrogels using PVA or gelatin as the polymer scaffold revealed superior rheological properties in PVA-based hydrogels, exhibiting solid-like gel behavior. Incorporating monomer E enhanced mechanical properties and elasticity (with loss tangent values of 0.09 and 0.14). SEM images unveiled distinct microstructures, including a sponge-like pattern in certain PVA-based hydrogels when monomer A was chosen, indicating the formation of highly superporous interpenetrated materials. In summary, this innovative approach presents a versatile methodology for obtaining advanced hydrogel-based systems with potential applications in various biomedical fields. [ABSTRACT FROM AUTHOR]

The growing interest in functional materials has resulted in the emergence of smart polymers, demonstrating practical performance in various applications especially for biomedical purposes. The properties of functional polymers are mainly determined by the presence of functional groups that differ from those in the main chains. While some polymers are naturally active and considered functional, others require modification for enhanced impact and functionality. Many functional polymers typically have a linear backbone, but very recently the attention has been shifted towards those with specific topologies and architecture, for example, bottlebrushes, stars, dendritic polymers, and gels. Over the past few years, there has been a rising emphasis on integrating selective bonds into complex polymer structures to enhance chain scission in single macromolecules. This review captures the most recent and promising approaches to the design of non-linear functional polymers containing selective/cleavable bonds and discusses the potential of these materials for biomedical applications. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Polyhydroxyurethanes (PHUs) have received considerable attention in the last decade as potential alternatives to traditional phosgene‐based polyurethanes (PUs). The development of suitable 5CC (five membered‐ring cyclic carbonate) precursors bearing multiple carbonate moieties (multi‐5CCs) is a key requisite for preparing PHUs by polyaddition reaction with bis‐ or polyamines. Producing sustainable PHUs from CO2‐based five‐membered cyclic carbonates (5CCs) obtained from biobased epoxides is a valuable strategy to bridge CO2 utilization and the upcycling of renewable substrates. In this context, while many multi‐5CC monomers reported in the literature are oil‐based, recent efforts have led to the development of a large variety of multifunctional 5CCs that are produced by the combination of CO2 and renewable resources such as fatty acids and vegetable oils, lignin, terpenes, and sugars. In this work, recent crucial advances (2019—2023) on PHUs prepared from bis‐ and multi‐5CCs produced from CO2 and (partially/potentially) biobased substrates are reviewed with respect to their synthesis, thermal and mechanical properties, and their recent, emerging applications. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Polyhydroxyurethanes (PHUs) have received considerable attention in the last decade as potential alternatives to traditional phosgene‐based polyurethanes (PUs). The development of suitable 5CC (five membered‐ring cyclic carbonate) precursors bearing multiple carbonate moieties (multi‐5CCs) is a key requisite for preparing PHUs by polyaddition reaction with bis‐ or polyamines. Producing sustainable PHUs from CO2‐based five‐membered cyclic carbonates (5CCs) obtained from biobased epoxides is a valuable strategy to bridge CO2 utilization and the upcycling of renewable substrates. In this context, while many multi‐5CC monomers reported in the literature are oil‐based, recent efforts have led to the development of a large variety of multifunctional 5CCs that are produced by the combination of CO2 and renewable resources such as fatty acids and vegetable oils, lignin, terpenes, and sugars. In this work, recent crucial advances (2019—2023) on PHUs prepared from bis‐ and multi‐5CCs produced from CO2 and (partially/potentially) biobased substrates are reviewed with respect to their synthesis, thermal and mechanical properties, and their recent, emerging applications. [ABSTRACT FROM AUTHOR]

Functional polymers as solid-supported reagents and catalysts for organic synthesis were conventionally based on cross-linked polystyrene (PS). Polyacrylamide (PAM), modified PAM and their copolymers as hydrophilic support, alternatively can be used as heterogeneous systems in several areas of chemistry and industry. After Regen's report in 1979 that applied cross-linked PAM as a solid phase cosolvent, PAM-supported reagents and catalysts manifest an excessively important function in various organic reactions. This review summarizes the entire features of PAM and its modified forms and focuses on their most recent and relevant applications in organic transformations. Oxidation–reduction reactions, C–C cross-coupling reactions, and Michael addition reactions are among the most important transformation in which PAM and its derivatives have been widely used. Other reactions like substitution reactions, H2O2 decomposition, 1,3-thiazoles synthesis, oxidative esterification, dichlorocyclopropanation, protection of carbonyl compounds, ring opening of epoxides, and dye decolorization have also been investigated. Furthermore, the efficiency, reusability, and limitations associated with these supported systems are discussed. Herein, applications of functional polymers based on polyacrylamide, modified PAM and their copolymers for the production of polymer supported reagents and catalysts are reviewed. This review summarizes the entire features of PAM and its modified forms and focuses on their most recent and relevant applications in organic transformations such as oxidation–reduction reactions, C–C cross-coupling reactions, Michael addition reactions etc. Furthermore, the efficiency, reusability, and limitations associated with these supported systems are discussed. [ABSTRACT FROM AUTHOR]

Abstract Low‐cost and high‐performance electronics based on synthetically simple materials are required to fuel the deployment of smart packaging and wearable electronics. Metal phthalocyanines (MPcs) are promising semiconductors for use in n‐type organic thin film transistors (OTFTs) but often require high operating voltages. The first silicon phthalocyanine‐based OTFT with a polymer dielectric is reported as an alternative to traditional metal oxide dielectrics. Incorporating poly(methyl methacrylate) (PMMA) as the dielectric successfully reduces the threshold voltage (VT) of bispentafluorophenoxy SiPc (F10‐SiPc) from 14.9V to 7.3V while retaining high mobility. Further reduction in VT is obtained by using copolymers and blends of PMMA and dimethylamino ethyl methacrylate (DMAEMA)‐containing polymers, where a higher molar fraction of DMAEMA leads to a consistent drop in VT to ‐0.7 V. The electron‐donating groups of the tertiary amines in the DMAEMA show clear interfacial doping of the semiconductor, reducing the voltage required to populate the dielectric/semiconductor interface with charge carriers and turn on the device. Blending trace amounts of DMAEMA‐containing copolymers with PMMA proves to be an effective strategy for reducing the VT while keeping the charge mobility high, unlike when using pure copolymers with elevated DMAEMA content. Time of flight secondary ion mass spectroscopy (ToF‐SIMS) and X‐ray photoelectron spectroscopy (XPS) demonstrate that the DMAEMA‐containing copolymer is floating to the surface of the PMMA blend at the dielectric–semiconductor interface, which explains the reduced VT. Synchrotron scanning transmission X‐ray microscopy (STXM) demonstrates that PMMA promotes a more edge‐on orientation of F10‐SiPc films, compared to the more face‐on orientation when deposited on the DMAEMA containing copolymer. This study demonstrates a straightforward process for designing dielectric polymers and their blends for the reduction in VT for n‐type OTFTs.

Herein, four hyper-cross-linked amide resins (DMDs) were synthesized by suspension polymerization and amination reaction. In the process of suspension polymerization, different feed ratios of divinylbenzene (DVB) and maleic anhydride (MAH) generated macroporous interpenetrating network resins (DMH) with different pore structures. After chemical modification of DMH with N,N'-dimethyl-1,3-propanediamine (DMAPA), the weak base exchange ability of the resulting resins was significantly improved, with values of 1.01 mmol/g (DMD1), 1.15 mmol/g (DMD2), 1.22 mmol/g (DMD3), and 1.34 mmol/g (DMD4), respectively. Salicylic acid (SA), benzoic acid (BA), gallic acid (GA), and phenol (PHE) were selected as adsorbents to investigate the adsorption performance of the resins. At 288 K, the maximum capacity (qmax) of SA, BA, and GA on the DMD4 were 193.7 mg/g, 143.8 mg/g, and 145.2 mg/g, respectively. The adsorption of BA and GA reached equilibrium within 100 min, and the kinetic data could be described using the pseudo second order (PSO) rate model. DMD4 resin had high adaptability for adsorbing salicylic acid in both aqueous and isopropanol solutions. This universal suspension polymerization synthesis method was of great significance for synthesizing other functionalized hyper-cross-linked polymers, and this weak alkaline functionalization strategy was universal for the amination modification of other resins. [ABSTRACT FROM AUTHOR]

The aggregate luminescence behaviors of polymeric luminescent materials have been attracting great attention. However, the importance of the polymerization process on luminescence, namely, polymerization‐induced emission (PIE), has rarely been overviewed. In this review, recent advances in polymerization with PIE effects are summarized, including PIE with aromatic rings based on one‐/two‐/multi‐component polymerizations, and PIE without aromatic rings according to disparate mechanisms of polymerizations. Typical examples are selected to elaborate the basic design principles, as well as the properties and potential applications of the luminous polymers. Moreover, the challenges and perspectives in this area are also discussed. [ABSTRACT FROM AUTHOR]

In this work, innovative hybrid poly(ethylene terephthalate) (PET) materials with strong luminescence were successfully synthesized by doping PET with silicon‐linked poly(ethylene glycol)‐PET copolymer nanostructures either with (Si‐PEG‐PET) or with (ETP@Si‐PEG‐PET) luminescent Eu3+‐complexes. The chemical properties and nanostructures of the hybrid materials were characterized by Fourier‐transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, x‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy. PET composites ranging from 0.25 to 4 wt% silicon additive were prepared by the melt blending method. The crystal properties, mechanical properties, and fluorescence properties of the composites were systematically studied by differential scanning calorimetry, x‐ray diffractometry, tensile testing, and fluorescence spectrometry. When the addition of Si‐PEG‐PET or ETP@Si‐PEG‐PET was 0.75 wt%, the relative crystallinity and maximum tensile strength increase substantially. Moreover, the fluorescence intensity of hybrid luminescent PET materials is the strongest at 0.75 wt% loading. ETP@Si‐PEG‐PET not only endows PET polyester with stronger fluorescence properties and mechanical properties but also acts as an effective nucleation additive for PET. Highlights: Silicon‐linked poly(ethylene glycol)‐poly(ethylene terephthalate) (PEG‐PET) nanostructures generate hybrid luminescent PET materials.ETP@Si‐PEG‐PET improves the crystallization rate and crystallinity of PET.The composite with 0.75% addition showed the best fluorescence performance.Three‐dimensional‐grid structure of ETP@Si‐PEG‐PET enhances the mechanical property of PET. [ABSTRACT FROM AUTHOR]

Conventional polymers, endowed with specific functionalities, are extensively utilized for filtering and extracting a diverse set of chemicals, notably metals, from solutions. The main structure of a polymer is an integral part for designing an efficient separating system. However, its chemical functionality further contributes to the selectivity, fabrication process, and resulting product morphology. One example would be a membrane that can be employed to selectively remove a targeted metal ion or chemical from a solution, leaving behind the useful components of the solution. Such membranes or products are highly sought after for purifying polluted water contaminated with toxic and heavy metals. An efficient water-purifying membrane must fulfill several requirements, including a specific morphology attained by the material with a specific chemical functionality and facile fabrication for integration into a purifying module Therefore, the selection of an appropriate polymer and its functionalization become crucial and determining steps. This review highlights the attempts made in functionalizing various polymers (including natural ones) or copolymers with chemical groups decisive for membranes to act as water purifiers. Among these recently developed membrane systems, some of the materials incorporating other macromolecules, e.g., MOFs, COFs, and graphene, have displayed their competence for water treatment. Furthermore, it also summarizes the self-assembly and resulting morphology of the membrane materials as critical for driving the purification mechanism. This comprehensive overview aims to provide readers with a concise and conclusive understanding of these materials for water purification, as well as elucidating further perspectives and challenges. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Various optically active polymers are known to afford sophisticated chirality‐related functionalities, i.e., asymmetric catalysis, chiroptical switching and memory in UV‐vis‐NIR region, chromatographic separation of enantiomers, and sensors for molecular chirality. Recently, material researchers have paid much attention to the design of chiral supramolecular architectures from achiral polymers upon intermolecular interactions with help of greener biosources. The present article reports an instantaneous generation of ambidextrous supramolecules revealing light‐driven chiroptical switching/memory in UV‐vis region when achiral azobenzene‐containing vinylpolymers are non‐covalently interacted with alkyl ester derivatives of natural cellulose and D‐/L‐glucose. It was recognized that the semi‐synthetic biomaterials efficiently work as chirality‐inducing scaffoldings to several achiral and optically inactive molecules, oligomers, and polymers. Our successful results shed light on a new approach of how inexpensive poly‐/mono‐saccharide derivatives can afford supramolecular chiroptical systems with the azobenzene pendant polymer as aggregates in suspension and liquid‐crystalline films with minimal energy, time, and cost. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Inflammation is associated with different stages of liver disease, including acute injury, fibrosis, cirrhosis, and hepatoma. During the progression of liver inflammation, activation of hepatic stellate cells (HSCs) and extracellular matrix (ECM) deposition are critical pathologies, and thus the combined therapy using HSCs and ECM as targets represents a promising strategy in the treatment of liver injury. Here, a novel CXCR4‐inhibiting nanomedicine that can simultaneously deliver AMD3100 (CXCR4 antagonist) and siPAI‐1 (siRNA of plasminogen activator inhibitor‐1) was designed and developed to reverse liver fibrosis by inhibiting HSCs activation and degrading ECM deposition. With this goal in mind, a Zn(II) coordinated polymeric AMD3100 named PAMD/Zn polymer with siRNA delivery and CXCR4 antagonism capabilities was synthesized. Overall, our results suggest that PAMD/Zn recruits pro‐inflammatory cells for fibrogenesis and inhibits the activation of HSCs for fibrolysis at various stages of liver injury. Its use in conjunction with PAI‐1 silencing achieved satisfactory therapeutic efficacy in liver injury and fibrosis. The derivative CXCR4‐inhibiting nanomedicine is a versatile platform that offers valuable benefits for the treatment of liver diseases. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Inflammation is associated with different stages of liver disease, including acute injury, fibrosis, cirrhosis, and hepatoma. During the progression of liver inflammation, activation of hepatic stellate cells (HSCs) and extracellular matrix (ECM) deposition are critical pathologies, and thus the combined therapy using HSCs and ECM as targets represents a promising strategy in the treatment of liver injury. Here, a novel CXCR4‐inhibiting nanomedicine that can simultaneously deliver AMD3100 (CXCR4 antagonist) and siPAI‐1 (siRNA of plasminogen activator inhibitor‐1) was designed and developed to reverse liver fibrosis by inhibiting HSCs activation and degrading ECM deposition. With this goal in mind, a Zn(II) coordinated polymeric AMD3100 named PAMD/Zn polymer with siRNA delivery and CXCR4 antagonism capabilities was synthesized. Overall, our results suggest that PAMD/Zn recruits pro‐inflammatory cells for fibrogenesis and inhibits the activation of HSCs for fibrolysis at various stages of liver injury. Its use in conjunction with PAI‐1 silencing achieved satisfactory therapeutic efficacy in liver injury and fibrosis. The derivative CXCR4‐inhibiting nanomedicine is a versatile platform that offers valuable benefits for the treatment of liver diseases. [ABSTRACT FROM AUTHOR]

The seminar "New Organic Functional Materials" was held from July 3 to 6, 2023, at St. Petersburg State University as part of the All-Russian Conference with international participation "Ideas and Legacy of A.E. Favorsky in Organic Chemistry." The seminar program included reports on organic materials with luminescence, photosensitizing, conductive, and magnetic properties and biological activity and also touched upon new methods for the synthesis of functional organic molecules and their crystallochemical design. The present review contains brief annotations of the reports, as well as references to relevant works of the speakers. [ABSTRACT FROM AUTHOR]

Anion exchange membranes (AEMs) are core components in fuel cells and water electrolyzers, which are crucial to realize a sustainable hydrogen society. The low anion conductivity and durability of AEMs have hindered the commercialization of AEM-based devices, and research and development (R&D) to improve AEM materials is often resource-intensive. Although machine learning (ML) is commonly used in many fields to accelerate R&D while reducing resource consumption, it is rarely used in the AEM field. Three problems hinder the adoption of ML models, namely, the low explainability of ML models; complication with expressing both homopolymers and copolymers in unity to train a single ML model; and difficulty in building a single ML model that comprehends various polymer types. This study presents the first ML models that solve all three problems. Our models predicted the anion conductivity for a diverse set of unseen AEM materials with high accuracy (root mean squared error = 0.014 S cm−1), regardless of their state (freshly synthesized or degraded). This enables virtual pre-synthesis screening of novel AEM materials, reducing resource consumption. Moreover, human-comprehensible prediction logic revealed new factors affecting the anion conductivity of AEM materials. Such capability to reveal new important variables for AEM materials design could shift the paradigm of AEM R&D. This proposed method is not limited to AEM materials, instead it presents a technology that is applicable to the diverse set of polymers currently available. This study reports a transparent and trustable machine learning model for use in researching polymeric materials, fueling the momentum towards data-driven research, which will significantly reduce research-originating environmental impact. [ABSTRACT FROM AUTHOR]

ABSTRACTAnion exchange membranes (AEMs) are core components in fuel cells and water electrolyzers, which are crucial to realize a sustainable hydrogen society. The low anion conductivity and durability of AEMs have hindered the commercialization of AEM-based devices, and research and development (R&D) to improve AEM materials is often resource-intensive. Although machine learning (ML) is commonly used in many fields to accelerate R&D while reducing resource consumption, it is rarely used in the AEM field. Three problems hinder the adoption of ML models, namely, the low explainability of ML models; complication with expressing both homopolymers and copolymers in unity to train a single ML model; and difficulty in building a single ML model that comprehends various polymer types. This study presents the first ML models that solve all three problems. Our models predicted the anion conductivity for a diverse set of unseen AEM materials with high accuracy (root mean squared error = 0.014 S cm−1), regardless of their state (freshly synthesized or degraded). This enables virtual pre-synthesis screening of novel AEM materials, reducing resource consumption. Moreover, human-comprehensible prediction logic revealed new factors affecting the anion conductivity of AEM materials. Such capability to reveal new important variables for AEM materials design could shift the paradigm of AEM R&D. This proposed method is not limited to AEM materials, instead it presents a technology that is applicable to the diverse set of polymers currently available.

Comprehensive Summary: The study of luminescence phenomena in non‐conjugated systems, namely clusteroluminescence, has gained significant attention for the development of advanced luminescent materials. While conventional strategies to manipulate the luminescent performances are based on complicated chemical reactions. In contrast, nature employs complexation to modulate luminescence, inspiring researchers to adopt an engineering approach for the construction of efficient clusteroluminogens. In this work, we explore the complexation‐ induced clusteroluminescence of carbonyl‐based polymers with nitrogen‐containing organic bases, exemplified by polyamide, polyester, polycarbonate, and poly(monothiocarbonate). The results demonstrate an increase in the intrinsic 440 nm emission of carbonyl groups and the emergence of new emission peaks upon complexation. The study proposes a through‐space n‧‧‧π complex mechanism, highlighting the potential of complexation as a strategy for modulating the clusteroluminescent properties of non‐conjugated systems. Further research is necessary to unravel underlying mechanisms, optimize cluster structures, and explore new materials for complexation, thereby advancing optoelectronics and photonics fields and enabling practical applications of clusteroluminescent materials. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The study of luminescence phenomena in non‐conjugated systems, namely clusteroluminescence, has gained significant attention for the development of advanced luminescent materials. While conventional strategies to manipulate the luminescent performances are based on complicated chemical reactions. In contrast, nature employs complexation to modulate luminescence, inspiring researchers to adopt an engineering approach for the construction of efficient clusteroluminogens. In this work, we explore the complexation‐ induced clusteroluminescence of carbonyl‐based polymers with nitrogen‐containing organic bases, exemplified by polyamide, polyester, polycarbonate, and poly(monothiocarbonate). The results demonstrate an increase in the intrinsic 440 nm emission of carbonyl groups and the emergence of new emission peaks upon complexation. The study proposes a through‐space n‧‧‧π complex mechanism, highlighting the potential of complexation as a strategy for modulating the clusteroluminescent properties of non‐conjugated systems. Further research is necessary to unravel underlying mechanisms, optimize cluster structures, and explore new materials for complexation, thereby advancing optoelectronics and photonics fields and enabling practical applications of clusteroluminescent materials. [ABSTRACT FROM AUTHOR]

A series of polyimide (PI)/V2CTx MXene composites was synthesized via polyamide acids (PAA) and two‐dimensional (2D) V2CTx MXene obtained by etching precursor V2AlC. PI/V2CTx MXene composites with different mass ratios were obtained by blending and heating with PAA. The results showed that V2CTx MXene has excellent dispersion in PI. In particular, V2CTx MXene exhibited excellent friction reduction and anti‐wear properties as a solid lubricant additive, and the wear rate (WR) was reduced by 43.2% by incorporating only 0.8 wt% of V2CTx MXene in the pristine PI and 71.9% by incorporating 1.2 wt%. Scanning electron microscopy (SEM) and x‐ray photoelectron spectroscopy (XPS) analyses showed that the continuous transfer film consisting of a high proportion of tribo‐chemical products formed on the contact surface is significant to improve the lubrication performances of the PI composites. This work broadens the application of MXene in the field of tribology and contributes to energy conservation and sustainable development of human society. Highlights: The tribological properties could be tuned by changing the ratio of PI to V2CTx MXene.The WR of PI composites was reduced by 71.9% with incorporating 1.2 wt% of V2CTx MXene.The formation of transfer films on the contact surface is significant for improving anti‐wear of PI. [ABSTRACT FROM AUTHOR]

Here, we demonstrate a simple and scalable approach of assembling the polyaniline (PANI) particles in polydimethylsiloxane (PDMS) matrix assisted by an external AC electric field. The PANI particles were polarized and assembled into a network structure along the field direction (out-of-plane). Compared to random oriented control samples, the network structure formed by PANI particles significantly increases the dielectric permittivity of the composite material, while the dielectric loss still remains at a relatively low value (0.439 for 10wt% PANI/PDMS, 102 Hz). In this work, the PANI structural rearrangement mechanism and its assembly kinetics under the electric field are revealed through in situ optical imaging. Specifically, by adding 10 wt% of PANI particles, the dielectric permittivity of the electric-field-assembled PANI/PDMS composite reaches up to 99.4, which is 30 times higher than pristine PDMS (3.38), and 20 times higher than the random dispersed counterpart (5.1). Additionally, PANI networks can improve the ability of composite for electromagnetic shielding application, which has been systemically investigated. We believe that our work provides a facile and promising strategy to fabricate functional composites with rationally designed network structures through the application of electric field, which can have broad applications such as sensors and multifunctional electromagnetic shielding. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Slide‐ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve high performance and multifunctionality of the material in various applications. There have been many reviews describing advances in the research of rotaxanes and polyrotaxanes. However, most of them typically focus on the precise synthesis of mechanically interlocked molecules and the control of microscopic molecular shuttles. In this review, we examine the effects of motion activity and conformational transition due to molecular slide on the performance of polyrotaxanes and the latest functional applications. Different designs of polyrotaxane‐based functional materials are presented to improve the potential for applications including self‐healing stretchable elastomers/gels, stimuli‐responsive smart devices, battery electrode binders, and biomedical drug delivery. It is anticipated that this review will provide insights and guidance for future developments in the design, synthesis and application of polyrotaxane‐based functional materials. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Pesticides, as the most common means of pest managements, have caused a series of problems such as pest resistance and environmental pollution. Aggregation‐induced emission (AIE) polymers exhibit great potential in biological applications because their fluorescent intensities significantly enhance in the aggregated state. In this paper, an AIE star polymer including a tetraphenyl ethylene (TPE) core and poly(2‐(dimethylamino)ethyl methacrylate) arms is designed and further developed as a multi‐functional nanocarrier for agricultural pest control. The nanocarrier shows high water solubility, good size stability and AIE imaging ability. Meanwhile, the twisted AIE core and positively charged polymer arms make the nanocarrier efficiently co‐load dinotefuran (DIN) and dsRNA via hydrogen bonds and electrostatic interactions, respectively. The AIE star polymer displays low toxicity and high fluorescence traceability. As a result, the nanocarrier co‐loading with DIN and dsRNA exhibits a highly synergistic insecticidal effect with higher pest mortality compared to the separate delivery of DIN and dsRNA. This study develops the AIE star polymer to improve the efficiency of co‐delivery of drug and dsRNA and proposes a new strategy toward efficient and synergistic pest control. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Slide‐ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve high performance and multifunctionality of the material in various applications. There have been many reviews describing advances in the research of rotaxanes and polyrotaxanes. However, most of them typically focus on the precise synthesis of mechanically interlocked molecules and the control of microscopic molecular shuttles. In this review, we examine the effects of motion activity and conformational transition due to molecular slide on the performance of polyrotaxanes and the latest functional applications. Different designs of polyrotaxane‐based functional materials are presented to improve the potential for applications including self‐healing stretchable elastomers/gels, stimuli‐responsive smart devices, battery electrode binders, and biomedical drug delivery. It is anticipated that this review will provide insights and guidance for future developments in the design, synthesis and application of polyrotaxane‐based functional materials. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Pesticides, as the most common means of pest managements, have caused a series of problems such as pest resistance and environmental pollution. Aggregation‐induced emission (AIE) polymers exhibit great potential in biological applications because their fluorescent intensities significantly enhance in the aggregated state. In this paper, an AIE star polymer including a tetraphenyl ethylene (TPE) core and poly(2‐(dimethylamino)ethyl methacrylate) arms is designed and further developed as a multi‐functional nanocarrier for agricultural pest control. The nanocarrier shows high water solubility, good size stability and AIE imaging ability. Meanwhile, the twisted AIE core and positively charged polymer arms make the nanocarrier efficiently co‐load dinotefuran (DIN) and dsRNA via hydrogen bonds and electrostatic interactions, respectively. The AIE star polymer displays low toxicity and high fluorescence traceability. As a result, the nanocarrier co‐loading with DIN and dsRNA exhibits a highly synergistic insecticidal effect with higher pest mortality compared to the separate delivery of DIN and dsRNA. This study develops the AIE star polymer to improve the efficiency of co‐delivery of drug and dsRNA and proposes a new strategy toward efficient and synergistic pest control. [ABSTRACT FROM AUTHOR]

Synthetic polymers sustain a wide range of applications but the quest for further sophistication and functionalization of polymers remains topical to improve their scope and performance. In this respect, the radical polymerization of exo-methylene heterocyclic compounds (MHCs) is attractive. Compared to the classical acyclic vinyl monomers constrained to the vinyl-type polymerization process, MHCs can undergo different polymerization modes, namely the radical ring-retaining polymerization (rRRP) and the radical ring-opening polymerization (rROP). In rRRP, the cyclic group is preserved and inserted as side group of the polymer backbone offering a myriad of post-polymerization modifications whereas functional groups are incorporated within the backbone of linear polymers and confer them some degradability in rROP. Herein, recent advances in the radical polymerization of MHCs as well as the variety of macromolecular structures and applications it offers are highlighted. The reversible deactivation radical polymerization of MHCs leading to well-defined MHC-based macromolecular architectures, including multifunctional, stimuli-responsive and degradable polymers, is also discussed. The review emphasizes the current limitations of the radical polymerization of MHCs as well as future prospects including the development of innovative bio-based MHCs. Overall, the radical polymerization of MCHs represents a powerful macromolecular engineering tool and a broad field of exploration for polymer chemists. [ABSTRACT FROM AUTHOR]

Melt‐extruded hollow thermoplastic fibers are a new class of materials for advanced applications, i.e., robotic clothes, stretchable touch and twist sensors, and programmable knitted textiles. Under large mechanical deformation (strain), such materials exhibit hyperelasticity. However, fundamental knowledge of strain‐energy density harnessing integrated computational materials engineering (ICME) has remained untapped for hollow fibers. Due to this key knowledge gap, most emerging applications demand iterative and costly approaches to producing and studying hollow fibers. Herein, a data‐driven pathway harnessing the ICME is introduced to study, predict, and optimize the hyperelastic behavior of hollow fibers. MCalibration software is used to calibrate the material properties of the fibers utilizing the Three‐Network Model (TNM) and emulated experimental stress–strain behavior in a finite‐element‐based multiphysics environment (COMSOL) with 99.99% confidence. The feasibility of predicting strain‐energy density is shown to modulate shape and geometries for new understandings without running cost‐incurring melt extrusions or experiments. Furthermore, the strain‐energy density is leveraged as a tool to attach fibers on fabrics that otherwise need iterations. As a proof‐of‐concept, fibers to fabrics are attached for wearable microfluidic demonstrations. This ICME approach can be extended to design the next generation of pre‐programmed, undiscovered functional devices fabricated from hyperelastic hollow fibers. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Low dielectric (low‐k) organosilicon polymers have received extensive interests from industry and academia due to good electrical insulation, high temperature resistance, flame retardancy and hydrophobicity. These attractive properties enable them to be utilized as low‐k materials in fabrication of electronic devices in high‐frequency communication technology. This review summarizes recent progress in developing low‐k organosilicon polymers, including the synthetic methods and properties of different organosilicon polymers classified according to the chemical structures. It may provide some inspiration to design new low‐k organosilicon polymers for application in the future. [ABSTRACT FROM AUTHOR]

Coiled‐polymer‐fiber‐based artificial muscles can provide large contractile actuation stroke. However, it is a challenge to achieve high actuation load and high actuation stroke for artificial muscle simultaneously. Herein, a powerful coiled‐polymer‐fiber‐based artificial muscle with a "rigid‐and‐flexible" structure is fabricated by cotwisting rigid heterocyclic aramid (HA) fibers with flexible silver‐plated nylon (SPN) fibers. The artificial muscle based on coiled HA@SPN fibers can lift a load over 108 MPa with a fast response time of 0.6 s, which is 309 times heavier than the load that human muscle can lift, and generate a work density per temperature of 41.3 J (kg °C)−1. The coiled HA@SPN fiber muscle exhibits high actuation stability of over 30 000 cycles. The coiled HA@SPN fiber muscle can provide a contractile actuation stroke of up to 8.2% and generate an average gravimetric mechanical energy density of 702 J kg−1, which is 18.1 times that of human skeletal muscle (≈38.8 J kg−1). An average contractile power density of 1168 W kg−1 is obtained for coiled HA@SPN fiber muscle, which is 23.4 times that of human skeletal muscle (≈50 W kg−1). [ABSTRACT FROM AUTHOR]

Identifying changes in the nanoscopic domain is a key challenge in the physicochemical sciences, where great interest is on sensing complex processes that involve cellular biochemical reactions, chemical heterogeneities, contact forces, and other interfacial phenomena. This has stimulated the development of diverse materials that allow subtle nanoscopic environments to be "seen". The challenge in the nano‐domain has always been the ability to sense changes on the minute scale and rapidly transduce the information out for macroscopical observation. Ideally, materials should inform when processes are occurring. Recently, new systems that leverage established concepts with fluorescence‐ and plasmonic‐based sensing have been devised, which has reinvigorated the domain, where functional polymers coupled in specific architectures to transducing motifs allow for a new basis of messenger materials to be realized. The key aspect in this regard is that the polymers allow for sensing to be achieved only when they are carefully coupled to the amplification system. In this perspective, the role of specific functional polymer architectures for the realization of nano‐to‐macro sensing of subtle nano‐messengers is discussed and where the exciting field of messenger materials is seen moving forward is pointed out. [ABSTRACT FROM AUTHOR]

Highlights: The most representative examples for the TM-free and TM-catalyzed mechano-synthesis of functional polymers are reported; The most common applications for the various types of functional polymers are precented; The advantage of solvent-free mechanosynthesis over conventional solvent-based synthesis are highlighted; In many cases the better performance of the mechanchemically-prepared polymers over those obtained by using conventional methods are demonstrated. Mechanochemically induced methods are commonly used for the depolymerization of polymers, including plastic and agricultural wastes. So far, these methods have rarely been used for polymer synthesis. Compared to conventional polymerization in solutions, mechanochemical polymerization offers numerous advantages such as less or no solvent consumption, the accessibility of novel structures, the inclusion of co-polymers and post-modified polymers, and, most importantly, the avoidance of problems posed by low monomer/oligomer solubility and fast precipitation during polymerization. Consequently, the development of new functional polymers and materials, including those based on mechanochemically synthesized polymers, has drawn much interest, particularly from the perspective of green chemistry. In this review, we tried to highlight the most representative examples of transition-metal (TM)-free and TM-catalyzed mechanosynthesis of some functional polymers, such as semiconductive polymers, porous polymeric materials, sensory materials, materials for photovoltaics, etc. [ABSTRACT FROM AUTHOR]

Synthesizing polymers with precise sequence structures is of great significance but is still a great challenge in polymer science. The exploration of alkyne-based polymerizations recently has attracted considerable attention due to their great potential to construct polymers with diverse structures and versatile functions, especially those with precise sequence structures. In this review, we summarized recent advances in the preparation of sequence-controlled polymers by alkyne-base polymerizations. Representative examples of each method were selected to illustrate the essential construction principles and implementation approaches, which are expected to provide guidance for the development of sequence-controlled polymers. In addition, we also systematically introduce the diverse and appealing properties and applications of the obtained sequence-controlled polymers, hoping to promote the development of polymeric materials with more superior and innovative properties and applications.

With the advent of a new 2D nanomaterial, namely, black phosphorus (BP) or phosphorene, the scientific community is now dedicated to focusing on and exploring this 2D material offering elusive properties such as a higher carrier mobility, biocompatibility, thickness-dependent band gap, and optoelectronic characteristics that can be harnessed for multiple applications, e.g., nanofillers, energy storage devices, field effect transistors, in water disinfection, and in biomedical sciences. The hexagonal ring of phosphorus atoms in phosphorene is twisted slightly, unlike how it is in graphene. Its unique characteristics, such as a high carrier mobility, anisotropic nature, and biocompatibility, have attracted much attention and generated further scientific curiosity. However, despite these interesting features, the phosphorene or BP poses challenges and causes frustrations when it comes to its stability under ambient conditions and processability, and thus in order to overcome these hurdles, it must be conjugated or linked with the suitable and functional organic counter macromolecule in such a way that its properties are not compromised while providing a protection from air/water that can otherwise degrade it to oxides and acid. The resulting composites/hybrid system of phosphorene and a macromolecule, e.g., a polymer, can outperform and be exploited for the aforementioned applications. These assemblies of a polymer and phosphorene have the potential for shifting the paradigm from exhaustively used graphene to new commercialized products offering multiple applications. [ABSTRACT FROM AUTHOR]

Due to the trend of multi-function, integration, and miniaturization of electronics, traditional dielectric materials are difficult to satisfy new requirements, such as balanced dielectric properties and good designability. Therefore, high dielectric polymer composites have attracted wide attention due to their outstanding processibility, good designability, and dielectric properties. A number of polymer composites are employed in capacitors and sensors. All these applications are directly affected by the composite's dielectric properties, which are highly depended on the compositions and internal structure design, including the polymer matrix, fillers, structural design, etc. In this review, the influences of matrix, fillers, and filler arrangement on dielectric properties are systematically and comprehensively summarized and the regulation strategies of dielectric loss are introduced as well. Finally, the challenges and prospects of high dielectric polymer composites are proposed. [ABSTRACT FROM AUTHOR]