化学•材料最新文献

{"title":"Diastereoselective Synthesis of β-Branched α-Amino Acids from β, γ-Unsaturated Amides and Glycine-Derived Imines via Tandem Isomerization-Conjugate Addition","authors":"Tesfaye Tebeka Simur,Tangji Chen,Qiaoyu Ou,Ting Li,Mandalaparthi Phanindrudu,Changjin Lu,Weiguang Yang,Yingmei Luo,Jia Zheng","doi":"10.1021/acs.joc.6c02088","DOIUrl":"https://doi.org/10.1021/acs.joc.6c02088","url":null,"abstract":"A base-promoted diastereoselective synthesis of β-branched α-amino acid derivatives is reported, proceeding via tandem isomerization–conjugate addition of β,γ-unsaturated amides with glycine-derived imines under transition-metal-free conditions. The operationally simple protocol tolerates a range of ester- and amide-derived imines, affording products in high diastereoselectivity (up to 20:1 dr). The products are readily transformed into γ-lactam and β-methylated glutamic acid analogues. Control experiments reveal a pronounced dependence of stereoselectivity on the bidentate tether, solvent, and alkali metals, supporting a chelation-controlled stereochemical model. This work highlights alkali metal-bidentate coordination as an effective strategy for stereocontrol in base promoted C–C bond-forming reactions. In addition, certain products also inhibited the growth of MCF-7 cancer cell lines.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"71 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Paternal Preconception Calcitriol Intervention Rescued DBDPE-Induced Transgenerational Developmental and Visual Toxicity in Zebrafish","authors":"Yindan Zhang,Lihua Yang,Tao Xu,Yue Guo,Tianzi Liu,Jianghuan Hua,Kaiyu Fu,Fan Li,Jie Gu,Yuxi Zhou,Jian Han,Bingsheng Zhou","doi":"10.1021/acs.est.6c09071","DOIUrl":"https://doi.org/10.1021/acs.est.6c09071","url":null,"abstract":"Growing evidence highlights the impact of preconception paternal environmental exposures on offspring health, yet the specific paternal contributions and transgenerational mechanisms of emerging contaminants remain poorly understood. Thus, we exposed male zebrafish to decabromodiphenyl ethane (DBDPE), a widely used replacement for legacy flame retardants, for 2 months to investigate its intergenerational (F1) and transgenerational (F2) effects. Paternal DBDPE exposure severely impaired sperm quality in F0 zebrafish, and induced transgenerational developmental toxicity with elevated malformations in F2 larvae. Moreover, significant eye malformations occurred even at low doses in F2 groups, revealing the visual system to be highly sensitive to transgenerational DBDPE toxicity. F1 and F2 larvae exhibited marked behavioral disorders, retinal thinning, and phototransduction gene dysregulation, indicating significant visual dysfunction. Notably, transcriptome analysis revealed that steroid biosynthesis (especially calcitriol synthesis) was consistently disrupted across dose levels and generations, with its enrichment factor progressively increasing from F1 to F2; this was accompanied by a pronounced deficiency of calcitriol in paternal F0 testes. Accordingly, paternal calcitriol supplementation during DBDPE exposure effectively restored F0 sperm quality and mitigated visual and developmental toxicity in offspring. These findings suggest that paternal exposure to emerging contaminants may induce intergenerational and transgenerational effects, and that targeted preconception nutritional intervention may reduce these risks.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"52 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine Learning Attribution of Atmospheric Black Carbon in a Coastal City: Source Variability and the Sea–Land Breeze Recirculation Mechanism","authors":"Hao Yu,&nbsp;Xingyue Guo,&nbsp;Xinyu He,&nbsp;Mengyuan Luo,&nbsp;Dan Yao,&nbsp;Wenkang Gao,&nbsp;Guangxuan Yan,&nbsp;Pengtuan Hu,&nbsp;Xue Li,&nbsp;Menglin Liu,&nbsp;Xu Han,&nbsp;Zhiguo Cao","doi":"10.1021/acs.est.6c10060","DOIUrl":"10.1021/acs.est.6c10060","url":null,"abstract":"<p>Black carbon (BC) variability in coastal environmentsreflectsthe combined effects of emission sources, regional transport, andmesoscale circulation. This study selected the typical coastal cityof Qingdao as the study area, collected BC online observation datafor one year in 2021, and integrated it with the Aethalometer model,trajectory analysis, and Random Forest (RF) machine learning frameworkto examine these mechanisms. The annual mean BC concentration was1.78 ± 1.29 μg m^–3, with fossil fuelcombustion contributing 88.2% of the total mass, while the biomassburning contribution increased to 19% in winter. Source-resolved attributionshowed distinct meteorological responses. Fossil-fuel black carbon(BC_ff) was more strongly associated with wind-controlledventilation and transport, whereas biomass burning BC (BC_bb) responded more strongly to low-temperature conditions. Under sea–landbreeze (SLB) conditions, BC enhancement was most evident at wind speedsof 2.0 to 3.5 m s^–1. Diurnal persistence, directionalshifts in elevated fossil fuel BC, and interactions between wind speedand wind direction further supported return transport and reaccumulationwithin coastal circulation. These findings provide process-based insightinto source-dependent BC variability and SLB-related reaccumulationin coastal environments.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"60 41","pages":"29502–29514"},"PeriodicalIF":12.2,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scalable and Interpretable Chemical Neurotoxicity Prediction via Multi-Modal Gated Fusion and ChemBERTa","authors":"Lilai Shen,&nbsp;Ziyu Chen,&nbsp;Yizhou Huang,&nbsp;Jianing Liu,&nbsp;Jinhui Yuan,&nbsp;Shulin Zhuang","doi":"10.1021/acs.est.6c10122","DOIUrl":"10.1021/acs.est.6c10122","url":null,"abstract":"<p>Chemical exposure causes adverse neurological outcomes,highlightingthe need for high-throughput screening of chemical neurotoxicity.However, existing computational methods rely on single-modality inputsand lack complementary molecular information to sufficiently enhancethe accuracy and efficiency of neurotoxicity risk assessment. Here,we present NeuroToxPredictor, a scalable and interpretable multimodalframework built on a curated chemical neurotoxicity dataset for accurateand efficient chemical neurotoxicity prediction. It integrates graphattention networks and molecular fingerprints with ChemBERTa, a pretrainedchemical language model that provides contextual encoding of SMILES.A gated fusion module adaptively weights these complementary representationsaccording to their predictive relevance to enhance modality-specificweight allocation through a gating fusion mechanism. NeuroToxPredictorachieved competitive performance across five independent trainingseeds (AUC = 0.919 ± 0.004; accuracy = 0.845 ± 0.014; F₁-score = 0.861 ± 0.011; recall = 0.884 ± 0.013;precision = 0.839 ± 0.024; MCC = 0.688 ± 0.028), outperformingboth single-modality and reduced-modality baselines. It demonstratesstrong generalizability with an AUC of 0.861, as externally validatedon an independent set of 279 compounds. NeuroToxPredictor is deployedon a publicly platform (https://www.ai4environ.cn/NeuroToxPredictor), enabling an end-to-end intelligent workflow from chemical retrieval,neurotoxicity prediction, applicability-domain assessment, and largelanguage model-assisted result interpretation.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"60 41","pages":"29441–29451"},"PeriodicalIF":12.2,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analysis of Multiple Tire Rubber-Derived Chemicals in Fish Bile and Plasma: Analytical Method and Field Assessment in Puget Sound, WA, USA","authors":"Denis da Silva,&nbsp;Jonelle Gates,&nbsp;Madison Hattaway,&nbsp;Louisa Harding,&nbsp;Sandra O’Neill,&nbsp;Irvin Schultz","doi":"10.1021/acs.est.6c07136","DOIUrl":"10.1021/acs.est.6c07136","url":null,"abstract":"<p>Tire rubber-derived chemicals (TRCs) are known to behighly toxicto fish, but understanding of their environmental levels and fateis still limited. This study presents a new method for the analysisof 18 TRCs, including phenylenediamines (TRC-PDs), their quinone derivatives(TRC-Qs), and rubber vulcanizing and curing-related chemicals (TRC-VCRs)in fish bile and plasma samples. We applied this method in bile andplasma samples from English sole collected in urban, near-urban, andnonurban sites in Puget Sound, WA, USA. TRCs were detected in 100%of bile and 96% of plasma samples from English sole collected fromall nine sites in Puget Sound. Mean TRC levels in bile samples persite ranged between 0.8 and 18 ng/mL, while plasma levels ranged between0.22 and 0.63 ng/mL, with total summed reaching up to 31 ng/mL inbile and 1.3 ng/mL in plasma. TRC-PDs were the most abundant groupof TRC in both bile and plasma. Higher levels of TRCs in bile suggeststhis matrix to be more valuable for environmental monitoring, providingmore sensitive detection of TRC during low exposures. To the bestof our knowledge, this is the first data set reporting environmentallevels of 18 TRCs in the bile and plasma of field-caught fish.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"60 41","pages":"29596–29607"},"PeriodicalIF":12.2,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insufficient Environmental Protection by the European Regulatory Framework for Pesticides","authors":"Ralf B. Schäfer,&nbsp;Thomas Backhaus,&nbsp;Juliane Filser,&nbsp;Mark O. Gessner,&nbsp;Matthias Liess,&nbsp;Martina Roß-Nickoll,&nbsp;Maj Rundlöf,&nbsp;Martin Scheringer,&nbsp;David J. Spurgeon,&nbsp;Teja Tscharntke,&nbsp;Paul J. Van den Brink,&nbsp;Andreas Schäffer","doi":"10.1021/acs.est.6c06604","DOIUrl":"10.1021/acs.est.6c06604","url":null,"abstract":"<p>Schrieveret al. (2025) argue that environmental risk assessmentof pesticides in the European Union is sufficiently protective andthat regulatory thresholds are rarely exceeded. Here, we reexaminethese claims based on existing evidence from monitoring, systematicreviews, and different types of field studies. The available evidenceindicates that measured pesticide concentrations frequently exceedpredicted concentrations and regulatory thresholds and are associatedwith adverse ecological impacts. The mechanisms driving this resultinclude the joint action of pesticides applied in temporal and spatialproximity, varied environmental conditions, interactive effects ofpesticides with additional stressors, and indirect ecological effectsthat propagate within biological communities. These neglected intricaciesexplain why current single-substance prospective assessments tendto underpredict real-world pesticide exposure and impact in fieldsettings. The corollary is that the current regulatory framework inEurope proves to be insufficient to protect biodiversity and ecosystems.Priority regulatory reforms include strengthening postregistrationmonitoring, refining predictive exposure models, and explicitly consideringlandscape context, indirect and mixture effects, and interactionswith nonchemical stressors.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"60 41","pages":"29260–29272"},"PeriodicalIF":12.2,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the Role of the Soil Matrix in Trichloroethylene Degradation by Ball-Milled Sulfidated Microscale Zero-Valent Iron","authors":"Dong Cheng,&nbsp;Yuansen Tan,&nbsp;Junjie Shu,&nbsp;Si Chen,&nbsp;Fan Wu,&nbsp;Jiaqing Luo,&nbsp;Hengli Ni,&nbsp;Liwei Yang,&nbsp;Bo Chen,&nbsp;Feng He","doi":"10.1021/acs.est.6c13776","DOIUrl":"10.1021/acs.est.6c13776","url":null,"abstract":"<p>Ball-milled sulfidated microscalezerovalent iron (S-mZVI^bm) is highly effective in degradingtrichloroethylene (TCE) in anoxicwater. This study investigated its performance and soil-mediated regulationin a soil-water mixed system (SWMS) using two natural soils. The resultsshow that soil addition markedly enhanced the reactivity of S-mZVI^bm. Compared with the aqueous system, the degradation rateconstant of TCE (<em>k</em>_TCE) exhibited a 6.0–8.4-foldincrease at a soil-to-water ratio (S/W) of 0.5 to 2.0, while H₂ production concurrently increased 210%–450%. Thisactivation was accompanied by a decrease in apparent electron efficiencyfrom 74.3% in water to 15.9%–27.6% in SWMS. S-mZVI^bm retained higher reactivity in SWMS than in water across pH 6–10,with a maximum <em>k</em>_TCE of 0.26 h^–1 at pH 8.0. SEM, XPS, and component-specific experiments indicatedthat soil-mediated surface restructuring and Fe(II) redistribution-induceddepassivation increased the accessibility of Fe⁰-rich domains,whereas organic matter and Ca/Mg-bearing phases imposed inhibitoryeffects. Sulfidation suppressed H₂ evolution and reducedsoil-specific variability under multicontaminant conditions involvingTCE, carbon tetrachloride, nitrobenzene, and perchloroethylene. Theseresults identify soil as an active regulator of Fe⁰ accessibilityand electron allocation rather than a passive reaction medium, providinga mechanistic basis for site-specific S-mZVI^bm remediation.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"60 41","pages":"29689–29699"},"PeriodicalIF":12.2,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dynamics of Long-Lived Carriers in Molybdenum Carbide Nanosheets","authors":"Xiangyu Zhu,Zhong Wang,Tao Li,Xi Wang,Zheng Zhang,Chunlong Hu,Kaifu Huo,Wenxi Liang","doi":"10.1021/acs.jpcc.6c04911","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c04911","url":null,"abstract":"Molybdenum carbide (MoC) is a promising candidate for substituting expensive platinum-group metals in many applications owing to its low cost and excellent properties; therefore, a comprehensive understanding of its carrier dynamics is demanded for advancing the synthesis strategy and implementation of MoC. In this work, the carrier relaxation in MoC nanosheets is investigated by combining femtosecond transient reflection spectroscopy with first-principles calculations. The measured processes of electron–electron, electron–phonon, and phonon–phonon scattering show significantly longer lifetimes compared with those of other transition-metal carbides. Based on the analysis of calculated phonon dispersion, the nanosecond-carrier lifetime is consistent with the restricted phonon decay pathways, which is induced by the large mass difference between Mo and C atoms. The observed slow carrier cooling rate in our study offers a straightforward approach for effectively utilizing hot carriers, which is expected to improve the performance of photothermal and photovoltaic devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Total Syntheses and Biological Evaluation of Lamellolactones A and B via Direct Butenolide Functionalization","authors":"Yuto Fuse,Hwanhee Moon,Ryuji Kouda,Kensyo Inoue,Haruna Shimura,Satoshi Ohte,Sena Fujisawa,Yuya Miyoshi,Masaharu Saito,Taichi Ohshiro,Tohru Nagamitsu,Masaki Ohtawa","doi":"10.1021/acs.joc.6c01907","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01907","url":null,"abstract":"Lamellolactones A and B are pseudoregioisomeric natural products bearing oxidized butenolide frameworks and have attracted interest in the context of fibrodysplasia ossificans progressiva (FOP). We achieved their first total syntheses via Ni-catalyzed reductive coupling of a common alkyl iodide with α- and β-bromobutenolides. A preliminary examination of alkyl electrophiles indicated that the coupling could be applied to simple primary and secondary alkyl iodides. The route also furnished analogues for comparison of γ-substitution effects on bone morphogenetic protein (BMP)-induced alkaline phosphatase inhibition and cytotoxicity.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"88 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A New Family of Electron-Bifurcating Enzymes Represented by Ferredoxin- and NAD-Dependent Glycerol-3-Phosphate Oxidoreductase","authors":"Gerrit J. Schut,&nbsp;Farris L. Poole,&nbsp;Michael W. W. Adams","doi":"10.1021/acs.biochem.6c00512","DOIUrl":"https://doi.org/10.1021/acs.biochem.6c00512","url":null,"abstract":"<p>Glycerol is abundantin natural environments and is utilized bymany microbes. In aerobes, it is typically converted, via glycerol-3-phosphate(G3P), to dihydroxyacetone phosphate (DHAP) by a quinone-linked dehydrogenasethereby coupling glycolysis and respiration. Under anaerobic conditions,an NAD⁺-dependent dehydrogenase has been proposed to oxidizeG3P to DHAP in several bacteria but this reaction is thermodynamicallyunfavorable. Herein, we have purified a heterotrimeric electron bifurcatingenzyme from the archaeon <em>Pyrococcus furiosus</em> where the simultaneous oxidation of both G3P (E_o′−190 mV) and reduced ferredoxin (E_m ∼ −450mV) enables reduction of NAD⁺(E_o′ −320mV) and production of DHAP. Surprisingly, this <span>f</span>erredoxin-dependent <span>N</span>AD⁺<span>G</span>3P oxidoreductase (FngABC) is unrelated evolutionarilyto the four known families of bifurcating enzyme. Analysis by UV–visiblespectroscopy and of its predicted structure suggest FngABC has a nonclassicalbifurcation mechanism. Phylogenetic and genome context analyses of4,273 <em>P. furiosus</em> FngA homologues revealedthey are widespread with ∼35% found mainly in Clostridia asFngABC and ∼10% found mainly in Actinomyces as FngAB, mostof which utilize polyols in addition to glycerol. The remaining ∼40%are present in Gammaproteobacteria and halophilic archaea but hereFngA is associated with homologues of <em>E. coli</em> GlpBC, which are unrelated to FngBC, and these enzymes typicallyonly use glycerol. It is therefore proposed that <em>P. furiosus</em> FngABC and the previously characterized <em>E. coli</em> GlpABC are disparate members of a new electronbifurcating family widespread in the microbial world that are involvedin the metabolism of a range of sugars as well as glycerol.</p>","PeriodicalId":28,"journal":{"name":"Biochemistry Biochemistry","volume":"65 20","pages":"3247–3257"},"PeriodicalIF":2.7,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}