Search Results (742)

The regio- and stereoselective adjacent bifunctionalization of olefins with amine and halogen groups can be effectively accomplished through catalytic haloamination methods. Stereoselective haloamination has emerged as a pivotal methodology for the introduction of halogen functional groups into chiral amines, demonstrating substantial applications in medicinal chemistry and organic synthesis. Since 1999, significant advancements have been achieved in this field, driven by innovations in catalytic systems and methodologies. The stereoselective haloamination of both functionalized and nonfunctionalized alkenes employing chiral catalysts has emerged as a prominent area of research. This review provides a comprehensive overview of the research progress in stereoselective haloamination reactions from 1999 to 2023. It examines the innovations in catalyst design that have facilitated more efficient and selective transformations. The review also analyzes the optimization of reaction conditions, which has been crucial in improving the overall performance and applicability of these reactions. Furthermore, it explores the diverse range of haloamination reactions that have been developed, emphasizing their potential for the synthesis of complex and valuable chemical structures. Additionally, this review offers insightful perspectives on future research directions in stereoselective haloamination reactions. Full article

This study investigates the emission characteristics and environmental impacts of pollutants from bagasse-fired biomass boilers through the integrated field monitoring of two sugarcane processing plants in Guangxi, China. Comprehensive analyses of flue gas components, including PM_2.5, NOx, CO, heavy metals, VOCs, HCl, and HF, revealed distinct physicochemical and emission profiles. Bagasse exhibited lower C, H, and S content but higher moisture (47~53%) and O (24~30%) levels compared to coal, reducing the calorific values (8.93~11.89 MJ/kg). Particulate matter removal efficiency exceeded 98% (water film dust collector) and 95% (bag filter), while NOx removal varied (10~56%) due to water solubility differences. Heavy metals (Cu, Cr, Ni, Pb) in fuel migrated to fly ash and flue gas, with Hg and Mn showing notable volatility. VOC speciation identified oxygenated compounds (OVOCs, 87%) as dominant in small boilers, while aromatics (60%) and alkenes (34%) prevailed in larger systems. Ozone formation potential (OFP: 3.34~4.39 mg/m³) and secondary organic aerosol formation potential (SOAFP: 0.33~1.9 mg/m³) highlighted aromatic hydrocarbons (e.g., benzene, xylene) as critical contributors to secondary pollution. Despite compliance with current emission standards (e.g., PM < 20 mg/m³), elevated CO (>1000 mg/m³) in large boilers indicated incomplete combustion. This work underscores the necessity of tailored control strategies for OVOCs, aromatics, and heavy metals, advocating for stricter fuel quality and clear emission standards to align biomass energy utilization with environmental sustainability goals. Full article

Hydroxymethyl 1,3-diol motifs are common structural motifs in natural products, particularly in polypropionates with important therapeutic potential. However, general and complementary methods for their regio- and diastereoselective synthesis remain limited. In this study, we expanded a second-generation epoxide-based methodology involving the regioselective cleavage of TIPS-monoprotected cis- and trans-2,3-epoxy alcohols using alkenyl Grignard reagents. Regioselective ring opening of cis-epoxides provided anti-1,3-diols, while trans-epoxides afforded the corresponding syn-1,3-diols. The use of cis-propenylmagnesium bromide and vinyl Grignard reagents enabled direct access to cis- and terminal homoallylic 1,3-diols, respectively, with moderate to good yields (46–88%) and excellent regioselectivities (95:5). In contrast, reactions with trans-propenyl Grignard reagent led to partial alkene isomerization, limiting their synthetic utility. To address this, a complementary two-step approach employing propynyl alanate addition followed by sodium/ammonia reduction was incorporated, providing access to trans-homoallylic 1,3-diols with high diastereoselectivity. All 1,3-diols were characterized by NMR spectroscopy, confirming regioselective epoxide opening. These combined strategies offer a practical and modular platform for the synthesis of syn- and anti-hydroxymethylated 1,3-diols and their application to the construction of polypropionate-type fragments, supporting future efforts in the total synthesis of polyketide natural products. Full article

Kujingcha (KJC) is a widely consumed substitute tea due to its unique flavor quality and health benefits. However, the biochemical basis for the formation of KJC’s unique flavor quality and health benefits remain unclear. In this study, using Camellia sinensis green tea and its processed fresh leaves as a control, we systematically analyzed the non-volatile and volatile components in KJC and its processed fresh leaves. The results indicate that high levels of flavonoids and water-soluble sugars, and low levels of amino acids and water-soluble proteins, are important biochemical foundations for the formation of taste quality in KJC. High aldehyde, alkene and heterocyclics contents contribute significantly to the aroma of KJC, among which heterocyclics are the key components for the formation of KJC’s rich pan-fried bean-like aroma. Flavonoids such as neohesperidin, hyperoside, rutin, astilbin and morin are important components for the formation of KJC’s health benefits. Full article

This study aims to investigate the influence of various metal compounds (ZnO, ZnCl₂, Zn(OH)₂, MgO, MgCl₂, and Mg(OH)₂) on the structural and electrochemical properties of chars derived from the pyrolysis of polyvinyl chloride (PVC). Raw PVC samples mixed with different metal compounds were firstly pyrolyzed at 500 °C in a fixed-bed reactor. The produced chars were further pyrolyzed at 800 °C. The objective was to evaluate the impact of these metal compounds on the char structure through comparative analysis. The pyrolytic chars were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, and Brunauer–Emmett–Teller (BET) analysis. Zinc-based additives notably increased carbon yield to 32–34 wt.%, attributed to ZnCl₂-induced cross-linking. Specifically, ZnO facilitated porous architectures and aromatic structures with six or more rings. Mg-based compounds induce the formation of a highly stacked carbon structure primarily composed of crosslinked cyclic alkenes, rather than large polyaromatic domains. Upon further thermal treatment, these aliphatic-rich stacked structures can be progressively transformed into aromatic frameworks through dehydrogenation reactions at elevated temperatures. A high-surface-area porous carbon material (PVC/ZnO-800, SSA = 609.382 m² g⁻¹) was synthesized, demonstrating a specific capacitance of 306 F g⁻¹ at 1 A g⁻¹ current density. Full article

We present a protocol for the facile conversion of linear alkenyl N-alkoxy carbamates into cyclic bromo carbonates. The reaction is operationally simple, uses widely available, inexpensive reagents, and requires no rigorous exclusion of air or moisture. A range of functional groups is compatible, and the reaction diastereoselectivities vary from good to excellent. The reactions are scalable, and the resultant carbonates can be further transformed. Full article

To characterize the temporal variation in and source contribution of volatile organic compounds (VOCs) in a polymer industrial park, a two-year offline monitoring campaign (2018–2019) at Shangyu Industrial Park in the Yangtze River Delta was conducted. The study quantified the VOCs composition, seasonal variation, and ozone formation potential (OFP), with source apportionment performed using the Positive Matrix Factorization (PMF) model. During the observation period, the average concentration of total VOCs in 2019 was 286.1 ppb, showing a 22.6% reduction compared to that in 2018. Seasonal analysis revealed decreases in the total VOCs concentration by 41.8%, 38.4%, and 6.1% during spring, summer and winter, respectively, while an increase of 13.8% was observed in autumn, primarily attributed to industrial restructuring in the second half of 2019. Notable reductions were observed in specific VOCs components: oxygen-containing volatile organic compounds (OVOCs), alkane, halogenated hydrocarbon, alkene, and alkyne decreased by 34.5%, 27.9%, 26.3%, 24.6%, and 20.4%, respectively. The average OFP in 2019 was 2402.0 μg/m³, representing a 1.8% reduction from 2018. Contributions to total OFP from alkane, OVOCs, alkyne, and alkene decreased by 32.9%, 26.0%, 20.7%, and 15.0%, respectively, while halogenated hydrocarbons and aromatic hydrocarbons increased by 50.1% and 7.0%. PMF analysis identified four major VOCs sources: industrial production (44.9%), biomass combustion (17.8%), vehicle exhaust (11.0%), and solvent usage (26.3%). From 2018 to 2019, contributions from vehicle exhaust and solvent usage increased by 4.8% and 5.9%, respectively, while industrial production and biomass combustion decreased by 10.5% and 0.3%. Full article

With the implementation of China’s low-sulfur fuel policy, the characteristics of volatile organic compounds (VOCs) emitted from ship exhausts have changed significantly, and the influence of these emissions on the local atmosphere of port cities needs to be evaluated. In this study, the characteristics of localized source profiles of ship-emitted VOCs with respect to different ship types, fuel types, and engine operating conditions were analyzed in Guangzhou Port. Oxygenated VOCs (OVOCs) dominated in ferry (91.1%), cargo ship (87.0%), and tugboat (54.4% ± 7.9%) emissions (diesel fuel), while alkanes (56.3% ± 1.6%) and alkenes (36.0% ± 0.9%) were major species in multi-purpose ship (LNG fuel) emissions. These results suggest the dominance of OVOCs in the exhaust emissions of diesel-type ships and the prominent difference in ship-emitted VOCs between diesel and LNG fuel ships, which also influenced the emission characteristics of VOCs from main and auxiliary engines. Based on the measured source profiles, ship emissions contributed 18.2% ± 0.8% (summer), 8.7% ± 1.9% (winter), 6.0% ± 1.1% (spring), and 5.6% ± 1.7% (autumn) to VOCs in the port area, and 7.8% ± 1.5% in July and 5.0% ± 0.5% in September in the urban area. An air mass trajectory analysis revealed that the south wind transported the ship exhaust emissions to the port area and inland urban area, which explained the higher contributions of ship emissions in summer and more ship emissions received in the port area than in the urban area. Therefore, estimating the influence of ship emissions on ambient air quality in port cities requires integrating local ship source profiles, locations, and meteorological conditions. This study provides insights into the ship-emitted VOC characteristics given China’s low-sulfur fuel policy and their differential contributions to urban atmospheric VOCs. Full article

This study presents a theoretical investigation of the electronic properties of mono- and pentasubstituted cyclopentadiene analogs and variously substituted conjugated nitroalkenes bearing electron-donating and electron-withdrawing groups. Conceptual Density Functional Theory (CDFT) and Electron Localization Function (ELF) analyses were employed to characterize the global and local reactivity indices of the reactants. The obtained data provided insights into the nucleophilic and electrophilic nature of the investigated systems, allowing for the prediction of their reactivity patterns in Diels–Alder reactions. A reactivity model for conjugated alkenes toward cyclopentadienes was developed based on correlation analysis using Hammett substituent constants. This approach enabled the prediction of reaction polarity in (4+2) cycloaddition processes, providing insight into how the electronic effects of substituents influence the reaction course. These findings contribute to a deeper understanding of structure–reactivity relationships in Diels–Alder processes. Full article

The phytochemical profile and antioxidant activities of Prunus africana bark, Leea indica and Paullinia pinnata leaves from Cameroon were investigated in this study. The yields of pure methanolic extraction were 11.9%, 11.1% and 10.8% in P. africana bark, L. indica and P. pinnata leaves, respectively. The total phenolic content was 189.0 ± 16.93, 163.6 ± 14.73 and 114.6 ± 10.38 mg GAE/g and total flavonoid content was 43.25 ± 6.43, 28.31 ± 4.44, and 19.75 ± 4.03 mg RU/g in P. africana bark, L. indica and P. pinnata leaves, respectively. The antioxidant activities of the plants were evaluated by DPPH, ABTS and FRAP assays. The IC₅₀ evaluated in P. africana bark, L. indica and P. pinnata leaves was 109.5 ± 13.2, 132.1 ± 18.7 and 156.1 ± 21.9 µg/mL for DPPH and 98.1 ± 4.8, 101.3 ± 12.1 and 133.9 ± 16.0 µg /mL for ABTS assay. The FRAP value was 61.1 ± 1.5, 50.5 ± 1.5 and 43.4 ± 2.1 µMFe²⁺/g in the same sequence. The functional groups for the corresponding phytochemicals, including alkane, alkene, aliphatic ether, ester, amine, α, β-unsaturated ester, alcohol, phenol, carboxylic acid, and aliphatic ketone, were identified through fourier-transform infrared analysis. The identified and quantified phenolic acids in this study were methyl-4-hydroxybenzoic, caffeic, protocatechuic and p-coumaric acid, identified using high-performance liquid chromatography. Full article

Vespa velutina is an invasive species introduced by accident into Europe. Since its entry, it has spread rapidly and become a threat to biodiversity and beekeeping. Chemical communication between hornets is one of the main reasons for the proper functioning of hornet colonies. These signals can be from endogenous and/or exogenous chemical compounds. In this work, the volatile organic compound profile of Vespa velutina larvae was obtained by GC-MS previous solvent extraction procedures. A total of 99 volatile compounds were identified in the larvae volatile profile, of which 33 were common to adult hornets, suggesting a possible endogenous origin and a functional role in physiological processes and chemical communication within the colony. A total of 42 compounds were detected exclusively in the larvae, belonging to aldehydes, alcohols, alkanes, alkenes, amines, ketones, piperidines, pyrrolidines, furanones, fatty acid esters, ethers, and pyridines chemical families. The detection of these compounds in larval stages, before environmental exposure, supports the hypothesis of their endogenous origin. The findings of this work can contribute to widening the knowledge of the biology and chemical composition of V. velutina and could help identify potential semiochemicals useful for the design of more selective and sustainable strategies for its control. Full article

This review focuses on photocyclization reactions involving alkenes and arenes. Photochemistry opens up synthetic opportunities difficult for thermal methods, using light as a versatile tool to convert stable ground-state molecules into their reactive excited counterparts. This difference can be particularly striking for aromatic molecules, which, according to Baird’s rule, transform from highly stable entities into their antiaromatic “evil twins”. We highlight classical reactions, such as the photocyclization of stilbenes, to show how alkenes and aromatic rings can undergo intramolecular cyclizations to form complex structures. When possible, we explain how antiaromaticity develops in excited states and how this can expand synthetic possibilities. The review also examines how factors such as oxidants, substituents, and reaction conditions influence product selectivity, providing useful insights for improving reaction outcomes and demonstrating how photochemical methods can drive the development of new synthetic strategies. Full article

In recent years, carbon-centered radical-initiated olefin transformation reactions, including alkene Heck-type alkylation, alkene hydroalkylation, and alkene difunctionalization reactions, have attracted increasing attention and been extensively developed. This review summarizes the recent advances in carbon-centered radical-initiated olefin transformation chemistry, such as radical-mediated alkene Heck-type alkylation, alkene hydroalkylation, and radical-mediated alkene difunctionalization reactions. This area of research is divided into several sections based on the types of olefin transformation reactions and the divergent formation processes of the carbon-centered radicals. Drawing extensively on our group’s investigations, we show that efficient olefin transformation strategies have gained significant traction in synthetic chemistry due to their ability to rapidly install functional groups and enhance molecular complexity. Full article

Exercise is one of the main challenges to the body’s homeostasis since it needs an immediate, substantial rise in ATP re-synthesis, which leads to the prevention of response capacity and performance of players. Therefore, it is vital to monitor sweat metabolites in soccer players during vigorous exercise to comprehend their functional variations. This flagged the requirement metabonomic approaches for the determination of the distinct metabolic pathways and signature metabolites that are involved in soccer players pre- and post-exercise. In this study, metabolomics and chemometrics approaches were integrated to accelerate and unravel signature-altered metabolites involved pre- and post-exercise. Metabolites profiling revealed a total of 57 signatures and the identified signature altered metabolites belonging to carboxylic acids, ketone, alcohols, aldehydes, aromatics, alkenes, hexoses, hydroxy fatty acids, tetracyclic N-heterocycles, aldopentose, benzenes, alkanes, phenols, and heterocyclic. Niacin is the most downregulated and abundant pre-induced exercise, which can employ its effects through energy metabolism as a precursor for nicotinamide adenine dinucleotide (NAD) and nicotinamide adenine dinucleotide phosphate (NADP). Significant alterations were also specifically observed in the Alanine, aspartate and glutamate, Valine, leucine and isoleucine, Pantothenate and CoA biosynthesis, and Galactose metabolisms following exercise. Full article

Sustainable hydrocarbons are one of the main methods of decreasing the use of fossil fuels and derivatives, contributing to the mitigation of environmental impacts and greenhouse gas emissions. Circular economic concepts focus on reusing waste by converting it into new products, which are then input again into industrial production lines, thus decreasing the necessity of fossils. Polypropylene-based plastic waste can be depolymerized into smaller chemical chains, producing a liquid phase rich in hydrocarbons. In the same way, triacylglycerol-based waste biomasses can also be converted into renewable hydrocarbons. Our research studied the co-processing of polypropylene (PP) and cottonseed oil dreg (BASOs) waste from the biodiesel industry using a micropyrolysis system at 550 °C, previously validated to predict the scale-up of the process. PP showed the production of alkanes and alkenes, while BASOs also produced carboxylic acids in addition to the PP products. The main impacts were observed in the conversion yields, reaching the highest values of pyrolytic liquid (64%), gas (14%), and solid product (13%) compared to the co-processing mixture of BASO:PP (1:2). Also, in this mixture, the production of carboxylic acids decreased to the lowest value (~10%), improving the conversion to sustainable hydrocarbons. Full article