Oxidation Mechanism and Toxicity Evolution of Linalool, a Typical Indoor Volatile Chemical Product.

Linalool, a high-reactivity volatile chemical product (VCP) commonly found in cleaning products and disinfectants, is increasingly recognized as an emerging contaminant, especially in indoor air. Understanding the gas-phase oxidation mechanism of linalool is crucial for assessing its impact on atmospheric chemistry and human health. Using quantum chemical calculations and computational toxicology simulations, we investigated the atmospheric transformation and toxicity evolution of linalool under low and high NO/HO2· levels, representing indoor and outdoor environments. Our findings reveal that linalool can undergo the novel mechanisms involving concerted peroxy (RO2·) and alkoxy radical (RO·) modulated autoxidation, particularly emphasizing the importance of cyclization reactions indoors. This expands the widely known RO2·-dominated H-shift-driven autoxidation and proposes a generalized autoxidation mechanism that leads to the formation of low-volatility secondary organic aerosol (SOA) precursors. Toxicological analysis shows that over half of transformation products (TPs) exhibited higher carcinogenicity and respiratory toxicity compared to linalool. We also propose time-dependent toxic effects of TPs to assess their long-term toxicity. Our results indicate that the strong indoor emission coupled with slow consumption rates lead to significant health risks under an indoor environment. The results highlight complex indoor air chemistry and health concerns regarding persistent toxic products during indoor cleaning, which involves the use of linalool or other VCPs.

Ultrathin 2D/2D ZnIn2S4/La2Ti2O7 nanosheets with a Z-scheme heterojunction for enhanced photocatalytic hydrogen evolution.

Layered lanthanum titanate (La2Ti2O7) perovskite is a good photocatalytic material owing to its high stability, strong redox ability, and non-toxicity. However, its inherent wide bandgap limits its application in photocatalytic hydrogen evolution. Therefore, combining La2Ti2O7 with two-dimensional (2D) narrow-bandgap semiconductors to form 2D/2D layered structures is the preferred strategy to improve its photocatalytic performance. In this study, a novel 2D/2D ZnIn2S4/La2Ti2O7 Z-scheme heterojunction was prepared through a solvothermal method. The experimental results show that when the molar ratio of La2Ti2O7 to ZnIn2S4 is 1 : 4, the hydrogen evolution rate of the composite under ultraviolet-visible light reaches 6.97 mmol g-1 h-1, which is 3.5 times higher than that of the pure ZnIn2S4. The results of the morphological characterization studies of the samples and the photoelectrochemical measurements show that channels for the rapid transfer of carriers are generated by the unique 2D/2D structure of these samples, and the separation and migration efficiency of the photogenerated carriers significantly improved due to the formation of the Z-scheme heterojunction. This study provides useful insights into the modulation of wide-bandgap semiconductors and research into solar energy conversion.

Novel hollow core-shell Zn0.5Cd0.5S@ZnIn2S4/MoS2 nanocages with Z-scheme heterojunction for enhanced photocatalysis of hydrogen generation.

The development of low-cost and efficient metal sulfide photocatalysts through morphological and structural design is vital to the advancement of the hydrogen economy. However, metal sulfide semiconductor photocatalysts still suffer from low carrier separation and poor solar-to-hydrogen conversion efficiencies. Herein, two-dimensional ZnIn2S4 nanosheets were grown on Zn0.5Cd0.5S hollow nanocages to construct Zn0.5Cd0.5S@ZnIn2S4 hollow nanocages for the first time. Novel hollow core-shell Zn0.5Cd0.5S@ZnIn2S4/MoS2 nanocages with Z-scheme heterojunction structures were obtained by incorporating MoS2 nanosheet co-catalyst via the solvothermal method. The resulting Zn0.5Cd0.5S@ZnIn2S4/MoS2 exhibited unique structural and compositional advantages, leading to remarkable photocatalytic hydrogen evolution rates of up to 8.5 mmol·h-1·g-1 without the use of any precious metal co-catalysts. This rate was 10.6-fold and 7.1-fold higher compared to pure ZnIn2S4 and Zn0.5Cd0.5S, respectively. Moreover, the optimized Zn0.5Cd0.5S@ZnIn2S4/MoS2 photocatalyst outperformed numerous reported ZnIn2S4-based photocatalysts and some ZnIn2S4-based photocatalysts based on precious metal co-catalysts. The exceptional photocatalytic performance of Zn0.5Cd0.5S@ZnIn2S4/MoS2 can be attributed to the Z-scheme heterojunction of core-shell structure that enhanced charge carrier separation and transport, as well as the co-catalytic action of MoS2. Overall, the proposed Zn0.5Cd0.5S@ZnIn2S4/MoS2 with heterojunction structure is a promising candidate for the preparation of efficient photocatalysts for solar-to-hydrogen energy conversion.

Low-NO-like Oxidation Pathway Makes a Significant Contribution to Secondary Organic Aerosol in Polluted Urban Air.

Anthropogenic pollutants can greatly mediate formation pathways and chemical compositions of secondary organic aerosol (SOA) in urban atmospheres. We investigated the molecular tracers for different types of SOA in PM2.5 under varying NO/NO2 conditions in Guangzhou using source analysis of particle-phase speciated organics obtained from an iodide chemical ionization mass spectrometer with a Filter Inlet for Gases and AEROsols (FIGAERO-I-CIMS). Results show that low-NO-like pathways (when NO/NO2 < 0.2) explained ∼75% of the total measured FIGAERO-OA during regional transport periods, which was enriched in more-oxidized C4-C6 non-nitrogenous compounds over ozone accumulation. Daytime high-NO chemistry played larger roles (38%) in local pollution episodes, with organic nitrates (ONs) and nitrophenols increasing with enhanced aerosol water content and nitrate fraction. Nighttime NO3-initiated oxidation, characterized by monoterpene-derived ONs, accounted for comparable percentages (10-12%) of FIGAERO-OA for both two periods. Furthermore, the presence of organosulfates (OSs) improves the understanding of the roles of aqueous-phase processes in SOA production. Carbonyl-derived OSs exhibited a preferential formation under conditions of high aerosol acidity and/or abundant sulfate, which correlated well with low-NO-like SOA. Our results demonstrate the importance of NO/NO2 ratios in controlling SOA compositions, as well as interactions between water content, aerosol acidity, and inorganic salts in gas-to-particle partitioning of condensable organics.

Particulate organic emissions from incense-burning smoke: Chemical compositions and emission characteristics.

Incense burning is a common practice in Asian cultures, releasing hazardous particulate organics. Inhaling incense smoke can result in adverse health effects, yet the molecular compositions of incense-burning organics have not been well investigated due to the lack of measurement of intermediate-volatility and semi-volatile organic compounds (I/SVOCs). To elucidate the detailed emission profile of incense-burning particles, we conducted a non-target measurement of organics emitted from incense combustion. Quartz filters were utilized to trap particles, and organics were analyzed by a comprehensive two-dimensional gas chromatography-mass spectrometer (GC × GC-MS) coupled with a thermal desorption system (TDS). To deal with the complex data obtained by GC × GC-MS, homologs are identified mainly by the combination of selected ion chromatograms (SICs) and retention indexes. SICs of 58, 60, 74, 91, and 97 were utilized to identify 2-ketones, acids, fatty acid methyl esters, fatty acid phenylmethyl esters, and alcohols, respectively. Phenolic compounds contribute the most to emission factors (EFs) among all chemical classes, taking up 24.5 % ± 6.5 % of the total EF (96.1 ± 43.1 µg g-1). These compounds are largely derived from the thermal degradation of lignin. Biomarkers like sugars (mainly levoglucosan), hopanes, and sterols are extensively detected in incense combustion fumes. Incense materials play a more important role in shaping emission profiles than incense forms. Our study provides a detailed emission profile of particulate organics emitted from incense burning across the full-volatility range, which can be used in the health risk assessments. The data processing procedure in this work could also benefit those with less experience in non-target analysis, especially GC × GC-MS data processing.

Copper-Catalyzed Radical Enantioselective Synthesis of γ-Butyrolactones with Two Non-vicinal Carbon Stereocenters.

Chiral heterocycles with two or more carbon stereocenters are quite important skeletons in many fields. However, powerful strategies for the construction of such synthetically valuable heterocycles, especially with two or more remote carbon stereocenters, have largely lagged behind. We report here a powerful method for the synthesis of chiral γ-butyrolactones with two non-vicinal carbon stereocenters from readily available chemical feedstocks under mild conditions. Both of the two diastereoisomers can be obtained with good to excellent enantioselectivities. The well-designed copper/PyBox catalytic system overrides the intrinsic stereoinduction of the close chirality center generated by the previous innocent radical addition step. Nevertheless, this work has the power to selectively provide one single diastereoisomer by taking advantage of the epimerization effect but also to synthesize all four diastereoisomers with the pair of chiral ligands L2 and L2' having opposite chirality. The obtained useful chiral γ-butyrolactones can be synthetically transformed into acyclic or cyclic molecules with two non-vicinal carbon stereocenters. Mechanistic studies reveal that this radical reaction follows a linear relationship and can be well performed with a less loading amount of ligand compared to that of the copper catalyst.

Investigation of partition coefficients and fingerprints of atmospheric gas- and particle-phase intermediate volatility and semi-volatile organic compounds using pixel-based approaches.

Ambient gas- and particle-phase intermediate volatility and semi-volatile organic compounds (I/SVOCs) of Beijing were analyzed by a thermal desorption comprehensive two-dimensional gas chromatography quadrupole mass spectrometry (TD-GC × GC-qMS). A pixel-based scheme combing the integration-based approach was applied for partition coefficients estimation and fingerprints identification. Blob-by-blob recognition was firstly utilized to characterize I/SVOCs from the molecular level. 412 blobs in gas-phase and 460 blobs in particle-phase were resolved, covering a total response of 47.5% and 43.5%. A large pool of I/SVOCs was found with a large diversity of chemical classes in both gas- and particle-phase. Acids (8.5%), b-alkanes (5.8%), n-alkanes (C8-C25, 5.3%), and aromatics (4.4%) were dominant in gas-phase while esters (7.0%, including volatile chemical product compounds, VCPs), n-alkanes (C9-C34, 5.7%), acids (4.6%), and siloxanes (3.6%) were abundant in particle-phase. Air pollutants were then evaluated by a two-parameter linear free energy relationship (LFER) model, which could be further implemented in the two-dimensional volatility basis set (2D-VBS) model. Multiway principal component analysis (MPCA) and partial least squares-discriminant analysis (PLS-DA) implied that naphthalenes, phenol, propyl-benzene isomers, and oxygenated volatile organic compounds (OVOCs) were key components in the gas-phase under different pollution levels. This work gives more insight into property estimation and fingerprints identification for complex ambient samples.

Field observations and quantifications of atmospheric formaldehyde partitioning in gaseous and particulate phases.

Formaldehyde (HCHO) can possibly be taken by atmospheric particles due to its moderate solubility. Although previous model studies have proposed that uptake by particles was a large sink for HCHO, direct observation of HCHO partitioning and estimation of HCHO uptake coefficient (γ) for tropospheric conditions are still limited. In this work, online measurements of gaseous HCHO (HCHOg) and particulate HCHO (HCHOp) were carried out simultaneously at an urban site in Beijing in winter and spring. The results indicated that the average concentrations of HCHOp ranged from 0.15 to 0.4 µg m-3, accounting for 1.2% to 10% of the total HCHO (i.e., HCHOg + HCHOp). The median values of estimated γ based on the measured data were in the range of about 1.09 ∗ 10-5-2.42 ∗ 10-4, with lower values during PM2.5 pollution episodes. Besides, the pH and liquid water content of aerosols that are mainly determined by ambient relative humidity (RH) and inorganic salt composition were identified as the main influencing factors of γ. We propose that the HCHO uptake process was mainly driven by hydrone and hydrogen ions in particles.

Research on accounting and detection of volatile organic compounds from a typical petroleum refinery in Hebei, North China.

A volatile organic compound (VOC) emissions inventory of the petroleum refinery in Hebei was established. This refinery emits 1859.2 tons of VOCs per year, with wastewater collection and treatment system being the largest emissions source, accounting for 59.6% individually, followed by the recirculating cooling water system (13.4%), storage tanks (11.1%), and equipment leaks (9.4%). Organized and fugitive samples were collected simultaneously for different processes of each emissions source. A total of 100 VOC species were characterized and quantified using a gas chromatography-mass spectrometry/flame ionization detection system. The VOC emissions concentrations and chemical composition of each process were quite different. Most of the processes used alkanes as the main chemome. We concluded from the composite source profile weighted by the amount of VOC emissions that the characteristic species of this petroleum refinery were ethane (15.4%), propylene (11.7%), propane (8.5%), iso-pentane (8.3%), and toluene (4.7%). The ozone (O3) formation potential (OFP) and secondary organic aerosol formation potential (SOAP) were evaluated, and the results indicated that alkenes (mainly propylene) and aromatics (mainly toluene) were the priority control compounds. This study clarifies the current status of VOC emissions in the refinery in terms of emissions intensity, emissions components, and O3 and SOA reactivity. The key emissions sources and species screened provide scientific support for reducing refined emissions from the petrochemical industry.

Regioselective Three-Component Synthesis of Vicinal Diamines via 1,2-Diamination of Styrenes.

The vicinal diamine motif plays a significant role in natural products, drug design, and organic synthesis, and development of synthetic methods for the synthesis of diamines is a long-standing interest. Herein, we report a regioselective intermolecular three-component vicinal diamination of styrenes with acetonitrile and azodicarboxylates. The diamination products can be produced in moderate to excellent yields via the Ritter reaction. Synthetic applications and theoretical studies of this reaction have been conducted.

Iron-Catalyzed Radical Asymmetric Aminoazidation and Diazidation of Styrenes.

Asymmetric aminoazidation and diazidation of alkenes are straightforward strategies to build value-added chiral nitrogen-containing compounds from feedstock chemicals. They provide direct access to chiral organoazides and complement enantioselective diamination. Despite the advances in non-asymmetric reactions, asymmetric aminoazidation or diazidation based on acyclic systems has not been previously reported. Here we describe the iron-catalyzed intermolecular asymmetric aminoazidation and diazidation of styrenes. The method is practically useful and requires relatively low loading of catalyst and chiral ligand. With mild reaction conditions, the reaction can be completed on a 20 mmol scale. Studies of the mechanism suggest that the reaction proceeds via a radical pathway and involves stereocontrol of an acyclic free radical which probably takes place through a group transfer mechanism.

Source profiles, emission factors and associated contributions to secondary pollution of volatile organic compounds (VOCs) emitted from a local petroleum refinery in Shandong.

An in-depth study was conducted to quantify and characterize VOC emissions from a petroleum refinery located in Shandong, China. The VOC emission inventory established in this study showed that storage tanks were the largest emission source, accounting for 56.4% of total emissions, followed by loading operations, wastewater collection and treatment system, process vents, and equipment leaks. Meanwhile, the localization factors for refining, storage tanks and loading operations were calculated, which were 1.33, 0.75 and 0.31g VOCs/kg crude oil refined. Furthermore, the characteristics of fugitive and organized emissions were determined for various processes and emission sources using a gas chromatography-mass spectrometry/flame ionization detection (GC-MS/FID) system. Most samples contained mainly alkanes, but the total VOC concentrations and key species varied greatly among processes. The source profile of the refinery, synthesized using the weighted average method, indicated that cis-2-butene (14.5%), n-pentane (10.2%), n-butane (7.4%), isopentane (6.5%) and MTBE (5.9%) were the major species released by this refinery. Assessment of O3 and secondary organic aerosol formation potentials were completed, and the results indicated that cis-2-butene, m/p-xylene, toluene, n-pentane, isopentane, benzene, o-xylene and ethylbenzene were the active species for which treatment should be prioritized.

Copper-Catalyzed Enantioselective Radical 1,4-Difunctionalization of 1,3-Enynes.

Chiral allenes are important structural motifs frequently found in natural products, pharmaceuticals, and other organic compounds. Asymmetric 1,4-difunctionalization of 1,3-enynes is a promising strategy to construct axial chirality and produce substituted chiral allenes from achiral substrates. However, the previous state of the art in 1,4-difunctionalization of 1,3-enynes focused on the allenyl anion pathway. Because of this, only electrophiles can be introduced into the allene backbones in the second functionalization step, consequently limiting the reaction and allene product types. The development of asymmetric 1,4-difunctionalization of 1,3-enynes via a radical pathway would complement previous methods and support expansion of the toolbox for the synthesis of asymmetric allenes. Herein, we report the first radical enantioselective allene formation via a group transfer pathway in the context of copper-catalyzed radical 1,4-difunctionalization of 1,3-enynes. This method addresses a longstanding unsolved problem in asymmetric radical chemistry, provides an important strategy for stereocontrol with free allenyl radicals, and offers a novel approach to the valuable, but previously inaccessible, chiral allenes. This work should shed light on asymmetric radical reactions and may lead to other enantioselective group transfer reactions.

The potential water-food-health nexus in urban China: A comparative study on dietary changes at home and away from home.

In China, urbanization strengthens the water-food-health nexus by driving dietary changes both at home and away from home (AFH). However, few studies have compared the effects of dining location on water footprint generation and/or linked such habits to the prevalence of non-communicable diseases (NCDs), such as hypertension, diabetes, asthma, myocardial infarction, stroke and cancer. Here, household survey data were used to develop a multiple-component urbanization sequence, on which the diet-related water footprint was quantified and the mechanisms under the water-food-health nexus were explored. Significant dietary changes due to urbanization have occurred at home (instead of AHF), and increases or decreases in various food groups are stratified across dining locations. Log mean Divisia index decomposition shows that the diet-structure effect outweighing the intake effect dominates the water footprint changes during China's urbanization. Animal products contribute 92(94)% of the diet-structure effect on net water footprint growth at home(AFH); in contrast, vegetal foods dominate the intake effect, contributing 67(49)%. The at-home water footprint ratio of animal products to vegetal foods is highly related to the prevalence of diabetes, hypertension, cancer, and asthma, and reaching statistical significance. Two urbanization components, namely housing situation and community diversity, serve as the key drivers of water-food-health nexus enhancement in urbanized China. Due to the complexity of water-food-health links, nexus thinking is needed to benefit human health and diet-related water consumption; besides, it may be reasonable to expand current dimension of food-energy-water nexus topic to include health issues.

Shift from feeding to sustainably nourishing urban China: A crossing-disciplinary methodology for global environment-food-health nexus.

Dietary change is a win-win opportunity to address the nexus of health and the environment. To prevent city dwellers from developing non-communicable diseases, in 2013, China updated the 2000 version of nutrition-based dietary reference intake (DRI) guidelines. However, whether the DRI guidelines have a positive effect on the environment is not well understood. Here, we explored the systematic effects of urbanization on China's health and environmental nexus based on survey data. Then, we optimized the diets of 18 age-gender groups to reduce carbon emissions, water consumption, and land use while meeting the healthy nutrition goals of both DRI guidelines. The results showed that the optimal diets based on the DRI 2013 outperformed these on DRI 2000 in improving China's environmental sustainability, although these diets did not always perform better at an individual scale. Our findings suggest that dietary changes can reduce carbon, water, and ecological footprints by 24%, 15%, and 22% in 2050, respectively; however, the differences in age-specific and gender-specific health goals cannot be neglected.