Pub Date : 2024-07-05Epub Date: 2024-06-21DOI: 10.1021/acs.joc.3c01845
Shyam Kumar Banjare, Saista Afreen, Wang-Yeuk Kong, Wentao Guo, Tanmayee Nanda, Gopal Krushna Das Adhikari, Naupada Preeyanka, Dean J Tantillo, Ponneri C Ravikumar
Selective functionalization of the indole-C3-C bond with aromatic/heteroaromatic 1,2-diketones has been uncovered for the first time. Cobalt catalyst was found to be an effective catalyst for this unusual transformation. This ipso-C-C bond functionalization occurred in the presence of easily available weakly coordinating groups such as ketone and ester. One of the salient features of this methodology is the in situ generation of water from hexafluoro-2-propanol which acts as a reactant for the removal of the pivaloyl/ester group in a deacylative manner. The plausible mechanism has been supported by DFT calculations. Moreover, photophysical studies show the potential utility of indole-C3-acyloin and indolo-fused carbazole, which could be used in photovoltaic and optoelectronic application.
{"title":"Cobalt-Catalyzed Deacylative <i>Ipso-</i>C-C Bond Functionalization: An Approach toward Indole-Acyloins and Its Photophysical Studies.","authors":"Shyam Kumar Banjare, Saista Afreen, Wang-Yeuk Kong, Wentao Guo, Tanmayee Nanda, Gopal Krushna Das Adhikari, Naupada Preeyanka, Dean J Tantillo, Ponneri C Ravikumar","doi":"10.1021/acs.joc.3c01845","DOIUrl":"10.1021/acs.joc.3c01845","url":null,"abstract":"<p><p>Selective functionalization of the indole-C3-C bond with aromatic/heteroaromatic 1,2-diketones has been uncovered for the first time. Cobalt catalyst was found to be an effective catalyst for this unusual transformation. This <i>ipso</i>-C-C bond functionalization occurred in the presence of easily available weakly coordinating groups such as ketone and ester. One of the salient features of this methodology is the <i>in situ</i> generation of water from hexafluoro-2-propanol which acts as a reactant for the removal of the pivaloyl/ester group in a deacylative manner. The plausible mechanism has been supported by DFT calculations. Moreover, photophysical studies show the potential utility of indole-C3-acyloin and indolo-fused carbazole, which could be used in photovoltaic and optoelectronic application.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430952","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}
Pub Date : 2024-07-05Epub Date: 2024-06-24DOI: 10.1021/acs.joc.4c00612
Pooja K Bagad, Ratanamala S Darole, G Rama Krishna, Beeran Senthilkumar
A direct electrosynthesis/photocatalyst-free, atom-economical, and efficient method for the selective synthesis of (E)-3-amino-2-thiocyanato-α,β-unsaturated carbonyl compounds is described through a given protocol. The present approach features the use of inexpensive ammonium thiocyanate to achieve dual functionalization of 1,3-dicarbonyl compounds using TBHP as an oxidant, providing a rapid and practical route to the selective formation of both C-N and C-S bonds via a radical process. This method offers a broad substrate scope with excellent yield and allows for further exploration of the products to construct heterocyclic compounds and other functionalities.
{"title":"Highly Selective C-N and C-S Dual Functionalization of 1,3-Dicarbonyl Derivatives Using TBHP as an Oxidant.","authors":"Pooja K Bagad, Ratanamala S Darole, G Rama Krishna, Beeran Senthilkumar","doi":"10.1021/acs.joc.4c00612","DOIUrl":"10.1021/acs.joc.4c00612","url":null,"abstract":"<p><p>A direct electrosynthesis/photocatalyst-free, atom-economical, and efficient method for the selective synthesis of (<i>E</i>)-3-amino-2-thiocyanato-α,β-unsaturated carbonyl compounds is described through a given protocol. The present approach features the use of inexpensive ammonium thiocyanate to achieve dual functionalization of 1,3-dicarbonyl compounds using TBHP as an oxidant, providing a rapid and practical route to the selective formation of both C-N and C-S bonds via a radical process. This method offers a broad substrate scope with excellent yield and allows for further exploration of the products to construct heterocyclic compounds and other functionalities.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141445523","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}
Pub Date : 2024-07-05Epub Date: 2024-06-24DOI: 10.1021/acs.joc.4c00659
Amol T Savekar, Ramesh A Gaikwad, Suresh B Waghmode
An efficient one-pot metal-free, base-catalyzed method has been developed for the regioselective [3 + 2]/[4 + 2] annulation reactions of electrophilic methyleneindolinones with haloalcohols to furnish spirooxindole derivatives under mild reaction conditions. This reaction afforded the corresponding products with two contiguous stereocenters including a quaternary center in good to excellent yield (up to 95%) with moderate to good diastereoselectivities (up to 12.5:1 dr) with complete regioselectivity.
{"title":"Metal-Free Regioselective Oxa-Michael Approach to Access Spirooxindole-Fused Tetrahydrofuran/Tetrahydropyran through [3 + 2]/ [4 + 2] Spirocyclization of Methyleneindolinones with Haloalcohols.","authors":"Amol T Savekar, Ramesh A Gaikwad, Suresh B Waghmode","doi":"10.1021/acs.joc.4c00659","DOIUrl":"10.1021/acs.joc.4c00659","url":null,"abstract":"<p><p>An efficient one-pot metal-free, base-catalyzed method has been developed for the regioselective [3 + 2]/[4 + 2] annulation reactions of electrophilic methyleneindolinones with haloalcohols to furnish spirooxindole derivatives under mild reaction conditions. This reaction afforded the corresponding products with two contiguous stereocenters including a quaternary center in good to excellent yield (up to 95%) with moderate to good diastereoselectivities (up to 12.5:1 <i>dr</i>) with complete regioselectivity.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141445525","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}
Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ34SSO4 and δ18OSO4 values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.
{"title":"Natural Attenuation of Groundwater Uranium in Post-Neutral-Mining Sites Evidenced from Multiple Isotopes and Dissolved Organic Matter.","authors":"Chongsheng Lu, Wei Xiu, Bing Yang, Haoyan Zhang, Guoxi Lian, Tianjing Zhang, Erping Bi, Huaming Guo","doi":"10.1021/acs.est.4c04498","DOIUrl":"https://doi.org/10.1021/acs.est.4c04498","url":null,"abstract":"<p><p>Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ<sup>34</sup>S<sub>SO4</sub> and δ<sup>18</sup>O<sub>SO4</sub> values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":null,"pages":null},"PeriodicalIF":10.8,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532918","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}
Pub Date : 2024-07-05Epub Date: 2024-06-12DOI: 10.1021/acs.joc.4c00690
Margot Duggin, Wesley J Olivier, Allan J Canty, Li Feng Lim, Nicholas Cox, Gemma F Turner, Stephen A Moggach, Stuart C Thickett, Alex C Bissember, Rebecca O Fuller
A new method for the preparation of the underrepresented 1,5-dimethyl-6-thioverdazyl radicals has been developed employing Lawesson's reagent (LR). The synthetic route involves the direct thionation of the carbonyl group of the corresponding dialkylbishydrazone followed by cyclization to give the tetrazinanthione verdazyl precursor on a gram scale. Subsequent oxidation yields the 6-thioverdazyl radical. It was determined that thionation of substrates containing electron-withdrawing groups in the ortho- or para-positions was high yielding. In contrast, for the parent phenyl group or substrates bearing weakly electron-donating substituents, thionation efficiency was significantly reduced. This could be overcome by utilizing partial in situ cyclization, which occurs during work up, to generate the tetrazinanthione directly via a one-pot synthesis. Density functional theory suggests that the LR fragment interacts with the carbonyl prior to cycloaddition and subsequent to cycloreversion, leading to the thiocarbonyl. The electronic nature of the radical is characterized with electron paramagnetic resonance as well as the first report of 6-thioverdazyl redox properties.
{"title":"Lawesson's Reagent: Providing a New Approach to the Forgotten 6-Thioverdazyl Radical.","authors":"Margot Duggin, Wesley J Olivier, Allan J Canty, Li Feng Lim, Nicholas Cox, Gemma F Turner, Stephen A Moggach, Stuart C Thickett, Alex C Bissember, Rebecca O Fuller","doi":"10.1021/acs.joc.4c00690","DOIUrl":"10.1021/acs.joc.4c00690","url":null,"abstract":"<p><p>A new method for the preparation of the underrepresented 1,5-dimethyl-6-thioverdazyl radicals has been developed employing Lawesson's reagent (LR). The synthetic route involves the direct thionation of the carbonyl group of the corresponding dialkylbishydrazone followed by cyclization to give the tetrazinanthione verdazyl precursor on a gram scale. Subsequent oxidation yields the 6-thioverdazyl radical. It was determined that thionation of substrates containing electron-withdrawing groups in the <i>ortho-</i> or <i>para-</i>positions was high yielding. In contrast, for the parent phenyl group or substrates bearing weakly electron-donating substituents, thionation efficiency was significantly reduced. This could be overcome by utilizing partial in situ cyclization, which occurs during work up, to generate the tetrazinanthione directly via a one-pot synthesis. Density functional theory suggests that the LR fragment interacts with the carbonyl prior to cycloaddition and subsequent to cycloreversion, leading to the thiocarbonyl. The electronic nature of the radical is characterized with electron paramagnetic resonance as well as the first report of 6-thioverdazyl redox properties.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141304879","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}
Two 6,5,6-fused 1,2,3-triazine-3-oxides (4 and 6) were designed and synthesized via the reaction of o-aminoamidoximes with sodium nitrite. In addition, the ring-opening products (5, 7, and 8) derived from 1,2,3-triazine-3-oxides were isolated and characterized. A comprehensive exploration of the reaction mechanism governing the ring-opening process was performed through a combination of theoretical and experimental studies. Notably, compound 4 exhibited commendable detonation properties and low sensitivity, demonstrating its promising potential as an energetic material.
{"title":"Diazotization of <i>o</i>-Aminoamidoximes for the Preparation of Energetic 6,5,6-Fused 1,2,3-Triazine-3-oxides.","authors":"Zhiwei Zeng, Chunhui Chen, Xuran Xu, Yuji Liu, Wei Huang, Yongxing Tang","doi":"10.1021/acs.joc.4c00821","DOIUrl":"10.1021/acs.joc.4c00821","url":null,"abstract":"<p><p>Two 6,5,6-fused 1,2,3-triazine-3-oxides (<b>4</b> and <b>6</b>) were designed and synthesized via the reaction of <i>o</i>-aminoamidoximes with sodium nitrite. In addition, the ring-opening products (<b>5</b>, <b>7</b>, and <b>8</b>) derived from 1,2,3-triazine-3-oxides were isolated and characterized. A comprehensive exploration of the reaction mechanism governing the ring-opening process was performed through a combination of theoretical and experimental studies. Notably, compound <b>4</b> exhibited commendable detonation properties and low sensitivity, demonstrating its promising potential as an energetic material.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141316022","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}
Cobalt-catalyzed borylative reduction of azobenzenes using pinacolborane is developed. The simple cobalt chloride catalyst and reaction conditions make this protocol attractive for hydrazobenzene synthesis. This borylative reduction shows good functional group compatibility and can be readily scaled up to the gram scale. Preliminary mechanistic studies clarified the proton source of the hydrazine products. This cobalt-catalyzed azobenzene borylative reaction provides a practical protocol to prepare synthetically useful diborylated hydrazines.
{"title":"Cobalt-Catalyzed Borylative Reduction of Azobenzenes to Hydrazobenzenes via a Diborylated-Hydrazine Intermediate.","authors":"Wenli Wang, Yuli Wang, Yiying Yang, Shanshan Xie, Qi Wang, Wenwen Chen, Shuo Wang, Fangjun Zhang, Yinlin Shao","doi":"10.1021/acs.joc.4c00203","DOIUrl":"10.1021/acs.joc.4c00203","url":null,"abstract":"<p><p>Cobalt-catalyzed borylative reduction of azobenzenes using pinacolborane is developed. The simple cobalt chloride catalyst and reaction conditions make this protocol attractive for hydrazobenzene synthesis. This borylative reduction shows good functional group compatibility and can be readily scaled up to the gram scale. Preliminary mechanistic studies clarified the proton source of the hydrazine products. This cobalt-catalyzed azobenzene borylative reaction provides a practical protocol to prepare synthetically useful diborylated hydrazines.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430951","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}
Pub Date : 2024-07-05Epub Date: 2024-06-22DOI: 10.1021/acs.joc.4c00486
Marcos D Codesal, Arthur H G David, Carla I M Santos, Maria J Álvaro-Martins, Ermelinda Maçôas, Araceli G Campaña, Victor Blanco
Heptagon-containing distorted nanographenes are used as stoppers for the capping of a [2]rotaxane through a Michael-type addition reaction to vinyl sulfone groups. These curved aromatics are bulky enough to prevent the disassembly of the rotaxane but also give emissive and nonlinear (two-photon absorption and emission) optical properties to the structure.
{"title":"Curved Nanographenes as Stoppers in a [2]Rotaxane with Two-Photon Excited Emission.","authors":"Marcos D Codesal, Arthur H G David, Carla I M Santos, Maria J Álvaro-Martins, Ermelinda Maçôas, Araceli G Campaña, Victor Blanco","doi":"10.1021/acs.joc.4c00486","DOIUrl":"10.1021/acs.joc.4c00486","url":null,"abstract":"<p><p>Heptagon-containing distorted nanographenes are used as stoppers for the capping of a [2]rotaxane through a Michael-type addition reaction to vinyl sulfone groups. These curved aromatics are bulky enough to prevent the disassembly of the rotaxane but also give emissive and nonlinear (two-photon absorption and emission) optical properties to the structure.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141440066","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}
Pub Date : 2024-07-05DOI: 10.1021/acs.jpclett.4c01416
Timo Glaser, Alexa Adamkiewicz, Julian Heep, Ulrich Höfer, Michael Dürr
Selective adsorption of multifunctional molecules is rarely observed when the different functional groups react via nonactivated reaction channels. Although the latter is also the case for ether cleavage and the adsorption of C=C double bonds on the highly reactive Si(001) surface, we find that allyl ethers, which combine both functional groups, react on Si(001) selectively via the cleavage of the molecules' ether group. In addition, our XPS measurements at 90, 150, and 300 K indicate an increased reactivity of the ether group when compared to monofunctional ethers. STM investigations furthermore reveal different final adsorption configurations after ether cleavage of allyl methyl ether when compared to diethyl ether as the monofunctional reference molecule. The interaction of the two functional groups in one molecule thus leads to new reaction channels with higher reactivity for ether cleavage on Si(001). As a further consequence, the reactivity of the C=C double bond is suppressed up to room temperature, leading to the observed selective adsorption.
{"title":"Chemoselective Adsorption of Allyl Ethers on Si(001): How the Interaction between Two Functional Groups Controls the Reactivity and Final Products of a Surface Reaction.","authors":"Timo Glaser, Alexa Adamkiewicz, Julian Heep, Ulrich Höfer, Michael Dürr","doi":"10.1021/acs.jpclett.4c01416","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c01416","url":null,"abstract":"<p><p>Selective adsorption of multifunctional molecules is rarely observed when the different functional groups react via nonactivated reaction channels. Although the latter is also the case for ether cleavage and the adsorption of C=C double bonds on the highly reactive Si(001) surface, we find that allyl ethers, which combine both functional groups, react on Si(001) selectively via the cleavage of the molecules' ether group. In addition, our XPS measurements at 90, 150, and 300 K indicate an increased reactivity of the ether group when compared to monofunctional ethers. STM investigations furthermore reveal different final adsorption configurations after ether cleavage of allyl methyl ether when compared to diethyl ether as the monofunctional reference molecule. The interaction of the two functional groups in one molecule thus leads to new reaction channels with higher reactivity for ether cleavage on Si(001). As a further consequence, the reactivity of the C=C double bond is suppressed up to room temperature, leading to the observed selective adsorption.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532837","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}
Air pollution, especially particulate matter (PM), is a significant environmental pollution worldwide. Studying the chemical, environmental, and life-related cellular physical characteristics of size-fractionated PMs is important because of their different degrees of harmful effects on human respiratory tracts and organ systems, causing severe diseases. This study evaluates the chemical components of size-fractionated PMs down to PM0.1 collected during a biomass-burning episode, including elemental/organic carbon and trace elements. Single particle sizes and distributions of PM0.1, PM0.5-0.1, PM1.0-0.5, and PM2.5-1.0 were analyzed by scanning electron microscopy and Zeta sizer. Two commonly used cell lines, e.g., HeLa and Cos7 cells, and two respiratory-related cell lines including lung cancer/normal cells were utilized for cell cytotoxicity experiments, revealing the key effects of particle sizes and concentrations. A high-speed scanning ion conductance microscope explored particle-stimulated subcellular physical characteristics for all cell lines in dynamics, including surface roughness (SR) and elastic modulus (E). The statistical results of SR showed distinct features among different particle sizes and cell types while a E reduction was universally found. This work provides a comprehensive understanding of the chemical, environmental, and cellular physical characteristics of size-fractionated PMs and sheds light on the necessity of controlling small-sized PM exposures.
空气污染,尤其是颗粒物(PM),是全球范围内的重大环境污染。由于可吸入颗粒物会对人体呼吸道和器官系统造成不同程度的危害,导致严重的疾病,因此研究颗粒物的化学、环境和与生命相关的细胞物理特性非常重要。本研究评估了在生物质燃烧过程中收集到的粒径分馏至 PM0.1 的可吸入颗粒物的化学成分,包括元素/有机碳和微量元素。通过扫描电子显微镜和 Zeta 分析仪分析了 PM0.1、PM0.5-0.1、PM1.0-0.5 和 PM2.5-1.0 的单一粒径和分布。利用两种常用细胞系(如 HeLa 和 Cos7 细胞)和两种与呼吸系统相关的细胞系(包括肺癌/正常细胞)进行细胞毒性实验,揭示了颗粒大小和浓度的关键影响。高速扫描离子电导显微镜对所有细胞系的颗粒刺激亚细胞物理特性进行了动态探索,包括表面粗糙度(SR)和弹性模量(E)。SR 的统计结果显示,不同粒径和细胞类型的细胞具有不同的特征,而 E 则普遍降低。这项研究全面了解了按粒度分馏的可吸入颗粒物的化学、环境和细胞物理特性,并揭示了控制小粒度可吸入颗粒物暴露的必要性。
{"title":"Characterizing Chemical, Environmental, and Stimulated Subcellular Physical Characteristics of Size-Fractionated PMs Down to PM<sub>0.1</sub>.","authors":"Worradorn Phairuang, Thaneeya Chetiyanukornkul, Phuchiwan Suriyawong, Muhammad Amin, Mitsuhiko Hata, Masami Furuuchi, Masahiro Yamazaki, Noriko Gotoh, Hirotoshi Furusho, Ayhan Yurtsever, Shinji Watanabe, Linhao Sun","doi":"10.1021/acs.est.4c01604","DOIUrl":"https://doi.org/10.1021/acs.est.4c01604","url":null,"abstract":"<p><p>Air pollution, especially particulate matter (PM), is a significant environmental pollution worldwide. Studying the chemical, environmental, and life-related cellular physical characteristics of size-fractionated PMs is important because of their different degrees of harmful effects on human respiratory tracts and organ systems, causing severe diseases. This study evaluates the chemical components of size-fractionated PMs down to PM<sub>0.1</sub> collected during a biomass-burning episode, including elemental/organic carbon and trace elements. Single particle sizes and distributions of PM<sub>0.1</sub>, PM<sub>0.5-0.1</sub>, PM<sub>1.0-0.5</sub>, and PM<sub>2.5-1.0</sub> were analyzed by scanning electron microscopy and Zeta sizer. Two commonly used cell lines, e.g., HeLa and Cos7 cells, and two respiratory-related cell lines including lung cancer/normal cells were utilized for cell cytotoxicity experiments, revealing the key effects of particle sizes and concentrations. A high-speed scanning ion conductance microscope explored particle-stimulated subcellular physical characteristics for all cell lines in dynamics, including surface roughness (SR) and elastic modulus (<i>E</i>). The statistical results of SR showed distinct features among different particle sizes and cell types while a <i>E</i> reduction was universally found. This work provides a comprehensive understanding of the chemical, environmental, and cellular physical characteristics of size-fractionated PMs and sheds light on the necessity of controlling small-sized PM exposures.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":null,"pages":null},"PeriodicalIF":10.8,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496257","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}