化学•材料最新文献

{"title":"Palladium-Catalyzed Heteroannulation of Bdan-Capped Alkynes: Rapid Access to Complex Indole Scaffolds","authors":"Dean D. Roberts, John M. Halford-McGuff, Marek Varga, Aidan P. McKay, Allan J. B. Watson","doi":"10.1021/acs.joc.5c01781","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01781","url":null,"abstract":"We report the synthesis of 2-indolylboramides via a palladium (Pd)-catalyzed heteroannulation of 2-iodoaniline derivatives and Bdan-capped alkynes (Bdan, 1,8-diaminonaphthalene boronamide). The process is highly regioselective, affording a diverse range of C2-borylated indoles. The synthetic utility of the process is demonstrated through the concise synthesis of the Tetradium alkaloid skeleton.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059588","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":"S-Benzylation of Sulfenamides with Tertiary Amine Using Methyl Propiolate as a Bifunctional Additive","authors":"Wentong Liu, Siyan Qiu, Ruiyang Jin, Liliang Huang, Junhai Huang, Huangdi Feng","doi":"10.1021/acs.joc.5c01561","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01561","url":null,"abstract":"Sulfilimines serve as key intermediates in the synthesis of pharmacologically and agriculturally relevant motifs. We herein report a practical and efficient protocol for the synthesis of sulfilimines via deaminative sulfur benzylation without the addition of a metal catalyst and a base. In the reaction, employing methyl propionate as a bifunctional reagent to activate the amino and sulfenamide groups enables the chemoselective coupling of various sulfenamides with tertiary amines, delivering the target products in high yield with excellent selectivity.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"78 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059590","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":"Placentation Disruption by Perfluorooctanoic Acid and Perfluorooctanesulfonate in Human Trophoblast Organoids","authors":"Mingzhu Li, Chenke Xu, Linwan Li, Fumei Gao, Cheng Xu, Yafei Yu, Chong Huang, Yanan Liu, Xinming Shen, Jianying Hu","doi":"10.1021/acs.est.5c07230","DOIUrl":"https://doi.org/10.1021/acs.est.5c07230","url":null,"abstract":"Prenatal exposure to perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) is associated with low birth weight, a condition often resulting from placental dysfunction. However, whether and how PFOA and PFOS affect human placentation and placental-specific functions remains unclear. In this study, we reconstructed a human trophoblast organoid model, incorporating a near-physiological proportion of extravillous trophoblast (EVT). The organoids were exposed to PFOA or PFOS for 7 days. Exposure to PFOA at 10 nM significantly increased the proportion of villous cytotrophoblast (CTB) cells, while reducing the proportion of EVT and syncytiotrophoblast (STB) cells at 10 and 100 nM, respectively. A similar pattern was observed with PFOS, albeit at concentrations 10 times higher than those of PFOA. Mechanistically, both PFOA and PFOS inhibited trophoblast differentiation by antagonizing the transcriptional activity of cAMP response element-binding protein (CREB). This disruption in placentation impaired placental function, as evidenced by significantly decreasing hormone secretion and invasion potential. Our investigation may provide mechanistic insight into the association of PFOA and PFOS with low birth weight observed in epidemiological studies, with PFOA demonstrating a stronger effect than PFOS. These findings may aid in evaluating the toxicity of emerging PFAS and support the development or selection of safer chemical alternatives.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"70 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059665","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":"High-Efficiency Enrichment of Precious Metals with Mechanochemically Enhanced Galvanic and Kirkendall Effects","authors":"Yuxiang Shi, Wei-xian Zhang","doi":"10.1021/acs.jpclett.5c02441","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02441","url":null,"abstract":"We report mechanochemical enrichment of metals (e.g., Ag(I), Au(III)) by harnessing microscopic galvanic and Kirkendall effects. Experimental results show the mechanochemical reactions can directly produce high-purity precious metals (e.g., 78.9% Ag and 68.6% Au, respectively) from wastewaters. One mole of zerovalent iron (ZVI) can harvest up to 2.18 mol of Au or 3.74 mol of Ag from wastewaters, respectively, which stand for 900% and 2291% enhancement above the results from conventional solution chemistry. The mechanochemical reactions foster highly favorable conditions for metal cation sequestration (alkaline pH, negatively charged nanoparticles, and low redox potential). Together with the continuous surface renewal, mechanochemical energy manifests an extraordinary efficiency for metal enrichment. Laboratory experiments further demonstrated that it performed equally well on other metal ions (e.g., Pd(II), Cu(II), Ni(II), Pb(II), and Co(II)), suggesting its potential as a versatile solution for metal enrichment and recycling.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"19 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059717","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":"Solvent Effects on C-H Abstraction by Hydroperoxyl Radicals: Implication for Antioxidant Strategies.","authors":"Andrea Baschieri,Zongxin Jin,Greta Tödtmann,Gino A DiLabio,Riccardo Amorati","doi":"10.1021/acs.joc.5c01140","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01140","url":null,"abstract":"Kinetic solvent effects (KSE) on hydrogen atom transfer (HAT) reactions play a pivotal role in processes such as photoredox catalysis, electrochemical synthesis, and antioxidant defense. While general principles of KSE are well established, the influence of solvent-radical interactions on the reactivity of the hydroperoxyl radical (HOO•) remains largely uncharacterized. Here, we examine the effects of noncovalent interactions and acid-base equilibria on HOO• reactivity, using the autoxidation of 1,4-cyclohexadiene (CHD) as convenient HOO• source in chlorobenzene (PhCl) or acetonitrile solutions containing cosolvents (S) with varying hydrogen bond acceptor basicities (β2H). Equilibrium (KS) and CHD + HOO• (kpS) rate constants in PhCl were determined for cosolvents including MeOH, MeCN, DMSO, pyridine, and DABCO. As β2H increased from 0.41 (MeOH) to ∼0.70 (DABCO), KS increased from 50 to 3 × 106 M-1, while kpS decreased from 90 to 0.1 M-1 s-1. MeCN (β2H = 0.44) gave KS = 70 M-1 and kpS = 130 M-1 s-1. For DMSO (β2H = 0.78) and pyridine (β2H = 0.62) KS values were 2.0 × 103 and 3 × 105 M-1, respectively, with corresponding kpS values of 20 and 5 M-1 s-1. The observed KS values show a qualitative correlation with the solvent β2H values of the solvents. Moreover, the calculated α2H values for HOO• in nonbasic cosolvents (MeOH, MeCN, DMSO) cluster around 0.87 ± 0.07, consistent with prior estimates. Experiments in MeCN solution suggest HOO• deprotonation with alkylamines, and the pKa of HOO• is estimated as 18-19. These findings provide mechanistic insight into HOO• reactivity in complex media and suggest new strategies for modulating oxidative radical chemistry in both synthetic and biological contexts.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"52 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059001","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":"Orbital Alignment as a Key Determinant of Nanotransport in Molecular Tunnel Junctions Despite Fermi Level Pinning: Exponential Correlation with Molecule–Electrode Coupling","authors":"Ioan Bâldea, Zuoti Xie","doi":"10.1021/acs.jpclett.5c02168","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02168","url":null,"abstract":"At first glance, interrogating the impact of molecular orbital alignment on charge transport in molecular tunnel junctions may appear out of place, given the well-documented strong Fermi level pinning effect. To demonstrate that the contrary is true, we investigated molecular junctions based on self-assembled monolayers (SAMs) of alkyl monothiols (CnT) and dithiols (CnDT) with Ag, Au, and Pt electrodes using the conducting probe atomic force microscopy (CP-AFM) platform. Analysis of these data reveals that the HOMO–metal electronic coupling Γ and the low bias conductance G are exponentially correlated with the HOMO energy offset relative to the Fermi level ε₀ = E_<i>MO</i> – E_<i>F</i> (Γ ∝ exp(−α̅|ε₀|), G ∝ exp(−α|ε₀|), α ≈ 2α̅). This impact is remarkably strong: for CnT junctions, a reduction by only 25% in |ε₀| translates into an increase of Γ by 1 order of magnitude and of G by 2 orders of magnitude. More broadly, this exponential correlation of Γ and G with ε₀ offers deeper insight into nanotransport and extends understanding of the previously reported exponential dependence of Γ and G on the SAM-induced work function shift ΔΦ, which reflects the linear correlation between ε₀ and ΔΦ. From a fundamental perspective, it is crucial to highlight that our data validate a formula for Γ (a property which depends on both electrodes of a junction), which features (i) ε₀ rather than ΔΦ (i.e., a property of a full junction versus a property of a “half a junction”) and (ii) ε₀ rather than its square root in the exponent, thereby invalidating the widely employed tunneling barrier picture.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"70 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059720","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":"Bioinspired Divergent Synthesis of Tricyclic Sesquiterpenoids: Cedrane, Angular Triquinane, allo-Cedrane, and Zizaene.","authors":"Jian Xiao,Zi-Hao Liu,Zi-Fan He,Qian-Yi He,Yi-Chao Ding,Ya-Wen Wang,Wei-Hua Han,Yu Peng,Wei-Dong Z Li","doi":"10.1021/acs.joc.5c01736","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01736","url":null,"abstract":"The cedrane-, angular triquinane-, allo-cedrane-, and zizaene-type natural products belong to the classic family of tricyclic sesquiterpenoids, and many of them possess highly complex molecular structures and display interesting biological activities. Herein, we report a unified strategy toward divergent and bioinspired syntheses of these four types of tricyclic sesquiterpenoid skeletons from common advanced intermediate cyclopentenone 12, which could be constructed by reductive oxy-Nazarov cyclization. Key late-stage transformations include (i) double Brown hydroboration and oxidation, followed by an intramolecular aldol condensation to form the cedrane (I) and angular triquinane (II) skeletons, and (ii) an effective anionic semipinacol rearrangement of tricyclic cedrane mesylate (derived from cis-diol 25 and trans-diol 30) to afford allo-cedrane (III) and zizaene (IV) skeletons, not only a pathway consistent with our proposal for the biogenesis between cedrane and zizaene sesquiterpenoids but also further evidence for the biogenetic relationship between the typical cedrane and allo-cedrane sesquiterpenoids.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"52 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059114","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":"Thermally Generated Cation Pool Enabled Condition-Controlled Synthesis of γ-Ketosulfones and β-Morpholinoketones from Methyl Ketone by α-Csp3-H Methylenation","authors":"Soumya Mohapatra, Niranjan Panda","doi":"10.1021/acs.joc.5c01278","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01278","url":null,"abstract":"A modular synthetic strategy has been developed for the preparation of γ-ketosulfones and β-ketoamines from methyl ketones. Upon heating dimethyl sulfoxide (DMSO) with dichloroethane, expectedly unstable chlorine cation pools are generated, which undergo Pummerer-type rearrangement to form a reactive methyl(methylene)sulfonium ion (CH₂═S⁺–Me). This intermediate reacts with methyl ketones in the presence of a base (amine) to afford γ-ketosulfones through C–C bond formation. Besides, sequential addition of morpholine to the in situ-generated unstable chlorine cation pools followed by a methyl ketone provides β-morpholinoketones. Remarkably, this one-pot transformation proceeds without transition metals or external oxidants, displaying excellent functional-group compatibility. In this process, dichloroethane serves as an activator of DMSO, effectively acting as a C1 donor.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"121 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059591","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":"YourJIC, MyJIC – OurJIC!","authors":"Axel Straube","doi":"10.1002/ejic.202500365","DOIUrl":"https://doi.org/10.1002/ejic.202500365","url":null,"abstract":"<p>It's a new chapter for the <i>European Journal of Inorganic Chemistry</i>! Newly appointed Editor-in-Chief Axel Straube thanks his predecessor, Preeti Vashi, reflects on the journal's history and activities, and presents his vision for <i>EurJIC</i> – to remain an attractive, fully society-owned journal for research on Inorganic and Organometallic Chemistry in all their flavors that gives back to the community.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 25","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500365","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145058033","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Disproportionately Higher Contribution of Endotoxin to PM2.5 Bioactivity than Its Mass Share Highlights the Need to Identify Low-Concentration, High-Potency Components.","authors":"Jinyan Yu,Tian Chen,Yong Han,Xintong Liu,Junrong Su,Polly Hang Mei Leung,Frank Kelly,Kin-Fai Ho,Guangbo Qu,Ling N Jin","doi":"10.1021/acs.est.5c07255","DOIUrl":"https://doi.org/10.1021/acs.est.5c07255","url":null,"abstract":"The contribution of microbial components and their sources to the bioactivity of airborne fine particulate matter (PM2.5) remains unclear. This study validated the concentration-additive mixture effects of ambient PM2.5 fractions on in vitro interleukin-8 (IL-8) induction, enabling quantification of the role of endotoxin from Gram-negative bacteria in IL-8 induction by PM2.5 from contrasting environments. Endotoxin consistently contributed to PM2.5-induced IL-8 at both the coastal site (0.1-10%) and the urban site (0.1-17%), far exceeding its mass fraction in PM2.5 (<0.0001%). Among reported components, endotoxin demonstrated the highest toxicity-to-mass contribution ratio (10,000:1-100,000:1) due to its high potency. This suggests that reducing PM2.5 toxicity may not necessarily require a proportional reduction in its mass. The sources of Gram-negative bacteria shifted from predominantly natural origins at the coastal site (natural-to-anthropogenic ratio of 1.6:1) to increasing anthropogenic contributions at the urban site (natural-to-anthropogenic ratio of 0.7:1). These anthropogenic sources, including the built environment, sewage treatment, and humans, fall outside conventional pollution-intensive categories. These findings highlight the importance of identifying high-potency, low-concentration components and their sources. Targeting such components is critical for cost-effective PM2.5 abatement strategies and achieving significant public health benefits, especially in regions with low-to-moderate PM2.5 levels.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"1 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145058988","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}