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Materials performance is primarily influenced by chemical composition, making compositional analysis (CA) essential in materials science. Traditional quantitative mass spectrometry, which deconvolutes analyte spectra into reference spectra, struggles with reactive systems where spectral variations occur, such as peak shifts and new peak emergences. Additionally, obtaining reference spectra for all pure constituents is often impractical. To address these challenges, I propose nonlinear reference-free quantitative mass spectrometry (NL-RQMS). This method simultaneously determines composition, reference spectra, and nonlinear interaction effects directly from a spectral dataset of mixtures, eliminating the need for prior reference spectra. In a benchmark test on ternary reactive polymers of epoxy and amines, NL-RQMS inferred compositions with an error margin of just 3 wt%, significantly outperforming the 6 wt% error margin of linear RQMS. The inferred interaction terms clearly indicate in situ reactions between epoxy and amine moieties. This framework enables accurate compositional analysis without prior knowledge of the constituents, even in systems with interactive components, and holds significant potential for applications such as grading recycled plastics, where pristine materials, degradation compounds, and stabilizers interact complexly, causing nonlinear spectral distortions. [ABSTRACT FROM AUTHOR]

Healthcare‐associated infections remain a significant health concern, particularly with the emergence of antibiotic resistance. While these antibiotics have saved countless lives, their overuse reduces their efficacy promoting the emergence of multidrug‐resistant (MDR) bacteria. This prompts researchers to explore new alternatives for treating bacteria proliferation. In this context, antibacterial photodynamic therapy (aPDT) has emerged as a promising approach for treating localized infections. It utilizes reactive oxygen species (ROS) as oxidative stress agents, thereby minimizing the risk of developing MDR. The success of aPDT significantly hinges on the careful selection of photosensitizers (PSs) and polymer matrices for the synthesis of polymer‐based photoactive materials. Various light‐absorbing PSs are therefore designed for enhancing ROS production and antimicrobial efficacy. By incorporating PSs into polymer matrices, these materials can harness the light power to generate ROS, destroying bacterial cells upon irradiation. This review aims to provide a comprehensive overview of advancements in this field, specifically focusing on the use of polymer‐based materials. The mechanism of the four main ROS generated in aPDT, the methods used for their detection, and their mode of action against bacteria has been outlined. The recent improvement in polymer‐based aPDT materials and their antibacterial efficacy have been also addressed. [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]

In the present study, a dynamic Monte Carlo (MC) model is applied for predicting the dynamic evolution of monomer Droplet Size Distribution (DSD) and polymer Particle Size Distribution (PSD) within the presence of an inventive time step in the MC algorithm for both non‐reactive (liquid–liquid dispersion) and reactive systems. Besides, a combining approach as a second inventive strategy is introduced for implementing the MC simulation with a high number of droplets. An optimization process generated the dimensionless Model Parameters (MPs) and is applied to the MC simulation. The MC algorithm is validated with the experimental data from the literature. The novel time step can predict the dynamic evolution of monomer droplets and polymer particles in the reactive systems and diminish the time of the simulation. The combining approach is an excellent strategy for mixing the same or different number of droplets for decreasing time consumption of MC simulation. Extraordinary findings depicted the model's effectiveness and the validity of the time step and combining strategies. [ABSTRACT FROM AUTHOR]

Two model substrates for the grafting to reaction are considered: not‐deglazed silicon, whose surface is coated by a thin oxide layer with reactive silanol groups on its surface; and deglazed silicon, where the oxide layer is removed by treatment with hydrofluoric acid. The reactive polymers are hydroxy‐terminated polystyrenes with molecular weights ranging from 3.9 to 13.9 kg mol⁻1. The grafting to reaction is carried out at different temperatures and for different periods of time on the two different substrates. The thickness and the thermal stability of the resulting brushes are evaluated. Furthermore, the grafting of a highly dispersed system is simulated by blending two polymers with different molecular weights. Although the brush thickness growth is found to be faster on deglazed silicon, the preferential grafting of short chains occurs with equal chain selection propensity on both substrates. [ABSTRACT FROM AUTHOR]

Controlling the structure and chemistry of solid electrolyte interphase (SEI) underpins the stability of electrolyte‐electrode interface, and is crucial for advancing rechargeable lithium metal batteries (LMBs). Here, we utilized photo‐controlled copolymerization to achieve the on‐demand synthesis of fluorosulfonyl fluoropolymers as unprecedented artificial SEI layers on Li metal anodes. This work not only enables instant formation of a hybrid polymer‐inorganic interphase that consists of a polymer‐enriched top layer and a LiF‐fortified bottom layer, originating from a single polymeric component, but also imparts various desirable physical properties (e.g. good mechanical strength and flexibility, high ion conductivity, low overpotential) to SEI via a single‐to‐divergent strategy. Model reactions and structural characterizations supported the formation of a divergent fluorinated interphase, which furnished prolonged stabilization of Li deposition, high coulombic efficiency and improved cycling behavior in electrochemical experiments. This work highlights the great potential of exploring reactive polymers as versatile coatings to stabilize Li metal anodes, providing a promising avenue to solve electrode‐electrolyte interfacial problems for LMBs. [ABSTRACT FROM AUTHOR]

Cryogels containing isocyanate reactive groups were synthesized via photopolymerization of 2-isocyanoethyl methacrylate (ICEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA). By changing the PEGMEMA and ICEMA ratios, cryogel series with varying ratios of reactive isocyanate groups were successfully prepared. The cryogels were characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis, scanning electron microscope, and rheometry. To demonstrate that molecules containing amine groups can be immobilized onto synthesized cryogels through isocyanate-amine reactions, the cryogels were conjugated with 4-(trifluoromethyl)benzylamine (TFBA) and fluorescein amine (FLA) molecules, and the conjugations were confirmed through FTIR and fluorescence microscopy, respectively, for TFBA and FLA. Additionally, immobilization of fluorescein isothiocyanate conjugated albumin from bovine serum (FITC-BSA) as fluorescein-labeled model proteins was studied to illustrate that biomolecules can also be bound to the cryogels without any linker. It was shown that the amount of immobilized FITC-labeled model proteins can be controlled by adjusting the concentration of isocyanate reactive groups within the cryogel matrix, and this functionalization was confirmed by fluorescence microscope. [ABSTRACT FROM AUTHOR]

This study aims to examine the 50/50 polypropylene/polyamide 6 (iPP/PA6) system molded under confined flow conditions, both in its original state and after being modified by two different interfacial agents. This study provides two main insights. Firstly, it focuses on a polymer blend close to phase inversion. Secondly, it investigates the impact of using two different types of interfacial agents (derived from polymer waste) to enhance the compatibility between iPP and PA6. Dynamic Mechanical Analysis (DMA) has been employed to achieve these objectives. It is important to note that the investigation of the 50/50 iPP/PA6 system is a crucial focus predicted in previous studies, where a series of mechanical properties were evaluated using Box–Wilson design of experiments (DOEs) over the whole compositional range on the iPP/PA6 binary system. Thus, two interfacial modifiers, namely succinic anhydride (SA)-grafted atactic polypropylene with terminal, side, and bridge SA grafts (aPP-SASA) and succinyl-fluoresceine (SF) with bridge succinic anhydride grafting atactic polypropylene (aPP-SFSA), were employed. The authors obtained and characterized these agents. The quantity of these agents used in the blend was identified as a critical coordinate in prior studies conducted by the authors. The processing method used, compression molding under confined conditions, was chosen to minimize any orientation effect on the emerging morphology. All characterization procedures were performed on samples processed by contour machining to retain the blend morphologies as they emerged from the processing stage. Results from WAXS and SAXS synchrotron tests concluded there were no changes in the crystal morphology of the iPP or the PA6 in the blends nor any co-crystallization process throughout the compositional range. These findings, and the long period fits on the PP crystalline phase for the fifty/fifty blends we are discussing, will support the present DMA study. Finally, the efficiency of these interfacial modifiers has been concluded, even in this unfavorable scenario. [ABSTRACT FROM AUTHOR]

Modern society relies heavily on producing commercial and industrial plastics to improve the quality and quantity of our lives. However, increased fire risks threaten commercial operations and the potential impact of high‐performance electronic and transportation technologies that utilize polymeric materials. Despite significant monitoring and reduction of commonly used halogenated flame retardants, their worldwide usage still poses environmental hazards. Many non‐halogenated flame‐retardant compounds are viable additives for synthetic polymers; however, their incorporation often results in reduced composite homogeneity and mechanical strength. This review focuses on reactive flame retardants and the effect of polymer structure on inherent flame retardance in recent studies. The synthesis and characterization of polymeric systems (e.g. polyurethanes, polyamides, polyimides, polyesters and epoxy resins) are discussed in terms of structure–flame‐retardant performance using a complement of analytical tools, including thermogravimetric analysis, cone calorimetry, limiting oxygen index and UL 94 testing. These commercially important polymeric systems represent a broad compositional space for future adaptation and the discovery of increasingly modular polymeric materials with, while also contributing to the fundamental understanding of unique combinations of gas‐ and condensed‐phase mechanisms of flame retardance. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Dyes employed in many production cycles are characterized by high toxicity and persistence in the environment, and conventional wastewater treatments often fail to reach high removal efficiencies. Consequently, there is an increasing research demand aimed at the development of more efficient and sustainable technologies. A two-step strategy consisting of dye sorption followed by sorbent bio-regeneration is proposed here, with a special focus on the regeneration step. The objective of this study was to establish the best operating conditions to achieve regeneration of dye-loaded polymers and concurrently the ultimate removal of the dyes. To this aim, the bio-regeneration of the Hytrel 8206 polymer, used as a sorbent material to remove Remazol Red dye from textile wastewater, was investigated in a two-phase partitioning bioreactor (TPPB) under alternated anaerobic–aerobic conditions. Comprehensive analysis of operational parameters, including sorbent load and initial contamination levels, was conducted to optimize bio-regeneration efficiency. Experimental data demonstrated high regeneration efficiencies (91–98%) with biodegradation efficiencies up to 89%. This study also examines the biodegradation process to investigate the fate of biodegradation intermediates; results confirmed the successful degradation of the dye without significant by-product accumulation. This research underscores the potential of TPPB-based bio-regeneration of polymeric sorbent material for sustainable wastewater treatment, offering a promising solution to the global challenge of dye pollution in water resources. [ABSTRACT FROM AUTHOR]

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a very promising biodegradable copolyester of high interest in food packaging. Its inherent brittleness and narrow processing window make it necessary to blend it with flexible biopolyesters, such as poly(butylene succinate-co-adipate) (PBSA). However, the resultant biopolyester blends are thermodynamically immiscible, which impairs their performance and limits their applications. This study is the first to explore the use of poly(butylene succinate-co-adipate) grafted with maleic anhydride (PBS-g-MAH) as a novel reactive additive to compatibilize PHBV/PBSA blends. The compatibilizer was prepared by a reactive melt-mixing process of PBSA and maleic anhydride (MAH) using dicumyl peroxide (DCP) as an organic radical initiator, achieving a grafting degree (Gd) of 5.4%. Biopolyester blend films were thereafter prepared via cast extrusion and their morphological, thermal, mechanical, and barrier properties were characterized. Compatibilization by PBSA-g-MAH was confirmed by observing an improved phase interaction and lower dispersed domain sizes in the blends with 15 wt% PBSA. These compatibilized PHBV/PBSA blends were thermally stable up to 285 °C, showed enhanced ductility and toughness, as well as providing an improved barrier against water and limonene vapors and oxygen. These findings suggest that the use of MAH-grafted biopolyesters can represent an effective strategy to improve the properties of biopolyester blends and open up new opportunities for the application of PHBV-based formulations for food packaging. [ABSTRACT FROM AUTHOR]

The characterization of phospholipid membrane permeability for small molecules is crucial for many applications in drug discovery and biomedical research in general. Here, chemosensor‐laden vesicles offer an attractive platform for permeability assays. In this work, the stability of immobilized chemosensor‐filled vesicles is explored on anti‐fouling polymer brush surfaces for potential use in monitoring small molecule membrane permeability. The study focuses on the development of a method for immobilizing sensor‐loaded vesicles into arbitrary patterns on surfaces and characterizing their stability under changing temperatures and compositions. As substrate to enable intact, long‐term stable vesicle immobilization reactive polymer brushes with anti‐fouling properties are used. Utilizing microchannel cantilever spotting, biotin moieties are introduced on the polymer brush surface, enabling stable tethering of vesicles through streptavidin‐biotin interactions. The immobilized vesicles are monitored through fluorescence microscopy for their response to analytes under changing environmental parameters and vesicle composition. A higher stability of immobilized vesicles compared to free‐floating ones is observed, with permeability only at elevated temperatures. By tuning vesicle compositions, permeability at lower temperatures can be raised again. Overall, the study provides insights into a novel approach for vesicle immobilization, showcasing the potential of surface‐bound vesicles for applications in microfluidic systems and as biosensors in various assays. [ABSTRACT FROM AUTHOR]

The azo linkage (N＝N) is one of the very few functional groups in organic chemistry that exhibits sensitivity towards thermal, chemical, photochemical, and biological stimuli. Consequently, this property has given rise to a distinct class of responsive materials. For example, thermal sensitivity has led to generation of free radical initiators useful in curing and polymerization applications. Chemically-induced cleavage has aided the development of self-immolative polymers and reactive scaffolds for proteomics applications. Photo-isomerization capability has given rise to photo-responsive systems. Azobenzene cleavage in biologically reducing environments, such as that of the colon, and under tumor hypoxia conditions has led to diagnostic, therapeutic, and delivery materials. Such conditions have also allowed for control over formation (assembly) and disruption (disassembly) of micellar nanoparticles. The aim of this review article is to look beyond the prevalent photosensitivity aspect of the aromatic azo compounds and draw attention to the azo scission reaction as a trigger of the change in the structure and properties of organic materials. Thus, the main discussion begins with the mechanism of the reductive cleavage. Then, its application in the design of molecules that can be activated as drugs and fluorescent sensors, (nano)materials with potential to release active substances, and polymers with side-chain and main-chain self-immolative capacity is discussed. Finally, the status and future challenges in this field are discussed. [ABSTRACT FROM AUTHOR]

This paper discusses the evolution of morphology in 80/20 (vol/vol) (polypropylene‐maleic anhydride)/polypropylene (PP)/(polystyrene‐oxazoline)/polystyrene (PS) reactive blends and nonreactive 80/20 PP/PS blends. For both the blends, the PS forms the continuous phase initially, traps the PP‐maleic anhydride or PP pellets within, and gradually deforms these pellets to lamellar sheets and elongated fibers. Eventually, the irregular domains of PP coalesce and invert to form the continuous phase in a transition known as the "processing phase inversion." The nonreactive PP/PS blend needed much higher torque to be deformed from pellets to a viscoelastic melt than their reactive counterparts. Despite the significant differences in their processing energy, the reactive and nonreactive blends have similar morphologies during the inversion process. The changes in the structure of the blends were captured on video by a custom‐built visualization system and correlated with scanning electron microscopy of the fractured surfaces, along with monitoring the changes in the torque levels during the processing. The solid‐state properties of the minor phase were crucial for deforming the major phase pellets and, consequentially, the work required to process the blends. Due to a suppression of coalescence due to the presence of in situ formed copolymers at the interface of the PP/PS, a finer dispersion was obtained in the case of the reactive blend systems. Highlights: Visualization of polymer melt blending.In situ reaction during processing.Processing energy requirements during blending. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Polymer mechanochemistry on reactive species has attracted more and more attentions over the past 20 years, as the mechanochemical generation of reactive species has a great potential in developing different polymeric materials for various purposes, such as stress detection, self‐healing, self‐strengthening, controllable degradation and release of small molecules. In this review, we first discuss the recent progress on polymer mechanochemistry of the reactive species that are generated from the mechanochemical reactions of mechanophores. Five types of reactive species, including radical, zwitterion, ionic, carbene and neutral intermediates, and their applications were reviewed in detail. Since mechanochemical reactions are sensitive to the mechanophore structure and polymer framework, we then discuss how mechanophore isomerism, polymer structure, polymer attachment point, and polymer architecture influence the mechanophore activation. At last, we provide our perspectives on the polymer mechanochemistry of reactive species. Key Scientists: In the 1930s, a seminal work by Staudinger showed that the molecular weight of poly(styrene) reduced after mastication. However, polymer mechanochemistry mainly focused on the destructive effects of mechanical force, until Moore reported that the azo‐mechanophore was cleaved selectively upon sonication in 2005. Afterwards, his group also found that mechanical force changed the reaction pathway of benzocyclobutene and made spiropyran display purple color under stress. In 2009, Sijbesma revealed that metal–NHC could be used as a latent catalyst to catalyze transesterification and polymerization. Subsequently, the Craig group disclosed the special mechanical reactivity of perfluorocyclobutane in 2011 and examined the influence of polymer backbone on the reactivity of epoxides in 2012. Later, they also reported that the lever‐arm effect enhanced gDBC or gDCC mechanochemistry. Since 2015, Otsuka's group has developed a series of mechanophores that generated various carbon radicals and showed different colors under mechanical force. De Bo subsequently investigated the effect of regio‐ and stereochemistry on the reactivity of furan–maleimide adduct in 2017, and he examined the different mechanisms of the mechanical activation of tetrafluorobenzene–NHC (N‐heterocyclic carbene) adduct in 2020. During that time, the Choi group explored the influence of polymer architecture on the mechanophore activation, and Robb's group utilized a furan‐maleimide adduct to achieve the release of different small molecules. In 2020, Göstl and Herrmann employed the scission of the disulfide within polymers to release drugs and reporting molecules by ultrasound, and the Chen group also investigated the mechanochemistry of diselenides which afforded selenium radicals. In 2021, Boydston's group realized the "flex‐activation" of NHC‐carbodiimide to release NHC small molecules. Recently, the Chen group achieved multistate mechanochromism by combining two Rh structures together through a conjugated connector. In addition, Robb designed a furan‐maleimide adduct to mechanically give a donor–acceptor Stenhouse adduct that reacted with different amines to display various colors. This review has focused on the chemistry of reactive species that are generated from mechanochemical reactions. [ABSTRACT FROM AUTHOR]

In this paper, we study the Cauchy problem of the two-species incompressible viscoelastic fluid of Oldroyd-B system, which involving a reaction effect between two species of polymers. We prove the local existence with initial data in Hk(k ≥ 2) in a classical solution framework, and then provide a blow-up criteria. We concentrate on the a priori estimate, by using the energy method. In particular, the variant system in a general formulation is also studied, and the corresponding local well-posedness is established. [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]

Comprehensive Summary: Polymer mechanochemistry on reactive species has attracted more and more attentions over the past 20 years, as the mechanochemical generation of reactive species has a great potential in developing different polymeric materials for various purposes, such as stress detection, self‐healing, self‐strengthening, controllable degradation and release of small molecules. In this review, we first discuss the recent progress on polymer mechanochemistry of the reactive species that are generated from the mechanochemical reactions of mechanophores. Five types of reactive species, including radical, zwitterion, ionic, carbene and neutral intermediates, and their applications were reviewed in detail. Since mechanochemical reactions are sensitive to the mechanophore structure and polymer framework, we then discuss how mechanophore isomerism, polymer structure, polymer attachment point, and polymer architecture influence the mechanophore activation. At last, we provide our perspectives on the polymer mechanochemistry of reactive species. Key Scientists: In the 1930s, a seminal work by Staudinger showed that the molecular weight of poly(styrene) reduced after mastication. However, polymer mechanochemistry mainly focused on the destructive effects of mechanical force, until Moore reported that the azo‐mechanophore was cleaved selectively upon sonication in 2005. Afterwards, his group also found that mechanical force changed the reaction pathway of benzocyclobutene and made spiropyran display purple color under stress. In 2009, Sijbesma revealed that metal–NHC could be used as a latent catalyst to catalyze transesterification and polymerization. Subsequently, the Craig group disclosed the special mechanical reactivity of perfluorocyclobutane in 2011 and examined the influence of polymer backbone on the reactivity of epoxides in 2012. Later, they also reported that the lever‐arm effect enhanced gDBC or gDCC mechanochemistry. Since 2015, Otsuka's group has developed a series of mechanophores that generated various carbon radicals and showed different colors under mechanical force. De Bo subsequently investigated the effect of regio‐ and stereochemistry on the reactivity of furan–maleimide adduct in 2017, and he examined the different mechanisms of the mechanical activation of tetrafluorobenzene–NHC (N‐heterocyclic carbene) adduct in 2020. During that time, the Choi group explored the influence of polymer architecture on the mechanophore activation, and Robb's group utilized a furan‐maleimide adduct to achieve the release of different small molecules. In 2020, Göstl and Herrmann employed the scission of the disulfide within polymers to release drugs and reporting molecules by ultrasound, and the Chen group also investigated the mechanochemistry of diselenides which afforded selenium radicals. In 2021, Boydston's group realized the "flex‐activation" of NHC‐carbodiimide to release NHC small molecules. Recently, the Chen group achieved multistate mechanochromism by combining two Rh structures together through a conjugated connector. In addition, Robb designed a furan‐maleimide adduct to mechanically give a donor–acceptor Stenhouse adduct that reacted with different amines to display various colors. This review has focused on the chemistry of reactive species that are generated from mechanochemical reactions. [ABSTRACT FROM AUTHOR]

The document is the contents list for the journal "Chemical Communications" published on June 7, 2024. It includes articles on various topics such as the rational design and biomedical application of BODIPY-based photocages, synthesis and applications of porous protein crystals, and the construction of stable radical hydrogen-bonded metal-organic frameworks. The journal is published by The Royal Society of Chemistry, a leading chemistry community that connects the world with the chemical sciences. [Extracted from the article]

Using thiol–ene chemistry, polymerization-induced phase separation, and DLP 3D printing, we present a method for manufacturing reactive macroporous 3D structures. This approach enables the fabrication of structures with tunable physicochemical properties and compressibility. Moreover, it facilitates post-functionalization through thiol-Michael addition reactions, thereby expanding performance and application potential. [ABSTRACT FROM AUTHOR]

We performed a series of six plate impact experiments on polyimide and modeled them using new reactant and products equations of state combined with an Arrhenius rate model. The first experiment was diagnosed with embedded electromagnetic velocity gauges through which we directly observed attenuation of the lead shock to an approximately constant state over a propagation distance of roughly 4 mm. Simulated gauge profiles were in excellent qualitative agreement with experiment and suggested a sluggish chemical reaction that did not proceed to completion. The remaining five experiments were conducted in a transmission geometry and diagnosed velocimetrically at the sample/window interface. All five of these yielded profiles with a sharp shock followed by a more gradual approach to maximum interface velocity that was "rounded" to varying degree. These profiles proved difficult to interpret unambiguously due to the convolution of the reactive wave upon first shock with reflection of the lead wave and reshock or release by the window. Comparison with thermochemical calculations strongly suggests that the point of maximum interface velocity corresponds to the equilibrium reshock or release locus. We discuss the implications of this point for the practice of impedance matching based on the reflected Hugoniot of reactive materials such as polymers. The reactant and thermochemical products equations of state are developmental SESAME tables 97710 and 97720, respectively. [ABSTRACT FROM AUTHOR]

The indicators of cavitation-erosion resistance of reactive plastic polymer materials, namely aminoplasts of KFA-1, KFA-2, and KMFA-3 grades in neutral, acidic, and alkaline environments were analyzed. The obtained results were considered from the standpoint of the physicochemical fracture mechanics of polymers, taking into account the specific features of the cavitation loading, the type of environment, and possible mechanisms of their fracture. [ABSTRACT FROM AUTHOR]

Some defects of polylactic acid (PLA), especially its poor mechanical properties, were modified using a minimum content of non-biodegradable maleated polypropylene (MAPP). To this end, first, the amount of MAPP was optimized, which was 20 wt.%. Second, MgO was used as a new catalyst to improve the exchange reactions between active groups in both polymers in a reactive blending process. Tensile and izod analyses showed that, compared to neat PLA, with a slight decrease in modulus and tensile strength, elongation at break, and impact resistance were improved in the presence of 20 and 0.1 wt.% of MAPP and MgO, respectively. This improvement in mechanical properties can be related to the exchange reactions between two polymers and the formation of PLA-MAPP block copolymers. MFI and WDCA analyses demonstrated the increase in melt flowability and surface hydrophilicity of the resulting blends, respectively. DSC analysis showed that the Tg values of both polymers approached each other in the presence of catalyst. Also, the elimination of cold crystallization of PLA and the decrease in the Tm and crystallinity of both polymers are clear reasons for the miscibility of the alloy. TEM displayed the proper dispersion of MgO nanoparticles within the polymer matrix, and in addition, the XRD test also proved the decrease in the crystallinity of both polymers and appropriate miscibility of the samples containing 20 and 0.1 wt.% of MAPP and MgO, respectively. These results can promise the design of a compound with the maximum amount of PLA for further use in various industries. [ABSTRACT FROM AUTHOR]

Developing artificial enzymes based on organic molecules or polymers for reactive oxygen species (ROS)‐related catalysis has broad applicability. Herein, inspired by porphyrin‐based heme mimics, we report the synthesis of polyphthalocyanine‐based conjugated polymers (Fe‐PPc‐AE) as a new porphyrin‐evolving structure to serve as efficient and versatile artificial enzymes for augmented reactive oxygen catalysis. Owing to the structural advantages, such as enhanced π‐conjugation networks and π‐electron delocalization, promoted electron transfer, and unique Fe−N coordination centers, Fe‐PPc‐AE showed more efficient ROS‐production activity in terms of Vmax and turnover numbers as compared with porphyrin‐based conjugated polymers (Fe‐PPor‐AE), which also surpassed reported state‐of‐the‐art artificial enzymes in their activity. More interestingly, by changing the reaction medium and substrates, Fe‐PPc‐AE also revealed significantly improved activity and environmental adaptivity in many other ROS‐related biocatalytic processes, validating the potential of Fe‐PPc‐AE to replace conventional (poly)porphyrin‐based heme mimics for ROS‐related catalysis, biosensors, or biotherapeutics. It is suggested that this study will offer essential guidance for designing artificial enzymes based on organic molecules or polymers. [ABSTRACT FROM AUTHOR]

Screw extruders as continuous flow reactors allow the synthesis of new polymers, preparation of polymer blends and composites, and modification or functionalization of commercially available polymers. Literature data shows that the twin screw extrusion is the most popular solution used for this purpose. In contrast, the number of scientific papers on alternative methods, such as multi-screw extruders, is somewhat limited. This paper is the first review of the application of planetary roller extruders in the compounding and reactive processing of polymer blends and composites. To fill current knowledge gaps, we discuss the advantages and disadvantages of planetary roller extruders compared to other screw extruders. Moreover, we summarize recent advances in planetary roller extrusion in producing thermal sensitive and biodegradable polymeric materials, rubber compounds, materials for 3D printing, or plastics and rubber recycling. This work also proposes the possible scenarios for further sustainable development of polymer blends and composites using planetary roller extruders. [ABSTRACT FROM AUTHOR]

Grafting polymers with reactive maleic anhydride is a common approach for the synthesis of new material with the capability of acting as a compatibilizer in polymer blends. Accordingly, this research showed a new approach for grafting maleic anhydride onto renewable cellulose acetate using an initiator. The grafting process through extrusion showed good stability with continuous production of all grafted samples. Moreover, two different grafting processes, namely one‐step and two‐step processes, were shown to produce materials with very similar characteristics. Grafting of maleic anhydride onto cellulose acetate by reacting with its hydroxyl groups was confirmed by both Fourier transform infrared spectroscopy and nuclear magnetic resonance analysis. Rheological studies also demonstrated the enhanced flowability and lower viscosity of the grafted material in comparison to the plasticized cellulose acetate. Highlights: Grafting maleic anhydride onto plasticized cellulose acetate by reactive extrusion.Detection of grafted maleic anhydride onto cellulose acetate through NMR analysis.High thermal stability of grafted materials.Significant reduction in viscosity of plasticized cellulose acetate after grafting [ABSTRACT FROM AUTHOR]

The steepest-entropy-ascent quantum thermodynamic framework is used to investigate the effectiveness of multi-chain polyethyleneimine-methylenephosphonic acid in sequestering rare-earth ions (Eu3+) from aqueous solutions. The framework applies a thermodynamic equation of motion to a discrete energy eigenstructure to model the binding kinetics of europium ions to reactive sites of the polymer chains. The energy eigenstructure is generated using a non-Markovian Monte Carlo model that estimates energy level degeneracies. The equation of motion is used to determine the occupation probability of each energy level, describing the unique path through thermodynamic state space by which the polymer system sequesters rare-earth ions from solution. A second Monte Carlo simulation is conducted to relate the kinetic path in state space to physical descriptors associated with the polymer, including the radius of gyration, tortuosity, and Eu-neighbor distribution functions. These descriptors are used to visualize the evolution of the polymer during the sequestration process. The fraction of sequestered Eu3+ ions depends upon the total energy of the system, with lower energy resulting in greater sequestration. The kinetics of the overall sequestration are dependent on the steepest-entropy-ascent principle used by the equation of motion to generate a unique kinetic path from an initial non-equilibrium state. [ABSTRACT FROM AUTHOR]

The modified suspension polymerization technique has been used for the preparation of composite microparticles from the mixture of glycidyl methacrylate (GMA), styrene (S), and divinylbenzene (DVB) in the presence of hydrophobized Fe3O4 nanoparticles. The obtained polymer microspheres were characterized using different instrumental and physicochemical techniques, modified with a zero-order PAMAM dendrimer, and impregnated with palladium(II) acetate solutions to immobilize palladium(II) ions. The resulting materials were preliminarily examined as catalysts in the Suzuki reaction between 4-bromotoluene and phenylboronic acid. It was found that the addition of magnetite particles to the composition of monomers provided polymer microparticles with embedded magnetic nanoparticles. The composite microparticles obtained showed a complex, multi-hollow, or raspberry-like morphology. After their modification, they could serve as recyclable catalysts for reactions that include both 4-bromotoluene and several other aryl bromides. [ABSTRACT FROM AUTHOR]

Poly(tetrafluoroethylene) (PTFE) is well known for its very low friction coefficient and thus widely used for antifriction applications, e.g., sliding lacquers, for many years. Because of the high wear rate and cold flow of the original polymer, PTFE is usually added in higher amounts to other polymer matrices as a lubricant. However, the incompatibility of PTFE requires lots of efforts to perform a homogeneous breaking down of agglomerates and particle distribution as well as dispersion stabilization of the physical mixtures during application and curing. PTFE can be functionalized by high energy irradiation and subsequently compatibilized with a polymer matrix by reactive extrusion resulting in chemical bonding of both polymers via suitable reactive groups. In this manner, poly(amide imide) (PAI) was coupled to γ-radiation modified PTFE micro-powder prior to the dispersion procedure. This study deals with the thermal and crystallization behavior of the PTFE lubricant in chemical bonded (cb) PAI-PTFEcb compound thin layers in comparison with those of the plain radiation modified PTFE depending on the cooling rate by DSC, Flash-DSC and WAXS. A morphological characterization of the extrudate as well as the coating gives information about the fragmentation and distribution of the PTFE phase in the PAI matrix. Furthermore, mechanical and surface properties of sliding lacquer films were analyzed after application on steel substrates by varying dry film thickness and curing. [ABSTRACT FROM AUTHOR]

The widespread use of highly complex synthetic dyes like reactive dyes in the textile industry has some adverse environmental impacts and deserves close attention. Biological treatment of these effluents utilizing various species of bacteria with remarkable efficiency in dye removal is still considered promising. Our current study deals with immobilizing an isolated bacterial strain into calcium alginate (Ca/Alg) gel beads and using it to treat pernicious pollutants like synthetic dyes. A potential Reactive Blue 19 (RB19)‐degrading Enterobacter cloacae strain A1 was isolated from the Kashan textile industry and was characterized by 16S rDNA gene sequencing. The decolorization ability of strain A1 was assessed by time‐based studies using free bacterial cells/immobilized in Ca/Alg. Based on the results of the 16S rDNA gene sequencing, it appears that strain A1 belonged to E. cloacae, with a 99.74% similarity. The findings suggest that immobilized strain A1 accomplished maximum decolorization activity compared with the free cells. The immobilized strain could utterly decompose and decolorize 0.05 mg/mL of RB19 within 48 h, while the free bacterial strain decolorized RB19 within 5 days. Moreover, Ca/Alg gel beads can maintain their efficiency for over three decolorization cycles. Further infrared spectroscopy (FTIR) and gas chromatograph mass spectrometer (GC/MS) investigation declared complete RB19 decomposition on reaction products. Artemia salina was used to investigate the toxicity of dye and its degraded metabolites. The LC50 values signified the pure dye as very toxic with 0.01 mg/mL concentration, while after‐treatment products showed no toxic effect on larvae. This immobilization technique increased the applicability of bacterial strain for dye removal. It was beneficial for the decolorization of RB19 from textile wastewater due to a remarkable reduction in time. Notably, strain A1‐immobilized beads can maintain their activity for three consecutive decolorization cycles without a considerable decrease in efficiency. Practitioner Points: The remarkable capacity of immobilized Enterobacter cloacae strain A1 for Reactive Blue 19 (RB19) removalImmobilized A1 strain showed two‐fold higher removal than free one over 48 hA promising method for enhancing RB19 decolorizationDecolorization was due to degradation based on UV–Vis, FTIR, and GC/MS analysisNon‐toxic posttreatment products for Artemia [ABSTRACT FROM AUTHOR]

Currently, active and intelligent packaging has been developed to solve the spoilage problem for protein-rich foods during storage, especially by adding anthocyanin extracts. In such a film system, the antioxidant and antibacterial properties were dramatically increased by adding anthocyanins. The physicochemical properties were enhanced through interactions between the active groups in the anthocyanins and reactive groups in the polymer chains. Additionally, the active and intelligent film could monitor the spoilage of protein-rich foods in response to pH changes. Therefore, this film could monitor the sensory acceptance and extend the shelf life of protein-rich foods simultaneously. In this paper, the structural and functional properties of anthocyanins, composite actions of anthocyanin extracts and biomass materials, and reinforced properties of the active and intelligent film were discussed. Additionally, the applications of this film in quality maintenance, shelf-life extension, and quality monitoring for fresh meat, aquatic products, and milk were summarized. This film, which achieves high stability and the continuous release of anthocyanins on demand, may become an underlying trend in packaging applications for protein-rich foods. [ABSTRACT FROM AUTHOR]

The new class of reactive polymers is designed to modify asphalt through chemical reactions with asphalt components. The complexity of such systems and the long experience with thermoplastic elastomers as well as with some other "classical" modifiers, and to a degree that our present testing methods and even specifications revolve around these materials, might obscure the fact that we are dealing with rather different modification systems and possibly with new emerging asphalt paving technologies. Our present work attempted to compare two different reactive polymer systems with the "classical" system which uses thermoplastic elastomer. The impact of reactive polymer systems on asphalt was studied through material properties manifested by specification tests and through the development of thermo-rheological properties in linear and non-linear viscoelastic regions. As expected, the behavior of reactive polymeric systems with different chemistries also differed among themselves. The available results showed that the reactive groups of polymers react with polar components of asphalt leading to higher stiffness at elevated pavement temperatures and differing impact on low temperature properties. The data point to a significantly improved resistance to plastic deformation of pavement in the case of reactive polymers, despite the fact that elastic recovery-based specification tests failed to identify this improvement. [ABSTRACT FROM AUTHOR]

In this work, the hysteresis of elastomer composites suitable for tire compounds was reduced by using CB functionalized with pyrrole compounds containing sulfur-based functional groups reactive with the elastomer chains. CB was functionalized with bio-based pyrrole compounds: 2-(2,5-dimethyl-1H-pyrrol-1-yl)ethane-1-thiol (SHP) and 1,2-bis(2-(2,5-dimethyl-1H-pyr-rol-1-yl)ethyl)disulfide (SSP), bearing an -SH and an -SS- functional group, respectively. SHP and SSP were synthesized via a one-pot two-step synthesis, with yields higher than 70%, starting from biosourced chemicals as follows: 2,5-hexanedione from 2,5-dimethylfuran, cysteine and cysteamine. The functionalization of CB was carried out by mixing the CB with PyC and heating, with quantitative yields ranging from 92 to 97%. Thus, the whole functionalization process was characterized by a high carbon efficiency. The formation of the covalent bond between SHP, SSP and CB, in line with the prior art of such a functionalization technology, was proven by means of extraction and TGA analyses. The reactivity of the sulfur-based functional groups with unsaturated polymer chains was demonstrated by using squalene as the model compound. Poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis were the elastomers employed for the preparation of the composites, which were crosslinked with a sulfur-based system. Pristine CB was partially replaced with CB/SHP (33%) and CB/SSP (33% and 66%). The PyC resulted in better curing efficiency, an increase in the dynamic rigidity of approximately 20% and a reduction in the hysteresis of approximately 10% at 70 °C, as well as similar/better ultimate tensile properties. The best results were achieved with a 66% replacement of CB with CB/SSP. This new family of reactive carbon blacks paves the way for a new generation of 'green tires', reinforced by a CB reactive with the polymer chains, which provides high mechanical properties and low rolling resistance. Such a reactive CB eliminates the use of silica, and thus the ethanol emission resulting from the condensation of silane is used as a coupling agent. In addition, CB-based tires are characterized by a higher mileage, at a moment in which the reduction in tire wear has become a primary concern. [ABSTRACT FROM AUTHOR]

Nonaqueous reaction foam polyurethane (PU) grouting materials have found wide applications in civil engineering. However, degradation laws and mechanism of the strength performance of PU grouting materials in different corrosion environments are not clear yet. Here, the uniaxial compression test, scanning electron microscopy (SEM) characterization, Fourier-transform infrared (FTIR) spectroscopy test, and molecular dynamics (MD) simulations were conducted to investigate the influences of acidic and alkaline corrosion environments on the compressive strength, microstructure, molecular structures, and nanoscale mechanical properties. Results show that with the increase of corrosion time, the compressive strength of PU grouting materials decreases more and more. The deterioration effect of an acidic environment is stronger than that of an alkaline environment, and it is stronger when the acidic environment is with a lower pH value. At the microscale, the damage of carbamate esters and the breakage of ether bonds results in the fracture, hydrolysis, and dissolution of the long PU molecule chains, which is the main reason leading to the destruction of microfoams. Compared with sodium hydroxide solution, sulfuric acid solution produces more pronounced damage to molecular structures as well as microstructures, and thus more significant deterioration effect on compressive strength. At the nanoscale, the compressive strength, tensile strength, and shear strength of the amorphous PU elastomers after corrosion decreased by 26.7%–35.7%, 13.4%–27.9%, and 4.26%–12.73%, respectively, compared with the original model, illustrating the damaging effect of chemical corrosion on the nanostrength of the PU elastomer. MD simulation results also show that the length of the molecular chain has a great influence on compressive strength and tensile strength, and the absence of molecular fragments has a great influence on shear strength. [ABSTRACT FROM AUTHOR]

This review covers strategies to prepare high-performance emissive polymer nanomaterials, combining very high brightness and photostability, to respond to the drive for better imaging quality and lower detection limits in fluorescence imaging and sensing applications. The more common approaches to obtaining high-brightness nanomaterials consist of designing polymer nanomaterials carrying a large number of fluorescent dyes, either by attaching the dyes to individual polymer chains or by encapsulating the dyes in nanoparticles. In both cases, the dyes can be covalently linked to the polymer during polymerization (by using monomers functionalized with fluorescent groups), or they can be incorporated post-synthesis, using polymers with reactive groups, or encapsulating the unmodified dyes. Silica nanoparticles in particular, obtained by the condensation polymerization of silicon alcoxides, provide highly crosslinked environments that protect the dyes from photodegradation and offer excellent chemical modification flexibility. An alternative and less explored strategy is to increase the brightness of each individual dye. This can be achieved by using nanostructures that couple dyes to plasmonic nanoparticles so that the plasmon resonance can act as an electromagnetic field concentrator to increase the dye excitation efficiency and/or interact with the dye to increase its emission quantum yield. [ABSTRACT FROM AUTHOR]

The aim of this work is to scientifically substantiate the mechanisms of plasma-chemical modification of polymeric materials in radio-frequency (RF) low-pressure discharge plasma. Using the method of molecular dynamics, a model describing the mechanisms of formation of oxygen- and nitrogen-containing functional groups on the surface of polymeric materials as a result of plasma modification was developed. The established mechanisms include multistep chemical reactions with the formation of alkyl dioxyl and alkoxyl radicals and unstable hydroperoxide groups. [ABSTRACT FROM AUTHOR]

We investigate reactive compatibilization by applying two multifunctional polymers grafted on a graphene surface, which leads to crosslinked interphase at immiscible polymer blends. Reactive compatibilizer‐grafted graphene (RCG) nanoparticles were synthesized through esterification and amidation reactions between oxidative groups of graphene oxide and reactive multifunctional groups of polymers. Polymer blends of polyisoprene (PI) and polydimethysiloxane (PDMS) with PI:PDMS ratio of 30:70 or 70:30 and RCG nanoparticle loadings from 0.1 and 1 wt% were evaluated by optical microscopy and rheometry. The results indicated that the blend with 0.1 wt% RCG showed unusual characteristics including nonspherical and bridged droplets, while those containing 1 wt% RCG showed usual droplet‐matrix morphology. The rheological results are also asymmetric: the blend with 0.1 wt% RCG displayed gel‐like behavior in the dynamic oscillatory tests, high viscosity, slow interfacial relaxation during startup shear flow, and divergence in the transient stress response due to coalesced and bridged droplets. However, the latter blend containing 1 wt% RCG reveals liquid‐like behavior, low viscosity, and convergence in the transient stress response due to stabilized droplet‐matrix morphology. Overall, it was suggested that these asymmetries are attributable to interfacial crosslinked interphase formed through an in‐situ reaction between multifunctional polymers grafted on graphene sheets. [ABSTRACT FROM AUTHOR]

Due to periodic variations in temperature and heavy traffic loading, hot-mix asphalt (HMA) pavements undergo considerable distress during their service life. The rheological properties of asphalt binder, when subjected to complex physical and chemical processes, make it stiff and sometimes brittle, which ultimately plays a huge part in pavement deterioration. This phenomenon is commonly known as asphalt aging. Incorporating polymer modifiers with virgin asphalt can work as an effective means to change the binder properties and alleviate the issues related to asphalt aging. Different types of polymers, including elastomers, plastomers, and reactive polymers, can mixed in different combinations with the virgin asphalt to create polymer-modified binders (PMBs). In general, polymers are typically added to the virgin asphalt binder in PMB manufacturing at weight percentages ranging from 3% to 7%. Previous research suggests that many polymer-modified binders (PMBs) show great resiliency and perform extremely well during field and laboratory testing, although the complex nature of asphalt itself makes it significantly difficult to understand the relationship and compatibility of the asphalt–polymer system. This paper aims to develop a comprehensive literature review on the chemical aspects, microscopic structure, and compatibility of polymers with virgin asphalt. It was found that swelling, storage stability, blend morphology, and the polymer mixing technique play a great role in the compatibility of asphalt–polymer systems. Thermoplastic elastomers (e.g., styrene–butadiene–styrene) and plastomers (e.g., ethylene–vinyl acetate) are the most used polymer modifiers for asphalt binders. The compatibility of the polymer–asphalt system can be improved by sulfur vulcanization, antioxidants, hydrophobic clay minerals, functionalization, and reactive polymers, among other techniques. [ABSTRACT FROM AUTHOR]

This paper addresses peculiarities in the formation and adherence of a tribofilm on the wear track surface of antifriction PI- and PEI-based composites, as well as a transfer film (TF) on a steel counterface. It is shown that during hot pressing, PTFE nanoparticles melted and coalesced into micron-sized porous inclusions. In the PEI matrix, their dimensions were much larger (up to 30 µm) compared to those in the PI matrix (up to 6 µm). The phenomenon eliminated their role as effective uniformly distributed nanofillers, and the content of 5 wt.% was not always sufficient for the formation of a tribofilm or a significant decrease in the WR values. At the loaded content, the role of MoS2 and graphite (Gr) microparticles was similar, although filling with MoS2 microparticles more successfully solved the problem of adhering to a PTFE-containing tribofilm in the point tribological contact. This differed under the linear tribological contact. The higher roughness of the steel counterpart, as well as the larger area of its sliding surface with the same PTFE content in the three-component PI- and PEI-based composites, did not allow for a strong adherence of either the stable PTFE-containing tribofilm on the wear track surface or the TF on the steel counterpart. For the PEI-based composites, the inability to shield the steel counterpart from the more reactive polymer matrix, especially under the conditions of PTFE deficiency, was accompanied by multiple increases in the WR values, which were several times greater than that of neat PEI. [ABSTRACT FROM AUTHOR]

Reactive powder concrete, or RPC, outperforms conventional or even high-performance concrete in terms of ultra-high strength and better durability. Several buildings were destroyed in Iraq, and recycling the garbage from these buildings can significantly help reduce waste and environmental pollution as well as serve as a source of aggregate for use in new construction. Reusing garbage and using sustainable building materials are now crucial environmental challenges, so this study aimed to replace the natural fine aggregate, NFA, used in preparations of polymer reactive powder concreter, "PRPC" with recycled aggregates, or RA, from crushed old concrete, COC, in order to make PRPC production more environmentally and sustainably friendly. In this study, RPC is modified by adding styrene butadiene rubber (SBR), a polymer, to the original mixture at a ratio of 13% by weight of cement. This study sought to determine the effect of using COC as recycled fine aggregate (RFA) on the compressive, splitting, and flexural strengths of PRPC. The main objective of this investigation is to study the effect of oil (water, new oil, and waste engine oil) on the compressive and tensile strengths of PRPC with COC and to compare the behavior with that of a control mix (PRPC with NFA). The mixtures were prepared using six different percentages of RFA, replacing 0, 20, 40, 60, 80, and 100% NfA. After 28 days, the six mixes were divided into three groups. The first was still being cured in water, W; the second in waste engine oil, WEO; and the third in kerosene oil, KO. The results showed that using COC as RFA in PRPC was viable, and according to this investigation, the mix with 40% COC replacement with NFA provides the highest values of compressive strength, tensile strength, and flexural strength before and after exposure to liquids (water, new oil, and waste engine oil). [ABSTRACT FROM AUTHOR]

Two in situ formed Fe(III) oxyhydroxides (FeOx) originated from ferrate reduction (designated FeOx–FeVI) and ferrous oxidation by H2O2 (designated FeOx–FeII) were compared in the aspects of morphology, hydrolyzed species, surface binding mechanism of lead. The theoretical maximum adsorption capacity calculated from the Langmuir model toward Pb(II) was 929.54 and 810.37 mg/g Fe by FeOx–FeVI and FeOx–FeII, respectively. At pH 6 and the same Fe/Pb ratio, the kinetic rate of Pb removal by the FeOx–FeVI process was 8 times faster. FTIR, SEM, and Ferron assay suggest FeOx–FeVI was associated with a lesser polymerization degree and contained more reactive hydroxyl-Fe polymers than those in the FeOx–FeII sample. SAXS verified that the particles possessed a smaller, more homogeneous, and open structure when Fe was hydrolyzed by ferrate reduction than ferrous oxidation. XPS coupled with fractal analysis suggests the different sorption capacities of Pb(II) can be ascribed to their distinct growth patterns. Fast cluster agglomeration during FeOx–FeII fabrication decreased the exposure of effective adsorption sites. In comparison, the incompact assemblies of FeOx–FeVI clusters facilitated Pb(II) ions to access the interstices of octahedral FeO6 units and formed an edge-sharing complex. This work provides new insight into mechanisms of particle fabrication and heavy metal removal of Fe(III) formed in situ. [ABSTRACT FROM AUTHOR]

Lithium (Li) metal anodes have the highest theoretical capacity and lowest electrochemical potential making them ideal for Li metal batteries (LMBs). However, Li dendrite formation on the anode impedes the proper discharge capacity and practical cycle life of LMBs, particularly in carbonate electrolytes. Herein, we developed a reactive alternative polymer named P(St‐MaI) containing carboxylic acid and cyclic ether moieties which would in situ form artificial polymeric solid electrolyte interface (SEI) with Li. This SEI can accommodate volume changes and maintain good interfacial contact. The presence of carboxylic acid and cyclic ether pendant groups greatly contribute to the induction of uniform Li ion deposition. In addition, the presence of benzyl rings makes the polymer have a certain mechanical strength and plays a key role in inhibiting the growth of Li dendrites. As a result, the symmetric Li||Li cell with P(St‐MaI)@Li layer can stably cycle for over 900 h under 1 mA cm−2 without polarization voltage increasing, while their Li||LiFePO4 full batteries maintain high capacity retention of 96 % after 930 cycles at 1C in carbonate electrolytes. The innovative strategy of artificial SEI is broadly applicable in designing new materials to inhibit Li dendrite growth on Li metal anodes. [ABSTRACT FROM AUTHOR]

Rare‐earth metal‐mediated group‐transfer polymerization (REM‐GTP) offers distinctive features over common polymerization techniques, such as living character, a broad scope of functional monomers, high activity, excellent control of the polymeric parameters as well as inherent chain‐end functionalization. Through the latter, polymers with reactive end‐groups become feasible, opening the pathway for further post‐polymerization functionalization. In this study, a straightforward graft‐to immobilization of the Michael‐type polymer poly(diethyl vinylphosphonate) (PDEVP) on multi‐walled carbon nanotubes (MWCNT) is reported. Hence, a customized azide initiator is synthesized and studied in the CH bond activation with various lanthanide‐based catalysts and the subsequent polymerization of diethyl vinylphosphonate (DEVP). The successful attachment of the azide end‐group is demonstrated via electrospray ionization mass spectrometry (ESI‐MS) and the synthesized polymers are subjected to immobilization on multi‐walled carbon nanotubes in a graft‐to approach. The prepared MWCNT:PDEVP composites are analyzed via thermogravimetric analysis (TGA), elemental analysis (EA), Raman spectroscopy, X‐Ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) and the versatility of this approach is shown via the stabilization of MWCNT dispersions in water. [ABSTRACT FROM AUTHOR]

Anything that is not recycled and/or recovered from waste represents a loss of raw materials. Recycling plastics can help to reduce this loss and to reduce greenhouse gases, improving the goal of the decarbonization of plastic. While the recycling of single polymers is well assessed, the recycling of mixed plastics is very difficult because of the strong incompatibility among the different polymers usually present in urban waste. In this work, heterogeneous mixed polymers, i.e., polyethylene (PE), polypropylene (PP), polystyrene (PS) and polyethylenetherephthalate (PET) were processed using a laboratory mixer under different conditions of temperature, rotational speed and time to evaluate the effect of the above parameters on morphology, viscosity and mechanical properties of the final blends. Morphological analysis shows a strong incompatibility between the polyethylene matrix and the other dispersed polymers. The blends show, of course, a brittle behavior, but this behavior slightly improves with decreasing temperature and increasing rotational speed. A brittle-ductile transition was observed only at a high level of mechanical stress obtained by increasing rotational speed and decreasing temperature and processing time. This behavior has been attributed to both a decrease in the dimensions of the particles of the dispersed phase and to the formation of a small amount of copolymers that act as adhesion promoters between matrix and dispersed phases. [ABSTRACT FROM AUTHOR]

Materials for biomedical applications often need to be coated to enhance their performance, such as their biocompatibility, antibacterial, antioxidant, and anti-inflammatory properties, or to assist the regeneration process and influence cell adhesion. Among naturally available substances, chitosan meets the above criteria. Most synthetic polymer materials do not enable the immobilization of the chitosan film. Therefore, their surface should be altered to ensure the interaction between the surface functional groups and the amino or hydroxyl groups in the chitosan chain. Plasma treatment can provide an effective solution to this problem. This work aims to review plasma methods for surface modification of polymers for improved chitosan immobilization. The obtained surface finish is explained in view of the different mechanisms involved in treating polymers with reactive plasma species. The reviewed literature showed that researchers usually use two different approaches: direct immobilization of chitosan on the plasma-treated surface or indirect immobilization by additional chemistry and coupling agents, which are also reviewed. Although plasma treatment leads to remarkably improved surface wettability, this was not the case for chitosan-coated samples, where a wide range of wettability was reported ranging from almost superhydrophilic to hydrophobic, which may have a negative effect on the formation of chitosan-based hydrogels. [ABSTRACT FROM AUTHOR]

Rational design of efficient cytosolic protein delivery carriers holds enormous promise for biotherapeutics development. Several delivery systems have been developed during the past decades, while tailoring the balance between extracellular protein binding and intracellular cargo release is still challenging. In this study, we synthesized a series of oxygen-sensitive reactive polymers, rich in boron, by radical polymerization and post-modification for cytosolic protein delivery in vitro and in vivo. The introduction of boronate building blocks into the polymer scaffold significantly enhanced its protein binding affinity, and the polymer/protein complexes with high stability were obtained by tailoring the molecular ratios between the boronate ligands and the amine groups. The lead material screened from the polymer library exhibited efficient protein delivery efficacy that can release cargo proteins in cytosol in a reactive oxygen species responsive manner, which enables intracellular delivery of proteins with maintained bioactivity. In addition, the polymer-based nanoformulations efficiently delivered saporin, a toxin protein, into osteosarcoma cells and tumor tissues, and exhibited high therapeutic efficacy in an osteosarcoma mouse model. The synthesized polymer in this study can be developed as a promising nanocarrier for cytosolic delivery of protein therapeutics to treat a variety of diseases. ROS-responsive boronic acid-rich polymer achieves efficient intracellular protein delivery in vitro and in vivo. [Display omitted] • A boronate-rich polymer exhibits efficient protein binding and ROS-responsive protein release. • Protein delivery efficacy can be tailored by the boronate ratios and the amine structures. • Efficient in vivo cancer therapy was achieved via tumor targeted protein delivery. [ABSTRACT FROM AUTHOR]

The amino acid derivative reactivity assay (ADRA), an alternative method for testing skin sensitization, has been established based on the molar concentration approach. However, the additional development of gravimetric concentration and fluorescence detection methods has expanded its range of application to mixtures, which cannot be evaluated using the conventional testing method, the direct peptide reactivity assay (DPRA). Although polymers are generally treated as mixtures, there have been no reports of actual polymer evaluations using alternative methods owing to their insolubility. Therefore, in this study, we evaluated skin sensitization potential of polymers, which is difficult to predict, using ADRA. As polymers have molecular weights ranging from several thousand to more than several tens of thousand Daltons, they are unlikely to cause skin sensitization due to their extremely low penetration into the skin, according to the 500‐Da rule. However, if highly reactive functional groups remain at the ends or side chains of polymers, relatively low‐molecular‐weight polymer components may penetrate the skin to cause sensitization. Polymers can be roughly classified into three major types based on the features of their constituent monomers; we investigated the sensitization capacity of each type of polymer. Polymers with alert sensitization structures at their ends were classified as skin sensitizers, whereas those with no residual reactive groups were classified as nonsensitizers. Although polymers with a glycidyl group need to be evaluated carefully, we concluded that ADRA (0.5 mg/ml) is generally sufficient for polymer hazard assessment. Regarding polymer involved reactive functional groups at the ends or side chains, relatively low‐molecular‐weight polymer components may penetrate the skin to cause sensitization. After classified into three major types, we investigated the sensitization capacity of each type of polymer using ADRA based on both molar concentration approach and gravimetric approach. As a result, polymers with alert sensitization structures at their ends were classified as skin sensitizers, whereas those with no residual reactive groups were classified as nonsensitizers. [ABSTRACT FROM AUTHOR]