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One of the challenges in the plastic industry is the cost and time spent on the characterization of different grades of polymers. Compressed sensing is a data reconstruction method that combines linear algebra with optimization schemes to retrieve a signal from a limited set of measurements of that signal. Using a data set of signal examples, a tailored basis can be constructed, allowing for the optimization of the measurements that should be conducted to provide the highest and most robust signal reconstruction accuracy. In this work, compressed sensing was used to predict the values of numerous properties based on measurements for a small subset of those properties. A data set of 21 fully characterized acrylonitrile-butadiene-styrene samples was used to construct a tailored basis to determine the minimal subset of properties to measure to achieve high reconstruction accuracy for the remaining nonmeasured properties. The analysis showed that using only six measured properties, an average reconstruction error of less than 5% can be achieved. In addition, by increasing the number of measured properties to nine, an average error of less than 3% was achieved. Compressed sensing enables experts in academia and industry to substantially reduce the number of properties that must be measured to fully and accurately characterize plastics, ultimately saving both costs and time. In future work, the method should be expanded to optimize not only individual properties but also entire tests used to simultaneously measure multiple properties. Furthermore, this approach can also be applied to recycled materials, of which the properties are more difficult to predict.

Chemical grafting of low-density polyethylene film blended with ethylene propylene diene monomer rubber (PE/EPDM) using styrene monomer followed by a sulfonation process was investigated. Different factors affecting the grafting process, such as monomer and initiator concentrations, time of reaction, and grafting temperature, were studied. Sulfonation of the grafted films was carried out using chlorosulfonic acid in dichloromethane. Characterization of the grafted and sulfonated films was performed using ATR-FTIR, SEM, TGA, and XRD instruments. The grafting was successfully performed in aqueous media using sodium bisulfite as initiator, reaching a grafting yield of 130% and an ion exchange capacity of 1.2 m eq /g. The removal of thorium ions from aqueous solution was studied using the obtained ion exchange films. The results showed that the maximum adsorption capacity of Th(IV) was 177.5 mg. g -1 (pH = 3, 298 K and 60 min). Removal isotherm and Kinetics were investigated, and the results revealed that the adsorption process was chemisorption homogeneous monolayer adsorption, exothermic, and spontaneous., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

This study introduces bis(1-cyanocyclohex-1-yl)trithiocarbonate (TTC-bCCH) as a novel trithiocarbonate chain transfer agent and compares its reactivity with the previously described bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP) for the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St), n-butyl acrylate (nBA), and methyl methacrylate (MMA). Significant findings include the effective control of M n and low dispersities from the onset of polymerization of St and nBA showing swift addition-fragmentation kinetics, leading to similar behaviors between the two RAFT agents. In contrast, a fourfold decrease of the chain transfer constant to MMA is established for TTC-bCCH over TTC-bCP. This trend is confirmed through density functional theory (DFT) calculations. Finally, the study compares thermoplastic elastomer properties of all-(meth)acrylic ABA block copolymers produced with both RAFT agents. The impact of dispersity of PMMA blocks on thermomechanical properties evaluated via rheological analysis reveals a more pronounced temperature dependence of the storage modulus (G') for the triblock copolymer synthesized with TTC-bCCH, indicating potential alteration of the phase separation., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Tire microplastics (TMPs) and antibiotics are emerging pollutants that widely exist in water environments. The coexistence of these pollutants poses severe threats to aquatic organisms. However, the toxicity characteristics and key molecular factors of the combined exposure to TMPs in aquatic organisms remain unknown. Therefore, the joint toxicity of styrene-butadiene rubber TMPs (SBR-TMPs) and 32 antibiotics (macrolides, fluoroquinolones, β-lactams, sulfonamides, tetracyclines, nitroimidazoles, highly toxic antibiotics, high-content antibiotics, and common antibiotics) in zebrafish was investigated using a full factorial design, molecular docking, and molecular dynamics simulation. Sixty-four combinations of antibiotics were designed to investigate the hepatotoxicity of the coexistence of SBR-TMPs additives and antibiotics in zebrafish. Results indicated that low-order effects of antibiotics (e.g., enoxacin-lomefloxacin and ofloxacin-enoxacin-lomefloxacin) had relatively notable toxicity. The van der Waals interaction between additives and zebrafish cytochrome P450 enzymes primarily affected zebrafish hepatotoxicity. Zebrafish hepatotoxicity was also affected by the ability of SBR-TMPs to adsorb antibiotics, the relation between antibiotics, the affinity of antibiotics docking to zebrafish cytochrome P450 enzymes, electronegativity, atomic mass, and the hydrophobicity of the antibiotic molecules. This study aimed to eliminate the joint toxicity of TMPs and antibiotics and provide more environmentally friendly instructions for using different chemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The solvated iron(II) salt [Fe(NCMe) 6 ](BF 4 ) 2 (Me = methyl) is shown to be a bifunctional catalyst with respect to aziridination of styrene. The salt serves as an active catalyst for nitrene transfer from PhINTs to styrene to form 2-phenyl-N-tosylaziridine (Ph = phenyl; Ts = tosyl, -S{O} 2 -p-C 6 H 4 Me). The iron(II) salt also acts as a Lewis acid in non-coordinating CH 2 Cl 2 solution, to catalyze heterolytic CN bond cleavage of the aziridine and insertion of dipolarophiles. The 1,3-zwitterionic intermediate is presumably supported by interaction of the metal dication with the anion, and by resonance stabilization of the carbocation. Nucleophilic dipolarophiles then insert to give a five-membered heterocyclic ring. The result is a two-step cycloaddition, formally [2 + 1 + 2], that is typically regiospecific, but not stereospecific. This reaction mechanism was confirmed by conducting a series of one-step, [3 + 2] additions of unsaturated molecules into pre-formed 2-phenyl-N-tosylaziridine, also catalyzed by [Fe(NCMe) 6 ](BF 4 ) 2 . Relevant substrates include styrenes, carbonyl compounds and alkynes. These yield five-membered heterocylic rings, including pyrrolidines, oxazolidines and dihydropyrroles, respectively. The reaction scope appears limited only by the barrier to formation of the dipolar intermediate, and by the nucleophilicity of the captured dipolarophile. The bifunctionality of an inexpensive, earth-abundant and non-toxic catalyst suggests a general strategy for one-pot construction of heterocyclic rings, as demonstrated specifically for pyrrolidine ring formation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Water pollution has become a serious issue, and mercury(II) ion (Hg(II)) is highly toxic even at low concentrations. Therefore, Hg(II) concentration should be strictly monitored. This study evaluated pyrazoline compounds as fluorescence chemosensor agents for Hg(II) detection. These compounds were prepared from vanillin via etherification, Claisen-Schmidt, and cyclocondensation reactions, to yield benzothiazole-pyrazoline-styrene hybrid compounds. The hybrid compound without styrene was successfully synthesized in 97.70% yield with limit of detection (LoD) and limit of quantification (LoQ) values of 323.5 and 1078 μM, respectively. Conversely, the hybrid compound was produced in 97.29% yield with the LoD and LoQ values of 8.94 and 29.79 nM, respectively. Further spectroscopic investigations revealed that Hg(II) ions can either chelate with three nitrogen of pyridine, pyrazoline, and benzothiazole structures or two oxygen of vanillin and styrene. Furthermore, the hybrid compound was successfully applied in the direct quantification of Hg(II) ions in tap and underground water samples with a validity of 91.63% and 86.08%, respectively, compared with mercury analyzer measurement. The regeneration of pyrazoline was also easily achieved via the addition of an ethylenediaminetetraacetic acid solution. These findings show the promising application of the benzothiazole-pyrazoline-styrene hybrid compound for Hg(II) monitoring in real environmental samples., (© 2024 John Wiley & Sons Ltd.)

Lead(II) is a potential carcinogen of heavy-metal ions (HIs). With the wide application of Pb-bearing products including lead alloy products, and new-energy lead-ion batteries, lead pollution has become a tricky problem. To solve such a difficulty, novel ultrathin MoS 2 -vinyl hybrid membranes (MVHMs) with a "spring" effect were synthesized via co-polymerization of acrylic acid, styrene and molybdenum disulfide (MoS 2 ) and their adsorptions for HIs were explored. The "spring" effect derived from the interaction between the tendency of the short polyacrylic acid (PAA) chain connected with MoS 2 to spread outward and the coulomb force between layers from MoS 2 (s-MoS 2 ), which enlarge the spacing of MoS 2 layers without changing the number of layers after membrane formation, which changes the swelling membrane to a dense membrane and reduces the original thickness from 0.5 cm to 0.011 mm in the thickness direction. The adsorption experiment revealed that these MVHMs had super adsorption performance and high selectivity for Pb 2+ by comparison with other five metal ions: Cu 2+ , Cd 2+ , Ni 2+ , Cr 3+ and Zn 2+ . Especially, the adsorption quantity of MVHMs for Pb 2+ could approach 2468 mg/g and the maximum adsorption ratio of q e [Pb 2+ ]/q e [Cu 2+ ] can reach 10.909. These values were much larger than the data obtained with the adsorbents reported in the last decade. A variety of models are applied to evaluate the effect of ionic groups. It was confirmed that -COOH plays a key role in adsorption of HIs and s-MoS 2 also has a certain contribution. Conversely, ion exchange plays only a minor role during the period of adsorption process. Effective diffusion coefficient (D eff ) of Pb(II) had the largest values among these metal ions. Hence, these hybrid membranes are promising adsorbents for the removal of Pb 2+ from water containing various ions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Enzymatic cascades have become a green and sustainable approach for the synthesis of valuable chemicals and pharmaceuticals. Using sequential enzymes to construct a multienzyme complex is an effective way to enhance the overall performance of biosynthetic routes. Here we report the design of an efficient in vitro hybrid biocatalytic system by assembling three enzymes that can convert styrene to ( S )-1-phenyl-1,2-ethanediol. Specifically, we prepared the three enzymes in different ways, which were cell surface-displayed, purified, and cell-free expressed. To assemble them, we fused two orthogonal peptide-protein pairs (i.e., SpyTag/SpyCatcher and SnoopTag/SnoopCatcher) to the three enzymes, allowing their spatial organization by covalent assembly. By doing this, we constructed a multienzyme complex, which could enhance the production of ( S )-1-phenyl-1,2-ethanediol by 3 times compared to the free-floating enzyme system without assembly. After optimization of the reaction system, the final product yield reached 234.6 μM with a substrate conversion rate of 46.9% (based on 0.5 mM styrene). Taken together, our strategy integrates the merits of advanced biochemical engineering techniques, including cellular surface display, spatial enzyme organization, and cell-free expression, which offers a new solution for chemical biosynthesis by enzymatic cascade biotransformation. We, therefore, anticipate that our approach will hold great potential for designing and constructing highly efficient systems to synthesize chemicals of agricultural, industrial, and pharmaceutical significance.

Structural studies require the production of target proteins in large quantities and with a high degree of purity. For membrane proteins, the bottleneck in determining their structure is the extraction of the target protein from the cell membranes. A detergent that improperly mimics the hydrophobic environment of the protein of interest can also significantly alter its structure. Recently, using lipodiscs with styrene-maleic acid (SMA), copolymers became a promising strategy for the purification of membrane proteins. Here, we describe in detail the one-step affinity purification of potassium ion channels solubilized in SMA and sample preparation for future structural studies., (© 2024. The Author(s), under exclusive license to Springer Science+Business Media, LLC, part of Springer Nature.)

Oxidation of organic amines (OAs) or aromatic hydrocarbons (AHs) produces carbonyls, which further react with OAs to form carbonyl-amine condensation products, threatening environmental quality and human health. However, there is still a lack of systematic understanding of the carbonyl-amine condensation reaction processes of OAs or between OAs and AHs, and subsequent environmental health impact. This work systematically investigated the carbonyl-amine condensation coupled ozonolysis kinetics, reaction mechanism, secondary organic aerosol (SOA) formation and cytotoxicity from the mixture of dipropylamine (DPA) and styrene (STY) by a combined method of product mass spectrometry identification, particle property analysis and cell exposure evaluation. The results from ozonolysis of DPA and STY mixture revealed that STY inhibited the ozonolysis of DPA to different degrees to accelerate its own decay rate. The barycenter of carbonyl-amine condensation reactions was shifted from inside of DPA to between DPA and STY, which accelerated STY ozonolysis, but slowed down DPA ozonolysis. For the first time, ozonolysis of DPA and STY mixture to complex carbonyl-amine condensation products through the reactions of DPA with its carbonyl products, DPA with STY's carbonyl products and DPA's bond breakage product with STY's carbonyl products was confirmed. These condensation products significantly contributed to the formation and growth of SOA. The SOA containing particulate carbonyl-amine condensation products showed definite cytotoxicity. These findings are helpful to deeply and comprehensively understand the transformation, fate and environmental health effects of mixed organics in atmospheric environment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The present study describes the facile synthesis and comprehensive characterization of new oxido and peroxidoniobium(V) complexes with biogenic ligands, maltol (malt) and deferiprone (def) in their co-ordination sphere, viz ., [NbO(malt) 3 ] 2 ·9H 2 O (1), Na 2 [Nb(O 2 ) 3 (malt)]·H 2 O (2) and Na 2 [Nb(O 2 ) 3 (def)]·2H 2 O (3). The complexes were characterized using various analytical and spectroscopic techniques (FTIR, Raman, NMR, UV-visible, TGA, ICP-OES and elemental analysis). The charge neutral complex 1 was further characterized by single crystal XRD analysis, and the proposed structures of the peroxidoniobium (pNb) complexes 2 and 3 were validated by density functional theory (DFT) studies. A comparative investigation on the in vitro effect of the title compounds and a set of previously reported polymer-anchored peroxidoniobium complexes, [Nb(O 2 ) 3 (sulfonate) 2 ] 3- -PSS [PSS = poly(sodium 4-styrene sulfonate)] (5), [Nb 2 (O 2 ) 6 (carboxylate) 2 ] 4- -PA [PA = poly(sodium acrylate)] (6) and [Nb(O 2 ) 3 (carboxylate)] 2- -PMA [PMA = poly(sodium methacrylate)] (7), on the activity of the model enzyme wheat thylakoid acid phosphatase has revealed that each of the compounds is an effective inhibitor of the enzyme (IC 50 values varying within the range 1-64 μM). The results of the detailed enzyme kinetic study demonstrated that the compounds induce their inhibitory effect via distinct pathways. The oxidoniobium complex 1 as well as polymer-anchored pNb complexes acted as classical non-competitive inhibitors of ACP, whereas the monomeric pNb complexes emerged as mixed inhibitors of the enzyme ( K ii > K i ). Notably, the complexes serve as excellent recyclable catalysts for selective styrene epoxidation with H 2 O 2 , affording 99% styrene conversion, ≥98% epoxide selectivity and a high turnover number of 1740 under eco-friendly solventless conditions.

Recent improvements in 3D printing technology have increased the usage of 3D printed materials in several areas. An exciting and emerging area of applying these next-generation manufacturing strategies is the development of devices for biomedical applications. The main aim of this work was to investigate the effect of tannic acid, gallic acid, and epicatechin gallate on the physicochemical characteristics of acrylonitrile butadiene-styrene (ABS) and Nylon 3D printing materials using the contact angle method. The adhesion of Staphylococcus aureus on untreated and treated materials was evaluated by scanning electron microscopy (SEM) analysis and the images were treated by MATLAB software. The results of the contact angle measurements showed a significant change in the physicochemical properties of both surfaces, indicated an increase in the electron donor character of 3D printing materials following treatment. Thus, the ABS surfaces treated with tannic acid, gallic acid, and epicatechin gallate have become more electron donating. Furthermore, our results proved the ability of S. aureus to adhere on all materials with a percentage of 77.86% for ABS and 91.62% for nylon. The SEM has shown that all actives molecules were sufficient to obtain better inhibition of bacterial adhesion, which tannic acid has shown a total inhibition of S. aureus on ABS. From these results, our treatment presents a high potential for utilization as an active coating to prevent bacterial attachment and the eventual biofilm development in medical field., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Biosynthesis is an environmentally benign and renewable approach that can be used to produce a broad range of natural and, in some cases, new-to-nature products. However, biology lacks many of the reactions that are available to synthetic chemists, resulting in a narrower scope of accessible products when using biosynthesis rather than synthetic chemistry. A prime example of such chemistry is carbene-transfer reactions 1 . Although it was recently shown that carbene-transfer reactions can be performed in a cell and used for biosynthesis 2,3 , carbene donors and unnatural cofactors needed to be added exogenously and transported into cells to effect the desired reactions, precluding cost-effective scale-up of the biosynthesis process with these reactions. Here we report the access to a diazo ester carbene precursor by cellular metabolism and a microbial platform for introducing unnatural carbene-transfer reactions into biosynthesis. The α-diazoester azaserine was produced by expressing a biosynthetic gene cluster in Streptomyces albus. The intracellularly produced azaserine was used as a carbene donor to cyclopropanate another intracellularly produced molecule-styrene. The reaction was catalysed by engineered P450 mutants containing a native cofactor with excellent diastereoselectivity and a moderate yield. Our study establishes a scalable, microbial platform for conducting intracellular abiological carbene-transfer reactions to functionalize a range of natural and new-to-nature products and expands the scope of organic products that can be produced by cellular metabolism., (© 2023. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

With styrene and acrylonitrile in ABS plastic toys as examples, this paper introduces to the development of a systematic strategy for studying the chemical migration risk in toys. The approach, included the detection method, establishment of migration model, model verification, and the practical application of the model in risk assessment. First, simple and sensitive methods for detecting analyte residues and migration were developed by headspace GC-MS. Then, the migration models were established based on the migration data from 5 min to 168 h and verified using 11 ABS samples. The results showed that the predicted values of the models and the experimental values had a good fit (RMSE=0.10-8.72 %). Subsequently, the migration of analytes in 94 ABS toys was predicted with these models at specific migration times. The daily average exposure level to styrene and acrylonitrile were estimated for children (3 months to 3 years). At last, the migration models reasonably predicted that the cancer risk of styrene and acrylonitrile in ABS toys were 1.6 × 10 -8 -1.4 × 10 -6 and 3.1 × 10 -8 -1.6 × 10 -6 , respectively. This research contributes to promote toy safety and child health by enriching migration models and risk assessments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Membrane proteins are an essential part of signaling and transport processes and are targeted by multiple drugs. To isolate and investigate them in their native state, polymer-bounded nanodiscs have become valuable tools. In this study, we investigate the lipid model system dimyristoyl-phosphocholine (DMPC) with the nanodisc-forming copolymers styrene maleic acid (SMA) and diisobutylene maleic acid (DIBMA). Using small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS), we studied the influence of polymer concentration and temperature on the nanodisc structure. In Tris buffer, the size of nanodiscs formed with SMA is smaller compared to DIBMA at the same polymer ratio. In both cases, the size decreases monotonically with increasing polymer concentration, and this effect is more pronounced when using SMA. Measurements at temperatures ( T ) between 5 and 30 °C in phosphate buffer showed an incomplete solubilization at high T even at polymer/lipid ratios above that required for complete lipid solubilization. For DIBMA, the nanodiscs developed at lower temperatures are stable and the net repulsion increases, while for SMA, the individual nanodiscs possess smaller sizes and are less affected by T . However, using DLS, one can observe SMA agglomerates at low T . Interestingly, for both polymers, no drastic changes of the observable parameters (radius and bilayer thickness) are seen upon cooling, which would indicate a sharp (first-order) phase transition from liquid-crystalline to gel, but only gradual changes. Hence, we conclude that the transition from a gel toward a liquid-crystalline lipid phase proceeds over a broad T -range compared to a continuous lipid bilayer. These results can pave the way toward the development of better protocols for studying membrane proteins stabilized in this type of membrane mimics.

Membrane proteins of Mycobacterium tuberculosis (Mtb) can be targeted for the development of therapeutic and prophylactic interventions against tuberculosis. We have utilized the unique membrane-solubilising properties of the styrene maleic acid copolymer (SMA) to prepare and characterise 'styrene maleic acid lipid particles' from the native membrane of Mtb (MtM-SMALPs). When resolved by SDS-PAGE and visualised with coomassie blue, the molecular weights of Mtb membrane (MtM) proteins solubilised by SMA were mostly in the range of 40-70 kDa. When visualised by transmission electron microscopy, MtM-SMALPs appeared as nanoparticles of discrete shapes and sizes. The discoid nanoparticles exhibited a range of diameters of ~10-90 nm, with largest portion (~61%) ranging from 20-40 nm. MtM proteins of a molecular weight-range overlapping with that of MtM-SMALPs were also amenable to chemical cross-linking, revealing protein complex formation. Characterisation using monoclonal antibodies against seven MtM-associated antigens confirmed the incorporation of the inner membrane protein PRA, membrane-associated proteins PstS1, LpqH and Ag85, and the lipoglycan LAM into MtM-SMALPs. Conversely, the peripheral membrane proteins Acr and PspA were nearly completely excluded. Furthermore, although MtM showed an abundance of Con A-binding glycoproteins, MtM-SMALPs appeared devoid of these species. Immune responses of healthcare workers harbouring 'latent TB infection' provided additional insights. While MtM-SMALPs and MtM induced comparable levels of the cytokine IFN-γ, only MtM-SMALPs could induce the production of TNF-α. Antibodies present in the donor sera showed significantly higher binding to MtM than to MtM-SMALPs. These results have implications for the development of MtM-based immunoprophylaxis against tuberculosis., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2023 Sinha et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

This study processes a facile and green approach for the Markovnikov-selective hydroamination of styrene with naphthylamine through irradiation with UV LED light (365 nm) via an electron donor-acceptor complexation between naphthylamines and oxygen in situ. This protocol showcases the synthetic potential for aerobic C-N bond formation without using a metal catalyst and photosensitizer. Three naphthylamines were examined and afforded desired C-N bond formation product in moderate yield.

In this research, the adsorption of styrene and styrene oxide, both biomass derivatives, on KTaO 3 (001) and LiTaO 3 (0001) perovskite-like structures was studied from a theoretical point of view. The study was carried out using density functional theory (DFT) calculations. The adsorption phenomenon was deeply studied by calculating the adsorption energies (E ads ), adsorbate-surface distances (Å) and evaluating the differences of charge density and charge transfer (ΔCT). For complexes adsorbed on KTaO 3 (TaO 2 , KO and K(OH) 2 exposed layers), the highest E ads was found for styrene oxide, attributed to the oxygen reactivity of the epoxy group describing a strong interaction with the surface. However, when evaluating a K(O) 2 model, a more favorable interaction of styrene with the surface is observed, resulting in a high E ads of -9.9 eV and a ΔCT of 3.1e. For LiTaO 3 , more favorable interactions are found for both adsorbates compared to KTaO 3 , evidenced by the higher adsorption energies and charge density differences, particularly for the styrene complex adsorbed on TaO 2 exposed layer (E ads : -10.2 eV). For the LiO termination, the surface exposed oxygens are fundamental for the adsorption of styrene and styrene oxide, leading to a considerable structural distortion. The obtained results thus provide understanding of the structural features, surface reactivity and adsorption sites of LiTaO 3 and KTaO 3 perovskite in the context of a heterogeneous catalytic process, such as the oxidation of styrene., (© 2022 Wiley-VCH GmbH.)

The synthesis of protein-polymer conjugates usually requires extensive and costly deoxygenation procedures, thus limiting their availability and potential applications. In this work, we report the ultrafast synthesis of polymer-protein bioconjugates in the absence of any external deoxygenation via an aqueous copper-mediated methodology. Within 10 min and in the absence of any external stimulus such as light (which may limit the monomer scope and/or disrupt the secondary structure of the protein), a range of hydrophobic and hydrophilic monomers could be successfully grafted from a BSA macroinitiator, yielding well-defined polymer-protein bioconjugates at quantitative yields. Our approach is compatible with a wide range of monomer classes such as (meth) acrylates, styrene, and acrylamides as well as multiple macroinitiators including BSA, BSA nanoparticles, and beta-galactosidase from Aspergillus oryzae . Notably, the synthesis of challenging protein-polymer-polymer triblock copolymers was also demonstrated, thus significantly expanding the scope of our strategy. Importantly, both lower and higher scale polymerizations (from 0.2 to 35 mL) were possible without compromising the overall efficiency and the final yields. This simple methodology paves the way for a plethora of applications in aqueous solutions without the need of external stimuli or tedious deoxygenation.

As a new example of intrinsically water-triggered phenomena, we report underwater dehydration of the statistical copolymers synthesized from triethanolamine borate (TEAB) methacrylate and styrene (St) induced by the hydrolysis of the pendant TEAB group. TEAB possesses high polarity owing to its internal Lewis adduct structure, which is lost by hydrolysis to triethanolamine (TEA) with a lower dipole moment. Therefore, the hydration of the copolymers became unfavorable through the hydrolysis of the pendant TEAB to TEA, despite polyol formation, and through a hydrophobic interaction based on St moieties becoming alternatively dominant. The dehydration behavior of the copolymers, along with the hydrolysis of the pendant TEAB group, was systematically investigated. The water solubility of the copolymers was found to be dependent on the gradient of the hydrolysis equilibrium of TEAB on the side chains and was the lowest for the TEA state. These findings offer a novel concept toward designing water-responsive materials.

Vibration and noise are ubiquitous in social life, which severely damage machinery and adversely affect human health. Thus, the development of materials with high-damping performance is of great importance. Rubbers are typically used as damping materials because of their unique viscoelasticity. However, they do not satisfy the requirements of different applications with various working conditions. In this study, the advantages of the high loss factor of styrene butadiene rubber (SBR) are combined with the strong designability of polyurethane. Hydroxyl-terminated solution-polymerized styrene butadiene rubbers (HTSSBRs) with different structures are prepared using anionic polymerization. HTSSBRs are then used as the soft segment during the synthesis of temperature-tunable high-damping performance polyurethanes (HTSSBR-polyurethanes (PUs)). The prepared HTSSBR-PUs with different structures exhibit excellent loss performance, a maximum loss factor (tan δ max ) of above 1.60, and an effective damping performance over a wide temperature range compared to traditional SBR and polyurethane. Therefore, this work offers an effective method for the design of damping materials with adjustable properties., (© 2022 Wiley-VCH GmbH.)

Styrene-acrylonitrile-copolymer (SAN) and acrylonitrile-butadiene-styrene-copolymer (ABS) are gaining in importance as food contact materials. Oligomers and other non-intentionally added substances can migrate into foodstuffs. Five SAN and four ABS samples from the German market and manufacturers were extracted and the extractable oligomers were characterised by high performance liquid chromatography-mass spectrometry/ultraviolet detection/chemiluminescence nitrogen detection/fluorescence detection and gas chromatography-mass spectrometry. Trimers, formed from acrylonitrile and styrene units, were determined to be the dominating group of extractable oligomers in SAN and ABS in concentrations of about 4900-15800 mg/kg material. Furthermore, styrene-acrylonitrile dimers, styrene oligomers, styrene monomer and ethylbenzene were identified in the sample extracts. Migration testing with three consecutive migrations for multiple use articles was performed for two SAN articles. Migration of trimers into water, 3% acetic acid, 10% and 20% ethanol under hot-fill conditions (70°C, 2 h) was not detectable above 9 µg/dm 2 , while 50% ethanol acting as a food simulant for milk (124 µg/dm 2 trimers during the third migration) was shown to overestimate the actual migration into milk (< 11 µg/dm 2 trimers at 70°C, 2 h). 2-Amino-3-methyl-1-naphthalenecarbonitrile (AMNC), an oligomer degradation product and a primary aromatic amine, was detected in all material sample extracts (0.3-17.1 mg/kg material) and was released into food simulants in low amounts (< 0.014 µg/dm 2 during the third migration into 50% ethanol at 70°C, 2 h).

Human amylin forms structurally heterogeneous amyloids that have been linked to type-2 diabetes. Thus, understanding the molecular interactions governing amylin aggregation can provide mechanistic insights in its pathogenic formation. Here, we demonstrate that fibril formation of amylin is altered by synthetic amphipathic copolymer derivatives of the styrene-maleic-acid (SMAQA and SMAEA). High-speed AFM is used to follow the real-time aggregation of amylin by observing the rapid formation of de novo globular oligomers and arrestment of fibrillation by the positively-charged SMAQA. We also observed an accelerated fibril formation in the presence of the negatively-charged SMAEA. These findings were further validated by fluorescence, SOFAST-HMQC, DOSY and STD NMR experiments. Conformational analysis by CD and FT-IR revealed that the SMA copolymers modulate the conformation of amylin aggregates. While the species formed with SMAQA are α-helical, the ones formed with SMAEA are rich in β-sheet structure. The interacting interfaces between SMAEA or SMAQA and amylin are mapped by NMR and microseconds all-atom MD simulation. SMAEA displayed π-π interaction with Phe23, electrostatic π-cation interaction with His18 and hydrophobic packing with Ala13 and Val17; whereas SMAQA showed a selective interaction with amylin's C terminus (residues 31-37) that belongs to one of the two β-sheet regions (residues 14-19 and 31-36) involved in amylin fibrillation. Toxicity analysis showed both SMA copolymers to be non-toxic in vitro and the amylin species formed with the copolymers showed minimal deformity to zebrafish embryos. Together, this study demonstrates that chemical tools, such as copolymers, can be used to modulate amylin aggregation, alter the conformation of species., Competing Interests: Declaration of interests The polymers used in this study SMAEA and SMAQA are produced in the Ramamoorthy lab at Michigan. They are US patented., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The objective of this study was to evaluate fungal and patulin contamination, together with its correlation with the volatile compounds (VCs), in 'Fuji Mishima' apples (up to 25% decayed) under controlled atmosphere (CA) and dynamic controlled atmosphere with respiratory quotient (DCA-RQ) of 1.3 combined with different partial pressures of carbon dioxide (0.8, 1.2, 1.6 and 2.0 pCO 2 ). Fruits were stored under the above conditions for 8 months at 0.5 °C plus 7 days shelf life at 20 °C. Toxigenic fungi and patulin accumulation were found in apples from all treatments. Penicillium expansum was the most prevalent species. For all storage conditions, patulin concentrations were above the maximum level allowed in Brazil (50  μg  kg -1 ) with an exception of DCA-RQ1.3 + 0.8 kPa CO 2 . This condition, with lower pCO 2 , showed the lowest patulin accumulation, below the legal limit. The CA provided the highest patulin concentration (166 μg  kg -1 ). It was observed that fungal growth could also contribute to changes in the volatile composition. Styrene and 3-methyl-1-butanol are considered P. expansum markers in some apple cultivars and were detected in the samples. However, it was not possible to identify volatile organic compounds (VOCs) that are biomarkers from P. expansum , because there were other fungi species present in all samples. In this study, styrene, n-decanoic acid, toluene, phenol and alpha-farnesene were the compounds that showed the most positive correlation with patulin accumulation. On the other hand, a negative correlation of patulin with acids has been shown, indicating that in treatments with a higher patulin concentration there were less acidic compounds.

Styrene acrylic emulsions (SAEs) have emerged as a promising material for water-based coatings. However, they are still limited by their own defects in practical applications, poor weatherability, and degradation of performance at lower or higher temperatures. Here, we introduce a facile approach to producing fluorescent carbon quantum dots (CQDs) from wood processing residues and fabricating fluorescent CQD/SAE coating films via emulsion-casting. The addition of the fluorescent CQDs enhanced the optical performance of the CQD/SAE coating films. The fluorescent CQDs were prepared via a hydrothermal approach and were obtained after heating at 180 °C for 6 h at a reaction concentration of 50 mg/mL. The synthesized CQDs resulted in a high fluorescence, and the CQDs had an average size of 1.63 nm. Various concentrations of the fluorescent CQDs were doped into the SAE coating film, which improved its optical properties. We also characterized and discussed the products and then explored their optical properties. This study presents the potential of fluorescent CQD/SAE coating films for applications in anti-counterfeiting coatings, fluorescent adhesives, and papermaking.

Iodosylbenzene (PhIO) and its derivatives have attracted significant attention due to their various applications in organic synthesis and biomimetic studies. For example, PhIO has been extensively used for generating high-valent metal-oxo species that have been regarded as key intermediates in diverse oxidative reactions in biological system. However, recent studies have shown that metal-iodosylbenzene adduct, known as a precursor of metal-oxo species, plays an important role in transition metal-catalyzed oxidation reactions. During last few decades, extensive investigations have been conducted on the synthesis and reactivity studies of metal-iodosylbenzene adducts with early and middle transition metals including manganese, iron, cobalt. Nevertheless, metal-iodosylbenzene adducts with late transition metals such as nickel, copper and zinc, still remains elusive. Herein, we report a novel copper(II)-iodosylbenzene adduct bearing a linear ligand composed of two pyridine rings and an ethoxyethanol side-chain, [Cu(OIPh)(HN 3 O 2 )] 2+ (1). The copper(II)-iodosylbenzene adduct was characterized by several spectroscopic methods including UV-vis spectroscopy, electrospray ionization mass spectrometer (ESI MS), and electron paramagnetic resonance (EPR) combined with theoretical calculations. Interestingly, 1 can carry out the catalytic sulfoxidation reaction. In sulfoxidation reaction with thioanisole under catalytic reaction condition, not only two-electron but also four-electron oxidized products such sulfoxide and sulfone were yielded, respectively. However, 1 was not an efficient oxidant towards CH bond activation and epoxidation reactions due to the steric hindrance created by the intramolecular H-bonding interaction between HN 3 O 2 ligand and iodosylbenzene moiety., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Precision surface engineering is key to advanced biomaterials. A new platform of PEGylated styrene-maleic acid copolymers for adsorptive surface biofunctionalization is reported. Balanced amphiphilicity renders the copolymers water-soluble but strongly affine for surfaces. Fine-tuning of their molecular architecture provides control over adsorptive anchorage onto specific materials-which is why they are referred to as "anchor polymers" (APs)-and over structural characteristics of the adsorbed layers. Conjugatable with an array of bioactives-including cytokine-complexing glycosaminoglycans, cell-adhesion-mediating peptides and antimicrobials-APs can be applied to customize materials for demanding biotechnologies in uniquely versatile, simple, and robust ways. Moreover, homo- and heterodisplacement of adsorbed APs provide unprecedented means of in situ alteration and renewal of the functionalized surfaces. The related options are exemplified with proof-of-concept experiments of controlled bacterial adhesion, human umbilical vein endothelial cell, and induced pluripotent cell growth on AP-functionalized surfaces., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Expression, purification, and functional reconstitution of mammalian ion channels are often challenging. Heterologous expression of mammalian channels in bacteria can be advantageous due to unrelated protein environment and the lack of risk of copurification of endogenous proteins, e.g., accessory channel subunits that can influence the channel activity. Also, direct recording of channel activity could be challenging due to their intracellular localization like in the case of mitochondrial channels. The activity of purified channels can be characterized at the single-molecule level by electrophysiological techniques, such as planar lipid bilayers (PLB). In this work, we describe a simple approach to accomplish PLB recording of the activity of single renal outer medullary potassium channels ROMK expressed in E. coli. We focused on the ROMK2 isoform that is present at low levels in the mitochondria and can be responsible for mitoK ATP activity. We screened for the best construct to express the codon-optimized ROMK proteins with a 6xHis tag for protein purification. The strategy involved the use of optimal styrene-maleic acid (SMA) copolymer, which forms so-called polymer nanodiscs, to solubilize and purify ROMK-containing SMA lipid particles (SMALPs), which were amenable for fusion with PLB. Reconstituted ROMK channels exhibited ion selectivity, rectification, and pharmacological properties, which are in agreement with previous work on ROMK channels., (Copyright © 2021. Published by Elsevier B.V.)

Background: Organocatalytic asymmetric Michael addition is a strong approach for C-C bond formation. The objective of the study is to design molecules by exploiting the efficiency of Michael Adducts. We proceeded with the synthesis of Michael adducts by tailoring the substitution pattern on maleimide and trans-β-nitro styrene as Michael acceptors. The synthesized compounds were evaluated for dual cyclooxygenases (COX) and lipoxygenase (LOX) inhibition., Methods: The compounds (4, 9-11) were synthesized through Michael additions. The cyclooxygenases (COX-1 and 2) and lipoxygenase (5-LOX) assays were used for in vitro evaluations of compounds. After the acute toxicity studies, the in vivo analgesic potential was determined with acetic acid induced writhing, tail immersion, and formalin tests. Furthermore, the possible roles of adrenergic and dopaminergic receptors were also studied. Extensive computational studies were performed to get a better understanding regarding the binding of this compound with protein target., Results: Four Michael adducts (4, 9-11) were synthesized. Compound 4 was obtained in enantio- and diastereopure form. The stereopure compound 4 showed encouraging COX-1 and-2 inhibitions with IC 50 values of 128 and 65 μM with SI of 1.94. Benzyl derivative 11 showed excellent COX-2 inhibition with the IC 50 value of 5.79 μM and SI value 7.96. Compounds 4 and 11 showed good results in in vivo models of analgesia like acetic acid test, tail immersion, and formalin tests. Our compounds were not active in dopaminergic and adrenergic pathways and so were acting centrally. Through extensive computational studies, we computed binding energies, and pharmacokinetic predictions., Conclusion: Our findings conclude that our synthesized Michael products (pyrrolidinedione 4 and nitroalkane 11) can be potent centrally acting analgesics. Our in silico predictions suggested that the compounds have excellent pharmacokinetic properties. It is concluded here that dual inhibition of COX/LOX pathways provides a convincing step towards the discovery of safe lead analgesic molecules., Competing Interests: The authors declare that they have no competing interest., (© 2021 Ahmad et al.)

Styrene monooxygenases are a group of highly selective enzymes able to catalyse the epoxidation of alkenes to corresponding chiral epoxides in excellent enantiopurity. Chiral compounds containing oxirane ring or products of their hydrolysis represent key building blocks and precursors in organic synthesis in the pharmaceutical industry, and many of them are produced on an industrial scale. Two-component recombinant styrene monooxygenase (SMO) from Marinobacterium litorale was expressed as a fused protein (StyAL2StyB) in Escherichia coli BL21(DE3). By high cell density fermentation, 35 g DCW /L of biomass with overexpressed SMO was produced. SMO exhibited excellent stability, broad substrate specificity, and enantioselectivity, as it remained active for months and converted a group of alkenes to corresponding chiral epoxides in high enantiomeric excess (˃95-99% ee). Optically pure ( S )-4-chlorostyrene oxide, ( S )-allylbenzene oxide, (2 R ,5 R )-1,2:5,6-diepoxyhexane, 2-(3-bromopropyl)oxirane, and ( S )-4-(oxiran-2-yl)butan-1-ol were prepared by whole-cell SMO.

In this study, a simple strategy to fabricate the cellulose aerogel with homogeneous porous structure and good compression strength properties has been demonstrated. The cellulose aerogel was simply prepared by adding styrene acrylic emulsion (SAE) to the TEMPO-oxidized cellulose nanofibrils (CNF), followed by freeze-drying and oven-heating, in which covalent bond between CNF and SAE was confirmed by FT-IR. Meanwhile, the regulation process of porous structure of cellulose aerogels was investigated by varying the properties of CNF, and the addition of carboxymethyl cellulose (CMC) and SAE. The results demonstrated that the porous structure of cellulose aerogel was gradually improved with increasing carboxyl content of CNF. CMC could effectively increase in specific surface area of cellulose aerogel, achieving a more preferred porous structure due to the elimination of hornification. SAE could highly enhance the uniformity of structure with specific surface area up to 184 m 2 /g, porosity up to 99%, and successfully improve the strength properties, showing the fabricated cellulose aerogel as a potential cushion packaging material., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Dysregulation of the biosynthesis of cholesterol and other lipids has been implicated in many neurological diseases, including Parkinson's disease. Misfolding of α-synuclein (α-Syn), the main actor in Parkinson's disease, is associated with changes in a lipid environment. However, the exact molecular mechanisms underlying cholesterol effect on α-Syn binding to lipids as well as α-Syn oligomerization and fibrillation remain elusive, as does the relative importance of cholesterol compared to other factors. We probed the interactions and fibrillation behaviour of α-Syn using styrene-maleic acid nanodiscs, containing zwitterionic and anionic lipid model systems with and without cholesterol. Surface plasmon resonance and thioflavin T fluorescence assays were employed to monitor α-Syn binding, as well as fibrillation in the absence and presence of membrane models. 1 H- 15 N-correlated NMR was used to monitor the fold of α-Syn in response to nanodisc binding, determining individual residue apparent affinities for the nanodisc-contained bilayers. The addition of cholesterol inhibited α-Syn interaction with lipid bilayers and, however, significantly promoted α-Syn fibrillation, with a more than a 20-fold reduction of lag times before fibrillation onset. When α-Syn bilayer interactions were analysed at an individual residue level by solution-state NMR, we observed two different effects of cholesterol. In nanodiscs made of DOPC, the addition of cholesterol modulated the NAC part of α-Syn, leading to stronger interaction of this region with the lipid bilayer. In contrast, in the nanodiscs comprising DOPC, DOPE and DOPG, the NAC part was mostly unaffected by the presence of cholesterol, while the binding of the N and the C termini was both inhibited., (© 2020 The Authors. The FEBS Journal published by John Wiley & Sons Ltd on behalf of Federation of European Biochemical Societies.)

Ligand-gated ion channels mediate signal transduction at chemical synapses and transition between resting, open, and desensitized states in response to neurotransmitter binding. Neurotransmitters that produce maximum open channel probabilities (Po) are full agonists, whereas those that yield lower than maximum Po are partial agonists. Cys-loop receptors are an important class of neurotransmitter receptors, yet a structure-based understanding of the mechanism of partial agonist action has proven elusive. Here, we study the glycine receptor with the full agonist glycine and the partial agonists taurine and γ-amino butyric acid (GABA). We use electrophysiology to show how partial agonists populate agonist-bound, closed channel states and cryo-EM reconstructions to illuminate the structures of intermediate, pre-open states, providing insights into previously unseen conformational states along the receptor reaction pathway. We further correlate agonist-induced conformational changes to Po across members of the receptor family, providing a hypothetical mechanism for partial and full agonist action at Cys-loop receptors., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Styrene monooxygenase (SMO) is a two-component flavoenzyme composed of NADH-dependent flavin reductase (SMOB) and FAD-specific styrene epoxidase (NSMOA) components. The enantioselective styrene epoxidation reaction catalyzed by this enzyme can be streamlined for chemosynthetic applications by substituting NADH and the reductase with an electrode to supply the epoxidase with reducing equivalents required for catalysis. Slow kinetics of adsorption and desorption of FAD from the electrode surface and unproductive side reactions of the reduced flavin with oxygen limit the efficiency of direct electroenzymatic catalysis. In the present work we develop a miniature spectroelectrochemical cell equipped with a copper electrode for the anodic synthesis of Cu(I) chelates of EDTA, glutamate, and citrate as FAD-reducing agents, and a platinum electrode for the electrolytic generation of oxygen. Copper oxidized in the flavin reduction reaction can be reclaimed subsequently as copper metal at the electrode surface. About 80% transformation of styrene is achieved in a single cell cycle of reduction and oxygenation at pH 7 and 25 °C in good agreement with that predicted by numerical simulation. When the cell is operated in two successive cycles, styrene oxide can be synthesized with an electroenzymatic epoxidation activity of 663U/g in 94% yield. This approach to electroenzymatic catalysis shows promise for the quantitative transformation of styrene to styrene oxide and may be applied more generally to other flavoprotein monooxygenases., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier B.V.)

Precious metals, in particular Pd, have a wide range of applications in industry. Due to their scarcity, precious metals have to be recycled, preferably with green and energy-saving recycling processes. In this article, palladium extraction from an aluminosilicate-supported catalyst, containing about 2 wt% (weight%) of Pd (100% PdO), with supercritical CO 2 (scCO 2 ) assisted by complexing polymers is described. Two polymers, p(FDA)SH homopolymer and p(FDA- co -DPPS) copolymer (FDA: 1,1,2,2-tetrahydroperfluorodecyl acrylate; DPPS: 4-(diphenylphosphino)styrene), were tested with regards to their ability to extract palladium. Both polymers showed relatively low extraction conversions of approximately 18% and 30%, respectively. However, the addition of piperidine as activator for p(FDA- co -DPPS) allowed for an increase in the extraction conversion of up to 60%.

The digital nucleic acid assay is a precise, sensitive, and reproducible method for determining the presence of individual target molecules separated in designated partitions; thus, this technique can be used for the nucleic acid detection. Here, we propose a multifunctional micropattern array capable of isolating individual target molecules into partitions and simultaneous on-site cell lysis to achieve a direct DNA extraction and digitized quantification thereof. The multifunctional micropattern array is fabricated by the deposition of a copolymer film, poly(2-dimethylaminomethyl styrene- co -hydroxyethyl methacrylate) (pDH), directly on a microfluidic chip surface via the photoinitiated chemical vapor deposition process, followed by hydrophobic microcontact printing (μCP) to define each partition for the nucleic acid isolation. The pDH layer is a positively charged surface, which is desirable for the bacterial lysis and DNA capture, while showing exceptional water stability for more than 24 h. The hydrophobic μCP-treated pDH surface is stable under aqueous conditions at a high temperature (70 °C) for 1 h and enables the rapid and reliable formation of thousands of sessile microdroplets for the compartmentalization of an aqueous sample solution without involving bulky and costly microfluidic devices. By assembling the multifunctional micropattern array into the microfluidic chip, the isothermal amplification in each partition can detect DNA templates over a concentration range of 0.01-2 ng/μL. The untreated bacterial cells can also be directly compartmentalized via the microdroplet formation, followed by the on-site cell lysis and DNA capture on the compartmentalized pDH surface. For Escherichia coli O157:H7, Salmonella enteritidis , and Staphylococcus aureus cells, cell numbers ranging from 1.4 × 10 4 to 1.4 × 10 7 can be distinguished by using the multifunctional micropattern array, regardless of the cell type. The multifunctional micropattern array developed in this study provides a novel multifunctional compartmentalization method for rapid, simple, and accurate digital nucleic acid assays.

Coumarins, derivatives of cinnamic acid, are found in wines aged in wooden barrels. The lab-made molecularly imprinted polymers (MIP), selective for simple coumarins, were used in three forms, as sorbents in solid phase extraction (SPE) cartridge or pipette tip and coated on to the surface of magnetite for magnetic extraction. MIP-7-hydroxycoumarin had greater selectivity and extraction efficiency (recoveries above 75%, RSDs less than 6%) compared with conventional SPE sorbents (C18 and styrene-divinylbenzene polymeric types). Batch extraction with MIP coated on to magnetic particles was relatively time-consuming compared with conventional and pipette tip SPE. The advantage of pipette tip SPE was reduced solvent volumes. LOQs for MISPE offline coupled with HPLC were less than 1.5 µg mL -1 and 12 ng mL -1 for UV and fluorescence detectors, respectively. 6-Methoxy-7-hydroxycoumarin and 4-methyl-7-hydroxycoumarin were detected in Slovak Tokaj wines using method with coumarin-specific sorbents., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

An open tubular capillary column (100 μm internal diameter and 120 cm length) was first fabricated with N-phenylacrylamide and styrene copolymer layer on the inner surface by in situ one-pot strategy, while ethylene dimethacrylate was used as the cross-linker. The pretreated silica-fused capillary was reacted with 3-trimethoxysilyl propyl methacrylate to attach a double-bond ligand onto the inner surface of the capillary. Further, a thick and stabile copolymer layer was generated on the inner surface of the capillary by the novel method in situ one-pot reaction of styrene-N-phenylacrylamide. The effects of reaction temperature and composition of the polymerization mixture on the morphology and permeability of the copolymer were investigated. The separation performance of the fabricated polymer columns were validated by separation of five synthetic peptides. The excellent efficiency (188 500 plates/m) of 100 μm internal diameter open tubular column with the separation media prepared by mixed one-pot copolymerization has not been achieved via the isocratic elution mode. The column to column, intraday, and interday repeatabilities evaluated from the relative standard deviation were found better than 4%, exhibiting considerable repeatability of the column., (© 2020 Wiley-VCH GmbH.)

A three-dimensional-printed microfluidic device made of a thermoplastic material was used to study the creation of molecular filters by controlled dielectric breakdown. The device was made from acrylonitrile butadiene styrene by a fused deposition modeling three-dimensional printer and consisted of two V-shaped sample compartments separated by 750 µm of extruded plastic gap. Nanofractures were formed in the thin piece of acrylonitrile butadiene styrene by controlled dielectric breakdown by application voltage of 15-20 kV with the voltage terminated when reaching a defined current threshold. Variation of the size of the nanofractures was achieved by both variation of the current threshold and by variation of the ionic strength of the electrolyte used for breakdown. Electrophoretic transport of two proteins, R-phycoerythrin (RPE; <10 nm in size) and fluorescamine-labeled BSA (f-BSA; 2-4 nm), was used to monitor the size and transport properties of the nanofractures. Using 1 mM phosphate buffer, both RPE and f-BSA passed through the nanofractures when the current threshold was set to 25 µA. However, when the threshold was lowered to 10 µA or lower, RPE was restricted from moving through the nanofractures. When we increased the electrolyte concentration during breakdown from 1 to 10 mM phosphate buffer, BSA passed but RPE was blocked when the threshold was equal to, or lower than, 25 µA. This demonstrates that nanofracture size (pore area) is directly related to the breakdown current threshold but inversely related to the concentration of the electrolyte used for the breakdown process., (© 2020 Wiley-VCH GmbH.)

A one-pot multicomponent copper-catalyzed protocol for borylation/ ortho -cyanation of styrene derivatives followed by a Suzuki-Miyaura coupling provides a platform to explore the factors that control the selectivity between distal or proximal functionalization of arenes. The development of divergent nitrile-directed C-H functionalization (acetoxylation, pivalation, and methoxylation) offers an effective approach to rapidly increase synthetic complexity. Finally, the development of a mild reductive decyanation allows a traceless method to access functionalized biaryl motifs.

A direct assembly of secondary benzylureas and related amine derivatives via copper-catalyzed carboamination of styrenes with potassium alkyltrifluoroborates and ureas, anilines, or an amide is reported. Terminal and 1,2-disubstituted alkenes, as well as dienes, participate in this three-component coupling reaction. The reaction mechanism likely involves the addition of an alkyl radical to the styrene, followed by metal-mediated oxidative coupling of the resulting benzylic radical with the amine derivative. Factors that impact substrate reactivity and regioselectivity are discussed.

The direct C-H carboxylation of aromatic compounds is an attractive route to the corresponding carboxylic acids, but remains challenging under mild conditions. It has been proposed that the first step in anaerobic microbial degradation of recalcitrant aromatic compounds is a UbiD-mediated carboxylation. In this study, we use the UbiD enzyme ferulic acid decarboxylase (Fdc) in combination with a carboxylic acid reductase to create aromatic degradation-inspired cascade reactions, leading to efficient functionalization of styrene through CO 2 fixation. We reveal that rational structure-guided laboratory evolution can expand the substrate scope of Fdc, resulting in activity on a range of mono- and bicyclic aromatic compounds through a single mutation. Selected variants demonstrated 150-fold improvement in the conversion of coumarillic acid to benzofuran + CO 2 and unlocked reactivity towards naphthoic acid. Our data demonstrate that UbiD-mediated C-H activation is a versatile tool for the transformation of aryl/alkene compounds and CO 2 into commodity chemicals.

A theoretical analysis of the reaction of oxidative sulfamidation of several alkenes was performed in order to explain the various experimental observations and different reactivity of triflamide and non-fluorinated sulfonamides. Transformations occurring in the system alkene-sulfonamide in the presence of oxidative system (Bu t OCl + NaI) were analyzed at the MP2/DGDZVP//B3LYP/DGDZVP level of theory using the IEF-PCM method for taking into account the solvent acetonitrile (MeCN) effect. As the model substrates, styrene, trimethyl(vinyl)silane, dimethyl(divinyl)silane and diphenyl(divinyl)silane were chosen and mesylamide, triflamide, tosylamide and p -nosylamide were taken as the reagents. Bu t OI generated from Bu t OCl and NaI reacts with sulfonamides to give N -iodinated sulfonamides RSO 2 NHI and RSO 2 NI 2 as active intermediates, the iodinating activity of the latter being notably higher. The analysis allowed to answer such challenging questions as different reactivity of nonfluorinated sulfonamides leading to aziridination and of triflamide resulting in the formation the main products of bis-triflamidation, or different regioselectivity of halogenation of styrene and trimethyl(vinyl)silane caused by a linear intermediate iodonium cation in the former case and a cyclic one in the latter.

Three-dimensional (3D) printing as a type of additive manufacturing shows continuing increase in application and consumer popularity. The fused filament fabrication (FFF) is an inexpensive method used most frequently by consumers. Studies with 3D printers have shown that during the printing process particulate and volatile substances are released. Handheld 3D printing pens also use the FFF method but the consumer's proximity to the 3D pens gives reason to higher exposure compared to a 3D printer. At the same time, 3D printing pens are often marketed for children who could be more sensitive to the printing emission. The aim of this study was to implement a low cost method to analyze the emissions of 3D printing pens. Polylactide (PLA) and acrylonitrile butadiene styrene (ABS) filaments of different colors were tested. In addition, filaments containing metal and carbon nanotubes (CNTs) were analyzed. An 18.5 L chamber and sampling close to the emission source was used to characterize emissions and concentrations near the breathing zone of the user. Particle emissions and particle size distributions were measured and the potential release of metal particles and CNTs investigated. Particle number concentrations were found in a range of 10 5 - 10 6 particles/cm 3 , which is comparable to previous reports from 3D printers. Transmission electron microscopy (TEM) analysis showed nanoparticles of the different thermoplastic materials as well as of metal particles and CNTs. High contents of metal were observed by inductively coupled plasma mass spectrometry (ICP-MS). These results call for a cautious use of 3D pens due to potential risk to the consumers.

The activity of membrane proteins and compounds that interact with the membrane is modulated by the surrounding lipid composition. However, there are no simple methods that determine the composition of these annular phospholipids in eukaryotic systems. Herein, we describe a simple methodology that enables the identification and quantification of the lipid composition around membrane-associated compounds using SMA-nanodiscs and routine 1 H- 31 P NMR.

The development of amphipathic polymers, including various formulations of styrene-maleic acid (SMA) copolymers, has allowed the purification of increasing sizes and complexities of biological membrane protein assemblies in native nanodiscs. However, the factors determining the sizes and shapes of the resulting bio-nano particles remain unclear. Here, we show how grafting on short alkyl amine sidechains onto the polar residues leads to a broad set of nanoparticle sizes with improved solution behavior. The solubilization of lipid vesicles occurs over a wide range of pH levels and calcium concentrations, providing utility across the physiologically relevant range of solution conditions. Furthermore, the active SMA derivatives can contain strictly alternating monomers, which have inherently lower sequence polydispersity. Pronounced differences in the shapes of native nanoparticles were formed from Escherichia coli bacterial outer membrane containing PagP protein using methyl, ethyl and propylamine derivatives of styrene-maleic anhydride. In particular, the methylamine-substituted polymer forms smaller, monodispersed nanodiscs, while the longer alkyl derivatives form worm-like nanostructures. Thus the introduction of hydrophobicity onto the polar sidechains of amphipathic polymers has profound effects on morphology of native nanodisc, with shorter methyl moieties offering more uniformity and utility for structural biology studies., Competing Interests: Declaration of competing interest The authors M.E. and M.O. have a competing financial interest. They have filed a patent on the polymers presented in this manuscript., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Styrene in indoor air can adversely affect human health. In this study, styrene monomer and other chemical emission fluxes for products containing expanded polystyrene beads (pillows, cushions, and soft toys) were measured at various temperatures to simulate typical product use. The contributions of the products to styrene and other chemical concentrations in indoor air and human exposure to these chemicals were estimated, and health risk assessments were performed. The styrene monomer emission fluxes for the samples at 25°C were between 25.3 and 8.73×103 μg/(m2 h). The styrene emission fluxes for the product surfaces increased strongly as the temperature increased, from between 124 and 2.44×104 μg/(m2 h) at 36°C (simulating human body temperature) to between 474 and 4.59×104 μg/(m2 h) at 50°C (simulating inside an automobile in summer). The hexane, heptane, toluene, octane, ethylbenzene, m- and p-xylene, o-xylene, and dodecane emission fluxes at 25°C for the sample that emitted the analytes most readily were high. The maximum estimated styrene and xylene concentrations in indoor air caused by emissions from expanded polystyrene beads at 36°C in a bedroom and automobile were higher than the relevant guidelines. The maximum contribution of a product containing expanded polystyrene beads in a living room, bedroom, or automobile could cause the total volatile organic compound concentration in air to exceed the advisable value (400 μg/m3). The estimated maximum hazard quotients for styrene, toluene, and xylene emitted by a product containing expanded polystyrene beads at 36°C in a bedroom were 0.59, 0.30, and 0.37, respectively. These non-carcinogenic risk values for single products could contribute to the non-carcinogenic risk thresholds being exceeded when multiple products and other sources of chemicals are taken into consideration. The estimated styrene concentrations suggest that products containing expanded polystyrene beads are important sources of styrene to indoor air., Competing Interests: The authors have declared that no competing interests exist.

The antibacterial effects of quaternary ammonium resins (QARs) have been reported for decades, but there are few practical applications because of limited improvements in bactericidal capacity and the absence of an efficient antibacterial-indicating parameter. An in-situ determination method of surficial N+ groups for QARs, defined as surficial N+ charge density, was first established to merely quantify the exposed surficial quaternary ammonium groups (QAs). The mechanism of the new method depends on the tetraphenylboron sodium standard solution (TS), which is a colloidal solution with high steric hindrance, making it difficult to permeate into QARs and further react with the inner QAs. The results showed that the antibacterial efficacy of QARs correlates with the surficial N+ charge density with R2 > 0.95 (R2 of 0.97 for Escherichia coli, R2 of 0.96 for Staphylococcus aureus) but not with the strong-base group exchange capacity or zeta potential. Furthermore, the surficial N+ charge density was demonstrated efficient to indicate the antibacterial capacities against both gram-negative and gram-positive bacteria for commercial QARs, including acrylic, styrene and pyridine resin skeletons, especially for the QARs with similar skeletons and similar QAs. Based on the finding that the bactericidal groups merely involve the surficial QAs of QARs, this study proposes a new direction for improving the antibacterial capacity by enriching the surficial QAs and enhancing the bactericidal property of these surficial QAs, and provides a practicable synthesis with two-step quaternization., Competing Interests: The authors have declared that no competing interests exist.

We report the enhanced cis- and enantioselective cyclopropanation of styrene catalysed by cytochrome P450BM3 in the presence of dummy substrates, i.e. decoy molecules. With the aid of the decoy molecule R-Ibu-Phe, diastereoselectivity for the cis diastereomers reached 91%, and the enantiomeric ratio for the (1S,2R) isomer reached 94%. Molecular dynamics simulations underpin the experimental data, revealing the mechanism of how enantioselectivity is controlled by the addition of decoy molecules.

Styrene is an important petroleum-derived molecule that is polymerized to make versatile plastics, including disposable silverware and foamed packaging materials. Finding more sustainable methods, such as biosynthesis, for producing styrene is essential due to the increasing severity of climate change as well as the limited supply of fossil fuels. Recent metabolic engineering efforts have enabled the biological production of styrene in Escherichia coli, but styrene toxicity and volatility limit biosynthesis in cells. To address these limitations, we have developed a cell-free styrene biosynthesis platform. The cell-free system provides an open reaction environment without cell viability constraints, which allows exquisite control over reaction conditions and greater carbon flux toward product formation rather than cell growth. The two biosynthetic enzymes required for styrene production were generated via cell-free protein synthesis and mixed in defined ratios with supplemented L-phenylalanine and buffer. By altering the time, temperature, pH, and enzyme concentrations in the reaction, this approach increased the cell-free titer of styrene from 5.36 ± 0.63 mM to 40.33 ± 1.03 mM, the highest amount achieved using biosynthesis without process modifications and product removal strategies. Cell-free systems offer a complimentary approach to cellular synthesis of small molecules, which can provide particular benefits for producing toxic molecules., (Copyright © 2020 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.)