ACS OmegaPub Date : 2024-12-09eCollection Date: 2024-12-17DOI: 10.1021/acsomega.4c09295
Kangbiao Chen, Rui Zhou, Gaofeng Zhu, Lei Tang, Lu Huang, Qing He
{"title":"Metal-Free Synthesis of Functionalized Indolizines via a Cascade Michael/S<sub>N</sub>2/Aromatization Reaction of 2-Alkylazaarene Derivatives with Bromonitroolefins.","authors":"Kangbiao Chen, Rui Zhou, Gaofeng Zhu, Lei Tang, Lu Huang, Qing He","doi":"10.1021/acsomega.4c09295","DOIUrl":"https://doi.org/10.1021/acsomega.4c09295","url":null,"abstract":"<p><p>A transition metal-free domino Michael/S<sub>N</sub>2/aromatization annulation of 2-pyridylacetates with bromonitroolefins has been developed. A wide range of substrates containing various substituted groups was compatible with the present methodology and afforded functionalized indolizines with moderate to excellent yield (up to 99% yield). In addition, the potential practicality of the method stood out through scale-up reactions and further transformations to other valuable compounds. In our view, this study is an essential complement for the rapid construction of indolizine derivatives through a metal-free strategy.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49980-49985"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656401/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09eCollection Date: 2024-12-17DOI: 10.1021/acsomega.4c09193
Junmei Wang, Qingkun Tian, Li Chen, Maoyou Yang, Xia Zhang, Xiaodan Wang
{"title":"TiO<sub>2</sub>-Mo<sub>2</sub>C Heterostructure for Enhanced Electrocatalytic Nitrogen Reduction to Ammonia.","authors":"Junmei Wang, Qingkun Tian, Li Chen, Maoyou Yang, Xia Zhang, Xiaodan Wang","doi":"10.1021/acsomega.4c09193","DOIUrl":"https://doi.org/10.1021/acsomega.4c09193","url":null,"abstract":"<p><p>The development of catalysts with high activity and selectivity for the electrochemical nitrogen reduction reaction (NRR) remains crucial. Molybdenum carbide (Mo<sub>2</sub>C) shows promise as an electrocatalyst for NRR but faces challenges due to the difficulty of N<sub>2</sub> adsorption and activation as well as the competitive hydrogen evolution reaction. In this study, we propose a strategy of combining TiO<sub>2</sub> with Mo<sub>2</sub>C to form heterostructure catalysts. Our first-principles theoretical calculations indicate that the TiO<sub>2</sub>-Mo<sub>2</sub>C heterostructure exhibits enhanced N<sub>2</sub> adsorption and activation, attributed to the increased interaction between the π<sub>4d</sub> <sup>*</sup> orbital of Mo and the π<sub>2p</sub> <sup>*</sup> orbital of N<sub>2</sub>, facilitated by the directional modulation of Mo's d-orbitals by TiO<sub>2</sub>. A more positive integrated crystal orbital Hamilton population and an elongated N≡N bond length prove this. Additionally, the higher Gibbs free energy for N<sub>2</sub> compared to that for H demonstrates a preference for N<sub>2</sub> adsorption. We further elucidate the catalytic mechanism for converting N<sub>2</sub> to NH<sub>3</sub> on the TiO<sub>2</sub>-Mo<sub>2</sub>C surface, identifying the associative distal pathway as the dominant route over the associative alternating pathway. This work highlights unique advantages of the TiO<sub>2</sub>-Mo<sub>2</sub>C heterostructure for the NRR and provides theoretical guidance for designing efficient NRR electrocatalysts.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49945-49952"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656252/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09eCollection Date: 2024-12-17DOI: 10.1021/acsomega.4c07132
Hui-Qin Liu, Xi-Dong Wu, Xue-Wen Fang, Yun-Song An, Meng Xia, Xiao-Hua Luo, Jun-Zheng Li, Guan-Hai Wang, Tao Liu
{"title":"Tumor-Targeted Magnetic Micelles for Magnetic Resonance Imaging, Drug Delivery, and Overcoming Multidrug Resistance.","authors":"Hui-Qin Liu, Xi-Dong Wu, Xue-Wen Fang, Yun-Song An, Meng Xia, Xiao-Hua Luo, Jun-Zheng Li, Guan-Hai Wang, Tao Liu","doi":"10.1021/acsomega.4c07132","DOIUrl":"https://doi.org/10.1021/acsomega.4c07132","url":null,"abstract":"<p><p>Nasopharyngeal carcinoma (NPC) is prevalent in Southern China. Unfortunately, current treatments encounter multidrug resistance (MDR). Overexpression of P-glycoprotein (P-gp), resulting in the efflux of chemotherapy drugs, is one of the significant mechanisms causing MDR. d-α-Tocopheryl poly(ethylene glycol) 1000 succinate (TPGS) has been demonstrated to effectively inhibit P-gp expression. The objectives of this study are to improve tumor MRI imaging, optimize docetaxel (DOC) administration, and target P-gp to overcome NPC resistance. Multifunctional micelles of TPGS (MM@DOC), loaded with magnetic nanoparticles, were synthesized for the targeted delivery of the first-line anticancer drug. MM@DOC exhibited greater toxicity and induced higher levels of apoptosis in DOC-resistant NPC cells (C666-1/DOC) compared to DOC. MM@DOC loaded with magnetic nanoparticles improved the quality of tumor MRI imaging. MM@DOC also demonstrated significant antitumor effects in nude mice with C666-1/DOC NPC. In conclusion, MM@DOC exhibited promising inhibitory effects on resistant tumors both in vitro and in vivo, optimized tumor MRI imaging, and showed great potential in drug delivery and overcoming resistance.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49566-49579"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656234/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875470","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09DOI: 10.1021/acsomega.4c0713210.1021/acsomega.4c07132
Hui-Qin Liu, Xi-Dong Wu, Xue-Wen Fang, Yun-Song An, Meng Xia, Xiao-Hua Luo, Jun-Zheng Li*, Guan-Hai Wang* and Tao Liu*,
{"title":"Tumor-Targeted Magnetic Micelles for Magnetic Resonance Imaging, Drug Delivery, and Overcoming Multidrug Resistance","authors":"Hui-Qin Liu, Xi-Dong Wu, Xue-Wen Fang, Yun-Song An, Meng Xia, Xiao-Hua Luo, Jun-Zheng Li*, Guan-Hai Wang* and Tao Liu*, ","doi":"10.1021/acsomega.4c0713210.1021/acsomega.4c07132","DOIUrl":"https://doi.org/10.1021/acsomega.4c07132https://doi.org/10.1021/acsomega.4c07132","url":null,"abstract":"<p >Nasopharyngeal carcinoma (NPC) is prevalent in Southern China. Unfortunately, current treatments encounter multidrug resistance (MDR). Overexpression of P-glycoprotein (P-gp), resulting in the efflux of chemotherapy drugs, is one of the significant mechanisms causing MDR. <span>d</span>-α-Tocopheryl poly(ethylene glycol) 1000 succinate (TPGS) has been demonstrated to effectively inhibit P-gp expression. The objectives of this study are to improve tumor MRI imaging, optimize docetaxel (DOC) administration, and target P-gp to overcome NPC resistance. Multifunctional micelles of TPGS (MM@DOC), loaded with magnetic nanoparticles, were synthesized for the targeted delivery of the first-line anticancer drug. MM@DOC exhibited greater toxicity and induced higher levels of apoptosis in DOC-resistant NPC cells (C666–1/DOC) compared to DOC. MM@DOC loaded with magnetic nanoparticles improved the quality of tumor MRI imaging. MM@DOC also demonstrated significant antitumor effects in nude mice with C666–1/DOC NPC. In conclusion, MM@DOC exhibited promising inhibitory effects on resistant tumors both in vitro and in vivo, optimized tumor MRI imaging, and showed great potential in drug delivery and overcoming resistance.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49566–49579 49566–49579"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c07132","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09eCollection Date: 2024-12-17DOI: 10.1021/acsomega.4c06671
Ryujiro Kishi, Shoichi Nishitani, Hiroyuki Kudo, Toshiya Sakata
{"title":"Charging and Discharging of Poly(<i>m</i>-aminophenylboronic Acid) Doped with Phytic Acid for Enzyme-Free Real-Time Monitoring of Human Sweat Lactate.","authors":"Ryujiro Kishi, Shoichi Nishitani, Hiroyuki Kudo, Toshiya Sakata","doi":"10.1021/acsomega.4c06671","DOIUrl":"https://doi.org/10.1021/acsomega.4c06671","url":null,"abstract":"<p><p>In this study, we realized a real-time and enzyme-free measurement of lactate in sweat in the same way as an enzyme-based amperometric method. A conductive polymer, which is based on polyaniline (PANI), was strongly coated on a glassy carbon electrode as a poly <i>m</i>-aminophenylboronic acid (PANI-PBA) membrane by drop-casting, which is a convenient method, owing to adhesive phytic acid (PA) molecules with negative charges included as a dopant. This polymer membrane had a functional structure with PBA in the PANI main chain, which expectedly induced electrical charges upon diol binding to lactate, owing to the formation of deprotonated boronate esters with negative charges. This indicates that PBA served as the self-dopant and as the site of binding to lactate. On the basis of the fundamental electrochemical characteristics such as the membrane resistance, the change in the current density of the PA-doped PANI-PBA electrode was quantitatively monitored with the change in lactate concentration from 1 to 300 mM under acidic conditions in real time, considering pH and interfering substances in sweat. Moreover, the sweat lactate concentration was determined to be ca. 60 mM using the PA-doped PANI-PBA electrode in a microfluidic system in measurements using sweat samples collected during exercise load. A change in current density induced a change in the density of charges in the capacitive PA-doped PANI-PBA membrane. This means that the detection mechanism for the change in the lactate concentration in sweat was based on repeated charging and discharging in the PA-doped PANI-PBA electrode.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49368-49376"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656369/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09eCollection Date: 2024-12-17DOI: 10.1021/acsomega.4c08405
Filippo Romeggio, Rasmus Bischoff, Clara B Møller, Victor L Jensen, Esteban Gioria, Rikke Egeberg Tankard, Rasmus S Nielsen, Ole Hansen, Ib Chorkendorff, Jakob Kibsgaard, Christian D Damsgaard
{"title":"Room-Temperature Deposition of δ-Ni<sub>5</sub>Ga<sub>3</sub> Thin Films and Nanoparticles via Magnetron Sputtering.","authors":"Filippo Romeggio, Rasmus Bischoff, Clara B Møller, Victor L Jensen, Esteban Gioria, Rikke Egeberg Tankard, Rasmus S Nielsen, Ole Hansen, Ib Chorkendorff, Jakob Kibsgaard, Christian D Damsgaard","doi":"10.1021/acsomega.4c08405","DOIUrl":"https://doi.org/10.1021/acsomega.4c08405","url":null,"abstract":"<p><p>Magnetron sputtering is a versatile method for investigating model system catalysts thanks to its simplicity, reproducibility, and chemical-free synthesis process. It has recently emerged as a promising technique for synthesizing δ-Ni<sub>5</sub>Ga<sub>3</sub> thin films. Physically deposited thin films have significant potential to clarify certain aspects of catalysts by eliminating parameters such as particle size dependence, metal-support interactions, and the presence of surface ligands. In this work, we demonstrate the potential of magnetron sputtering for the synthesis and analysis of thin film catalysts, using Ni<sub>5</sub>Ga<sub>3</sub> as a model system. Initially, deposition conditions were optimized by varying the deposition pressure, followed by an investigation of the temperature effects, aiming to map a structure zone dependence on temperature and pressure as in the Thornton model. The evolution of film crystallinity was monitored using a combination of grazing incidence X-ray diffraction (GI-XRD) and high-resolution scanning electron microscopy (HR-SEM). Additionally, ultrathin films were synthesized and annealed in H<sub>2</sub> at high temperatures to demonstrate the possibility of producing size-controlled nanoparticles by adjusting the annealing conditions. This work demonstrates the full potential of magnetron sputtering as a technique for synthesizing model system catalysts in various forms, opening new avenues for the research and development of additional catalytic systems.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49759-49766"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656207/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09eCollection Date: 2024-12-17DOI: 10.1021/acsomega.4c08622
João Marcos Costa Monteiro, Elso Drigo Filho
{"title":"Tunneling Times in an Asymmetric Harmonic Double-Well with Application to Electron Transfers in Biological Macromolecules.","authors":"João Marcos Costa Monteiro, Elso Drigo Filho","doi":"10.1021/acsomega.4c08622","DOIUrl":"https://doi.org/10.1021/acsomega.4c08622","url":null,"abstract":"<p><p>Tunneling times were calculated in electron transfer processes using an asymmetric harmonic double-well model. The simplicity of a direct variational calculation in the approximate solution of the Schrödinger equation, along with the interpretation of tunneling times within the probabilistic framework of a two-level system, allows for the efficient and accurate determination of tunneling times with minimal computational cost. These calculations were applied to electron transfer processes in the study of the photosynthetic reaction center and in the context of catalysis in UV-induced DNA lesion repair and are in agreement with the experimental, computational, and theoretical results with which they were compared. It was seen that the donor-acceptor distance needed to be adjusted for closer agreement between the calculated and experimentally observed times. However, the adjusted values for this distance remain close to those reported in the literature.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49832-49838"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656229/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09eCollection Date: 2024-12-17DOI: 10.1021/acsomega.4c05742
Leonardo R de Almeida, Antônio S N Aguiar, Alex B R M da Anunciação, Giulio D C d'Oliveira, Wesley F Vaz, Jean M F Custódio, Caridad N Pérez, Hamilton B Napolitano
{"title":"Three Dihydroquinolin-4-one Derivatives as Potential Biodiesel Additives: From the Molecular Structure to Machine Learning Approach.","authors":"Leonardo R de Almeida, Antônio S N Aguiar, Alex B R M da Anunciação, Giulio D C d'Oliveira, Wesley F Vaz, Jean M F Custódio, Caridad N Pérez, Hamilton B Napolitano","doi":"10.1021/acsomega.4c05742","DOIUrl":"https://doi.org/10.1021/acsomega.4c05742","url":null,"abstract":"<p><p>Biodiesel offers an alternative to fossil fuels, primarily because it is derived from renewable sources, with the potential to mitigate issues such as pollutant and greenhouse gas emissions, resource scarcity, and the market instability of petroleum derivatives. However, lower durability and stability pose challenges. To address this, researchers worldwide are exploring technologies that employ specific molecules to slow down biodiesel's oxidation process, thereby preserving its key physicochemical properties. This study investigates heterocyclic dihydroquinolinone derivatives as potential additives to enhance the oxidative stability of diesel-biodiesel blends. Comprehensive structural and computational analyses were carried out by density functional theory to investigate the reactivity aspects of these compounds as potential additive candidates. The supramolecular arrangements were predominantly stabilized by weak molecular interactions, such as C-H···O and C-H···π, which are associated with antioxidant and antibacterial properties. We demonstrate that these groups can act as electron-donating or electron-withdrawing substituents. We explored frontier molecular orbitals, which provide insights into chemical reactivity, acidity, basicity, and the best oxidizing and reducing agents. Finally, the molecular chemical potential maps indicate the nucleophilic and electrophilic regions and the Fukui indices show the sites of nucleophilic, electrophilic, and radical attacks. This comprehensive study paves the way to understanding how dihydroquinolinone-based compounds serve as alternatives for fuel additives.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49188-49204"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656225/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-09DOI: 10.1021/acsomega.4c0919310.1021/acsomega.4c09193
Junmei Wang*, Qingkun Tian, Li Chen, Maoyou Yang, Xia Zhang and Xiaodan Wang,
{"title":"TiO2–Mo2C Heterostructure for Enhanced Electrocatalytic Nitrogen Reduction to Ammonia","authors":"Junmei Wang*, Qingkun Tian, Li Chen, Maoyou Yang, Xia Zhang and Xiaodan Wang, ","doi":"10.1021/acsomega.4c0919310.1021/acsomega.4c09193","DOIUrl":"https://doi.org/10.1021/acsomega.4c09193https://doi.org/10.1021/acsomega.4c09193","url":null,"abstract":"<p >The development of catalysts with high activity and selectivity for the electrochemical nitrogen reduction reaction (NRR) remains crucial. Molybdenum carbide (Mo<sub>2</sub>C) shows promise as an electrocatalyst for NRR but faces challenges due to the difficulty of N<sub>2</sub> adsorption and activation as well as the competitive hydrogen evolution reaction. In this study, we propose a strategy of combining TiO<sub>2</sub> with Mo<sub>2</sub>C to form heterostructure catalysts. Our first-principles theoretical calculations indicate that the TiO<sub>2</sub>–Mo<sub>2</sub>C heterostructure exhibits enhanced N<sub>2</sub> adsorption and activation, attributed to the increased interaction between the π<sub>4d</sub><sup>*</sup> orbital of Mo and the π<sub>2p</sub><sup>*</sup> orbital of N<sub>2</sub>, facilitated by the directional modulation of Mo’s d-orbitals by TiO<sub>2</sub>. A more positive integrated crystal orbital Hamilton population and an elongated N≡N bond length prove this. Additionally, the higher Gibbs free energy for N<sub>2</sub> compared to that for H demonstrates a preference for N<sub>2</sub> adsorption. We further elucidate the catalytic mechanism for converting N<sub>2</sub> to NH<sub>3</sub> on the TiO<sub>2</sub>–Mo<sub>2</sub>C surface, identifying the associative distal pathway as the dominant route over the associative alternating pathway. This work highlights unique advantages of the TiO<sub>2</sub>–Mo<sub>2</sub>C heterostructure for the NRR and provides theoretical guidance for designing efficient NRR electrocatalysts.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49945–49952 49945–49952"},"PeriodicalIF":3.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c09193","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS OmegaPub Date : 2024-12-08DOI: 10.1021/acsomega.4c0715910.1021/acsomega.4c07159
Avijit Pramanik, Olorunsola Praise Kolawole, Sanchita Kundu, Kaelin Gates, Shivangee Rai, Manoj K. Shukla and Paresh Chandra Ray*,
{"title":"Cooperative Molecular Interaction-Based Highly Efficient Capturing of Ultrashort- and Short-Chain Emerging Per- and Polyfluoroalkyl Substances Using Multifunctional Nanoadsorbents","authors":"Avijit Pramanik, Olorunsola Praise Kolawole, Sanchita Kundu, Kaelin Gates, Shivangee Rai, Manoj K. Shukla and Paresh Chandra Ray*, ","doi":"10.1021/acsomega.4c0715910.1021/acsomega.4c07159","DOIUrl":"https://doi.org/10.1021/acsomega.4c07159https://doi.org/10.1021/acsomega.4c07159","url":null,"abstract":"<p >The short-chain (C<sub>4</sub> to C<sub>7</sub>) and ultrashort-chain (C<sub>3</sub> to C<sub>2</sub>) per- and polyfluoroalkyl substances (PFAS) are bioaccumulative, carcinogenic to humans, and harder to remove using current technologies, which are often detected in drinking and environmental water samples. Herein, we report the development of nonafluorobutanesulfonyl (NFBS) and polyethylene-imine (PEI)-conjugated Fe<sub>3</sub>O<sub>4</sub> magnetic nanoparticle-based magnetic nanoadsorbents and demonstrated that the novel adsorbent has the capability for highly efficient removal of six different short- and ultrashort-chain PFAS from drinking and environmental water samples. Reported experimental data indicates that by capitalizing the cooperative hydrophobic, fluorophilic, and electrostatic interaction processes, NFBS-PEI-conjugated magnetic nanoadsorbents can remove ∼100% short-chain perfluorobutanesulfonic acid within 30 min from the water sample with a maximum absorption capacity <i>q</i><sub>m</sub> of ∼234 mg g<sup>–1</sup>. Furthermore, to show how cooperative interactions are necessary for effective capturing of ultrashort and short PFAS, a comparative study has been performed using PEI-attached magnetic nanoadsorbents without NFBS and acid-functionalized magnetic nanoadsorbents without PEI and NFBS. Reported data show that the ultrashort-chain perfluoropropanesulfonic acid capture efficiency is the highest for the NFBS-PEI-attached nanoadsorbent (<i>q</i><sub>m</sub> ∼ 187 mg g<sup>–1</sup>) in comparison to the PEI-attached nanoadsorbent (<i>q</i><sub>m</sub> ∼ 119 mg g<sup>–1</sup>) or carboxylic acid-attached nanoadsorbent (<i>q</i><sub>m</sub> ∼ 52 mg g<sup>–1</sup>). In addition, the role of cooperative molecular interactions in highly efficient removal of ultrashort-chain PFAS has been analyzed in detail. Moreover, reported data demonstrate that nanoadsorbents can be used for effective removal of short-chain PFAS (<92%) and ultrashort-chain PFAS (<70%) simultaneously from reservoir, lake, tape, and river water samples within 30 min, which shows the potential of nanoadsorbents for real-life PFAS remediation.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 50","pages":"49452–49462 49452–49462"},"PeriodicalIF":3.7,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c07159","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}