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To fill a research gap on firefighter exposures and breast cancer risk, and guide exposure reduction, we aimed to identify firefighter occupational exposures linked to breast cancer. We conducted a systematic search and review to identify firefighter chemical exposures and then identified the subset that was associated with breast cancer. To do this, we compared the firefighter exposures with chemicals that have been shown to increase breast cancer risk in epidemiological studies or increase mammary gland tumors in experimental toxicology studies. For each exposure, we assigned a strength of evidence for the association with firefighter occupation and for the association with breast cancer risk. We identified twelve chemicals or chemical groups that were both linked to breast cancer and were firefighter occupational exposures, including polycyclic aromatic hydrocarbons, volatile aromatics, per- and polyfluoroalkyl substances, persistent organohalogens, and halogenated organophosphate flame retardants. Many of these were found at elevated levels in firefighting environments and were statistically significantly higher in firefighters after firefighting or when compared to the general population. Common exposure sources included combustion byproducts, diesel fuel and exhaust, firefighting foams, and flame retardants. Our findings highlight breast-cancer-related chemical exposures in the firefighting profession to guide equitable worker's compensation policies and exposure reduction.

Ir-Ni alloys supported on SiO2 have been reported to show high catalytic activity for styrene hydrogenation; however, precise control of compositions and sizes of the Ir-Ni alloys is difficult when conventional metal salts are used as precursors. Furthermore, the concomitant formation of unalloyed Ni nanoparticles disturbs quantitative discussion about Ir-Ni alloy compositions. We report herein a preparation method of Ir-Ni alloys with precisely controlled compositions on SiO2 using Ni(NO3)2 and an Ir complex possessing CN- ligands, [Ir(CN)6]3- or [Ir(ppy)2(CN)2]- (ppy = 2-phenylpyridine), as precursors. The in situ formation of cyano-bridged coordination polymers involving Ir and Ni promotes the formation of Ir-Ni alloys, whose compositions are virtually the same as expected from the amounts of Ir and Ni used for the preparation, after heat treatment under H2. The use of [Ir(ppy)2(CN)2]- as the precursor resulted in the formation of smaller Ir-Ni alloy particles than those with [Ir(CN)6]3- related to the structures of the formed coordination polymers. [ABSTRACT FROM AUTHOR]

We present an intramolecular [3+2] cycloaddition of innovative (E)-α-aryl enal derivatives with 4-aminopyrazolone hydrochlorides/3-aminooxindole hydrochlorides to afford an array of atropisomeric benzoxepinone-based styrenes fused to spiro[pyrrolidine–pyrazolone/oxindole] scaffolds, and kinetic resolutions of the racemic adducts were implemented by reacting with benzyl alcohols, giving the corresponding two types of axially chiral styrenes in enantioenriched form with high s-factor. In addition, product transformations such as oxidative dehydrogenation and cross-coupling reactions have been demonstrated. [ABSTRACT FROM AUTHOR]

Building on traditional emulsion polymerization research, which continues to yield results up to the present day, techniques have emerged to produce hybrid materials. One such technique is Pickering emulsion polymerization, with numerous industrial applications. Despite a growing interest in Pickering emulsion polymerization, the intrinsic mechanisms involved have been based mainly on the findings of classical emulsion polymerization. In this work, by relying on a minimum of assumptions and using a simple model and experimental data on conversion and particle size, we obtain information about the prevailing mechanisms. More specifically, we present four main findings based on data reported previously in the literature. First, in contrast to the three rate-of-reaction intervals reported in classical emulsion polymerization, the integro-differential method yielded only two rate-of-reaction intervals against conversion. Second, a master curve is constructed by plotting the reaction rate against overall conversion, showing a maximum of approximately 55% conversion. Third, despite having a semicontinuous process, monomer concentration inside the particles is not constant. Finally, particle density is a strong function of the Pickering agent concentration, where two fitting parameters (nucleation and coagulation) allowed an accurate description for the particle number time evolution. Both parameters showed a power-law dependence with clay concentration. [ABSTRACT FROM AUTHOR]

The recently reported electrochemical, organo‐mediator enabled deuteration of styrenes, a reaction referred to as "electrochemical deuterium atom transfer", differs mechanistically from reported direct electrochemical hydrogenations/deuterations only by a mediated, homogeneous SET to the substrates. By comparing direct vs. mediated processes in general and for styrene reduction, we display that Qiu's work does not change the concept of this chemistry. Experiments with mediators and the direct reduction of examples from the reported scope show that even electron‐rich substrates can be reduced when our direct protocol, published six months before Qiu's work, is applied. [ABSTRACT FROM AUTHOR]

The control of the microstructures of polymer materials derived from diene‐based monomers is crucial, and various synthetic methods, including anionic, radical, and coordination polymerization reactions, have been extensively explored. Here, we demonstrated the coordination polymerization of 2‐phenyl[3]dendralenes (P3D) as a diene monomer. The polymerization process using monocyclopentadienyltitanium trichloride (CpTiCl3) as a catalyst and modified methylaluminoxane (MMAO) as a cocatalyst (CpTiCl3/MMAO) yielded polymers with an exclusive 4,6‐structure that is distinct from those produced by anionic polymerization. Furthermore, the copolymerization of P3D with isoprene and styrene proceeded randomly. [ABSTRACT FROM AUTHOR]

1,2‐Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods are usually limited in scope and produce diamines where one or both nitrogens are protected, adding synthetic steps for deprotection and further N‐functionalization to reach a desired target. Furthermore, the range of amino groups that can be introduced at the internal position is fairly limited. Here we describe a 1,2‐diamination of styrenes that directly installs a free amino group at the terminal position and a wide variety of unprotected nitrogen nucleophiles (primary or secondary alkyl or aromatic amines, sulfoximines, N‐heterocycles, and ammonia surrogate) at the internal position. Two complementary sets of conditions encompass electronically activated and deactivated styrenes with diverse substitution patterns and functional groups. Moreover, this strategy can be extended to the 1,2‐aminothiolation of styrenes. [ABSTRACT FROM AUTHOR]

This work was devoted to the investigation of the contribution of various species in plasma to styrene decomposition. Different background gases (air, argon, nitrogen, and oxygen) and plasma reactor (in‐plasma, post‐plasma, and post‐plasma with buffer tube) were employed in this experiment. The results showed that degradation and polymerization of styrene occur simultaneously in the plasma treatment process. In the discharge zone, the bombardment of electrons and energetic particles on styrene and its degradation intermediates played a role in breaking its weak bond energy and promoting their conversion. The short‐lived reactive species with high oxidation potential in plasma were the prerequisite for complete degradation of styrene, due to its ability of breaking bonds with large bond energies, such as benzene ring. Away from the discharge zone, long‐lived reactive oxygen species further oxidized and degraded styrene, and its intermediates outside the discharge zone, promoting their mineralization. [ABSTRACT FROM AUTHOR]

The papermaking, packaging, and printing industry are actively seeking sustainable material alternatives to address growing concerns about environmental consciousness and finite resources. Synthetic latex, a frequently utilized binder in paper coating formulations, present difficulties due to their dependence on fossil fuel resources and their reduced recyclability in comparison to eco‐friendly sustainable products. In this study, synthetic latex was replaced with a starch‐based nanoparticle (starch NP) binder at a 1:1 ratio in a coating formulation. Printing trials to assess colorimetric characteristics was made using electrophotography (EP) printing, given the current upward trajectory and expansion of EP technology into the label, packaging, and folding carton sectors. The in‐depth investigations reveal that incorporating starch NP binder result in improved optical, color, and dot characteristics. Moreover, it maintains consistent and comparable coefficients of friction. Partial replacement of synthetic latex with the starch NP binder yields significant enhancements in surface roughness and text quality. Importantly, the starch NP binder not only improves the dielectric relaxation properties of the paper and enhances toner transfer but also accelerates the distribution of the electrical field compared to synthetic latex, optimizing toner transfer and thereby enhancing color gamut volume. The study demonstrates that employing the starch NP binder leads to substantial improvements in colorimetric performance without any drawbacks in EP printing, making it highly advantageous to replace 50% of the synthetic binder. [ABSTRACT FROM AUTHOR]

In this study, we explored the use of Mes‐Acr‐MeClO4 as a visible light photocatalyst for multicomponent reactions involving quinoxalin‐2(1H)‐ones with CBrCl3 and styrene. The method showcases regioselective functionalization of quinoxalin‐2(1H)‐ones in a three‐component system, forming two C─C bonds in one pot. Mechanistic investigations suggest a radical‐mediated pathway, initiated by the photoexcitation of Mes‐Acr‐MeClO4, followed by halogen atom abstraction from CBrCl3. This approach provides a versatile and sustainable route for quinoxalin‐2(1H)‐one functionalization, with Mes‐Acr‐MeClO4 effectively facilitating the photocatalyzed multicomponent reaction under mild conditions and visible light irradiation, yielding high selectivity and efficiency. [ABSTRACT FROM AUTHOR]

The cleavage of heteroaromatic endocyclic carbon–heteroatom bonds to assemble C–Si bonds is scarce. Here, we demonstrate an unprecedented dearomatization silylation of N-arylindoles arising from reductive activation initiated by electron-rich silylboronic complexes to deliver silyl styrenes with perfect stereoselectivity. [ABSTRACT FROM AUTHOR]

C(sp3)‐rich heterocycles are privileged building blocks for pharmaceuticals and agrochemicals. Therefore, synthetic methods that provide access to novel saturated nitrogen‐containing heterocycles are in high demand. Herein, we report a general synthesis of 1‐azabicyclo[2.1.1]hexanes (1‐aza‐BCH) via a formal cycloaddition of azabicyclo[1.1.0]butanes (ABB) with styrenes under photochemical conditions. To overcome the challenging direct single electron reduction of ABBs, we designed a polar‐radical‐polar relay strategy that leverages a fast acid‐mediated ring‐opening of ABBs to form bromoazetidines, which undergo efficient debrominative radical formation to initiate the cycloaddition reaction. The reaction is applicable to a broad range of ABB‐ketones and we demonstrate the 1‐aza‐BCH products can be further functionalized to access larger saturated, conformationally rigid heterocycles. [ABSTRACT FROM AUTHOR]

Skeletal editing of single-atom insertion to basic chemicals has been demonstrated as an efficient strategy for the discovery of structurally diversified compounds. Previous endeavors in skeletal editing have successfully facilitated the insertion of boron, nitrogen, and carbon atoms. Given the prevalence of oxygen atoms in biologically active molecules, the direct oxygenation of C-C bonds through single-oxygen-atom insertion like Baeyer-Villiger reaction is of particular significance. Herein, we present an approach for the skeletal modification of styrenes using O2 via oxygen insertion, resulting in the formation of aryl ether frameworks under mild reaction conditions. The broad functional-group tolerance and the excellent chemo- and regioselectivity are demonstrated in this protocol. A preliminary mechanistic study indicates the potential involvement of 1,2-aryl radical migration in this reaction. The direct oxygenation of C–C bonds through single-oxygen-atom insertion like the Baeyer-Villiger reaction is of particular significance. Herein, the authors present an approach for the skeletal modification of styrene using O2 via oxygen insertion, resulting in the formation of aryl ether frameworks under mild reaction conditions. [ABSTRACT FROM AUTHOR]

This article explores the fatigue characteristics of acrylonitrile butadiene styrene (ABS) components fabricated using fused filament fabrication (FFF) additive manufacturing technology. ABS is frequently used as a polymeric thermoplastic material in open-source FFF machines for a variety of engineering applications. However, a comprehensive understanding of the mechanical properties and execution of FFF-processed ABS components is necessary. Currently, there is limited knowledge regarding the fatigue behavior of ABS components manufactured using FFF AM technology. The primary target of this study is to evaluate the results of part-build directions and build orientation angles on the tensile fatigue behavior exhibited by ABS material. To obtain this target, an empirical investigation was carried out to assess the influence of building angles and orientation on the fatigue characteristics of ABS components produced using FFF. The test samples were printed in three distinct directions, including Upright, On Edge, and Flat, and with varying orientation angles ([0°, 90°], [15°, 75°], [30°, 60°], [45°]), using a 50% filling density. The empirical data suggest that, at each printing angle, the On-Edge building orientation sample exhibited the most prolonged vibrational duration before fracturing. In this investigation, we found that the On-Edge printing direction significantly outperformed the other orientations in fatigue life under cyclic loading with 1592 loading cycles when printed with an orientation angle of 15°–75°. The number of loading cycles was 290 and 39 when printed with the same orientation angle for the Flat and Upright printing directions, respectively. This result underscores the importance of orientation in the mechanical performance of FFF-manufactured ABS materials. These findings enhance our comprehension of the influence exerted by building orientation and building angles on the fatigue properties of FFF-produced test samples. Moreover, the research outcomes supply informative perspectives on the selection of building direction and building orientation angles for the design of 3D-printed thermoplastic components intended for fatigue cyclic-loading applications. [ABSTRACT FROM AUTHOR]

A very simple and atom‐economical method for the synthesis of vicinal trifluoromethyl thioethers via DBN‐catalyzed hydrothiolation of α‐(trifluoromethyl)styrenes with thiols was reported. The reaction proceeded smoothly under mild reaction conditions and provided the β‐CF3‐thioethers in moderate to good yields in an anti‐Markovnikov manner. Furthermore, this method features several remarkable advantages, such as the use of a catalytic amount of DBN, broad substrate scope, excellent functional group compatibility, and easy scalability. [ABSTRACT FROM AUTHOR]

In the field of industrial semi‐hydrogenation of trace alkynes amidst alkene feedstocks, the pivotal challenge lies in circumventing the hydrogenation of alkenes. Herein, we present Zr(OH)4 as an innovative catalyst for the semi‐hydrogenation of phenylacetylene, demonstrating remarkable selectivity towards styrene (>96 %), while exhibiting inactivity towards free styrene. Notably, Zr(OH)4 achieves a 95 % conversion of quasi‐industry 1 mol % phenylacetylene within styrene, with a mere 0.44 % styrene loss. Experimental and theoretical results confirm both terminal Zr−O−H and bridge Zr−O−H can dissociate H2, while the terminal Zr−O−H plays a crucial role on activating phenylacetylene through the sequential hydrogenation process of C6H5C≡CH→C6H5C=CH2→C6H5CH=CH2. The high rate of phenylacetylene removal is attributed to its strong adsorption capacity, while Zr(OH)4 has a significantly weaker adsorption capacity for styrene. [ABSTRACT FROM AUTHOR]

The carbon steel pipe line of the dehydrogenation tail gas system in a certain styrene unit has a thinning rate of 55.51% and a corrosion rate of up to 5.29 mm/a after one year of use, which restricts the long-term stable operation of the plant. The corrosion of the dehydrogenation tail gas carbon steel pipeline was inspected through electromagnetic eddy current scanning, ultrasonic thickness measurement, and macroscopic inspection. The impact of corrosive medium, process operating parameters, on-site pipeline location and material on pipeline thinning in the dehydrogenation tail gas system was analyzed. The results indicate that the localized corrosion and thinning of the dehydrogenation tail gas carbon steel pipeline are caused by a combination of carbon dioxide corrosion and erosion corrosion under certain temperature and pressure. To alleviate corrosion issues, it is recommended to re-evaluate the process operating conditions of the dehydrogenation tail gas system, add cooling equipment before the dehydrogenation tail gas compressor, or upgrade the pipeline material to 304 austenitic stainless steel. Or consider adding corrosion inhibitors to the dehydrogenation exhaust system. At the same time, regular electromagnetic eddy current scanning or ultrasonic thickness measurement should be carried out to monitor the relevant pipelines and prevent leaks in a timely manner. [ABSTRACT FROM AUTHOR]

A self‐developed Serial Rubber Continuous Mixing Device (SRCMD) based on the shear and elongation flow fields was adopted to continuously prepare the carbon nanotubes (CNTs)/expanded graphite (EG)/Solution‐polymerized styrene butadiene rubber (SSBR) composite. Meanwhile, the silanization reaction between the Silica and Si69 was introduced to improve the performance of the CNTs/EG/SSBR composite. When comparing the sample prepared using the two‐stage mixing process based on the shear flow field in the internal mixer, the continuously prepared CNTs/EG/SSBR composite with 3 wt% CNTs and 15 wt% EG demonstrates a higher thermal conductivity of 1.32 W/m·K. At the same time, it exhibits significant advantages in terms of mechanical properties, processability and dispersion rating. In addition, the mechanism for the continuous preparation of CNTs/EG/SSBR composite was revealed through visual experiments. This study aims to achieve the real continuous production of high‐performance thermally conductive polymer composites to meet the urgent demand for thermal conductivity materials in 5G technology. Highlights: Real continuous preparation of CNTs/EG/SSBR composite was realized.The silanization index of 92.26% between Silica and Si69 was achieved.Good silanization promotes the construction of thermal conductivity networks.High‐performance CNTs/EG/SSBR composite with low Payne effect was obtained. [ABSTRACT FROM AUTHOR]

A computational mechanistic study was performed to investigate the transfer hydrogenation of styrene catalysed by a potassium tris‐hexamethyldisilazide magnesiate in the presence of 1,4‐cyclohexadiene. Exploiting cooperative effects between Mg and K centres present in this tris(amide) complex results in the selective formation of the desired product ethylbenzene. The calculations demonstrate the synergy of the metal centres within the bimetallic complex, since neither the monometallic potassium amide K(HMDS) nor the magnesium amide Mg(HMDS)2 on their own can efficiently execute this transformation under the experimental conditions. Several distinct mechanistic pathways have been explored, leading to the identification of the most plausible sequence in which both metal centres act in a synchronised manner. [ABSTRACT FROM AUTHOR]

The bond dissociation enthalpy of the N–H bond was calculated for the following compounds: 1-((E)-1,5-diphenylpent-1-en-4-yn-3-ylidene)-2-(o-tolyl)hydrazine, 1-((E)-1-(4-methoxyphenyl)-5-phenylpent-1-en-4-yn-3-ylidene)-2-phenylhydrazine, 1-((E)-1-phenylpent-1-en-4-yn-3-ylidene)-2-(p-tolyl)hydrazine, 1-((E)-1-(4-methoxyphenyl)-5-trimethylsilyl-1-en-4-yn-3-ylidene)-2-phenylhydrazine, and 1-((E)-1-(toiphenyl-2)-5-phenylpent-1-en-4-yn-3-ylidene)-2-phenylhydrazine. The calculations were performed by the M06-2X/6-311+G(2df,2pd)//B3LYP/6-31G(d) method using the homodesmotic approach. The bond dissociation enthalpy is lower than 77 kcal/mol for all the cross-conjugated hydrazone derivatives under study. The experimental rate constants for the reactions of the derivatives with peroxyl radicals in chlorobenzene during the initiated styrene oxidation are comparable to those of aromatic amines and are in the range (1.1–2.5) × 105 M−1 s−1. The stoichiometric inhibition coefficient depends on the structure of the derivatives and varies from 0.7 to 1.9. The inhibition is discussed within the framework of the radical mechanism. [ABSTRACT FROM AUTHOR]

Following a request from the European Commission, EFSA was asked to deliver a scientific opinion on the assessment of the application for the renewal of authorisation of a preparation containing a smoke flavouring extract for cats and dogs. The applicant provided data demonstrating that the additive currently on the market does not fully comply with the conditions of authorisation, but with newly proposed specifications based on different analytical methods. Considering that the additive under assessment contains benzofuran and styrene, for which a potential concern for genotoxicity has been identified, and that the whole mixture raises a potential concern for genotoxicity, additional data would be needed to complete the assessment. Therefore, the FEEDAP Panel is not in the position to conclude on the safety for cats and dogs. The additive is authorised for use in feed for cats and dogs, and therefore, there is no need to perform an assessment of the safety for the consumer and the environment. Regarding user safety, the additive should be considered as irritant to skin and eyes, and as a dermal and respiratory sensitiser. When handling the additive, exposure of unprotected users to potential genotoxic substances may occur. Therefore, to reduce the risk, the exposure of the users should be minimised. There was no need for assessing the efficacy of the additive in the context of the renewal of the authorisation. [ABSTRACT FROM AUTHOR]

This article provides information on the synthesis and properties of polylactic acid (PLA), a biodegradable plastic made from renewable resources. It discusses the use of tin(II) chloride for PLA synthesis and the addition of additives to alter its properties. The article also explores the environmental impact and sustainability of bioplastics, highlighting the need for comprehensive life cycle assessments and improved recycling infrastructure. It suggests that a focus on energy aspects and global recycling may be more promising than solely relying on bioplastics. [Extracted from the article]

A precautionary specific migration limit of 40 µg/kg for styrene from food contact materials is currently under evaluation in Europe. In the ongoing discussion about applicable methods to demonstrate compliance, testing with food instead of simulants or total transfer calculations has been proposed. In this study, the residual styrene levels in high-impact polystyrene (HIPS) blended with general-purpose polystyrene (GPPS) were determined at several levels of the processing chain of yoghurt pots (from pellets to sheets, then to pots). The styrene migration from extruded sheets and thermoformed pots was analyzed in food simulants at 10 days/20 °C and 40 °C, as well as in yoghurt after storage at 8 °C after 50 days. The obtained results show that the residual styrene content in the PS materials correlates with migration. However, the migration of styrene was far below the total transfer assumption. Styrene migration from the sheets into food simulants and into yoghurt exceeded that migrating from the pots. Styrene migration into food simulants in 20% ethanol at 10 days/20 °C and 40 °C and, more clearly, in 50% ethanol at 10 days/40 °C, was higher than that into yoghurt tested on the best-before date. Styrene migration from PS pots into yoghurt after storage at 8 °C for 50 days reached up to 15 µg/kg (applying the EU cube model), which would be conservatively covered by testing the PS pots with 20% ethanol at 10 days/20 °C. [ABSTRACT FROM AUTHOR]

The present study aims to explore the impact of different types of powder on the latex dispersibility index and pigment binding capacity in Acrylic-Styrene latexes. The methodology employed in this study involves investigating the latex dispersibility index by monitoring the Brookfield viscosity of pre-wetted powder when added to latex. Furthermore, the pigment binding capacity of the powders was evaluated through the wet scrub resistance of the latex paint. The findings from this study emphasize the importance of the size, shape, hydrophobicity, and hydrophilicity of powders in influencing the dispersibility of latex. Additionally, the physical and chemical properties of the powder also influence the binding strength between the powder and latex in the dried film. The implications of this study are discussed in terms of the ability to predict the powder-latex dispersion behavior using the viscosity-latex content curve for each type of powder. The results revealed that the maximum viscosity for the latex mixtures containing talc powder and calcium carbonate occurs at the amount of latex lower than 5 g. In contrast, the mixtures with titanium dioxide powder reach their maximum viscosity in the presence of higher than 10 g latex. Overall, this paper provides valuable insights into the characteristics of powders and their impact on the latex dispersibility index and pigment binding capacity in Acrylic-Styrene-based latexes. [ABSTRACT FROM AUTHOR]

The commonly used hole transport layer (HTL) Poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) still has some shortcomings that will limit the development of Pb–Sn perovskite solar cells (PSCs). In this work, multifunctional ammonium sulfide (AS) is attempted to modify PEDOT:PSS/perovskite interface. AS has multiple effects on different functional layers and the device as a whole: a) optimize the perovskite crystallization by the formation of PbS nucleation sites; b) neutralize the acidity of PEDOT:PSS by reaction with PSS; c) promote carrier transport at HTL/perovskite interface by tuning the energy level of PEDOT:PSS. As a result, a power conversion efficiency of 24.23% is obtained in the reverse scanning direction and 23.84% in the steady‐state output power test for the single‐junction Pb–Sn PSCs, and 27.48% for all‐perovskite tandem solar cells. These results show that AS modification can be an effective way to boost the development of Pb–Sn PSCs. [ABSTRACT FROM AUTHOR]

Here, we report the synthesis of tetrahydroquinolines between newly developed N-benzylhydroxylamine reagents and alkenes using HFIP as a solvent. This transformation is notably applicable to highly electronically deactivated styrenes and aliphatic alkenes, expanding the range of tetrahydroquinolines attainable. [ABSTRACT FROM AUTHOR]

The synthesis and structural analysis of (Me3SiC5H4)TiCl2(OAr) [OAr = O-2,6-iPr2-4-RC6H2; R = H, SiEt3] revealed that it exhibits higher catalytic activities than (tBuC5H4)TiCl2(OAr), Cp*TiCl2(OAr), with efficient comonomer incorporation in ethylene/styrene copolymerization in the presence of a methylaluminoxane (MAO) cocatalyst. The catalytic activity in the copolymerization increased upon increasing the charged styrene concentration along with the increase in the styrene content in the copolymers, whereas the activities of other catalysts showed the opposite trend. (Me3SiC5H4)TiCl2(O-2,6-iPr2C6H3) displayed the most suitable catalyst performance in terms of its activity and styrene incorporation, affording amorphous copolymers with styrene contents higher than 50 mol% (up to 63.6 mol%) and with random styrene incorporation confirmed by 13C-NMR spectra. [ABSTRACT FROM AUTHOR]

ABSTRACT Physiological characterization of microorganisms in the context of solvent tolerance is a tedious process with a high investment of manual labor while often being limited in throughput capability simultaneously. Therefore, we developed a small‐scale solvent‐impervious cultivation system consisting of screw cap‐sealed glass vials in combination with a 3D‐printed vial holder for the Growth Profiler (EnzyScreen) platform. Components and cultivation conditions were empirically tested, and a suitable setup was found for the intended application. To demonstrate the capability of this cultivation system, an adaptive laboratory evolution was performed to further increase the tolerance of Pseudomonas taiwanensis GRC3 toward styrene. This approach yielded heterogenic cultures with improved growth performances in the presence of styrene from which individual clones were isolated and characterized in high throughput. Several clones with improved growth in the presence of 1% (v/v) styrene were analyzed through whole‐genome sequencing, revealing mutations in the co‐chaperone‐encoding gene dnaJ, RNA polymerase α subunit‐encoding gene rpoA, and loss‐of‐function mutations in the ttgGHI solvent efflux pump repressor encoded by ttgV. The developed cultivation system has proven to be a very useful extension of the Growth Profiler, as it reduces manual workload and allows high‐throughput characterization. [ABSTRACT FROM AUTHOR]

The kinetics of gelation in the Activators Regenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET ATRP) of styrene, using a bifunctional initiator and no crosslinking agents are investigated. By applying the method of moments, we develop a system of differential equations that accounts for the formation of polymer rings. The kinetic rate constants of this model are optimized on the experimentally determined kinetics, varying the reaction temperature and ethanol fraction. Subsequently, we explore how variations in the amounts of catalyst, initiator, and reducing agents affect the simulated equilibria of ARGET ATRP, the emergence of gelation, and the swelling properties of the resulting networks. These findings suggest that favoring ring formation enhances the gelation phenomenon, supporting the hypothesis that the networks formed under the reported reaction conditions are olympic gels. [ABSTRACT FROM AUTHOR]

In this work, with the aim of increasing the monomer conversion rate in the styrene-graphite in situ polymerization system, graphite modification methods have been investigated. Modification of the graphite in the presence of nitric acid, sodium hydroxide or sodium dodecyl benzene sulfate (SDBS) was investigated with five different methods in order to reduce its adverse effects on the polymerization rate of styrene. The most effective modification approach was determined using quantitative data such as polymerization conversion and graphite dispersion in organic phase. Compared to other modified samples and unmodified graphite, graphite modified in sodium hydroxide solution with SDBS showed the most compatibility with the polymerization system and caused a significant increase in the monomer conversion rate. Monomer conversion increases by 22% and 29% respectively in the presence of 0.5% and 2% of the best modified graphite compared to non-modified graphite. Also, the results showed that this modification method stabilizes the suspension of graphite particles in styrene for a longer period of time than other methods. [ABSTRACT FROM AUTHOR]

Rodent inhalation studies indicate styrene is a mouse lung-specific carcinogen. Mode-of-action (MOA) analyses indicate that the lung tumors cannot be excluded as weakly quantitatively relevant to humans due to shared oxidative metabolites detected in rodents and humans. However, styrene also is not genotoxic following in vivo dosing. The objective of this review was to characterize occupational and general population cancer risks by conservatively assuming mouse lung tumors were relevant to humans but operating by a non-genotoxic MOA. Inhalation cancer values reference concentrations for respective occupational and general population exposures (RfCcar-occup and RfCcar-genpop) were derived from initial benchmark dose (BMD) modeling of mouse inhalation tumor dose–response data. An overall lowest BMDL10 of 4.7 ppm was modeled for lung tumors, which was further duration- and dose-adjusted by physiologically based pharmacokinetic (PBPK) modeling to derive RfCcar-occup/genpop values of 6.2 ppm and 0.8 ppm, respectively. With the exception of open-mold fiber reinforced composite workers not using personal protective equipment (PPE), the RfCcar-occup/genpop values are greater than typical occupational and general population human exposures, thus indicating styrene exposures represent a low potential for human lung cancer risk. Consistent with this conclusion, a review of styrene occupational epidemiology did not support a conclusion of an association between styrene exposure and lung cancer occurrence, and further supports a conclusion that the conservatively derived RfCcar-occup is lung cancer protective. [ABSTRACT FROM AUTHOR]

The widespread industrial use of styrene highlights the urgent need for detecting and monitoring its harmful gases. The innovation of this study lies in synthesizing uniform Fe 2 O 3 nanoparticles using Ginkgo biloba and calcining them with CuOHF to prepare nanostructured materials, enhancing the performance of gas sensors. The effects of varying α-Fe 2 O 3 additions and calcination temperatures on the structure and gas-sensitive properties of the composites were systematically investigated. The results revealed that the optimal operating temperatures of the CuO–10%Fe 2 O 3 -400 sensor were reduced by 80 and 50 °C, and its response to 100 ppm styrene at 200 °C was significantly enhanced by 3.2-fold and 4.2-fold, respectively, compared to the single Fe 2 O 3 and CuOHF sensors. It is particularly noteworthy that the sensor exhibits excellent detection performance at a 50 ppb styrene concentration, with a response value of 1.2. The lamellar structure of CuOHF serves as a precursor for CuO, thereby increasing the surface area of the sensor in contact with the gas. During the calcination process, the released gases contribute to the formation of a porous structure, which together improves the adsorption capacity and stability of the sensor. Additionally, the heterojunction formed by the calcination of CuO (p-type) and Fe 2 O 3 (n-type) enhances charge transfer and increases gas adsorption capacity, highlighting its potential as a gas sensor. This composite material exhibits good sensitivity and reliability in monitoring hazardous gases like styrene, underscoring the significant value of this study in environmental monitoring and safety control. [ABSTRACT FROM AUTHOR]

In the production of sulfuric acid, sulfur cake—a waste product of the sulfur purification process—is formed in large quantities, which requires its disposal and use. For its use in composite materials, modification is necessary to convert sulfur into a polymer form. The aim of the study was to develop a method for modifying sulfur cake—a waste product of sulfuric acid production—for its disposal. Available reagents—styrene, glycerol, and oleic acid—were tested as modifiers in the work. The sample compositions consisted of 100% sulfur cake (no. 1) and its mixtures: 97% sulfur cake + 3% styrene (no. 2), 97% sulfur cake + 3% glycerol (no. 3), 97% sulfur cake + 3% oleic acid (no. 4), 95% sulfur cake + 3% styrene, 1% glycerol, and 1% oleic acid (no. 5). Modification of sulfur cake was carried out at a temperature of 140 °C for 30 min. The composition, crystal structure, and thermal properties of the samples of the original and modified sulfur cake were studied using X-ray phase and X-ray structural analyses, IR spectroscopy, differential scanning calorimetry, differential thermal and thermogravimetric analysis. The optimal modifier for sulfur cake was a mixture of styrene, glycerol, and oleic acid, which led to the formation of acetal (polyoxymethylene) and an improvement in the structure due to a decrease in the content of impurities. Modification of sulfur cake with styrene resulted in the appearance of a CAr–S bond band at 571 cm−1, and modification with oleic acid a C–S band in the region of 694 cm−1 in the IR spectra. The results of differential scanning calorimetric analysis showed an increase in the heat of fusion of sulfur by 12.45 J/g in the samples of sulfur cake modified with glycerol and styrene. Modification of sulfur cake with oleic acid and a mixture of reagents resulted in the appearance of a third peak with maxima at 244.2 and 264.0 °C, which demonstrated a significant effect of the indicated additives on the thermal behavior of the sulfur cake. Proposed schemes for modifying sulfur cake with styrene and oleic acid are presented. [ABSTRACT FROM AUTHOR]

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Anticorrosion coatings are specialized products designed to protect metal surfaces from costly and dangerous corrosion, acting as barriers against corrosive organisms. Therefore, this study examined the physical and mechanical properties of epoxy resin in the presence of reactive diluents. Reactive diluents were synthesized based on styrene (St) and glycidyl methacrylate (GMA) through the free radical method using benzoyl peroxide (BPO) as a catalyst with various feed ratios of St and GMA. Diluents were characterized by Fourier Transform Infrared (FTIR) spectroscopy and Thermogravimetric Analyzer (TGA). Epoxy resins and hardener were at a ratio of 1:1, 1:0.5, and 1:0.3, respectively. The results showed that reactive diluents [Poly(St-co-GMA)] had an excellent dilution effect on epoxy resin with a decrease in epoxy resin viscosity from 8592 mPa-s to 1656, 680, and 430 mPa-s. Furthermore, the adhesion, tensile, and hardness properties contained 70% GMA and 30% St at a hardener ratio of 1:0.3. The increase in the mechanical properties was attributed to the reaction between modified epoxy resins with hardener.

Solid‐state cross‐polarization magic angle spinning (CPMAS) 13C NMR is employed to examine the morphological factors that contribute to the enhanced hole mobility observed in poly(3‐hexylthiophene) (P3HT) by the introduction of electrically inert poly(styrene) (PSt). Chain mobilities of crystalline and amorphous phases in the P3HT domain are evaluated utilizing T1C (13C spin‐lattice relaxation time in the laboratory frame). The crystallinity of P3HT component is estimated based on the spectral editing method through T1ρH (1H spin‐lattice relaxation time in the rotating frame) filtered CPMAS. Moreover, the miscibility of P3HT crystalline and P3HT amorphous domains is estimated. These results suggest the formation of the rigid amorphous (short‐range ordered amorphous) in a block copolymer (P3HT‐block‐PSt). An increase in the proportion of the crystallite and proximate presence of each crystallite in a blend sample of P3HT with PSt (P3HT‐blend‐PSt) are also indicated. Enhanced mobility is attributed to the larger portion of rigid amorphous domain for P3HT‐block‐PSt, and to higher crystalline content for P3HT‐blend‐PSt. [ABSTRACT FROM AUTHOR]

In order to provide more evidence to understand the termination mechanism in styrene free‐radical polymerization, (1‐bromoethyl) benzene and polystyrene with bromide end group (PSt‐Br) synthesized by atom transfer radical polymerization (ATRP) were used as the model compound and model polymer to study the termination behavior of styrenic radical by atom transfer radical coupling (ATRC), and then the NMR chemical shifts of the head‐to‐head enchainment from coupling termination were obtained. SEC and different NMR measurement methods were used to analyze and characterize the products. It is confirmed that there is no bimolecular disproportionation termination between styrenic free radicals, but only coupling termination to form the head‐to‐head enchainment. The proton and carbon chemical shifts of the head‐to‐head enchainment from coupling termination for (1‐bromoethyl) benzene are 2.7–2.86 ppm and ~47.3 ppm. As for the polystyrene through ATRC from PSt‐Br, the corresponding chemical shifts are 2.61–3.29 ppm and ~46.4 ppm, respectively, they are almost the same as the data in our previous paper (~3.05 ppm, ~46.6 ppm) for polystyrene initiated by BPO, proving that the chain termination in free‐radical polymerization of styrene initiated by BPO occurs through primary termination between chain radical and primary radical rather than bimolecular termination between chain radicals. [ABSTRACT FROM AUTHOR]

Statistical copolymers are commercially important because their properties can be tuned by comonomer selection and composition. Rubbery‐state styrene (S)/n‐butyl acrylate (nBA) copolymers have previously been reported to exhibit facile, autonomous self‐healing over a narrow composition band (47/53 to 53/47 mol%). The need for a narrow composition band is explained by alternating comonomer sequences that accommodate interchain secondary bonding. It is hypothesized that copolymers that achieve interchain secondary bonding without alternating sequences can exhibit facile self‐healing over a broad composition range. 2‐ethylhexyl acrylate (EHA) is identified as yielding sequence‐independent secondary bonding interactions. For these interactions it is tested experimentally by glass transition breadth in rubbery‐state S/EHA copolymers, with S/n‐hexyl acrylate (nHA) and S/nBA copolymers as controls. The n‐alkyl acrylate random copolymers exhibit enhanced glass transition breadths over narrow composition bands that correspond to autonomous self‐healing. In contrast, S/EHA copolymers exhibit much greater glass transition breadths than S/nHA and S/nBA copolymers at all compositions tested as well as self‐healing of damage over a broad composition range with full tensile‐property recovery, often in 3–10 h. Characterization of glass transition breadth may serve as a simple screening tool for identifying copolymers that exhibit broad‐composition‐range, facile, autonomous self‐healing and contribute to polymer resilience and sustainability. [ABSTRACT FROM AUTHOR]

Acrylonitrile butadiene styrene (ABS) is a polymer used for diverse applications such as automobile parts, electronic components, and consumer goods owing to properties like high impact strength, lightweight nature, and chemical resistance. However, the extensive use of ABS polymer generates a significant amount of waste, which has environmental repercussions due to improper disposal, such as landfilling and incineration, which severely threaten the ecosystems around us. Recycling ABS waste reduces the burden on landfills and enables us to reuse waste ABS, which aligns with the principles of sustainability. This article discusses the processes involved in recycling ABS waste, including collection, segregation, recycling technologies, preparation of blends, and applications of recycled ABS. Mechanical and chemical recycling technologies are comprehensively covered as these are the two main recycling technologies employed for ABS waste recycling. This review attempts to cover recent ABS recycling techniques and highlight the significance of ABS plastic recycling for the circular economy. Recycling ABS waste is vital in extending its lifespan, leading to more cost-effective and resource-efficient industrial processes. Embracing the transformative potential of ABS waste unlocks many possibilities and opportunities for innovation while upholding sustainability principles. [ABSTRACT FROM AUTHOR]

The effect of solvents on kinetic parameters of anionic polymerization is complex and a comprehensive theoretical study has been rare. In this work, four solvent polarity descriptors (i.e., polarizability, dipole moment, nucleophilic index, electrophilic index) are correlated with solvent parameters (Ea, A, ΔH‡, and ΔS‡) by multiple linear regression using the Catalan linear free‐energy relationship (LFER) equation for the anionic polymerization of styrene. The results show that Ea, ΔH‡, and ΔS‡ have a low correlation with dipole moment, whereas A is strongly correlated with dipole moment. Given the fact that the larger A the larger effective collision frequency Z, it is hypothesized that in polar solvents, the polymer chains are more extended, enabling more effective collisions between monomers and active anionic species during polymerization. In contrast, in nonpolar solvents, the polymer chains collapse, making it more difficult for the monomer to be inserted into the ion pairs. Subsequently, n‐pentane and tetrahydrofuran are chosen as representatives to confirm this conjecture by molecular simulations. Lastly, Ea, A and kp are predicted for 173 solvents using well‐established descriptive relationships. [ABSTRACT FROM AUTHOR]

Sulfur‐containing amino acids and peptides play critical roles in organisms. Thiol‐ene reactions between the thiol residues of L‐cysteine and the alkenyl fragments in the designed coupling partners serve as primary tools for constructing C─S bonds in the synthesis of unnatural sulfur‐containing amino acid derivatives. These reactions are favored due to the preference for hydrogen transfer from thiol to β‐sulfanyl carbon radical intermediates. In this paper, the study proposes utilizing carbon‐centered radicals stabilized by the capto‐dative effect, generated under photocatalytic conditions from N–aryl glycine derivatives. The aim is to compete with the thiol hydrogen, enabling radical C─C bond formation with β‐sulfanyl carbon radicals. This protocol is robust in the presence of air and water, offers significant potential as a modular and efficient platform for synthesizing sulfur‐containing amino acids and modifying peptides, particularly with abundant disulfides and styrenes. [ABSTRACT FROM AUTHOR]

A stable iron(III) complex with the cross‐bridged cyclam 4,11‐dimethyl‐1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane catalyzes the epoxidation of aromatic alkenes and the fixation of CO2 into cyclic carbonates. Best results were obtained for styrene conversion to styrene carbonate. [ABSTRACT FROM AUTHOR]

Linear and nonlinear rheological properties were examined for unentangled polystyrene (PS), poly（p-tert butyl styrene) （PtBS), and their copolymer samples. All samples exhibited similar linear viscoelastic behavior, which was well predicted by the Rouse model owing to their similar average number of Kuhn segments per chain (about 30) . Under the fast uniaxial elongational flow (with Weissenberg number Wi＞1), the sample exhibited “thickening” followed by “thinning” with increasing the elongational rate. This transition was attributable to the reduction of friction coefficient owing to the chains' coalignment along the elongational direction. Under the condition that the samples have a similar maximum stretch ratio λmax= √nK（≈6), the characteristic Wi for this transition increased with the content of tBS, reflecting that the tert-butyl groups may serve as the solvent to weaken the frictional reduction. [ABSTRACT FROM AUTHOR]

The polymer/nano-inorganics composite microsphere possesses excellent application prospects, but it is difficult to resolve the problem of the aggregation of nano-inorganic particles in polymer and the affinity between inorganics and polymer matrix. In this study, the preparation and characterization of polystyrene (PS)/ethylene vinyl acetate copolymer (EVA)/CaCO3 microspheres fabricated via a novel phase inversion emulsion process are described. By this one-pot method, the PS/EVA/CaCO3 microspheres are obtained by firstly converting styrene monomer containing EVA and nano CaCO3 into droplets dispersed in water with help of emulsifiers and a following polymerization. Because the inorganic nanoparticles are ultrasonically dispersed in liquid monomer mixture before the polymerization, the aggregation of nano-inorganic particles could be prevented to a great extent. The EVA is designed to enhance toughness of polystyrene matrix and increase the affinity between polymer and inorganic particles. The morphological structure of PS/EVA/CaCO3 microspheres is that nano CaCO3 particles are embedded both in the interior and on the surface of the microspheres. The micro-sized PS/EVA/CaCO3 microspheres showed a significantly improved mechanical property and a better heat resistance. This technique also offers the possibility for fabricating many kinds of new and useful polymer/inorganic microspheres with tailored performance by using special monomers and inorganic particles. [ABSTRACT FROM AUTHOR]

The interactions of polyelectrolyte poly (sodium styrene sulfonate or NaPSS) and anionic surfactants, sodium glycodeoxycholate (SGDC) and sodium tetradecyl sulfate (STS), as well as their combination (SGDC + STS) at different mole fraction ratios, were investigated using surface tension analysis. In the SGDC + STS binary mixture, when the amount of NaPSS (0.005–0.03%) increased from α SGDC 0.0 to 1.0, increasing the critical micellization concentration (cmc) of the mixtures. The minimum cmc values were found from 0.833 to 1.480 mmol L−1 in the presence of 0.03% of NaPSS. Clint, Rubingh, Motomura, and Rodenas approaches were used to evaluate the ideal cmc, activity coefficients (fi), interaction parameter (–β), micellar compositions (x), and ideal micellar composition of (xid) of SGDC + STS mixtures. Synergism has been demonstrated by the experimental values of c0m being lower than the ideal values in water. Moreover, by adding NaPSS from 0.005 to 0.03%, the synergism interaction was eliminated and antagonism behavior was developed. The standard Gibb's free energy of micellization ( Δ G m 0) and surface excess (Γ) and surface area per absorbed molecules (Amin) was decreased or increased depending on NaPSS amount in the SGDC + STS mixture with varying a SGDC . [ABSTRACT FROM AUTHOR]

The primary objective of this work is to delve into the intricacies of allylic fluorination reactions through the application of density functional theory (DFT) calculations. These reactions hold significant importance in the realm of synthesizing organofluorine compounds. The specific focus lies on comprehending the interaction mechanisms when styrenes, a class of organic molecules, come in contact with an electrophilic fluorinating reagent known as Selectfluor. Notably, this interaction pathway demonstrates remarkable efficiency in yielding allylic fluoride products. The proposed mechanism for this transformation involves a sequential process. To unveil the microcosmic intricacies governing this reaction between the alkene substrate and Selectfluor, advanced computational methodologies are employed. The paper systematically outlines the computational strategies harnessed to probe the minute details of the reaction mechanism. The outcomes of these computations are subsequently subjected to thorough analysis, encompassing crucial facets such as transition states and energy barriers. This analytical depth enhances the fundamental understanding of the reaction mechanism and sheds light on the underlying factors influencing its feasibility and efficiency. In a broader context, the insights garnered from this study carry significant utility. They provide pivotal guidance for the optimization of reaction conditions, facilitating the fine-tuning of experimental setups. Moreover, the elucidated mechanism serves as a platform for the design of even more efficient and selective allylic fluorination reactions. This paper, by amalgamating theoretical insights with practical synthetic objectives, contributes to the broader advancement of organofluorine compound synthesis and allied fields. [ABSTRACT FROM AUTHOR]

The controlled polymerization of α‐methylene‐γ‐butyrolactone (MBL, a naturally occurring sesquiterpene lactone found in tulips) was performed by nitroxide mediated polymerization (NMP) using the alkoxyamine Dispolreg 007 as the initiating system at 80 °C in 50 wt% DMSO. Features of a reversible‐deactivation radical polymerization (RDRP) were observed with a linear growth of the macro‐radical with conversion and a relatively low dispersity (Ð ≤ 1.45). The P(MBL) homopolymer chain ends were mostly re‐activatable as the chain extensions with styrene (S) and glycidyl methacrylate (GMA) in DMSO were successful. Interestingly, the polymerization of MBL initiated by 2‐methyl‐2‐[N‐tert‐butyl‐N‐(1‐diethoxyphosphoryl‐2,2‐dimethylpropyl)‐aminoxy]‐N‐propionyloxysuccinimide (known as NHS‐BlocBuilder) under various experimental conditions did not produce well‐defined P(MBL), possibly due to an excessively high equilibrium constant. However, the bulk copolymerization of MBL with 10–21 mol% of β‐myrcene (Myr, another renewable monomer from the terpene family) initiated by NHS‐BlocBuilder at 100–110 °C led to all the features of a controlled system. The SG1 chain end fidelity of the resulting P(MBL‐co‐Myr) copolymer was confirmed via 31P NMR and by re‐initiating successfully the copolymer chains with a mixture of GMA and Myr monomers at 120 °C in DMSO. [ABSTRACT FROM AUTHOR]

Thermal runaway of polymerization reactions causes serious accidents. To study the emergency inhibition process of thermal runaway, a styrene thermal polymerization reaction model is established by using computational fluid dynamics (CFD) combined with a thermodynamic model. The DIV critical criterion is used to determine the critical point of the runaway reaction. The inhibitory effect of injection diameter, injection rate, and injection angle of inhibitor (ethylbenzene) on the styrene polymerization reaction is studied comprehensively. The injection mixing trajectory of the inhibitor is visualized by using the Lagrangian particle tracking method. The injection parameters are optimized to suppress thermal runaway by the response surface method. The result shows that a combination of injection parameters with 2 mm injection port diameter, 5 m/s injection rate, and 90° injection angle can improve the suppression effect of thermal runaway for the established model in this paper. This work provides a theoretical basis for preventing thermal runaway for polymerization reactions. [ABSTRACT FROM AUTHOR]

Metal‐Organic Frameworks (MOFs) represent a highly promising class of materials with diverse applications, particularly as catalytic materials. However, their synthesis typically yields powders available only at laboratory‐scale quantities, usually in the gram range or less. This study addresses the challenge of testing limited amounts of MOF catalysts for demanding applications, such as multiphase gas‐liquid‐solid reactions in flow, utilizing a packed‐bed microreactor. Specifically, we investigate the performance of a nanoparticle (NP) ‐immobilized Pd@UiO‐66 MOF catalyst in the selective semi‐hydrogenation of phenylacetylene to styrene, serving as a model reaction. Maintaining the Taylor flow regime upstream of the catalyst bed was crucial to ensure reproducible and reliable experimental results. We conducted 88 experiments at varying liquid flow rates, temperatures ranging from 15 to 45 °C, and relative pressures spanning 0.28 to 8 bar. Styrene selectivity within the range of 80–92.3 % was achieved at phenylacetylene conversions below 20 %. Notably, the optimal condition for styrene selectivity (70 %) was attained at 98.9 % phenylacetylene conversion under the lowest H2 pressure and highest temperature, demonstrating the significance of low H2 concentration for achieving optimal styrene selectivity. Remarkably, the catalyst exhibited stable activity and selectivity over a 20 h testing period, indicating its robust performance under prolonged reaction conditions. This study demonstrates the potential of the proposed catalyst testing system as a rapid and efficient approach for early‐stage exploration studies, particularly when limited quantities of catalyst, typically in the gram scale or less, are available. [ABSTRACT FROM AUTHOR]