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Although widely studied experimentally in the 1990s, the structure and properties of low-dimensional or high-pressure phases of fullerenes have recently been re-examined. Remarkably, recent experiments have shown that transparent, nearly pure amorphous sp3-bonded carbon phases can be obtained by heating a C60 molecular crystal at a high pressure. With the additional aim of testing the ability of three classical carbon potentials reactive empirical bond order, environment-dependent interatomic potential, and reactive force-field to reproduce these results, we investigate the details of the structural transformations undergone by fullerene crystals over a wide range of pressures and temperatures. All the potentials tested show that the initial polymerization of fullerenes is accompanied by negative thermal expansion, albeit in slightly different ranges. However, more significant differences in structural and mechanical properties are observed in the amorphous phases, in particular the sp3 carbon fraction and the existence of layered amorphous carbon. Overall, these results indicate to which extent classical reactive potentials can be used to explore phase transitions over a wide range of pressures and temperatures. [ABSTRACT FROM AUTHOR]

Polymerization of nucleotides under prebiotic conditions simulating the early Earth has been extensively studied. Several independent methods have been used to verify that RNA-like polymers can be produced by hot wet-dry cycling of nucleotides. However, it has not been shown that these RNA-like polymers are similar to biological RNA with 3'-5' phosphodiester bonds. In the results described here, RNA-like polymers were generated from 5'-monophosphate nucleosides AMP and UMP. To confirm that the polymers resemble biological RNA, ribonuclease A should catalyze hydrolysis of the 3'-5' phosphodiester bonds between pyrimidine nucleotides to each other or to purine nucleotides, but not purine-purine nucleotide bonds. Here we show AFM images of specific polymers produced by hot wet-dry cycling of AMP, UMP and AMP/UMP (1:1) solutions on mica surfaces, before and after exposure to ribonuclease A. AMP polymers were unaffected by ribonuclease A but UMP polymers disappeared. This indicates that a major fraction of the bonds in the UMP polymers is indeed 3'-5' phosphodiester bonds. Some of the polymers generated from the AMP/UMP mixture also showed clear signs of cleavage. Because ribonuclease A recognizes the ester bonds in the polymers, we show for the first time that these prebiotically produced polymers are in fact similar to biological RNA but are likely to be linked by a mixture of 3'-5' and 2'-5' phosphodiester bonds.

Age-related hearing loss (ARHL) is a common sensory impairment with complex underlying mechanisms. In our previous study, we performed a meta-analysis of genome-wide association studies (GWAS) in mice and identified a novel locus on chromosome 18 associated with ARHL specifically linked to a 32 kHz tone burst stimulus. Consequently, we investigated the role of Formin Homology 2 Domain Containing 3 (Fhod3), a newly discovered candidate gene for ARHL based on the GWAS results. We observed Fhod3 expression in auditory hair cells (HCs) primarily localized at the cuticular plate (CP). To understand the functional implications of Fhod3 in the cochlea, we generated Fhod3 overexpression mice (Pax2-Cre+/-; Fhod3Tg/+) (TG) and HC-specific conditional knockout mice (Atoh1-Cre+/-; Fhod3fl/fl) (KO). Audiological assessments in TG mice demonstrated progressive high-frequency hearing loss, characterized by predominant loss of outer hair cells, and a decreased phalloidin intensities of CP. Ultrastructural analysis revealed loss of the shortest row of stereocilia in the basal turn of the cochlea, and alterations in the cuticular plate surrounding stereocilia rootlets. Importantly, the hearing and HC phenotype in TG mice phenocopied that of the KO mice. These findings suggest that balanced expression of Fhod3 is critical for proper CP and stereocilia structure and function. Further investigation of Fhod3 related hearing impairment mechanisms may lend new insight towards the myriad mechanisms underlying ARHL, which in turn could facilitate the development of therapeutic strategies for ARHL.

An emerging cellular engineering method creates synthetic polymer matrices inside cells. By contrast with classical genetic, enzymatic, or radioactive techniques, this materials-based approach introduces non-natural polymers inside cells, thus modifying cellular states and functionalities. Here, we cover various materials and chemistries that have been exploited to create intracellular polymer matrices. In addition, we discuss emergent cellular properties due to the intracellular polymerization, including nonreplicating but active metabolism, maintenance of membrane integrity, and resistance to environmental stressors. We also discuss past work and future opportunities for developing and applying synthetic cells that contain intracellular polymers. The materials-based approach will usher in new applications of synthetic cells for broad biotechnological applications.

In this paper, a series of novel trans-1, 4-polyisoprene/isotactic polybutene (TPI/iPB) in-reactor blends were synthesized by isoprene and butene sequential two-stage polymerization technology with spherical Ti[Cl.sub.4]/Mg[Cl.sub.2] type Ziegler-Natta catalyst. The components, structures, and properties of the asobtained TPI/iPB reactor blends were characterized by gel permeation chromatography, Fourier transform Infrared spectroscopy, and differential scanning calorimetry. The active trans-1, 4-polyisoprene (TPI) particles obtained in the initial isoprene polymerization by the Z-N catalyst can be acted as microreactors to initiate butene polymerization subsequently. The TPI/iPB reactor blends with varied components were in situ synthesized within the reactor. The preparative-temperature rising elution fractionation (p-TREF) technique was used to fractionate the TPI/iPB reactor blends based on the elution temperature ranged from -40[degrees]C to 90[degrees]C. The weight distribution and microstructure of each fraction were investigated. The reactor blends are composed of crystallizable high trans-1, 4-uint polyisoprene obtained from the first-stage isoprene polymerization, high isotactic polybutene obtained from the secondstage butene polymerization and TPI-b-iPB block copolymer with different sequence structure obtained from the initial time of the second stage. This work is expected to propose the possible polymerizations of a-olefins and conjugated dienes by using heterogeneous Ziegler-Natta catalyst and provide a kind of novel rubber/plastic reactor blend materials. Highlights * The first synthesis of the trans-1,4-polyisoprene/isotactic polybutene reactor blends. * p-TREF technique was used to analyze the composition of TPI/iPB reactor blends. * Detailed structure characterization of the fractions including GPC and NMR * TPI-b-iPB block copolymer can be obtained through the sequential polymerization. * Rubber/plastic reactor blend materials were fabricated by the Z-N catalyst. KEYWORDS 4-polyisoprene, in-reactor blends, polybutene, temperature rising elution fractionation, trans-1, Ziegler-Natta catalyst, 1 | INTRODUCTION The discovery of Ziegler-Natta catalysts has been one of the greatest developments in the synthesis of stereospecific polymers in both academy and modern industry. (1-4) The first [...]

Purpose: To measure the influence of postpolymerization condition (dry and water-submerged) and time (2, 10, 20, and 40 minutes) on the accuracy of additively manufactured model material. Materials and Methods: A bar standard tessellation language (STL) file was used to manufacture all the resin specimens using a 3D printer. Two groups (n = 80 each) were created based on postpolymerization condition: dry (D group) and water-submerged (W group). Each group was then divided into four subgroups (D1 to D4 and W1 to W4; n = 20 each), which were each assigned a postpolymerizing time (2, 10, 20, and 40 minutes). The specimens' dimensions were measured using a low-force digital caliper. The volume was calculated as follows: V = l × w × h. Shapiro-Wilk test revealed that the data were not normally distributed. Data were analyzed using Kruskal-Wallis and pairwise Mann-Whitney U tests (a = .05). Results: Significant differences in length, width, height, and volume were found among the subgroups (P < .0018). In all groups, the width dimension (x-axis) presented less accuracy compared to height (z-axis) and length (y-axis) (P < .0018). The D2 and D4 subgroups obtained the closest dimensions to the virtual design, and there were no significant differences between these subgroups (P < .0018). The dry condition showed higher manufacturing accuracy than the water-submerged condition. In the water-submerged subgroups, the highest accuracy was obtained in the W2 and W4 subgroups (P < .0018). Conclusions: Postpolymerization condition and time influenced the accuracy of the material tested. The dry postpolymerization condition with times of 10 and 40 minutes obtained the highest accuracy. [ABSTRACT FROM AUTHOR]

Polymeric applications with extended service life and low energy loss due to friction are of great interest in conveyor and power transmission technology. Self‐lubricating systems utilizing microcapsules hold significant potential for increasing energy efficiency and extending the operational life of these applications. This study focuses on synthesizing oil‐filled microcapsules through in situ polymerization of polyamide and their incorporation in polyamide 6 and polyamide 6.6. Microcapsules with a core made of thermally stable lubricant Food Lube, and particle diameter D90 of 50 μm were synthesized and isolated as a free‐flowing powder via spray‐drying procedure. The resulting powder demonstrated high thermal stability (loss of 5% at 350°C) due to the high thermal stability of both core and shell materials. A compounding process utilizing a twin‐screw extruder was developed to blend microcapsules into thermoplastic matrices. An injection molding machine forms tension rods. The composites' tribological properties are assessed through ball‐on‐disc tests conducted in both oscillation and rotation. The friction coefficient and wear rate of the composites experience a reduction of 79% and 56% for polyamide 6, as well as 77% and 75% for polyamide 6.6. Mechanical testing of the microcapsule composites reveals a decrease in mechanical properties. [ABSTRACT FROM AUTHOR]

The synthesis, spectroscopic characterisation and catalytic olefin polymerisation behaviour of a class of binuclear titanium bis(benzyl) complexes bearing bis-(pyridine-2-phenolate-6-methine)-[μ-(arylene-1,4-diyl-2,3-X2)] ligands [X2 = -C4H4-- (1), F2 (2), H2 (3)], and mononuclear analogues, are described. These bi-metallic catalyst frameworks are designed to exhibit a degree of conformational flexibility, which is regulated by steric effects and crucially permits tuning of intermetallic distances and geometry, yet their shape-persistent nature can also confer favourable entropic terms. Complexes 1-3 are characterised as two diastereomers [meso (RS) and rac (RR,SS)] in ratios of 1.32, 1.18 and 1.13 respectively, according to ¹H NMR spectroscopy. In contrast to 3,[¹H, ¹H]-ROESY experiments for 1 and 2 revealed that the X² substituents can impose preferred conformations with syn orientations of Ti2 centres and benzyl groups, thus implying that the activated catalysts would present binding sites with the same direction of access. For ethylene-(1-octene) copolymerisation reactions, in conjunction with [Ph3C][B(C6F5)4], catalyst 1 displayed superior efficiencies and produced polymers with higher Mw values and enhanced comonomer incorporation ratios (up to 41%), when compared with the mononuclear 5m (22%). These results are indicative of enhanced comonomer enchainment and cooperative reactivity by the Ti2 sites. [ABSTRACT FROM AUTHOR]

Reconfigurable and tunable holograms hold significant practical value in the fields of anti‐counterfeiting, optical security, and information display due to their ability to reprogram holographic patterns and create variable visual effects. However, current encryption techniques face challenges in achieving rapid encryption/decryption and ensuring consistent methods. In this study, a method for producing a reconfigurable encryption hologram utilizing the deformation and recovery properties of micropillars in response to liquid is demonstrated. Micron‐scale micropillars are fabricated using femtosecond laser two‐photon polymerization. By exploiting the rapid deformation and recovery capabilities of micropillars with specific pitches and aspect ratios in response to liquids, micropillar structures and holograms are combined to construct reconfigurable holograms. The encrypted pattern information in the reconfigurable holograms is only readable following immersion in alcohol and laser irradiation. The proposed method offers a facile, reversible, reusable, and practical solution for information encryption, with significant potential in anti‐counterfeiting and optical security. [ABSTRACT FROM AUTHOR]

Here, the use of cellulose films (CFs) produced from low‐quality cotton is reported as a template for in situ synthesis of well‐known conductive polymers, e.g., polyaniline (PANI) and polypyrrole (PPY) via oxidative polymerization. Three successive monomer loading/polymerization cycles of aniline (ANI) and pyrrole (PY) within CFs as PANI@CF or PPY@CF are carried out to increase the amount of conductive polymer content. The contact angle (CA) for three times ANI and PPY loaded and polymerized CFs as 3PANI@CF and 3PPY@CF are determined as 26.3±2.8 and 42.3±0.6 degrees, respectively. As the electrical conductivity is increased with increased number of conductive polymer synthesis within CF, the higher conductivity values, 3×10−4±8.1×10−5 S.cm−1 and 2.1×10−3±5.8×10−4 S.cm−1, respectively are measured for 3PANI@CF and 3PPY@CF composites. It is found that PANI@CF composites are hemolytic, whereas PPY@CF composites are not at 1 mg mL−1 concentrations. All PPY@CF composites exhibit better biocompatibility than PANI@CF composites on L929 fibroblast cells with more than 70±8% viability at 1 mg of CF‐based conductive polymer composites. Moreover, MIC and MBC values of 3PPY@CF composites for Escherichia coli (ATCC8739) and Staphylococcus aureus (ATCC6538) are determined as 2.5 and 5.0 mg.mL−1, whereas these values are estimated as 5 and 10 mg.mL−1 for Candida albicans (ATCC10231). [ABSTRACT FROM AUTHOR]

Lead halide perovskite nanocrystals (LHP‐NCs) incorporated within polymer matrices have emerged as promising materials for various photonic applications. However, challenges persist in achieving high‐quality nanocomposites due to low monomer conversion yields, restricted LHP‐NCs loadings, and difficulty in maintaining NCs integrity post‐polymerization. A novel protocol for synthesizing LHP‐NCs/poly(methyl methacrylate) nanocomposites in a single step via the NC‐initiated photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) method is presented. Polymerization initiation mediated by NCs surfaces under blue light enables the fabrication of homogeneous nanocomposites with NCs loadings up to 7% w/w and ≈90% monomer conversion even in the presence of oxygen. This process preserves the optical quality of the NCs and passivates NCs surface defects, resulting in nanocomposites exhibiting near unity luminescence efficiencies. The potential of this approach for producing highly loaded nanocomposites for radiation detection is validated by radioluminescence measurements showing light yield values of 6000 ph MeV−1 and fast scintillation dynamics with effective lifetime of 490 ps, showing promise for time‐of‐flight radiometry. [ABSTRACT FROM AUTHOR]

A series of bimetallic rare-earth complexes {[μ-η1:(μ-η1:η1):η1-1-(2-C5H4N)-3-(2-C7H4NS)C8H4N]RE(CH2SiMe3)2}2 (RE = Y(7a), Er(7b), Yb(7c), Lu(7d)) were synthesized by treatment of rare-earth metal trialkyl complexes RE(CH2SiMe3)3(THF)2 with one equiv. of the proligand 1-(2-C5H4N)-3-(2-C7H4NS)C8H5N (6) in good isolated yields. Complex 7c can be converted to the divalent rare-earth metal complexes (η4:σ:κ1-L)2YbII [L = 1-(2-C5H4N)-3-(2-C7H4NS)C8H4N(CHSiMe3)] (8) at elevated temperature in toluene solution. Complexes 7a, 7d and 8 were characterized by NMR spectroscopy. Additionally, the yttrium (7a), erbium (7b) and lutetium (7d) complexes exhibited high activity in the polymerization of 2-vinylpyridine with isotactic selectivity and high molecular weight. [ABSTRACT FROM AUTHOR]

Fourteen new phenoxy-azo aluminium complexes comprising two series, namely, dimethyl{phenoxy-azo}aluminium complexes 1a–7a and monomethyl{phenoxy-azo}aluminium complexes 1b–7b, were successfully synthesised and characterised. The molecular structure of complex 4a, determined using X-ray diffraction analysis, displayed a distorted tetrahedral geometry. The 1H NMR spectrum of complex 5b revealed fluxional behaviour caused by isomeric transformation that occurs in the solution at room temperature. The activation parameters determined by lineshape analysis of variable-temperature 1H NMR spectra in toluene-d8 are as follows: ΔH‡ = 70.05 ± 1.19 kJ mol−1, ΔS‡ = 21.78 ± 3.58 J mol−1 K−1 and ΔG‡ (298 K) = 63.56 ± 0.11 kJ mol−1. All aluminium complexes are active initiators for the ring-opening polymerisation of rac-lactide, and the polymerisations proceeded in a controlled manner and were living. In comparison, the catalytic activity of the dimethyl{phenoxy-azo}aluminium complexes was insignificantly different from that of the corresponding monomethyl{phenoxy-azo}aluminium complexes. The steric factor of the ortho-phenoxy substituent was observed to exert a decelerating effect on the catalytic rate. Kinetic investigations revealed first-order dependency on both monomer and initiator concentrations. Comparative catalytic investigations conducted on phenoxy-azo aluminium and phenoxy-imine aluminium complexes revealed that the former complexes exhibited lower catalytic activity. [ABSTRACT FROM AUTHOR]

Vinyl‐substituted hydridopolycarbosilane (VHPCS) is widely studied for its low viscosity, abundance of active functional groups, rapid curing, and high ceramic yield. The curing reactions mainly involve the free radical polymerization of vinyl and hydrosilylation reactions, but these reactions typically require high temperatures such as 160–250°C. The curing behavior of VHPCS‐17 with a tert‐butyl peroxybenzoate/Nickel acetylacetonate (TBPB/NIAA) system is investigated using differential scanning calorimetry and in situ Fourier transform infrared. The properties of VHPCS‐17 with different initiator systems and VHPCS with different vinyl contents (under TBPB/NIAA system) are studied using thermogravimetric analysis and x‐ray diffraction. The results demonstrate that the TBPB/NIAA system can facilitate the free radical polymerization of vinyl; moreover, this system decreases the peak temperature of the curing reaction from 251 to 141°C and increases the ceramic yield from 80.49% to 89.88%. The ceramic yield of cured VHPCS increases gradually, reaching 89.88% when the vinyl content is 17%. The grain size of β‐SiC decreases continuously with the increase in vinyl content, while the high‐temperature oxidation‐resistant properties of SiC ceramics obtained from different VHPCSs are not negatively affected. [ABSTRACT FROM AUTHOR]

Cell processes require precise regulation of actin polymerization that is mediated by plus-end regulatory proteins. Detailed mechanisms that explain plus-end dynamics involve regulators with opposing roles, including factors that enhance assembly, e.g., the formin mDia1, and others that stop growth (capping protein, CP). We explore IQGAP1's roles in regulating actin filament plus-ends and the consequences of perturbing its activity in cells. We confirm that IQGAP1 pauses elongation and interacts with plus ends through two residues (C756 and C781). We directly visualize the dynamic interplay between IQGAP1 and mDia1, revealing that IQGAP1 displaces the formin to influence actin assembly. Using four-color TIRF, we show that IQGAP1's displacement activity extends to formin-CP "decision complexes," promoting end-binding protein turnover at plus-ends. Loss of IQGAP1 or its plus-end activities disrupts morphology and migration, emphasizing its essential role. These results reveal a new role for IQGAP1 in promoting protein turnover on filament ends and provide new insights into how plus-end actin assembly is regulated in cells. [ABSTRACT FROM AUTHOR]

The precise synthesis of chiral polymers remains a significant challenge in polymer chemistry, particularly for applications in advanced biomedical and electronic materials. The development of degradable polymers is important for eco‐friendly and advanced materials. Here, we introduce a stereo‐controlled degradable polymer via cascade enyne metathesis polymerization and enantioselective acetal synthesis through Pd‐catalyzed asymmetric hydroamination. This approach allows for the creation of chiral acetal‐based polymers with controlled stereochemistry and degradability, highlighting their potential for use in drug delivery and electronic applications. This concept article reviews the background, development, and potential applications of these stereo‐controlled degradable polymers. [ABSTRACT FROM AUTHOR]

A process for photocatalytically synthesizing hydrogen peroxide while simultaneously degrading organic pollutants is of interest. In this study, a dendritic nanopolymer was synthesized and utilized as a photocatalyst for the production of hydrogen peroxide, which was then used in tandem with the degradation of Tetracycline (TC) and Rhodamine B (Rh B) organic pollutants under a 36 W incandescent bulb. The yield of H2O2 was measured at 8.4 mg g−1 h−1, with photocatalytic degradation rates of 93.90 % for Rh B and 72.92 % for TC. The degradation kinetics of TC and Rh B by the dendritic polymer were found to follow pseudo‐first‐order kinetics, and a higher affinity for degradation was observed for Rh B. The photocatalytic degradation mechanism of TC in a Fenton‐like system was attributed to an oxidation system involving hydrogen peroxide and ferrous ions. [ABSTRACT FROM AUTHOR]

In this paper, we describe the synthesis of indolyl aryl sulfonamide conjugates (6 a–n). The anti‐tumour activity was assessed on three human cancer cell lines: A‐549 (lung), HeLa (cervix), and MCF‐7 (breast). Nocodazole was used as a standard drug by employing the MTT assay method. The results show that the compounds 6 b, 6 l, and 6 m have shown more potent activity as compared to the standard drug Nocodazole. In a cell survivability test (MCF‐10 A), three potent compounds (6 b, 6 l, and 6 m) were evaluated against the normal breast cell line, although neither of them displayed any significant cytotoxicity with IC50 values greater than 78.45 μM. Furthermore, the compounds 6 b, 6 l, and 6 m were tested for tyrosine kinase EGFR inhibitory action using Combretastatin A‐4 as the reference drug. The in vitro tubulin polymerization inhibitory activity indicates that the compounds 6b and 6 l showed promising potency with IC50 values of 2.40±0.02 and 2.34±0.03 mM, respectively. In addition to this, molecular docking studies of compounds 6 b, 6 l, and 6 m demonstrated that these compounds had more EGFR binding interactions. The potent compounds 6 b, 6 l, and 6 m were subjected to in silico pharmacokinetic assessment by SWISS, ADME, and pkCSM. While the compounds 6 b, 6 l, and 6 m followed five filters (Lipinski rule, Ghose rule, Veber rule, Egan rule, and Muegge rule) without any deviation. [ABSTRACT FROM AUTHOR]

With the ever-growing reliance on polymeric materials for numerous applications, new avenues to induce, design and control degradation are clearly important. Here, we describe a previously unreported approach to controlling enzymatic hydrolysis of high molecular weight branched polymers formed from the new free-radical polymer synthesis strategy transfer-dominated branching radical telomerisation (TBRT). Modifying the chemical nature of TBRT polymers may be accomplished through telogen selection and multi-vinyl taxogen (MVT) design, and we show telogen-driven control of enzyme-catalysed hydrolysis and the impact of careful placement of hydrolytically susceptible groups within readily synthesised MVTs. Our results indicate that utilising conventional free-radical chemistries and unsaturated monomers as feedstocks for highly branched polymer architectures has considerable potential for the design of future materials that degrade into very low molecular weight byproducts at variable and controllable rates. With the ever-growing reliance on polymeric materials for numerous applications, new avenues to induce, design and control degradation are clearly important. Here, the authors report an approach to controlling the enzymatic hydrolysis of high molecular weight branched polymers formed from transfer-dominated branching radical telomerisation, through telogen selection and multi-vinyl taxogen design. [ABSTRACT FROM AUTHOR]

Herein we demonstrate an effective and facile end‐capping technique for ring‐opening metathesis polymerization (ROMP) using readily available allyl compounds as a new type of terminating agents. This new type of end‐capping reactions, which are based on the base‐promoted decomposition of ruthenocyclobutane intermediates, introduce diene moiety onto the chain end of ROMP polymers while simultaneously deactivating the ruthenium complex. These termination reactions are highly efficient, typically completing within 1 minute at 0 °C with >95 % end‐capping fidelity. [ABSTRACT FROM AUTHOR]

Membrane materials that resist nonspecific or specific adsorption are urgently required in widespread practical applications, such as water purification, food processing, and life sciences. In water purification, inevitable membrane fouling not only limits membrane separation performance, leading to a decline in both permeance and selectivity, but also remarkably increases operation requirements, and augments extra maintenance costs and higher energy consumption. In this work, we report a freestanding interfacial polymerization (IP) fabrication strategy for in situ creation of asymmetric block copolymer (BCP) nanofilms with antifouling properties, greatly outperforming the conventional surface post‐modification approaches. The resultant free‐standing asymmetric BCP nanofilms with highly‐dense, highly‐hydrophilic polyethylene glycol (PEG) brushes on one side, can be readily formed via a typical IP process of a well‐defined double‐hydrophilic BCP composed of a highly‐efficient antifouling PEG block and a membrane‐forming multiamine block. The asymmetric BCP nanofilms have been applied for efficient and sustainable natural water purification, demonstrating extraordinary antifouling capabilities accompanied with superior separation performance far beyond commercial polyamide nanofiltration membranes. The antifouling behaviors of asymmetric BCP nanofilms derived from the combined effect of the hydration layer, electrostatic repulsion and steric hindrance were further elucidated by water flux and fouling resistance in combination with all‐atom molecular dynamics (MD) simulation. This work opens up a new avenue for the large‐scale and low‐cost creation of broad‐spectrum, asymmetric membrane materials with diverse functional "defect‐free" surfaces in real‐world applications. [ABSTRACT FROM AUTHOR]

Transport of monomer from droplets to growing latex particles in emulsion polymerization in general is assumed to proceed via diffusion through the aqueous phase. Especially in miniemulsion polymerizations the direct transfer of very hydrophobic species from droplet to droplet is assumed to also proceed via collisions. Amongst the hydrophobic species where this is shown to play a role are monomers, initiators, inhibitors and (catalytic) chain transfer agents. It is well known that the reactor geometry and the stirring speed can have a profound effect on emulsion polymerizations. The 1972 paper of Nomura on the effect of stirring on emulsion polymerization is cited more than 100 times and until today keeps scientists intrigued. Diffusion limitations of monomer going from the droplet into the aqueous phase can occur for very hydrophobic monomers. The alternative route of transport via collisions is often not considered. In this perspective, paper will discuss the evidence for collision based transfer in miniemulsion polymerization and also consider whether collision based monomer transport can play a role in regular emulsion polymerizations. [ABSTRACT FROM AUTHOR]

Organic bipolar electrodes can undergo both n‐type and p‐type reactions for energy storage due to numerous active sites, which can usually deliver a high theoretical specific capacity. Herein, a new bipolar polymer cathode material PQPZ is designed and synthesized. The electron‐donating phenazine group undergoes a two‐electron redox reaction which can store anions, the electron‐withdrawing phenanthraquinone can store sodium‐ions through a two‐electron redox reaction. Notably, as a bipolar cathode material for sodium‐ion batteries, PQPZ exhibits a reversible specific capacity of up to 270 mAh g−1 in the voltage range of 1.0–4.0 V (vs. Na+/Na) and achieves a high energy density of 696 Wh kg−1 in a half‐cell. A capacity retention rate of 90% is obtained after 300 cycles at a current density of 0.5C. More excitingly, even after being cycled for 10000 cycles at 10C, the PQPZ electrode shows an average decay rate as low as 0.0036% per cycle, manifesting a very stable cycling performance. In addition, PQPZ also shows excellent performances when tested at −10 °C, making it promising in practical applications. Considering the bipolar character of PQPZ, symmetric batteries are also successfully constructed, fulfilling the “ready‐to‐charge” property without a pre‐activation process. The results reveal the potential application of PQPZ in practical use. [ABSTRACT FROM AUTHOR]

Intracellular polymerization in living cells motivated chemists to generate polymeric structures with a multitude of possibilities to interact with biomacromolecules. However, out-of-control of the intracellular chemical reactions would be an obstacle restricting its application, providing the toxicity of non-targeted cells. Here, we reported intracellular thioesterase-mediated polymerization for selectively occurring polymerization using disulfide bonds in cancer cells. The acetylated monomers did not form disulfide bonds even under an oxidative environment, but they could polymerize into the polymeric structure after cleavage of acetyl groups only when encountered activity of thioesterase enzyme. Furthermore, acetylated monomers could be self-assembled with doxorubicin, providing doxorubicin loaded micelles for efficient intracellular delivery of drug and monomers. Since thioesterase enzymes were overexpressed in cancer cells specifically, the micelles were disrupted under activity of the enzyme and the polymerization could occur selectively in the cancer mitochondria. The resulting polymeric structures disrupted the mitochondrial membrane, thus activating the cellular death of cancer cells with high selectivity. This strategy selectively targets diverse cancer cells involving drug-resistant cells over normal cells. Moreover, the mitochondria targeting strategy overcomes the development of drug resistance even with repeated treatment. This approach provides a way for selective intracellular polymerization with desirable anticancer treatment. [Display omitted] • Thioesterase enzyme is overexpressed in cancer cells due to abnormal metabolism. • The acetylated thiol monomers can form disulfide bonds only under activity of thioesterase. • Thioesterase-meditated polymerization using disulfide bonds generates polymeric structures selectively in cancer cells. • The enzyme-meditated polymerization induces cancer cellular death without the development of drug-resistance. [ABSTRACT FROM AUTHOR]

This work compared C4F8 and C4H2F6 gases (as third components in CF4 + He gas mixture) for the high aspect ratio etching of SiO2 through the amorphous carbon layer (ACL) mask. The research scheme included the study of gas‐phase plasma characteristics, etching kinetics, and etching profiles. It was found that CF4 + C4F8 + He and CF4 + C4H2F6 + He gas mixtures are featured by quite close plasma parameters, the kinetics of electron‐impact processes, and ion bombardment intensities. At the same, the use of C4H2F6 provides a bit lower F atom density together with a bit higher polymerizing ability. All these factors cause lower absolute etching rates for both SiO2 and ACL but provide better SiO2/ACL/ACL selectivity and profile features. [ABSTRACT FROM AUTHOR]

[Display omitted] By combination of dendritic topological structures with photopolymerizable diacetylene, here we report on supramolecular chiral assembly of the dendronized diacetylenes in water. These dendronized diacetylenes are constituted with three-fold dendritic oligoethylene glycols (OEGs), bridged with a dipeptide from phenylalanine and glycine. These dendronized amphiphiles exhibit intensive propensity to aggregate in water and form helical fibers, which show characteristic thermoresponsive behavior with phase transition temperatures dominated by hydrophilicity of the dendritic OEGs. Topochemical polymerization of these supramolecular fibers through UV irradiation transfers them into the covalent helical dendronized polydiacetylenes. Chirality of these dendronized polydiacetylenes can be mediated through the thermally-induced phase transitions, but is also intriguingly dependent on vortex via stirring. Through stirring the solutions, chiralities of the dendronized polydiacetylenes are inverted, which can be reversibly recovered after keeping still the solution. Hydrogels are formed from these dendronized diacetylenes through concentration-enhanced interactions between the supramolecular fibers. Their mechanical properties can be greatly increased through thermally-enhanced interactions between the fibers with storage moduli increased from 20 Pa to a few hundred Pa. In addition, through photo-polymerization, the supramolecular fibers are transferred into covalent dendronized polydiacetylenes, and the corresponding hydrogels show much improved mechanical properties with storage moduli about 10 kPa. [ABSTRACT FROM AUTHOR]

This in vitro study evaluated the influence of radiant exposure and material shade on the degree of conversion (DC) and microhardness of a resin-based composite (RBC). Sixty-four RBC specimens in shades A1E (enamel) and A4D (dentin) were light cured at a calibrated exitance of 1000 mW/cm² for 5, 10, 15, or 20 seconds, resulting in radiant exposure levels of 5. 10. 15 or 20 J/cm². The DC was determined using Fourier-transform infrared spectroscopy (n = 3 per shade per exposure level). The Knoop hardness number (KHN) was measured on the top and bottom surfaces of each specimen (n = 5 per shade per exposure level). Data were analyzed using 2- and 3-way analyses of variance and post hoc Tukey tests (α = 0.05). The RBC shade did not affect the DC (P = 0.860), and the lowest DC values were achieved with an exposure level of 5 J/cm² (P < 0.001). The shade did not affect the KHN on the top surface, but the radiant exposure level did, with the application of 5 J/cm² resulting in significantly lower values (P< 0.05). For the bottom surface, shade A1E showed significantly higher KHN values than A4D (P < 0.001). An increase in the radiant exposure led to increased DC and KHN for both shades of RBC until reaching a saturation point of 10 J/cm² for A1E and the top surface of A4D. The darker and more opaque shade was not adequately polymerized at a 2-mm depth, even when the highest radiant exposure level was applied. [ABSTRACT FROM AUTHOR]

A novel magnetic molecular-imprinted polymer (MMIP) was used to selectively extract folic acid directly from real samples. Folic acid was used as template molecule, Fe3O4/SiO2-3-triethoxysilyl-propyl-acrylamide as functional monomer, azobisisobutyronitrile as initiation, ethylene glycol dimethacrylate as crosslinker agent, and acrylamide as the secondary monomer in a mixed ethanol-water solvent. The effect of different parameters on the extraction efficiency was studied, and the optimum conditions were established as follows: the concentrations of crosslinking and template were fixed at 0.05 and 0.06 g, absorption percentage was 96.5, pH was adjusted to 8, and extraction time was 8 h with a temperature of 25 °C. By examining the effect of pH, we tried to investigate the effect of the amide groups that present in MMIP and its intermolecular hydrogen interaction with folic acid. After optimising the effective parameters in polymer synthesis and adsorption rate, a magnetic imprinting dispersive solid-phase extraction method combined with fluorescence spectrophotometry at λem = 367 nm (MMIP-DSPE-FL) was constructed for sensitive determination of folic acid in tomato samples. The limit of quantification (LOQ) and limit of detection (LOD) values were 30.00 ± 0.01 μg L−1 and 10.00 ± 0.03 μg L−1, respectively, after the MMIP-DSPE preconcentration. Three tomato samples were analysed to give recoveries in the range of 80.2–81.6%, with relative standard deviation values below 0.6% (n = 3). The prepared MMIP-DSPE showed high selectivity toward folic acid, which could be used six times without changing adsorption capacity. The adsorption isotherm of the folic acid-imprinted polymer pursued the Langmuir model (RL = 0.029), and the kinetics model followed pseudo-first-order (R 2 = 0.9974). [ABSTRACT FROM AUTHOR]

Innovative and renewable polymers and additives are the focus of increased research due to public and environmental pressure. There has been a recent uptick in interest from scientists in biobased "green" plasticizers that can be covalently bonded to replace harmful and migratory phthalate‐based plasticizers. Vegetable oils (VOs) are one of the biosources, as they are both plentiful and sustainable. This review aims to highlight the synthesis methods for soy‐based polyesters. Therefore, the chemistry of soybean oil as a polymeric material and its role in the synthesis of polyesters derived from soybeans are the primary topics of this review. This review covers the many ways in which soybean oil and its derivatives can be used to synthesize polyester, either directly or indirectly. Highlights: The need for sustainable polymers is explored.Soybean oil‐based polyesters are covered.Modification and chemistry to convert soybean oil into polyester are described.Applications of soybean‐based polyesters are provided. [ABSTRACT FROM AUTHOR]

New psychoactive substances, including 2-aminoindane, pose significant health risks due to their availability and structural similarity to amphetamines. Current detection methods are limited by lengthy analysis times and complex sample preparation. To address this, we present the first voltammetric determination of 2-aminoindane in oral fluid using a graphite electrode modified with a methoxyphenylthiophene-based layer. The electrochemically deposited layer was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and both infrared and Raman spectroscopies. After the electropolymerization of methoxyphenylthiophene, the electrode was homogeneously covered with shorter oligomers of the substituted polythiophene. Cyclic and square-wave voltammetry were used to gain insight into the interaction between the modified electrode and 2-aminoindane. The modification of the electrode surface enables to record the oxidation of the primary amino group at 0.85 V, with an additional signal assigned to specific interactions being observed at 1.33 V. Determination of a 1.0 × 10–4 M 2-aminoindane concentration in oral fluids was possible, with a recovery ranging from 98 to 100%. [ABSTRACT FROM AUTHOR]

Poly(lactide‐co‐glycolide) (PLGA) is a biodegradable copolymer and widely used in pharmaceuticals. Commercially available PLGAs are produced through ring‐opening polymerization, which results in inevitable dispersity in molecular weight and chemical composition (i.e., lactide‐to‐glycolide ratio), influencing bulk properties such as degradation, mechanics, and morphology. In this study, an automated chromatographic separation technique was employed to generate a series of well‐defined, low‐dispersity fractionated PLGAs from a single commercially available PLGA (lactide‐to‐glycolide ratio = 50:50). The structural and compositional dependence of properties for pharmaceutical applications in the form of nanofibers and nanoparticles were systematically investigated. The properties of new PLGAs by further separation were significantly dependent on composition. The molecular weight ranges were reduced, while the morphology of nanofibers and nanoparticles became more uniform. Importantly, the stability, mechanical strength, and drug loading increased, and the period of sustained release profile also increased. In brief, our data show that the automated chromatographic separation technique allows for precise control of the molecular weight and lactide‐to‐glycolide composition ratio of PLGA, in contrast to the traditional method. The use of well‐defined and fractionated new PLGA materials holds significant promise for enhancing the potential of PLGA in future pharmaceutical applications. [ABSTRACT FROM AUTHOR]

Significant advancements have been achieved in polymer nanogel synthesis, yet there is a dearth of methods for easily preparing size‐adjustable, surface‐modifiable, and biocompatible nanogels. This study introduces a straightforward method for fabricating hyperbranched polyglycerol (HPG) nanogels in water through self‐assembly and disulfide bond crosslinking, avoiding the use of surfactants. The process involves modifying HPG with thioctic acid (TA) to create amphiphilic HPG‐TA rich in disulfide bonds, which is then reduced to facilitate water introduction and self‐assembly. Photocrosslinking is used to finalize the formation of HPG nanogels. These nanogels feature a uniform size distribution, with hydrodynamic diameters tunable from around 90 to 400 nm by tweaking synthesis variables. They have shown low cytotoxicity and high stability in aqueous media, with notable sensitivity to pH, especially in acidic conditions (e.g., pH 3), and redox‐responsiveness, as evidenced by reactions to 10 mM dithiothreitol (DTT). The nanogels' multiple hydroxyl groups enable easy functionalization, exemplified by the synthesis of fluorescent HPG‐RB nanogels. This work presents an efficient strategy for producing robust HPG nanogels, potentially spurring further advancements in the field of polymer nanogel synthesis and application. [ABSTRACT FROM AUTHOR]

Controlled radical polymerization (CRP) techniques enable the preparation of diverse, chemically tailored polymers with a variety of chain architectures. Separately, light‐mediated polymerization reactions offer a number of advantages over thermal polymerizations in terms of energy efficiency, sustainability, and versatility. Recent work has combined photopolymerization and CRP techniques to advance the synthesis of polymers with nonlinear architectures, including bottlebrush polymers, star polymers, hyperbranched polymers, and cyclic polymers. These photoCRP methods offer novel routes to nonlinear polymers using mild reaction conditions. In this review, we provide an overview of photoCRP techniques for the synthesis of nonlinear polymers. We start with a discussion of photoCRP applied to the synthesis of linear polymers and discuss the underlying reaction mechanisms. Then, we discuss photoCRP applied to the synthesis of bottlebrush, star, hyperbranched, cyclic, and surface‐initiated polymer brushes. For each case, we discuss the synthetic strategy and the unique properties and characteristics of the resulting polymers, and we provide a perspective on potential future directions for research. [ABSTRACT FROM AUTHOR]

Vanillyl alcohol has emerged as a widely used building block for the development of biobased monomers. More specifically, the cationic (photo‐)polymerization of the respective diglycidyl ether (DGEVA) is known to produce materials of outstanding thermomechanical performance. Generally, chain transfer agents (CTAs) are of interest in cationic resins not only because they lead to more homogeneous polymer networks but also because they strikingly improve the polymerization speed. Herein, the aim is to compare the cationic chain‐growth photopolymerization with the thermally initiated anionic step‐growth polymerization, with and without the addition of CTAs. Indeed, CTAs lead to faster polymerization reactions as well as the formation of more homogeneous networks, especially in the case of the thermal anionic step‐growth polymerization. Resulting from curing above the TG of the respective anionic step‐growth polymer, materials with outstanding tensile toughness (>5 MJ cm−3) are obtained that result in the manufacture of potential shape‐memory polymers. [ABSTRACT FROM AUTHOR]

Hydrogels are useful drug release systems and tissue engineering scaffolds. However, synthetic hydrogels often require harsh gelation conditions and can contain toxic by‐products while naturally derived hydrogels can transmit pathogens and in general have poor mechanical properties. Thus, there is a need for a hydrogel that forms under ambient conditions, is non‐toxic, xeno‐free, and has good mechanical properties. A recombinant spider silk protein‐derived hydrogel that rapidly forms at 37 °C is recently developed. The temperature and gelation times are well‐suited for an injectable in situ polymerising hydrogel, as well as a 3D cell culture scaffold. Here, it is shown that the diffusion rate and the mechanical properties can be tuned by changing the protein concentration and that human fetal mesenchymal stem cells encapsulated in the hydrogels show high survival and viability. Furthermore, mixtures of recombinant spider silk proteins and green fluorescent protein (GFP) form gels from which functional GFP is gradually released, indicating that bioactive molecules are easily included in the gels, maintain activity and can diffuse through the gel. Interestingly, encapsulated ARPE‐19 cells are viable and continuously produce the growth factor progranulin, which is detected in the cell culture medium over the study period of 31 days. [ABSTRACT FROM AUTHOR]

Recent progress in additive manufacturing has enabled the application of stereolithography (SLA) in bioprinting to produce 3D biomimetic structures. Bioinks for SLA often require synthetic polymers as supplements to ensure the structural integrity of the printed cell‐laden constructs. High molecular weight (MW) poly(ethylene‐glycol)‐diacrylate (PEGDA) (MW ≥ 3400 Da) is commonly used to enhance the mechanical property of crosslinked hydrogels. However, the production of bioink with high MW PEGDA requires in‐house polymer synthesis or the acquisition of costly reagents, which may not be readily available in all laboratory settings. As an alternative to high MW PEGDA, this research investigated the use of poly(ethylene‐glycol)‐dimethacrylate (PEGDMA) (MW = 1000 Da) as a supplement of a bioink to enhance the mechanical properties of the SLA‐printed constructs. The successful demonstration showcases 1) the fabrication of 3D constructs with overhang and complex architecture, and 2) the cytocompatibility, with high cell viability of 71–87% over 6 days of culture, of the GelMA‐PEGDMA bioink to enable cell‐laden bioprinting. This study suggests PEGDMA as a viable supplement in the formulation of SLA bioink. The accessibility to PEGDMA will facilitate the advance in 3D bioprinting to fabricate complex bioinspired structures and tissue surrogates for biomedical applications. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Aluminum nanoparticles (Al NPs) have significant potential applications in various fields due to their unique LSPR. Significant advancements have been achieved in controlling the size and morphology of Al NPs. However, the efficient modification of Al NPs with polymers has not been implemented. Herein, we report a facile and efficient free‐radical polymerization induced grafting‐to (FRPIGt) method for grafting polymer chains onto Al NPs. By optimizing polymerization conditions, we were able to achieve a polymer brush layer with a weight loss fraction of up to 43.3%, which was higher than those of other polymers with carboxyl or primary amine end groups. Moreover, a broad range of vinyl monomers, including styrene, methacrylate, and methyl methacrylate, can be applied using the FRPIGt method to modify Al NPs. In addition, the FRPIGt method can be extended to photoinduced organocatalyzed atom‐transfer‐radical polymerization. This work paves a new path for the preparation of a wide range of polymer‐functionalized Al NPs and their polymer composites to be utilized in various fields. [ABSTRACT FROM AUTHOR]

The transition to a sustainable future requires the use of waste‐free technologies for production. Potentially, additive technologies can be a promising approach for accessing circular economy due to the precise amount of feeding materials and the absence of molds. However, the initial feeding materials for additive approaches are often based on non–renewable hydrocarbon sources. This work focused on the use of polymers derived from terpene alcohols to develop a filament suitable for 3D printing. Initially, the vinylation of menthol using calcium carbide was optimized and scaled up, then a series of terpenyl–based vinyl ethers were obtained under optimal conditions. The cationic polymerization of vinyl ethers was also scaled up and resulted in 99 % yield of the polymers, which was subsequently subjected to hot extrusion. The initial terpenol was used as an additive to increase polymer flexibility. The addition of menthol (30 wt %) to polyvinyl menthol led to the suitable filament. Using the filament, a series of objects were 3D printed at 125 °C. The material demonstrated good sinterability and adhesion to glass and shrinkage comparable to that of commercial 3D printing filaments. Furthermore, the polymers obtained were used as additives to enhance the adhesion of commercially available filaments. [ABSTRACT FROM AUTHOR]

Since 5-(hydroxymethyl)furfural (HMF) has been labelled as the "sleeping giant" of the bio-based platform-chemical realm, numerous investigations have been devoted to the exploitation of this versatile molecule and its endless chemical transformations into novel monomers for producing bio-based polymers. However, beyond 2,5-furandicarboxylic acid (2,5-FDCA), little attention has been devoted to key aspects that deserve being addressed before bringing forward other HMF-derivatives into the bio-based plastic market, i.e., procedures, scaling-up of the syntheses, products' purification, physical–thermal properties, and above all green metrics (sustainability/greenness of procedures). This critical review focuses on the most investigated derivatives of HMF beyond 2,5-FDCA, assessing their exploitation as monomers for bio-based polymers. HMF-derived compounds have been classified according to their functionalities, i.e., aldehyde-, diol-, polyol-, amine-, acid-, ester-, carbonate-, acrylate-, and epoxy-based monomers. The related synthetic approaches are discussed, evaluating the sustainability of the procedures reported so far, based on green metrics such as the environmental factor (E-factor) and the process mass intensity (PMI). For each family of HMF derivatives, their use as monomers for the synthesis of bio-based polymers has been addressed, taking into consideration the efficiency of the polymerisation reactions, the physical–chemical and thermal properties of the resulting bio-based polymers, as well as their biodegradability if applicable. The overall picture that emerges is that much has been achieved for the synthesis of furan monomers; however, many obstacles still need to be overcome prior to massively introducing these compounds into the bio-based plastic market. Hopefully, the data reported in this review will shed light on the goals achieved so far, and on some critical issues that must still be tackled in the short- or medium-term for a more sustainable and however efficient industrial process. [ABSTRACT FROM AUTHOR]

AMPA-type receptors (AMPARs) are rapidly inserted into synapses undergoing plasticity to increase synaptic transmission, but it is not fully understood if and how AMPAR-containing vesicles are selectively trafficked to these synapses. Here, we developed a strategy to label AMPAR GluA1 subunits expressed from their endogenous loci in cultured rat hippocampal neurons and characterized the motion of GluA1-containing vesicles using single-particle tracking and mathematical modeling. We find that GluA1-containing vesicles are confined and concentrated near sites of stimulation-induced structural plasticity. We show that confinement is mediated by actin polymerization, which hinders the active transport of GluA1-containing vesicles along the length of the dendritic shaft by modulating the rheological properties of the cytoplasm. Actin polymerization also facilitates myosin-mediated transport of GluA1-containing vesicles to exocytic sites. We conclude that neurons utilize F-actin to increase vesicular GluA1 reservoirs and promote exocytosis proximal to the sites of synaptic activity. [ABSTRACT FROM AUTHOR]

Coordinative chain transfer polymerization (CCTP) of ethylene and its copolymerization with 1,3‐butadiene is conducted in toluene at 80 °C using a combination of {(Me2Si(C13H8)2)Nd(μ‐BH4)[(μ‐BH4)Li(THF)]}2 (1) metal complex and various organomagnesium compounds used as chain transfer agents including n‐butyl‐n‐octyl‐magnesium (BOMAG), n‐butyl‐mesityl‐magnesium (n‐BuMgMes), n‐butyl‐magnesium chloride (n‐BuMgCl), n‐pentyl‐magnesium bromide (n‐C5H11MgBr), pentanediyl‐1,5‐di(magnesium bromide) (PDMB) and isobutyl‐magnesium chloride (i‐BuMgCl). Kinetics and performance in terms of control of the (co)polymerization are comparatively discussed particularly considering the presence of ether and the nature of the organomagnesium compounds employed. Taking advantage of the well‐known reactivity between nitrile and molecular organomagnesium compounds, the functionalization of the chains is further carried out by deactivation of the polymerization medium with benzonitrile or methoxybenzonitrile compounds leading to ketone ω‐functionalized chains. The success of the functionalizations is extended to coupling strategies using dinitrile reagents and to the functionalization of high molar mass ethylene butadiene rubber (EBR). [ABSTRACT FROM AUTHOR]

Inspired by the favorable impact of heteroatom‐containing groups in phenoxy‐imine titanium and late transition metal catalysts, a series of novel pyridylamido hafnium catalysts bearing ─OMe (Cat‐OMe), ─CF3 (Cat‐CF3), and ─C6F5 (Cat‐C6F5) substituents are designed and synthesized. Together with the established hafnium catalysts Cat‐H and Cat‐iPr by Dow/Symyx, these catalysts are applied in the polymerization of α‐olefins, including 1‐hexene, 1‐octene, and 4M1P, as well as in the copolymerization of these α‐olefins with a specifically designed polar monomer. The enhancement of polymer molecular weight derived from catalyst modification and the incorporation of polar monomers is discussed in detail. Notably, the new catalysts are all highly active for α‐olefins polymerization, with catalyst Cat‐CF3 producing isotactic polymers with the highest molecular weight (Mw = 1649 kg mol−1); in copolymerization with polar monomers, catalyst Cat‐OMe yields isotactic copolymer with the highest molecular weight (Mw = 2990 kg mol−1). Interestingly, catalyst Cat‐C6F5 bearing a ─C6F5 group in the N‐aryl moiety gives rise to poly(α‐olefin) with reduced stereoselectivity. The findings of this study underscore the potential of heteroatom‐containing groups in the development of early transition metal catalysts and the synthesis of polymer with novel structures. [ABSTRACT FROM AUTHOR]

Methylene blue was electropolymerized on the surface of stainless steel 316. The addition of sodium oxalate and working at a pH near 11 allowed us to obtain steel electrodes coated with an electroactive polymer. This polymer shows electrochromic properties like those of the monomer, but also exhibits electroactivity at more positive potentials, which is associated with the active centers in the bridges between monomeric units. A digital video electrochemistry study allowed us to simultaneously quantify, on the one hand, the color changes on the entire surface of the stainless steel and on the other to separate the contribution of the active centers of the phenothiazine ring and of the inter-monomer bonds to the overall polymer response by means of assessing the mean color intensities. A reduction mechanism for the polymer, compatible with the pH variation of the observed electrochemical behavior, was proposed. [ABSTRACT FROM AUTHOR]

The continuous preparation scheme EPO-Poly-indol-nido-carborane (E-P-INDOLCAB), L100-55-Poly-indol-nido-carborane (L-P-INDOLCAB), RS-Polyindol-nido-carborane (S-P-INDOLCAB), and RL-Poly-indol-nido-carborane (R-P-INDOLCAB) were used to prepare the four types of acrylic resin-coated nido-carborane indole fluorescent polymers. After testing their spectral properties and the fluorescence stability curve trend at various acidic pH values (3.4 and 5.5, respectively), L-P-INDOLCAB and S-P-INDOLCAB were determined to be the best polymers. The stable states of the two polymers and the dispersion of the nanoparticles on the system's surface during Atomic Force Microscope (AFM) test are shown by the zeta potentials of -23 and -42 mV. The dispersion of nanoparticles on the system's surface and the stable condition of the two polymers were examined using zeta potential and atomic force microscopy (AFM). Transmission electron microscopy (TEM) can also confirm these findings, showing that the acrylic resin securely encases the interior to forman eyeball. Both polymers' biocompatibility with HELA cells was enhanced in cell imaging, closely enclosing the target cells. The two complexes displayed strong inhibitory effects on PC-3 and HeLa cells when the concentration was 20 ug/mL, as validated by subsequent cell proliferation toxicity studies. [ABSTRACT FROM AUTHOR]

Molecularly imprinted polymers (MIPs) are synthetic polymers that mimic the functions of antibodies. Though MIPs are promising tools in various areas, achieving high selectivity in MIPs can be difficult. To improve selectivity, various approaches have been implemented; however, the role of polymerization methods or synthetic techniques in enhancing the selectivity of MIPs has not been studied and remains a crucial area for further research. MIPs are typically prepared from free radical reactions. Recently, we found that Dielectric Barrier Discharge (DBD) plasma can be used to initiate the polymerization of vinyl monomers. The DBD plasma method allows the monomers to associate with the template molecules and initiate polymerization with minimal disruption to the positioning of the monomers. We hypothesize that this could be a preferred method to prepare MIPs over the traditional radical reaction that may cause a disturbance of the pre-associated monomers on the templates for the polymerization. Chicken egg white serum albumin (CESA) was used as the template protein for the MIPs. Our results show that in all test conditions, approximately twofold improvement in selectivity was achieved, which is the primary performance metric for MIPs. This enhancement was evident across all categories, including MIPs prepared from various monomer combinations. [ABSTRACT FROM AUTHOR]

Surface modification of membranes through facile coating methods is a promising way to improve their pollution resistance and separation performance. Herein, a tea polyphenol (TP)-coated PVDF membrane (PVDF-TP) was prepared via a simple temperature-regulated oxidative polymerization. The obtained membrane exhibited a water contact angle of 0° and underwater oil contact angle of 168.2°. This superhydrophilic/underwater superoleophobic membrane showed good separation capabilities with fluxes of 88.3–169.9 L m−2 h−1 and separation efficiencies of over 98.7% for various oil-in-water emulsions under a gravity-driven process. The PVDF-TP membrane exhibited excellent stability and was capable of withstanding ultrasonic waves, bending, and agitation. Even after recycling for more than 15 times, the separation efficiency of the membrane was still above 98.7% and the flux decreased by approximately 37%, demonstrating a good antifouling performance. Considering the characteristics of its simple preparation, good antifouling performance, high separation efficiency, and good stability, the PVDF-TP membrane has broad application prospects in the field of oil–water separation. [ABSTRACT FROM AUTHOR]

Improving composite cathode function is key to the success of the solid‐state battery. Maximizing attainable cathode capacity and retention requires integrating suitable polymeric binders that retain a sufficiently high ionic conductivity and long‐term chemo‐mechanical stability of the cathode active material‐solid‐electrolyte‐carbon mixture. Herein, we report block copolymer networks composed of lithium borate polycarbonates and poly(ethylene oxide) that improved the capacity (200 mAh g−1 at 1.75 mA cm−2) and capacity retention (94 % over 300 cycles) of all‐solid‐state composite cathodes with nickel‐rich LiNi0.8Co0.1Mn0.1O2 cathode active material, Li6PS5Cl solid electrolyte, and carbon. Tetrahedral B(OR)2(OH)2− anions immobilized on the polycarbonate segments provide hydrogen‐bonding chain crosslinking and selective Li‐counterion conductivity, parameterized by Li‐ion transference numbers close to unity (tLi+~0.94). With 90 wt % polycarbonate content and a flexible low glass transition temperature backbone, the single‐ion conductors achieved high Li‐ion conductivities of 0.2 mS cm−1 at 30 °C. The work should inform future binder design for improving the processability of cathode composites towards commercializing solid‐state batteries, and allow use in other cell configurations, such as lithium‐sulphur cathode designs. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) are an emerging crystalline polymer that is constructed by the organic blocks through reversible polymerization. In this review, we have summarized the strategies for designing covalent organic frameworks for the oxygen reduction reaction. The discussion involved the new structural design of COFs and modifications fitting to the applications. Active sites manipulated scale from the single atom's electron states to the body framework arrangements. This review has anticipated the researchers to enlighten new ORR catalyst designing and optimization. [ABSTRACT FROM AUTHOR]

Topochemical polymerization is a highly promising and effective method for constructing complex three-dimensional structures and functionalized polymers. Herein, we present for the first time a topochemical reaction of diacetylene within a meticulously designed covalent organic framework (ZNUC-1). Our experimental results revealed that ZNUC-1 underwent a 1,4-addition reaction under thermal induction, forming an ene–yne-conjugated structure. [ABSTRACT FROM AUTHOR]

The construction of poly‐dioxolane (PDOL) solid‐state electrolytes by in situ polymerization is an effective way to achieve high performance lithium‐metal batteries. However, the poor electrochemical stability and safety issues of linear PDOL limit their further application. In this work, a multifunctional crosslinker has been introduced to construct a flame retardant crosslinked quasi solid‐state electrolyte (FCDOL). Due to the synergistic effect of the crosslinked network, the prepared FCDOL achieves excellent room temperature ionic conductivity (0.72 mS cm−1), high Li+ transference number (0.655), wide electrochemical stabilization window (4.8 V vs Li/Li+), and impressive performance when matched with lithium metal anodes (>4000 h plating/stripping) and high‐voltage cathodes, and the corresponding pouch cells can withstand abusive tests such as bending and cutting, encouraging that in situ polymerization of SPEs provides new insights into high‐energy density and high‐safety solid‐state batteries. [ABSTRACT FROM AUTHOR]