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The electrooxidation of catalyst surfaces is across various electrocatalytic reactions, directly impacting their activity, stability and selectivity. Precisely characterizing the electrooxidation on well‐defined surfaces is essential to understanding electrocatalytic reactions comprehensively. Herein, we employed in situ Raman spectroscopy to monitor the electrooxidation process of palladium single crystal. Our findings reveal that the Pd surface's initial electrooxidation process involves forming *OH intermediate and ClO4− ions facilitate the deprotonation process, leading to the formation of PdOx. Subsequently, under deep electrooxidation potential range, the oxygen atoms within PdOx contribute to creating surface‐bound peroxide species, ultimately resulting in oxygen generation. The adsorption strength of *OH and the coverage of ClO4− can be adjusted by the controllable electronic effect, resulting in different oxidation rates. This study offers valuable insights into elucidating the electrooxidation mechanisms underlying a range of electrocatalytic reactions, thereby contributing to the rational design of catalysts. [ABSTRACT FROM AUTHOR]

Electrochemical reactions are very complex and involve a variety of physicochemical processes. Accurate and systematic monitoring of intermediate process changes during the reaction is essential for understanding the mechanism of electrochemical reactions and is the basis for rational design of new electrochemical reactions. On‐line electrochemical analysis based on mass spectrometry (MS) has become an important tool for studying electrochemical reactions. This technique is based on different ionization and sampling means and realizes on‐line analysis of electrochemical reactions by establishing electrochemistry‐MS (EC‐MS) coupling devices. In particular, it provides key evidence for elucidating the reaction mechanism by capturing and identifying the reactive reaction intermediates. This review will categorize various EC‐MS devices and the organic electrochemical reaction systems they study, highlighting the latest research progress in recent years. It will also analyze the properties of various devices and look forward to the future development of EC‐MS. [ABSTRACT FROM AUTHOR]

The paper compares the properties and activity of palladium clusters deposited on aluminum oxides of different phase compositions obtained by different methods. The numbers of palladium atoms available for the adsorption of hydrazine were determined for each catalyst. A correlation was found between the number of such atoms and the rate of hydrogen formation in the decomposition reaction of hydrazine monohydrate. It was concluded that an active palladium catalyst for the decomposition of hydrazine can be obtained using a modified support with a large specific surface area. The specific surface area and its modification determined the surface coverage with the active reagent. Obviously, the study of the role of various properties of supports in the formation of the active phase should be continued. [ABSTRACT FROM AUTHOR]

The direct conversion of syngas into hydrocarbons, catalyzed by a combination of metal oxide and acidic zeolite, has garnered increasing attention in the scientific community. The remarkable hydrocarbon selectivity achieved in the OX‐ZEO process is a key factor in this growing interest. This process involves two distinct steps: CO activation over the oxide and subsequent C−C coupling within the zeolite pores, connected by an unidentified oxygenate intermediate. In this study, we explored three proposed oxygenates as potential intermediates and compared their conversion within the OX‐ZEO process. Using a bifunctional ZnCr2O4/H‐MOR catalyst in a syngas‐fed batch reactor, we found that methanol (MeOH) and dimethyl ether (DME) produced a hydrocarbon distribution similar to syngas conversion. However, the conversion of acetic acid (AcOH) resulted in a notably distinct range of hydrocarbons, including short olefins not detected with other reagents. Our findings suggest that methanol/DME might serve as active intermediates in the OX‐ZEO process over the ZnCr2O4/H‐MOR catalyst. This study provides a deeper insight into the transformation of proposed intermediates, contributing to the identification of the bridging intermediate that links the two catalytic functions. [ABSTRACT FROM AUTHOR]

Aryl diazonium intermediates have emerged as highly versatile intermediates in modern organic synthesis and chemical biology, demonstrating remarkable reactivity under mild reaction conditions. Their significance has extended to DNA‐encoded libraries (DELs), where they serve as valuable alternatives to traditional aryl halide‐based cross‐coupling reactions. Aryl diazonium intermediates as N2‐annulation synthons can efficiently transform into benzotriazinone core on DNA besides C−C coupling. This concept paper illuminates recent advances in this field, emphasizing their applications and potential across various facets of DELs, off‐DNA chemistry, DELs selection, and DNA‐based probes. It is anticipated that these developments will propel the broader utilization of DNA‐conjugated aryl diazonium salt intermediates in DELs, protein labeling, hit discovery, and other interdisciplinary fields. [ABSTRACT FROM AUTHOR]

Regional trade agreements (RTAs) are playing an increasingly crucial role in the current international trade pattern of ebbing globalization, making it increasingly important to comprehensively analyse RTAs' impacts. Trade creation and trade diversion have been hot-button topics on RTAs since Jacob Viner raised, many scholars had conducted extensive research on their economic impacts, but little is known about their environmental impacts. In this paper, we take the China-ASEAN Free Trade Area (CAFTA) as an example, comprehensively consider the tariff, geographic and temporal dimensions of trade to characterize the proxy variables that identify the two effects. Based on data of Chinese enterprises from 2002 to 2007, we empirically tests the impact of the trade effects on energy-related carbon emissions of enterprises from a fixed-effects panel model. Research finds the trade creation effect increases enterprises' $${\rm{C}}{{\rm{O}}_2}$$ C O 2 emissions intensity, whereas the trade diversion effect reduces and is more influential. Further mechanism analyses show coal use status of enterprises, especially coal consumption, utilization intensity, and share in primary energy consumption are important influence channels. Additionally, the scale and factors composition of production and technical efficiency are also important mechanisms. Furthermore, enterprises in different regions and of different ownership types show heterogeneity. [ABSTRACT FROM AUTHOR]

Chemical manufacturing utilizing renewable sources and energy emerges as a promising path towards sustainability and carbon neutrality. The electrocatalytic reactions involving nitrogen oxides (NOx) offered a potential strategy for synthesizing various nitrogenous chemicals. However, it is currently hindered by low selectivity/efficiency and limited reaction pathways, mainly due to the difficulties in controllable generation and utilization of nitrogenous intermediates. In this minireview, focusing on nitrogenous intermediates in NOx‐involved electrocatalytic reactions, we discuss newly developed methodologies for studying and controlling the generation, conversion, and utilizing of nitrogenous intermediates, which enable recent developments in NOx‐involved electrocatalytic reactions that yield various products, including ammonia (NH3), organonitrogen molecules, and nitrogenous compounds exhibiting unconventional oxidation states. Furthermore, we also make an outlook to highlight future directions in the emerging field of NOx‐involved electrocatalytic reactions. [ABSTRACT FROM AUTHOR]

Mechanochemical reactions offer methodological and environmental advantages for chemical synthesis, constantly attracting attention within the scientific community. Besides unmistakable sustainability advantages, the conditions under which mechanochemical reactions occur, namely solventless conditions, sometimes facilitate the isolation of otherwise labile or inaccessible products. Despite these advantages, limited knowledge exists regarding the mechanisms of these reactions and the types of intermediates involved. Nevertheless, in an expanding number of cases, ex situ and in situ monitoring techniques have allowed for the observation, characterization, and isolation of reaction intermediates in mechanochemical transformations. In this Minireview, we present a series of examples in which reactive intermediates have been detected in mechanochemical reactions spanning organic, organometallic, inorganic, and materials chemistry. Many of these intermediates were stabilized by non‐covalent interactions, which played a pivotal role in guiding the chemical transformations. We believe that by uncovering and understanding such instances, the growing mechanochemistry community could find novel opportunities in catalysis and discover new mechanochemical reactions while achieving simplification in chemical reaction design. [ABSTRACT FROM AUTHOR]

Degradation of antibiotic sulphamethoxazole (SMX) was studied by applying modified photo-Fenton reactions (MPF) with the novel choice of using sodium tripolyphosphate (STP) and sodium hexametaphosphate (SHP) complexing agents. STP and SHP have a strong ability as complexing agents because they can sequester and complex with different ions. Process optimisation was performed using Doehlert design at pH = 6. This study presented higher performance for MPF using STP and SHP complexing agents than conventional photo-Fenton and H2O2 + UV process. The best yields were associated with the formation of a smaller number of intermediates with high degradation efficiency and low oxidative stress, environment-friendly and promising processes. [ABSTRACT FROM AUTHOR]

Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant; however, it is a persistent organic pollutant as well as affects the human thyroid hormones and causes cancer. However, the degradation of HBCD has received little attention from researchers. Due to its bioaccumulative and hazardous properties, an appropriate strategy for its remediation is required. In this study, we investigated the biodegradation of HBCD using Shewanella oneidensis MR-1 under optimized conditions. The Box-Behnken design (BBD) was implemented for the optimization of the physical degradation parameters of HBCD. S. oneidensis MR-1 showed the best degradation performance at a temperature of 30 °C, pH 7, and agitation speed of 115 rpm, with an HBCD concentration of 1125 μg/L in mineral salt medium (MSM). The strain tolerated up to 2000 μg/L HBCD. Gas chromatography-mass spectrometry analysis identified three intermediates, including 2-bromo dodecane, 2,7,10-trimethyldodecane, and 4-methyl-1-decene. The results provide an insightful understanding of the biodegradation of HBCD by S. oneidensis MR-1 under optimized conditions and could pave the way for further eco-friendly applications. Key points: • HBCD biodegradation by Shewanella oneidensis • Optimization of HBCD biodegradation by the Box-Behnken analysis • Identification of useful metabolites from HBCD degradation [ABSTRACT FROM AUTHOR]

Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant; however, it is a persistent organic pollutant as well as affects the human thyroid hormones and causes cancer. However, the degradation of HBCD has received little attention from researchers. Due to its bioaccumulative and hazardous properties, an appropriate strategy for its remediation is required. In this study, we investigated the biodegradation of HBCD using Shewanella oneidensis MR-1 under optimized conditions. The Box-Behnken design (BBD) was implemented for the optimization of the physical degradation parameters of HBCD. S. oneidensis MR-1 showed the best degradation performance at a temperature of 30 °C, pH 7, and agitation speed of 115 rpm, with an HBCD concentration of 1125 μg/L in mineral salt medium (MSM). The strain tolerated up to 2000 μg/L HBCD. Gas chromatography-mass spectrometry analysis identified three intermediates, including 2-bromo dodecane, 2,7,10-trimethyldodecane, and 4-methyl-1-decene. The results provide an insightful understanding of the biodegradation of HBCD by S. oneidensis MR-1 under optimized conditions and could pave the way for further eco-friendly applications. Key points: • HBCD biodegradation by Shewanella oneidensis • Optimization of HBCD biodegradation by the Box-Behnken analysis • Identification of useful metabolites from HBCD degradation [ABSTRACT FROM AUTHOR]

Pd-containing catalysts (1% Pd/Al2O3 and 5% Pd/Al2O3) supported on aluminum oxide were studied in the decomposition reaction of hydrazine monohydrate. According to in situ IR-spectroscopic data, hydrazine monohydrate was adsorbed in a linear form on the coordinatively unsaturated sites of the catalyst surface. As the temperature was increased, the adsorbed hydrazine monohydrate lost a water molecule with a change in the geometry of the molecular complex. The adsorption of hydrazine on a support and its diffusion onto palladium clusters is a more advantageous process than direct adsorption on active sites. This circumstance shows that the hydrazine adsorbed on the support can be an intermediate in the process of its decomposition. The test catalysts had a maximum activity at a temperature of about 100°C. At temperatures in a range of 100−120°C, the ratio between hydrogen and nitrogen concentrations in the reaction products was 2, which corresponds to 100% selectivity for hydrogen. The selectivity decreased significantly with the reaction temperature. The high selectivity for hydrogen at low temperatures was explained by the fact that N2H4 was chemisorbed through the formation of hydrogen–metal bonds. The hydrogen–metal bond strength in such a complex is higher than the nitrogen–metal bond strength; hence, the N−H bond breaking barrier is lower than the N−N bond breaking barrier, and this fact led to the breaking of an N–H bond and the preservation of an N–N bond. At elevated temperatures, some of the formed hydrogen atoms recombined, and the other reacted with the surface complexes of hydrazine to form the intermediate NH3−NH3, in which N–N bond breaking led to the appearance of ammonia molecules in the gas phase. [ABSTRACT FROM AUTHOR]

Nonanal, (E)-2-nonenal, (E,E)-2,4-nonadienal, and (E,Z)-2,6-nonadienal were used to study the effect of number and position of the unsaturated bond in aliphatic aldehydes on meat flavorings. Cysteine-Amadori and thiazolidine derivatives were synthesized, identified by UPLC-TOF/MS and NMR, and quantitatively by UPLC-MS/MS. The polyunsaturated aldehydes exhibited higher inhibition than monounsaturated aldehydes, and monounsaturated aldehydes exhibited higher inhibition than saturated aldehydes, mainly manifested by the inhibition of the cysteine-Amadori formation and acceleration of the thiazolidine derivatives formation. The effect of unsaturated bonds position in aliphatic aldehydes on the initial Maillard reaction stage was similar. The cysteine played an important role in catalyzing the reaction of aliphatic aldehydes. A total of 109 volatile compounds derived by heating prepared thiazolidine derivatives degradation were detected by GC-MS. Formation pathways of volatile compounds were proposed by retro-aldol, oxidation, etc. Particularly, a route to form thiazole by the decarboxylation reaction of thiazolidine derivatives which derivatives from formaldehyde reacting with cysteine was proposed.

In this work, an assessment and analysis of the goods flow chain ratio is used to estimate structural change in the trade sector of the EU-27. For the purposes of the quantitative research, official Eurostat secondary data statistics of for the period 2005-2020 are used. The general trend formed throughout the EU to reduce intermediaries is not reproduced in the same way across countries and is sometimes characterized by unpredictable variation. This leads to the conclusion that middlemen are important for the distribution of products in the open market system. Therefore, the downsizing in goods flow chain intermediaries can be linked to the processes of digitization, globalization, the search for sustainable and socially and environmentally responsible business development. [ABSTRACT FROM AUTHOR]

In the present study, sequencing batch moving-bed biofilm reactor (SBMBBR) was developed as a new treatment system and was used to treat wastewater containing cefixime antibiotic (CFX). The effect of initial concentration of CFX (0–122 mg/L) on common parameters including total nitrogen (TN), nitrite (NO2−), nitrate (NO3−), and chemical oxygen demand (COD) was also evaluated. When a small concentration of CFX (45 mg/L) was added to the SBMBBR, good removal efficiencies were obtained for CFX, COD, and TN. Slight changes in mixed liquor-suspended solids (MLSS) and specific oxygen uptake rates (SOUR) in the reactor containing 92 mg/L of CFX showed that microorganisms had high adaptation in the new SBMBBR system. Biological removal of TN, COD, and CFX was decreased from 70.75, 74.81, and 70.9% to 27.38, 23.2, and 34.8%, respectively, when the initial CFX concentration was increased from 45 to 122 mg/L. Also, value of MLSS was decreased at CFX concentrations of 92 and 122 mg L-1, indicating that bacterial growth was inhibited. CFX degradation products were detected by performing the liquid chromatography-mass spectroscopy (LC-MS/MS) and the results obtained from analysis showed that the CFX was first converted into 5-vinyl-3,6-dihydro-2H-1,3-thiazine-4-carboxylic acid and thiazol-2-amine by breaking C-N bond and chain ring. Then, acetic acid and ethyl (methyl) sulphone were formed with further destruction of the chain ring and ring opening. Finally, these by-products can be converted into CO2 and H2O. Accordingly, the results of the present study demonstrated that hybrid process of SBMBBR with minimal reduction in the concentration of MLSS and SOUR can be a good alternative to processes alone in treatment of high concentrations of CFX. [ABSTRACT FROM AUTHOR]

Ni(OH) 2 and H 4 SiO 4 are the two key intermediates for the synthesis of Ni-phyllosilicate, and the purpose of this work is to reveal which one is more efficient. The silica (D) was extracted from distillers' grains, which was used as the sacrificial template for Ni-phyllosilicate. The formation of Ni(OH) 2 and H 4 SiO 4 was enhanced by NaOH and NH 4 F, respectively, and Ni/D-S (assisted by sodium hydroxide) and Ni/D-A (assisted by ammonium fluoride) were obtained. Although the amount of NaOH and NH 4 F and hydrothermal synthesis procedures were identical, there was a significant difference of their Ni contents. The Ni content of Ni/D-S and Ni/D-A was 17.7 wt% and 2.5 wt%, respectively. As a result, Ni/D-S was more active for CO 2 methanation, whose CH 4 yield reached 61.6% at 450 °C, 0.1 MPa, 60 L g−1·h−1, while the maximum CH 4 yield of Ni/D-A was only 16.4% at 500 °C. However, the formation of Ni-phyllosilicate could also be improved after addition of more NH 4 F, and the increased amount of H 4 SiO 4 led to the high Ni content (33.4 wt%) of Ni/D-A-M (M refers to the addition of more ammonium fluoride) and enhanced catalytic performance for CO 2 methanation. It was concluded that Ni(OH) 2 and H 4 SiO 4 were both important for the synthesis of Ni-phyllosilicate, while Ni(OH) 2 was the more efficient one. [Display omitted] • NaOH was used to accelerate the formation of Ni(OH) 2. • NH 4 F was used to accelerate the formation of H 4 SiO 4. • Ni(OH) 2 or H 4 SiO 4 were both important for the synthesis of Ni-phyllosilicate. • Ni(OH) 2 was the more efficient intermediate compared with H 4 SiO 4. [ABSTRACT FROM AUTHOR]

Artificial photosynthesis, which converts carbon dioxide into hydrocarbon fuels, is a promising strategy to overcome both global warming and energy crisis. Herein, the geometric position of Cu and Ga on ultra‐thin CuGaS2/Ga2S3 is oriented via a sulfur defect engineering, and the unprecedented C2H4 yield selectivity is ≈93.87% and yield is ≈335.67 µmol g−1 h−1. A highly delocalized electron distribution intensity induced by S vacancy indicates that Cu and Ga adjacent to S vacancy form Cu–Ga metallic bond, which accelerates the photocatalytic reduction of CO2 to C2H4. The stability of the crucial intermediates (*CHOHCO) is attributed to the upshift of the d‐band center of ultra‐thin CGS/GS. The C–C coupling barrier is intrinsically reduced by the dominant exposed Cu atoms on the 2D ultra‐thin CuGaS2/Ga2S3 in the process of photocatalytic CO2 reduction, which captures *CO molecules effectively. This study proposes a new strategy to design photocatalyst through defect engineering to adjust the selectivity of photocatalytic CO2 reduction. [ABSTRACT FROM AUTHOR]

Artificial photosynthesis, which converts carbon dioxide into hydrocarbon fuels, is a promising strategy to overcome both global warming and energy crisis. Herein, the geometric position of Cu and Ga on ultra‐thin CuGaS2/Ga2S3 is oriented via a sulfur defect engineering, and the unprecedented C2H4 yield selectivity is ≈93.87% and yield is ≈335.67 µmol g−1 h−1. A highly delocalized electron distribution intensity induced by S vacancy indicates that Cu and Ga adjacent to S vacancy form Cu–Ga metallic bond, which accelerates the photocatalytic reduction of CO2 to C2H4. The stability of the crucial intermediates (*CHOHCO) is attributed to the upshift of the d‐band center of ultra‐thin CGS/GS. The C–C coupling barrier is intrinsically reduced by the dominant exposed Cu atoms on the 2D ultra‐thin CuGaS2/Ga2S3 in the process of photocatalytic CO2 reduction, which captures *CO molecules effectively. This study proposes a new strategy to design photocatalyst through defect engineering to adjust the selectivity of photocatalytic CO2 reduction. [ABSTRACT FROM AUTHOR]

The Electro-Fenton process is an electrochemical advanced oxidation method based on electrocatalytic in situ production of hydroxyl radicals (•OH). The decontamination of water polluted by Oxytetracycline (OTC) as being a toxic and persistent organic contaminant was carried out by the Electro-Fenton process (EF). Using a platinum anode and a carbon felt, many experiments have been carried out while studying the effect of several parameters on the efficiency of EF such as the applied current, the concentration of the catalyst, and the initial concentration of OTC. The degradation kinetics were studied and monitored by HPLC during electrolysis using an OTC initial concentration of 0.03 mM, 500 mA as applied current, and 0.1 mM of Fe2+ as optimal parameters. As for the mineralization, the chemical oxygen demand COD gave a reduction rate greater than 97% for 500 mA and 0.2 mM of Fe2+. The identification of some intermediate compounds was carried out by HPLC and LC-MS/MS. [ABSTRACT FROM AUTHOR]

Triclocarban (TCC), an emerging organic contaminant (EOC), has become a severe threat to soil microbial communities and ecological security. Here, the TCC-degrading strain Rhodococcus rhodochrous BX2 and DCA-degrading strain Pseudomonas sp. LY-1 (together referred to as TC1) were immobilized on biochar to remove TCC and its intermediates in TCC-contaminated soil. High-throughput sequencing was used to investigate the microbial community structure in TCC-contaminated soil. Analysis of co-occurrence networks was used to explore the mutual relationships among soil microbiome members. The results showed that the immobilized TC1 significantly increased the removal efficiency of TCC from 84.7 to 92.7% compared to CK (no TC1 cells on biochar) in 10mg/L TCC liquid medium. The utilization of immobilized TC1 also significantly accelerated the removal of TCC from contaminated soil. Microbial community analysis revealed the crucial microorganisms and their functional enzymes participating in TCC degradation in soil. Moreover, the internal labor division patterns and connections of TCC-degrading microbes, with a focus on strains BX2 and LY-1, were unraveled by co-occurrence networks analysis. This work provides a promising strategy to facilitate the bioremediation of TCC in soil, which has potential application value for sustainable biobased economies. [ABSTRACT FROM AUTHOR]

Microbial cell factories provide a green and sustainable opportunity to produce value‐added products from renewable feedstock. However, the leakage of toxic or volatile intermediates decreases the efficiency of microbial cell factories. In this study, membraneless organelles (MLOs) were reconstructed in Saccharomyces cerevisiae by the disordered protein sequence A‐IDPs. A regulation system was designed to spatiotemporally regulate the size and rigidity of MLOs. Manipulating the MLO size of strain ZP03‐FM, the amounts of assimilated methanol and malate were increased by 162 % and 61 %, respectively. Furthermore, manipulating the MLO rigidity in strain ZP04‐RB made acetyl‐coA synthesis from oxidative glycolysis change to non‐oxidative glycolysis; consequently, CO2 release decreased by 35 % and the n‐butanol yield increased by 20 %. This artificial MLO provides a strategy for the co‐localization of enzymes to channel C1 starting materials into value‐added chemicals. [ABSTRACT FROM AUTHOR]

Unsymmetrical dimethylhydrazine（UDMH） wastewater was degraded by microwave enhanced manganese dioxide oxidation, and the degraded liquid was analyzed by solid phase microextraction combined with gas chromatography mass spectrometry（SPME-GC-MS）.The toxicity of intermediates was analyzed by Ecosar software. Fenton oxidation method was used to degrade the UDMH wastewater, and the reaction conditions were optimized: the amount of hydrogen peroxide, the pH of the wastewater before the reaction, and the ratio of ferrous ion to hydrogen peroxide.The optimal reaction conditions were as follows: the amount of hydrogen peroxide was 100 mL/L, and the initial pH of the wastewater was 3,the molar ratio of ferrous ion to hydrogen peroxide is 1∶12.The results showed that Fenton oxidation method could relatively reduce the toxicity of intermediate products. Further reduce the toxicity of wastewater and make the chemical oxygen demand(CODCr) of treated wastewater, this study further treated UDMH wastewater by activated carbon adsorption method after Fenton reaction, the potimal amount of activated carbon is 50 g/L. The result showed that Fenton oxidation activated carbon adsorption combined method was constructed to treat UDMH wastewater, which finally achieved the goal of significantly reducing the biological toxicity of wastewater, and made the CODCr and formaldehyde concentration of wastewater meet the secondary and primary discharge standards of integrated wastewater discharge standard（GB 8978—1996). [ABSTRACT FROM AUTHOR]

• Differences and similarities between ice and aqueous photochemistry were revealed. • Photodegradation kinetics are clearly influenced by the matrix phases, ice and water. • Different photodegradable potential orders between in the two phases were discovered. • Unidentical effects of key constituents in the two phases account for the differences. • Ice photolysis shows fewer products / simpler pathways compared to water photolysis. The photochemical behavior of organic pollutants in ice is poorly studied in comparison to aqueous photochemistry. Here we report a detailed comparison of ice and aqueous photodegradation of two representative OH-PAHs, 2-hydroxyfluorene (2-OHFL) and 9-hydroxyfluorene (9-OHFL), which are newly recognized contaminants in the wider environment including colder regions. Interestingly, their photodegradation kinetics were clearly influenced by whether they reside in ice or water. Under the same simulated solar irradiation (λ > 290 nm), OHFLs photodegraded faster in ice than in equivalent aqueous solutions and this was attributed to the specific concentration effect caused by freezing. Furthermore, the presence of dissolved constituents in ice also influenced photodegradation with 2-OHFL phototransforming the fastest in 'seawater' ice (k = (11.4 ± 1.0) × 10−2 min−1) followed by 'pure-water' ice ((8.7 ± 0.4) × 10−2 min−1) and 'freshwater' ice ((8.0 ± 0.7) × 10−2 min−1). The presence of dissolved constituents (specifically Cl−, NO 3 −, Fe(III) and humic acid) influences the phototransformation kinetics, either enhancing or suppressing phototransformation, but this is based on the quantity of the constituent present in the matrixes, the specific OHFL isomer and the matrix type (e.g., ice or aqueous solution). Careful derivation of key photointermediates was undertaken in both ice and water samples using tandem mass spectrometry. Ice phototransformation exhibited fewer by-products and 'simpler' pathways giving rise to a range of hydroxylated fluorenes and hydroxylated fluorenones in ice. These results are of importance when considering the fate of PAHs and OH-PAHs in cold regions and their persistence in sunlit ice. [Display omitted] [ABSTRACT FROM AUTHOR]

This work shows why it is imperious to use an excess of butyllithium for a directed ortho‐lithiation of a trifluoromethyl sulfoximine. The analysis of mixtures of n‐BuLi and sulfoximine 1 in THF‐d8 using {1H, 6Li, 13C, 15N, 19F} NMR experiments at low temperatures reveal that a first deprotonation occurs that leads to dimeric and tetrameric N‐lithiated sulfoximine (93 : 7). Using an excess n‐BuLi (5 equivalents), the second deprotonation on the ortho‐position of the aromatic occurs. Six species were observed and characterized on the way. It includes three aggregates involving a sulfoximine: i) a [dilithiated sulfoximine/(n‐BuLi)] dimer solvated by four molecules of THF (Agg2, 39 %); ii) a [dilithiated sulfoximine/(n‐BuLi)3] tetramer solvated by six molecules of THF (Agg3, 39 %); iii) a [dilithiated sulfoximine/(n‐BuOLi)3] tetramer solvated by four molecules of THF (Agg1, 22 %). A DFT study afforded optimized solvated structures for all these aggregates, fully consistent with the NMR data. [ABSTRACT FROM AUTHOR]

Due to the structure of acylhydrazones both by the pharmacophore –CO–NH–N= group and by the different substituents present in the molecules of compounds of this class, various pharmacological activities were reported, including antitumor, antimicrobial, antiviral, antiparasitic, anti-inflammatory, immunomodulatory, antiedematous, antiglaucomatous, antidiabetic, antioxidant, and actions on the central nervous system and on the cardiovascular system. This fragment is found in the structure of several drugs used in the therapy of some diseases that are at the top of public health problems, like microbial infections and cardiovascular diseases. Moreover, the acylhydrazone moiety is present in the structure of some compounds with possible applications in the treatment of other different pathologies, such as schizophrenia, Parkinson's disease, Alzheimer's disease, and Huntington's disease. Considering these aspects, we consider that a study of the literature data regarding the structural and biological properties of these compounds is useful. [ABSTRACT FROM AUTHOR]

In this study, we systematically investigated the phase diversity and crystallization pathways of the FABr excessive regions of two ternary systems of FABr-PbBr2-DMF and FABr-PbBr2-DMSO (where FA+—formamidinium cations, DMF—dimethylformamide and DMSO—dimethyl sulfoxide solvents). In these systems, a new FA3PbBr5 phase with a structure containing chains of vertex-connected PbBr6 octahedra is discovered, and its crystal structure is refined. We experimentally assess fundamental information on differences in the mechanisms of crystallization process in FABr-PbBr2-DMF and FABr-PbBr2-DMSO systems and determine possible pathways of crystallization of hybrid perovskites. We show that intermediate solvate phases are not observed in the system with DMF solvent, while a number of crystalline solvates tend to form in the system with DMSO at various amounts of FABr excess. [ABSTRACT FROM AUTHOR]

Bisphenol-A (BPA) is a monomer found in polycarbonate plastics, food cans, and other everyday chemicals; this monomer and its counterparts are widely used, culminating in its presence in water, soil, sediment, and the atmosphere. Furthermore, because of its estrogenic and genotoxic properties, it has been acknowledged as an endocrine disruptor; contamination of BPA in the environment is becoming a growing concern, and ways to effectively mitigate BPA from the environment are currently explored. Hence, the focal point of the review is to collate the bacterial degradation of BPA with the proposed degradation mechanism, explicitly focusing on researches published between 2017 and 2022. BPA breakdown is dependent primarily on bacterial metabolism, although numerous factors influence its fate in the environment. The metabolic routes for BPA breakdown in crucial bacterial strains were postulated, sourced on the transformed metabolite-intermediates perceived through degradation; enzymes and genes associated with the bacterial degradation of BPA have also been included in this review. This review will be momentous to generate a conceptual strategy and stimulate the progress on bacterial mitigation of BPA as a path to a sustainable cleaner environment. [ABSTRACT FROM AUTHOR]

A qualitative approach to the mechanism of occurrence of phase transitions and equilibria of various types in the dispersions of a globular protein in the temperature range, where the structural state of the protein is considered native, is proposed. It is assumed that two types of native conformers N and N* are possible, having stability maxima in different temperature ranges, between which there is a reversible structural transition. It is also assumed that there are two types of protein intermediates I and I*, coexisting with conformers N and N* in the corresponding temperature ranges. The issue of finding possible ways of transition from the thermodynamics of (pre)denaturation transitions of protein to the thermodynamics of condensation phase transitions of the entire dispersion as a whole, with the formation of phase boundaries, is discussed. It is assumed that intermediates I and I* can participate in "liquid–liquid" (L–L) phase transitions with the formation of microphases (clusters) from them in metastable equilibrium with the solution phase consisting of native conformers. The onset of phase transitions depends both on the microenvironment of protein macromolecules in the dispersion and on the properties of protein intermediates. On phase diagrams constructed in the coordinates "temperature–entropy" {T, S} and "chemical potential of the conformers–temperature"{μi, T}, the zones of metastable states N ↔ I and N* ↔ I*, the upper and lower critical solution temperatures, and the zone of supercritical phase transitions are determined. The conditions under which the metastable equilibria N ↔ I and N* ↔ I* are the result of phase transitions of an L–L type are discussed. It is established that the maximum stability of the protein is achieved precisely in the region of critical phase transitions. This region is homogeneous and is characterized as a zone of reduced thermodynamic stability of the protein dispersion as a whole. [ABSTRACT FROM AUTHOR]

The negative environmental impact by the presence of organic contaminants in industrial and domestic effluents requires the development of treatment technologies. In this work, recent advances of three important electrochemical advanced oxidation processes (EAOPs) are presented. The review focuses on recent electro-oxidation (EO), electro-Fenton (EF), and photoassisted electro-Fenton (PA-EF) studies aimed to treat effluents contaminated with dyes, pharmaceuticals, and pesticides. The fundamentals of the three EAOPs are briefly described in the first part of the corresponding section. Later, changes in degradation with increasing current and pH are presented. Then, the use of different electrode materials involved in the electrochemical generation of •OH radicals is discussed showing the superiority of BDD. Approaches such as the way in which iron is added for the EF and PA-EF processes as well as different irradiation sources for PA-EF are also examined and finally, recently reported hybrid systems, as well as novel arrangements and electrochemical reactors, are presented along with information on energy consumption and the intermediates produced during the EO, EF, and PA-EF treatments. From the literature review, the EO process proved to be more efficient for simpler chemical organic molecules, while for more complex molecules the EF and PA-EF processes seem to be more suitable. [ABSTRACT FROM AUTHOR]

Abstract Converting CO2 into high‐value fuels and chemicals by renewable‐electricity‐powered electrochemical CO2 reduction reaction (CRR) is a viable approach toward carbon‐emissions‐neutral processes. Unlike the thermocatalytic hydrogenation of CO2 at the solid‐gas interface, the CRR takes place at the three‐phase gas/solid/liquid interface near the electrode surface in aqueous solution, which leads to major challenges including the limited mass diffusion of CO2 reactant, competitive hydrogen evolution reaction, and poor product selectivity. Here we critically examine the various methods of surface and interface engineering of the electrocatalysts to optimize the microenvironment for CRR, which can address the above issues. The effective modification strategies for the gas transport, electrolyte composition, controlling intermediate states, and catalyst engineering are discussed. The key emphasis is made on the diverse atomic‐precision modifications to increase the local CO2 concentration, lower the energy barriers for CO2 activation, decrease the H2O coverage, and stabilize intermediates to effectively control the catalytic activity and selectivity. The perspectives on the challenges and outlook for the future applications of three‐phase interface engineering for CRR and other gas‐involving electrocatalytic reactions conclude the article.

[Display omitted] • Oxophilic metals alters the geometry and electronic structure of the Ni catalyst. • Regulates intermediate adsorption, boosting methane selectivity. • Co and Mn addition speeds up formic acid synthesis. • Ni-Fe and Ni-Mo show higher methane selectivity than pure Ni. The introduction of oxophilic metals can enhance the selectivity of CO 2 reduction reactions (CO 2 RR) by modulating the adsorption of oxygen-associated active substances on the catalyst surface. Alloying lanthanide atoms into metals has been shown to improve CH 4 selectivity by breaking the linear relationship between the adsorption energies of CO* and H x CO*. In this work, a series of oxophilic transition metals (Fe, Mo, Co, Mn) are introduced to explore the influence on the CO 2 RR. DFT results demonstrate that the doping of oxophilic metals regulates the adsorption strength between the catalyst surface and intermediates, thereby affecting the CH 4 and H 3 COH pathways. Notably, COOH* formation is enhanced on Ni surfaces, leading to increased H 3 COH production. Ni-Fe and Ni-Mo exhibit significant H 3 CO* and CO 2 * binding energies, which reduces the barrier for H 3 CO*. Meanwhile, the bond energy of M−O is higher than that of C-O in H 3 CO*, promoting the generation of CH 4. The addition of Co and Mn makes the desorbed of HCOOH smaller than the hydrogenation energy barrier, which accelerates the synthesis of formic acid. This research provides a new pathway for the development of inexpensive and resource-rich catalysts. [ABSTRACT FROM AUTHOR]

Harnessing the power of the sun, the photocatalytic CO 2 reduction process emerges as a pivotal sustainable solution, utilizing solar energy a premier, clean energy source known for its efficiency and economic viability in the current energy paradigm. This study investigates the impact of metals (Cu, Ag, Au) on enhancing the photocatalytic CO 2 reduction capabilities of TiO 2. In-depth mechanistic analysis conducted using in-situ DRIFTS for identifying the key reaction intermediates, highlights that the catalytic performance, both in terms of activity and product selectivity, is tightly linked to the underlying reaction mechanisms route, optoelectronic properties, and substrate's (CO 2 and H 2 O) affinities to the catalyst surface. Enhanced light absorption and reduced charge recombination (lifetime enhancement from 0.21 ns to ∼1.2 ns) in case of metal incorporated resulted in enhanced overall photocatalytic performance. With Au as dopant, demonstrated highest electron selectivity for H 2 (>97%) compared to Ag and Cu, which showed relatively higher CO 2 reduction electron selectivity (∼20% for Cu). The study reveals the crucial interplay of intermediate stabilization, demonstrating its critical role in governing the reaction pathways i.e., carbene or formaldehyde routes as observed in case of Ag and Cu respectively and thus the specific final products. For enhancing the selectivity of CO, engineering the catalyst surface to favour weak CO adsorption is vital. Observations in the CO-TPD measurements demonstrated that Ag sites were effective in promoting the weaker CO* stabilization thus displayed more selectivity towards CO as compared to Cu. While higher CH 3 OH formation rates in case of Cu, were found to be related to the augmented reactive M=O species stabilization which promotes the oxidation of CH 4 to CH 3 OH. Additionally, in case of Cu, the CH 3 O* intermediates stabilized effectively, which contributed to more Methanol selectivity through favoured formaldehyde route. While in case of Ag, the CH 2 * stabilization suggests more probability of the carbene pathway in comparison to the formaldehyde route (as in case of Cu) for producing the CH 4 as the final hydrogenated C1 product. These insights guide the strategic design of catalysts for controlling the reaction pathways and thus selective C1 product production in photocatalytic CO 2 reduction, offering insights for advanced catalyst design. [Display omitted] • Cu, Ag, Au doping in TiO 2 boosts CO 2 photoreduction capabilities. • Distinct CO 2 reduction pathways induced by metal doping in TiO 2. • Enhanced CO 2 adsorption/activation on doped TiO 2 fosters intermediates. • Intermediate stabilization in TiO 2 dictates product selectivity and hydrogenation. • Active catalytic sites, such as M=O, crucial for CH 3 OH production selectivity. [ABSTRACT FROM AUTHOR]

E-peroxone process is an emerging electrochemical oxidation process, based on ozone and the in-situ cathodic generation of H 2 O 2 , but the stability of cathode is one of the key restraining factors. In this study, we designed a multilayer gas diffusion electrode (GDE) decorated with a commercial hydrophobic membrane for the degradation of pyridine. It was found that a proper control of membrane pore sizes and hot-pressing temperature can significantly promote the GDE stability. Subsequently, key operational parameters of the constructed E-peroxone system were investigated, including the ozone concentration, current density, pH value, electrolyte type and initial concentration of pyridine. The degradation pathways were proposed according to six identified transformation products. The toxicity variation along the degradation progress was evaluated with microbial respiration tests and Toxicity Estimation Software Tool (T.E.S.T.) calculation and an efficient detoxification capacity of E-peroxone was observed. This research provides a theoretical basis and technical support for the development of highly efficient and stable E-peroxone system for the elimination of toxic organic contaminants. [Display omitted] • The multilayer gas diffusion electrode decorated with PP membrane (0.45μm) shows a stable performance generating H 2 O 2. • The reaction parameters of gas diffusion electrode (GDE) on pyridine degradation were investigated. • The degradation pathways were proposed according to the six identified transformation products. • The acute toxicity of the transformation products was evaluated by the microbial respiration and T.E.S.T. calculation. [ABSTRACT FROM AUTHOR]

Negishi cross‐coupling reaction of organozinc compounds as nucleophiles with aryl halides has drawn immense focus for C−C bond formation reactions. In comparison to the well‐established library of Pd complexes, the C−C cross‐coupling of this particular approach is largely primitive with nickel‐complexes. Herein, we describe the syntheses of Ni(II) complexes, [(MeBICAAC)2NiX2] (X=Cl (1), Br (2), and I (3)) by employing the bicyclic (alkyl)(amino)carbene (MeBICAAC) ligand. The reduction of complexes 1–3 using KC8 afforded the two coordinate low valent, Ni(0) complex, [(MeBICAAC)2Ni(0)] (4). Complexes 1–4 have been characterized by spectroscopic techniques and their solid‐state structures were also confirmed by X‐ray crystallography. Furthermore, complexes 1–4 have been applied in a direct and convenient method to catalyze the Negishi cross‐coupling reaction of various aryl halides with 2,6‐difluorophenylzinc bromide or phenylzinc bromide as the coupling partner in the presence of 3 mol % catalyst. Comparatively, among all‐pristine complexes, 1 exhibit high catalytic potential to afford value‐added C−C coupled products without the use of any additive. The UV‐vis studies and HRMS measurements of controlled stochiometric reactions vindicate the involvement of Ni(I)−NI(III) cycle featured with a penta‐coordinated Ni(III)‐aryl species as the key intermediate for 1 whereas Ni(0)/Ni(II) species are potentially involved in the catalytic cycle of 4. [ABSTRACT FROM AUTHOR]

Hollow nanoreactors show great potential in catalysis due to the void‐confinement effect. Yet few studies have investigated the void‐confinement effect of hollow nanoreactors on intermediates. Herein, electrochemical NO reduction to NH3 (ENOR) is used as a probe reaction to study the void‐confinement effect of hollow Cu2O@CoMn2O4 nanoreactors on intermediates. Combined with the results of catalytic activity, H2‐treated in situ diffusion Fourier transform infrared spectroscopy and the finite‐element method simulation confirm that the void‐confinement effect on the intermediate is the main reason for enhanced ENOR efficiency. Additionally, theoretical calculations also show that the Cu sites of Cu2O@CoMn2O4 nanoreactors are favorable for the formation of *NOH intermediates. This work not only gives an insight into void‐confinement effect of hollow nanoreactors on intermediates but also provides a valuable strategy for improving ENOR. [ABSTRACT FROM AUTHOR]

In this paper, removal of malachite green (MG) by two separate processes, namely electrochemical oxidization polymerization and electrochemical reduction precipitation process, was studied. Reaction rate constants (k0), exchange current density i0, the transfer coefficients β and the diffusion coefficient D values were all tested. TR-FTIR (time-resolved Fourier transform infrared spectroscopy), UPLC-MS (ultra-performance liquid chromatography–mass spectrometry), and GC–MS (gas chromatography–mass spectrometer) analyses were applied to investigate the pathway and mechanism of MG degradation. The results show that both electrochemical oxidization polymerization and electrochemical reduction precipitation process were efficient to remove MG. [ABSTRACT FROM AUTHOR]

The electrochemical nitric oxide reduction reaction (NORR), which utilizes water as the sole hydrogen source, has the potential to facilitate ammonia production while concurrently mitigating pollutants. However, limited research has been dedicated to characterizing the structure of interfacial water due to the challenges associated with probing this intricate system, impeding the development of more efficient catalysts for the NORR process. Herein, the Cu 2 O microcrystals with distinct exposed facets, including {100}, {110}, and {111}, are employed for the model catalysts to investigate interfacial water structure and intermediate species in the NORR process. The results from shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) indicated that the NORR performance in 0.1 M Na 2 SO 4 (with heavy water as the solvent) was positively correlated to the proportion of hydrated Na + ion water. In addition, a sequence of intermediates from the NORR, including *NOH, *NH, *NH 2 , and *NH 3 , was detected by employing a combination of multiple in situ characterization methods. Furthermore, in conjunction with experimental results and theoretical calculations, we revealed the potential reaction pathway of NORR. This study offers novel insights into the NORR mechanism and valuable guidance for the design of high-performance catalysts for ammonia production.

Hydrazine and hydrazine monohydrate are commonly used in various fields of science and technology. Conventionally, these reagents are used as reducing agents for heavy metals. Recent interest in hydrazine and hydrazine monohydrate is attributed to the problem of producing impurity-free hydrogen via the catalytic decomposition of these reagents. A large number of various catalyst systems exhibiting fundamentally different activity and selectivity in the formation of hydrogen have been tested in the decomposition of hydrazine and hydrazine monohydrate. The review provides a detailed systematization of these data and analysis of the causes of the differences in the properties of the different catalyst systems. The available data suggest that the main role in determining the process direction is played by the form of activation of hydrazine. In addition, results of studying the hydrazine decomposition mechanism at low and high temperatures are discussed. The test results discussed in the review show that hydrazine and hydrazine monohydrate are fairly promising for both storing hydrogen and producing impurity-free hydrogen for the efficient operation of fuel cells. [ABSTRACT FROM AUTHOR]

[Display omitted] • The aging process of MPs and characteristics of aged MPs. • The aging process significantly changed the physicochemical characteristic of MPs. • The additives and intermediates released from aging process of MPs. • Temperature, pH, salinity and light had certain effects on the release of MPs. • Aged MPs and release of aging led to potential risks on organisms. Microplastics (MPs) have attracted significant concern due to their persistence and adverse effects on organisms. In this review, we summarize the recent literature on the natural and artificial aging process of MPs, and also discuss the associated aging characteristics and mechanisms of MPs. The aged MPs show different morphological and chemical properties from the pristine MPs. Furthermore, to evaluate associated aging effects, the corresponding release of aging process of MPs were systematically evaluated, including the additives and intermediates. Different types of organic pollutants and heavy metals additives are listed. In addition, the release of MPs is affected by environmental factors (i.e., Illumination, salinity, temperature and pH). Aged MPs are more easily absorbed by organisms and have different toxic effects from the pristine MPs. The potential risks of aging MPs and the release of MPs during aging are discussed in detail. This overview provides a direction for further study on the behavior and the toxic effects of MPs in the environment. [ABSTRACT FROM AUTHOR]

Electrochemical reduction of CO(2) to value-added chemicals and fuels is a promising strategy to sustain pressing renewable energy demands and to address climate change issues. Direct observation of reaction intermediates during the CO(2) reduction reaction will contribute to mechanistic understandings and thus promote the design of catalysts with the desired activity, selectivity, and stability. Herein, we combined in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy and ab initio molecular dynamics calculations to investigate the CORR process on Cu single-crystal surfaces in various electrolytes. Competing redox pathways and coexistent intermediates of CO adsorption (*COatop and *CObridge), dimerization (protonated dimer *HOCCOH and its dehydrated *CCO), oxidation (*CO2 - and *CO3 2-), and hydrogenation (*CHO), as well as Cu-Oad/Cu-OHad species at Cu-electrolyte interfaces, were simultaneously identified using in situ spectroscopy and further confirmed with isotope-labeling experiments. With AIMD simulations, we report accurate vibrational frequency assignments of these intermediates based on the calculated vibrational density of states and reveal the corresponding species in the electrochemical CO redox landscape on Cu surfaces. Our findings provide direct insights into key intermediates during the CO(2)RR and offer a full-spectroscopic tool (40-4,000 cm-1) for future mechanistic studies. [ABSTRACT FROM AUTHOR]

Aims/hypothesis: Plant-based diets, especially when rich in healthy plant foods, have been associated with a lower risk of type 2 diabetes. However, whether plasma metabolite profiles related to plant-based diets reflect this association was unknown. The aim of this study was to identify the plasma metabolite profiles related to plant-based diets, and to evaluate the associations between the identified metabolite profiles and the risk of type 2 diabetes. Methods: Within three prospective cohorts (Nurses' Health Study, Nurses' Health Study II and Health Professionals Follow-up Study), we measured plasma metabolites from 10,684 participants using high-throughput LC MS. Adherence to plant-based diets was assessed by three indices derived from the food frequency questionnaire: an overall Plant-based Diet Index (PDI), a Healthy Plant-based Diet Index (hPDI), and an Unhealthy Plant-based Diet Index (uPDI). Multi-metabolite profiles related to plant-based diet were identified using elastic net regression with a training/testing approach. The prospective associations between metabolite profiles and incident type 2 diabetes were evaluated using multivariable Cox proportional hazards regression. Metabolites potentially mediating the association between plant-based diets and type 2 diabetes risk were further identified. Results: We identified multi-metabolite profiles comprising 55 metabolites for PDI, 93 metabolites for hPDI and 75 metabolites for uPDI. Metabolite profile scores based on the identified metabolite profiles were correlated with the corresponding diet index (Pearson r = 0.33–0.35 for PDI, 0.41–0.45 for hPDI, and 0.37–0.38 for uPDI, all p<0.001). Metabolite profile scores of PDI (HR per 1 SD higher = 0.81 [95% CI 0.75, 0.88]) and hPDI (HR per 1 SD higher = 0.77 [95% CI 0.71, 0.84]) showed an inverse association with incident type 2 diabetes, whereas the metabolite profile score for uPDI was not associated with the risk. Mutual adjustment for metabolites selected in the metabolite profiles, including trigonelline, hippurate, isoleucine and a subset of triacylglycerols, attenuated the associations of diet indices PDI and hPDI with lower type 2 diabetes risk. The explainable proportion of PDI/hPDI-related diabetes risk by these metabolites ranged between 8.5% and 37.2% (all p<0.05). Conclusions/interpretation: Plasma metabolite profiles related to plant-based diets, especially a healthy plant-based diet, were associated with a lower risk of type 2 diabetes among a generally healthy population. Our findings support the beneficial role of healthy plant-based diets in diabetes prevention and provide new insights for future investigation. [ABSTRACT FROM AUTHOR]

The chalcogenide composite FeIn2S4 was prepared by hydrothermal route and, for the first time, investigated as a heterogeneous catalyst in the photo-Fenton treatment for Ponceau 4R dye (C20H11N2Na3O10S3) under visible irradiation. The composite was characterized by X-ray diffraction (DRX), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectrometry (EDS) and elemental mapping, band gap energy and X-ray photoelectron spectroscopy (XPS). The optimal experimental conditions were investigated and determined to be pH 3.0, 0.5 g L−1 of catalyst and 2.5 mmol L−1 of H2O2. A decolorization efficiency of 93.3% was achieved in 60 min of reaction and a TOC removal of 92.3% was reached in 180 min. The stability and recycle capacity of FeIn2S4 indicated that the catalyst can be used more than four times without considerable loss of efficiency. Free radicals investigation revealed that •OH and O2•− radicals were the major oxygen reactive species involved on Ponceau 4R degradation. The lower-mass intermediates from Ponceau 4R degradation were identified, and a mechanism for the photo-Fenton treatment was suggested. Therefore, the composite showed a performance that makes it a promising catalyst for removing emerging contaminants in water. [ABSTRACT FROM AUTHOR]

[Display omitted] • Oxidation mechanisms of turpentine oil are explored using the ReaxFF method. • Analysis of the initial decomposition of turpentine oil's components is conducted. • The formation of epoxy structure C-O-C is obtained in the oxidation of turpentine. • The evolution of intermediates under different oxygen concentrations is examined. To gain insights into the combustion mechanism of turpentine oil, the oxidation reaction of turpentine was investigated using ReaxFF reactive molecular dynamics simulations. The results revealed that the decomposition of camphene, a component of turpentine, was significantly slow due to the presence of bridged rings in the molecular structure. The oxidation of camphene requires the destruction of six-membered and five-membered rings in sequence. Different oxygen concentrations influenced the initial reactions of turpentine oil. In oxygen-rich conditions, O radicals primarily attacked the C C bonds of turpentine, resulting in the formation of an epoxy structure, C-O-C. In oxygen-poor environments, the thermal decomposition of turpentine is primarily associated with reactions involving C–C bonds. In oxidation, free radicals such as OH, HO 2 , and H played a significant role in accelerating the reaction rate, with OH exerting the most substantial influence on the reaction involving turpentine oil. The oxidation products of turpentine (C 10 H 16 O 2 and C 10 H 15 O) were unstable at high temperatures and decomposed to yield the earliest intermediate, acetone (C 3 H 6 O), with the dehydrogenation reaction mainly assisted by OH radicals. The formation and consumption of intermediate ketene were closely linked to C2 compounds. Furthermore, almost all formaldehyde was consumed by the free radical OH. The activation energy value of α-pinene is 80.68 kJ/mol, aligns well with the experimentally estimated activation energy (81.3 ± 3.1 kJ/mol). This study elucidates the intricate effects of environmental variations on the oxidation process of turpentine oil, providing crucial atomic-level insights for designing environmentally friendly fuels. [ABSTRACT FROM AUTHOR]

The effect of acrolein on the formation of the 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) was investigated in a chemical model. Acrolein was found to increase PhIP formation at each tested addition level. 0–0.2 mmol of acrolein increased PhIP formation dose-dependently, while high levels of acrolein (>0.2 mmol) did not further increase PhIP formation. Mechanistic study showed that acrolein addition decreased the residue of phenylalanine and creatinine, but increased the content of some key intermediates. Further analysis indicated that acrolein can react with phenylalanine, creatinine, and PhIP to form adducts. These results suggested that acrolein was able to contribute to PhIP formation as a consequence of its comprehensive ability to facilitate Strecker degradation of phenylalanine and react with phenylalanine, creatinine, and PhIP. In addition, oxidation of the tilapia fish increased the PhIP formation in the roasted fish patties, further supporting the potential contribution role of lipid oxidation products to the formation of PhIP.

Photocatalysis was an attractive strategy that had potential to tackle the Microcystin-LR (MC-LR) contamination of aquatic ecosystems. Herein, magnetic photocatalyst Fe 3 O 4 /Bi 2 WO 6 /Reduced graphene oxide composites (Bi 2 WO 6 /Fe 3 O 4 /RGO) were employed to degrade MC-LR. The removal efficiency and kinetic constant of the optimized Bi 2 WO 6 /Fe 3 O 4 /RGO (Bi 2 WO 6 /Fe 3 O 4 -40%/RGO) was 1.8 and 2.3 times stronger than the pure Bi 2 WO 6. The improved activity of Bi 2 WO 6 /Fe 3 O 4 -40%/RGO was corresponded to the expanded visible light adsorption ability and reduction of photogenerated carrier recombination efficiency through the integration of Bi 2 WO 6 and Fe 3 O 4 -40%/RGO. The MC-LR removal efficiency exhibited a positive tendency to the initial density of algae cells, fulvic acid, and the concentration of MC-LR decreased. The existed anions (Cl−, CO 3 −2, NO 3 −, H 2 PO 4 −) reduced MC-LR removal efficiency of Bi 2 WO 6 /Fe 3 O 4 -40%/RGO. The Bi 2 WO 6 /Fe 3 O 4 -40%/RGO could degrade 79.3% of MC-LR at pH = 7 after 180 min reaction process. The trapping experiments and ESR tests confirmed that the h+, ∙OH, and ∙O 2 − played a significant role in MC-LR degradation. The LC-MS/MS result revealed the intermediates and possible degradation pathways. • The Bi 2 WO 6 /Fe 3 O 4 -40%/RGO could be easily separated from the water body by the magnet. • The MC-LR removal rate of Bi 2 WO 6 /Fe 3 O 4 -40%/RGO is 1.8-fold higher than Bi 2 WO 6. • The fulvic acid and algae cells have the significant influence on the MC-LR removal rate. • The h+ is mainly involved in the degradation of MC-LR, followed by ∙OH and ∙O 2 − • The m/z 823.4298 and 807.4371 intermediates are generated and subsequently degraded. [ABSTRACT FROM AUTHOR]

High-quality perovskite polycrystalline thin films are generally achieved through antisolvent-assisted crystallization, a crucial process that facilitates desolvation. However, antisolvent method is limited by issues of toxicity and fabrication complexity. Here, we introduce a "binary volatile additive" strategy using methylammonium chloride (MACl) and trifluoroacetamide (TFAA) in dimethylformamide/N-methyl-2-pyrrolidone co-solvent system, enabling end-to-end management of antisolvent-free crystallization process. Combining in-situ characterizations and DFT calculations, we prove that TFAA adjusts coordination with perovskite intermediates, facilitating solvent removal and promoting the formation of nuclei, while MACl reduces the formation energy of α-phase formamidinium-based perovskite. Moreover, TFAA not only releases the residual strain caused by MACl, but also in combination with MACl, synergistically widens crystallization window and regulates ripening process, allowing for precise fabrication of homogeneous perovskite films with suppressed defects. By employing the "binary volatile additive" approach, we achieve perovskite solar cells with a power conversion efficiency up to 22.4% and elongated storage life (93% PCE retention over 1000 hours). Our study offers a simple and sustainable approach to produce high-quality perovskite films without the acquisition of antisolvent, streamlining the fabrication process. [Display omitted] • Introduction of 'binary volatile additives' widens crystallization window, promotes high-quality perovskite films, increasing PCE to 22.4%. • DFT calculations and characterizations reveal intermediate interactions, connecting crystallization window expansion with molecular dynamics. • Binary additives offer synergistic benefits and offset weaknesses, enhancing stability—maintaining >90% of initial PCE after 1000 hours at 35±5% RH, unencapsulated. [ABSTRACT FROM AUTHOR]