Pub Date : 2024-07-11DOI: 10.1021/acs.inorgchem.4c01101
M Sachithra Somachandra, Boris Averkiev, Peter E Sues
Designing ligand architectures that can mimic enzyme active sites is a promising approach for developing efficient small molecule activation catalysts for sustainable energy applications. Some key design features include chemically distinct binding pockets for multiple metal centers and a three-dimensional structure that controls the positioning of catalytic sites. With these principles in mind, mono- and bimetallic unsymmetric cofacial palladium complexes, 2 and 3, respectively, bearing ligands with calixpyrrole and salen coordination sites, or "salixpyrrole" ligands, are reported. These species were accessed in a straightforward Schiff-base reaction with appreciable yields. In addition, both 2 and 3 were found to be active hydrogen evolution electrocatalysts using para-toluenesulfonic acid monohydrate as the proton source. The two salixpyrrole species displayed different mechanisms of action, with 2 showing a second-order dependence on acid concentration, whereas 3 exhibited a first-order dependence. Moreover, the bimetallic catalyst was significantly more efficient, with higher turnover frequencies, 4640 s-1 vs 1680 s-1 for 2, and lower overpotentials, 0.39 V vs 0.69 V for 2. The results reported herein provide proof-of-concept that bimetallic catalysts with chemically distinct binding sites demonstrate enhanced catalytic properties in comparison to monometallic or symmetric analogues.
{"title":"Unsymmetric Co-Facial \"Salixpyrrole\" Hydrogen Evolution Catalysts: Two Metals are Better than One.","authors":"M Sachithra Somachandra, Boris Averkiev, Peter E Sues","doi":"10.1021/acs.inorgchem.4c01101","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01101","url":null,"abstract":"<p><p>Designing ligand architectures that can mimic enzyme active sites is a promising approach for developing efficient small molecule activation catalysts for sustainable energy applications. Some key design features include chemically distinct binding pockets for multiple metal centers and a three-dimensional structure that controls the positioning of catalytic sites. With these principles in mind, mono- and bimetallic unsymmetric cofacial palladium complexes, <b>2</b> and <b>3</b>, respectively, bearing ligands with calixpyrrole and salen coordination sites, or \"salixpyrrole\" ligands, are reported. These species were accessed in a straightforward Schiff-base reaction with appreciable yields. In addition, both <b>2</b> and <b>3</b> were found to be active hydrogen evolution electrocatalysts using <i>para</i>-toluenesulfonic acid monohydrate as the proton source. The two salixpyrrole species displayed different mechanisms of action, with <b>2</b> showing a second-order dependence on acid concentration, whereas <b>3</b> exhibited a first-order dependence. Moreover, the bimetallic catalyst was significantly more efficient, with higher turnover frequencies, 4640 s<sup>-1</sup> vs 1680 s<sup>-1</sup> for <b>2</b>, and lower overpotentials, 0.39 V vs 0.69 V for <b>2</b>. The results reported herein provide proof-of-concept that bimetallic catalysts with chemically distinct binding sites demonstrate enhanced catalytic properties in comparison to monometallic or symmetric analogues.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578211","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}
Antireflective coatings with superhydrophobicity have many outdoor applications, such as solar photovoltaic panels and windshields. In this study, we fabricated an omnidirectional antireflective and superhydrophobic coating with good mechanical robustness and environmental durability via the spin coating technique. The coating consisted of a layer of phytic acid (PA)/polyacrylamide (PAM)/calcium ions (Ca2+) (referred to as Binder), an antireflective layer composed of chitin nanofibers (ChNFs), and a hydrophobic layer composed of methylsilanized silica (referred to as Mosil). The transmittance of a glass slide with the Binder/ChNFs/Mosil coating had a 5.2% gain at a wavelength of 550 nm, and the antireflective coating showed a water contact angle as high as 160° and a water sliding angle of 8°. The mechanical robustness and environmental durability of the coating, including resistance to peeling, dynamic impact, chemical erosion, ultraviolet (UV) irradiation, and high temperature, were evaluated. The coating retained excellent antireflective capacity and self-cleaning performance in the harsh conditions. The increase in voltage per unit area of a solar panel with a Binder/ChNFs/Mosil coating reached 0.4 mV/cm2 compared to the solar panel exposed to sunlight with an intensity of 54.3 × 103 lx. This work not only demonstrates that ChNFs can be used as raw materials to fabricate antireflective superhydrophobic coatings for outdoor applications but also provides a feasible and efficient approach to do so.
{"title":"Antireflective Superhydrophobic and Robust Coating Based on Chitin Nanofibers and Methylsilanized Silica for Outdoor Applications.","authors":"Li Zhang, Jian Xu, Zhiqing Hu, Peizhuang Wang, Jiaqi Shang, Jiang Zhou, Lili Ren","doi":"10.1021/acsami.4c05778","DOIUrl":"https://doi.org/10.1021/acsami.4c05778","url":null,"abstract":"<p><p>Antireflective coatings with superhydrophobicity have many outdoor applications, such as solar photovoltaic panels and windshields. In this study, we fabricated an omnidirectional antireflective and superhydrophobic coating with good mechanical robustness and environmental durability via the spin coating technique. The coating consisted of a layer of phytic acid (PA)/polyacrylamide (PAM)/calcium ions (Ca<sup>2+</sup>) (referred to as Binder), an antireflective layer composed of chitin nanofibers (ChNFs), and a hydrophobic layer composed of methylsilanized silica (referred to as Mosil). The transmittance of a glass slide with the Binder/ChNFs/Mosil coating had a 5.2% gain at a wavelength of 550 nm, and the antireflective coating showed a water contact angle as high as 160° and a water sliding angle of 8°. The mechanical robustness and environmental durability of the coating, including resistance to peeling, dynamic impact, chemical erosion, ultraviolet (UV) irradiation, and high temperature, were evaluated. The coating retained excellent antireflective capacity and self-cleaning performance in the harsh conditions. The increase in voltage per unit area of a solar panel with a Binder/ChNFs/Mosil coating reached 0.4 mV/cm<sup>2</sup> compared to the solar panel exposed to sunlight with an intensity of 54.3 × 10<sup>3</sup> lx. This work not only demonstrates that ChNFs can be used as raw materials to fabricate antireflective superhydrophobic coatings for outdoor applications but also provides a feasible and efficient approach to do so.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":8.3,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141582029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-11DOI: 10.1021/acs.analchem.4c02500
Yonghong Zha, Yansong Li, Jianhua Zhou, Xiaolan Liu, Ki Soo Park, Yu Zhou
Given the harmful effect of pesticide residues, it is essential to develop portable and accurate biosensors for the analysis of pesticides in agricultural products. In this paper, we demonstrated a dual-mode fluorescent/intelligent (DM-f/DM-i) lateral flow immunoassay (LFIA) for chloroacetamide herbicides, which utilized horseradish peroxidase-IgG conjugated time-resolved fluorescent nanoparticle probes as both a signal label and amplification tool. With the newly developed LFIA in the DM-f mode, the limits of detection (LODs) were 0.08 ng/mL of acetochlor, 0.29 ng/mL of metolachlor, 0.51 ng/mL of Propisochlor, and 0.13 ng/mL of their mixture. In the DM-i mode, machine learning (ML) algorithms were used for image segmentation, feature extraction, and correlation analysis to obtain multivariate fitted equations, which had high reliability in the regression model with R2 of 0.95 in the range of 2 × 102-2 × 105 pg/mL. Importantly, the practical applicability was successfully validated by determining chloroacetamide herbicides in the corn sample with good recovery rates (85.4 to 109.3%) that correlate well with the regression model. The newly developed dual-mode LFIA with reduced detection time (12 min) holds great potential for pesticide monitoring in equipment-limited environments using a portable test strip reader and laboratory conditions using ML algorithms.
{"title":"Dual-Mode Fluorescent/Intelligent Lateral Flow Immunoassay Based on Machine Learning Algorithm for Ultrasensitive Analysis of Chloroacetamide Herbicides.","authors":"Yonghong Zha, Yansong Li, Jianhua Zhou, Xiaolan Liu, Ki Soo Park, Yu Zhou","doi":"10.1021/acs.analchem.4c02500","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c02500","url":null,"abstract":"<p><p>Given the harmful effect of pesticide residues, it is essential to develop portable and accurate biosensors for the analysis of pesticides in agricultural products. In this paper, we demonstrated a dual-mode fluorescent/intelligent (DM-f/DM-i) lateral flow immunoassay (LFIA) for chloroacetamide herbicides, which utilized horseradish peroxidase-IgG conjugated time-resolved fluorescent nanoparticle probes as both a signal label and amplification tool. With the newly developed LFIA in the DM-f mode, the limits of detection (LODs) were 0.08 ng/mL of acetochlor, 0.29 ng/mL of metolachlor, 0.51 ng/mL of Propisochlor, and 0.13 ng/mL of their mixture. In the DM-i mode, machine learning (ML) algorithms were used for image segmentation, feature extraction, and correlation analysis to obtain multivariate fitted equations, which had high reliability in the regression model with <i>R</i><sup>2</sup> of 0.95 in the range of 2 × 10<sup>2</sup>-2 × 10<sup>5</sup> pg/mL. Importantly, the practical applicability was successfully validated by determining chloroacetamide herbicides in the corn sample with good recovery rates (85.4 to 109.3%) that correlate well with the regression model. The newly developed dual-mode LFIA with reduced detection time (12 min) holds great potential for pesticide monitoring in equipment-limited environments using a portable test strip reader and laboratory conditions using ML algorithms.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In situ sensitive detection of multiple biomarkers in a single cell was highly necessary for understanding the pathogenesis mechanism and facilitating disease diagnosis. Herein, a bipolar electrode (BPE)-electrochemiluminescence (ECL) imaging chip was designed for ultrasensitive in situ detection of multiple miRNAs in single cells based on a dual-signal amplification strategy. A single cell was trapped and lysed within the microtrap of the cathode chamber and an HCR amplification process and nanoprobes (Fc/DNA/Fe3O4) were introduced, leading to a large number of electroactive molecules (Fc) being modified on the surface. Under a suitable potential, Fc+ in the cathodic chamber was reduced to Fc and L-012 was oxidized in the anodic chamber according to the electric neutrality principle of the bipolar electrode system, resulting in the ECL signal recorded by EMCCD. Ascribed to the dual-signal amplification, sensitive visual detection of miRNA-21 and miRNA-155 in single cells was achieved. For MCF-7 cells, miRNA-21 and miRNA-155 were calculated to be 4385 and 1932 copies/cell (median), respectively. For HeLa cells, miRNA-21 and miRNA-155 were calculated to be 1843 and 1012 copies/cell (median), respectively. The comprehensive evaluation of two kinds of miRNA could effectively eliminate error signals, and the detection precision was improved by 10%.
{"title":"Ultrasensitive Electrochemiluminescence Imaging Detection of Multiple miRNAs in Single Cells with a Closed Bipolar Electrode Array Chip.","authors":"Yafeng Wu, Qinglin Gu, Zhi Wang, Zhaoyan Tian, Hui Liu, Songqin Liu","doi":"10.1021/acs.analchem.4c02186","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c02186","url":null,"abstract":"<p><p>In situ sensitive detection of multiple biomarkers in a single cell was highly necessary for understanding the pathogenesis mechanism and facilitating disease diagnosis. Herein, a bipolar electrode (BPE)-electrochemiluminescence (ECL) imaging chip was designed for ultrasensitive in situ detection of multiple miRNAs in single cells based on a dual-signal amplification strategy. A single cell was trapped and lysed within the microtrap of the cathode chamber and an HCR amplification process and nanoprobes (Fc/DNA/Fe<sub>3</sub>O<sub>4</sub>) were introduced, leading to a large number of electroactive molecules (Fc) being modified on the surface. Under a suitable potential, Fc<sup>+</sup> in the cathodic chamber was reduced to Fc and L-012 was oxidized in the anodic chamber according to the electric neutrality principle of the bipolar electrode system, resulting in the ECL signal recorded by EMCCD. Ascribed to the dual-signal amplification, sensitive visual detection of miRNA-21 and miRNA-155 in single cells was achieved. For MCF-7 cells, miRNA-21 and miRNA-155 were calculated to be 4385 and 1932 copies/cell (median), respectively. For HeLa cells, miRNA-21 and miRNA-155 were calculated to be 1843 and 1012 copies/cell (median), respectively. The comprehensive evaluation of two kinds of miRNA could effectively eliminate error signals, and the detection precision was improved by 10%.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578226","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-11DOI: 10.1021/acs.analchem.4c01758
Chaoshuang Xia, Elias Mernie, Joseph Zaia, Catherine E Costello, Cheng Lin
Ion mobility-mass spectrometry (IM-MS) is a powerful analytical tool for structural characterization. IM measurement provides collision cross section (CCS) values that facilitate analyte identification. While CCS values can be directly calculated from mobility measurements obtained using drift tube ion mobility spectrometry (DT-IMS), this method has limited mobility resolution due to the practical constraints on the length of the ion drift path. Consequently, DT-IMS cannot differentiate analytes with similar mobilities or resolve fine mobility features of individual ions. Cyclic IMS (cIMS) instruments leverage a cyclic path enabled by traveling wave ion mobility (TWIM) technology and offer increased mobility solution to address this challenge. While TWIM devices must first be calibrated to enable CCS measurements, current calibration strategies are primarily tailored for single-pass analyses. This preference is partly attributed to the challenges associated with multipass calibration methods, which require both calibrants and analytes to experience the same number of passes. Achieving this consistency can be complicated due to factors like peak splitting and diffusion, and may not be feasible for online IM-MS analyses. A recent report employed average ion velocities obtained from multiple measurements under different separation pathlengths as a path length-independent metric for CCS calibration. However, the ability to exploit this averaging approach is limited by observed variation in ion drift time/velocity in these measurements. In this study, we introduce a novel calibration strategy designed for multipass cIMS analyses, directly targeting the root cause for the path length- and mobility-dependent variations in ion drift time. With this method, we demonstrate that CCS values derived from multipass measurements closely align with those obtained from single-pass analyses, with an average deviation of 0.1%. We apply this method to characterize four isomeric trisaccharides. Our approach not only results in excellent agreement between our measured cIMSCCS values and the reported DTCCS values, with an average difference of only 0.5%, but also allows us to effectively identify subtle mobility characteristics of each compound and determine their respective CCS values. This level of detail and accuracy was previously unattainable using DT-IMS or single-pass cIMS measurements. We developed an algorithm for reconstructing arrival time distribution in cases where wrap-around has resulted in peak splitting. Collectively, the new calibration strategy and the reconstruction procedure maintain reproducibility and precision in CCS measurements while largely eliminating the need for meticulous selection of separation times. We expect that our method will empower researchers to harness the high mobility resolution offered by multipass cIMS analyses without compromising the accuracy of CCS measurement, making it appropriate for straig
{"title":"Accurate Collisional Cross Section Measurement by Multipass Cyclic Ion Mobility Spectrometry.","authors":"Chaoshuang Xia, Elias Mernie, Joseph Zaia, Catherine E Costello, Cheng Lin","doi":"10.1021/acs.analchem.4c01758","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c01758","url":null,"abstract":"<p><p>Ion mobility-mass spectrometry (IM-MS) is a powerful analytical tool for structural characterization. IM measurement provides collision cross section (CCS) values that facilitate analyte identification. While CCS values can be directly calculated from mobility measurements obtained using drift tube ion mobility spectrometry (DT-IMS), this method has limited mobility resolution due to the practical constraints on the length of the ion drift path. Consequently, DT-IMS cannot differentiate analytes with similar mobilities or resolve fine mobility features of individual ions. Cyclic IMS (cIMS) instruments leverage a cyclic path enabled by traveling wave ion mobility (TWIM) technology and offer increased mobility solution to address this challenge. While TWIM devices must first be calibrated to enable CCS measurements, current calibration strategies are primarily tailored for single-pass analyses. This preference is partly attributed to the challenges associated with multipass calibration methods, which require both calibrants and analytes to experience the same number of passes. Achieving this consistency can be complicated due to factors like peak splitting and diffusion, and may not be feasible for online IM-MS analyses. A recent report employed average ion velocities obtained from multiple measurements under different separation pathlengths as a path length-independent metric for CCS calibration. However, the ability to exploit this averaging approach is limited by observed variation in ion drift time/velocity in these measurements. In this study, we introduce a novel calibration strategy designed for multipass cIMS analyses, directly targeting the root cause for the path length- and mobility-dependent variations in ion drift time. With this method, we demonstrate that CCS values derived from multipass measurements closely align with those obtained from single-pass analyses, with an average deviation of 0.1%. We apply this method to characterize four isomeric trisaccharides. Our approach not only results in excellent agreement between our measured <sup>cIMS</sup>CCS values and the reported <sup>DT</sup>CCS values, with an average difference of only 0.5%, but also allows us to effectively identify subtle mobility characteristics of each compound and determine their respective CCS values. This level of detail and accuracy was previously unattainable using DT-IMS or single-pass cIMS measurements. We developed an algorithm for reconstructing arrival time distribution in cases where wrap-around has resulted in peak splitting. Collectively, the new calibration strategy and the reconstruction procedure maintain reproducibility and precision in CCS measurements while largely eliminating the need for meticulous selection of separation times. We expect that our method will empower researchers to harness the high mobility resolution offered by multipass cIMS analyses without compromising the accuracy of CCS measurement, making it appropriate for straig","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Howard Díaz-Salazar, Gabriel Osorio-Ocampo, Susana Porcel
We describe herein a gold-catalyzed three-component reaction of o-alkynylbenzaldehydes, aryldiazonium salts, and trimethoxybenzene. This process enables the one-pot formation of valuable isoindoles and 1,2-dihydrophathalazines. The regioselectivity of the reaction is dictated by the nature of the aryldiazonium salt. Noticeably, the reaction is performed at room temperature under mild conditions and tolerates a variety of functional groups on both the o-alkynylbenzaldehyde and the aryldiazonium salt. Experimental mechanistic studies suggest that it is catalyzed by arylAu(III) species.
{"title":"Straightforward Access to Isoindoles and 1,2-Dihydrophthalazines Enabled by a Gold-Catalyzed Three-Component Reaction.","authors":"Howard Díaz-Salazar, Gabriel Osorio-Ocampo, Susana Porcel","doi":"10.1021/acs.joc.4c01039","DOIUrl":"https://doi.org/10.1021/acs.joc.4c01039","url":null,"abstract":"<p><p>We describe herein a gold-catalyzed three-component reaction of <i>o</i>-alkynylbenzaldehydes, aryldiazonium salts, and trimethoxybenzene. This process enables the one-pot formation of valuable isoindoles and 1,2-dihydrophathalazines. The regioselectivity of the reaction is dictated by the nature of the aryldiazonium salt. Noticeably, the reaction is performed at room temperature under mild conditions and tolerates a variety of functional groups on both the <i>o</i>-alkynylbenzaldehyde and the aryldiazonium salt. Experimental mechanistic studies suggest that it is catalyzed by arylAu(III) species.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578287","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}
FeNC catalysts are considered one of the most promising alternatives to platinum group metals for the oxygen reduction reaction (ORR). Despite the extensive research on improving ORR activity, the undesirable durability of FeNC is still a critical issue for its practical application. Herein, inspired by the antioxidant mechanism of natural enzymes, CeO2 nanozymes featuring catalase-like and superoxide dismutase-like activities were coupled with FeNC to mitigate the attack of reactive oxygen species (ROS) for improving durability. Benefiting from the multienzyme-like activities of CeO2, ROS generated from FeNC is instantaneously eliminated to alleviate the corrosion of carbon and demetallization of metal sites. Consequently, FeNC/CeO2 exhibits better ORR durability with a decay of only 5 mV compared to FeNC (18 mV) in neutral electrolyte after 10k cycles. The FeNC/CeO2-based zinc-air battery also shows minimal voltage decay over 140 h in galvanostatic discharge-charge cycling tests, outperforming FeNC and commercial Pt/C.
{"title":"Improvement in ORR Durability of Fe Single-Atom Carbon Catalysts Hybridized with CeO<sub>2</sub> Nanozyme.","authors":"Yiwei Qiu, Yu Wu, Xiaoqian Wei, Xin Luo, Wenxuan Jiang, Lirong Zheng, Wenling Gu, Chengzhou Zhu, Yusuke Yamauchi","doi":"10.1021/acs.nanolett.4c02178","DOIUrl":"https://doi.org/10.1021/acs.nanolett.4c02178","url":null,"abstract":"<p><p>FeNC catalysts are considered one of the most promising alternatives to platinum group metals for the oxygen reduction reaction (ORR). Despite the extensive research on improving ORR activity, the undesirable durability of FeNC is still a critical issue for its practical application. Herein, inspired by the antioxidant mechanism of natural enzymes, CeO<sub>2</sub> nanozymes featuring catalase-like and superoxide dismutase-like activities were coupled with FeNC to mitigate the attack of reactive oxygen species (ROS) for improving durability. Benefiting from the multienzyme-like activities of CeO<sub>2</sub>, ROS generated from FeNC is instantaneously eliminated to alleviate the corrosion of carbon and demetallization of metal sites. Consequently, FeNC/CeO<sub>2</sub> exhibits better ORR durability with a decay of only 5 mV compared to FeNC (18 mV) in neutral electrolyte after 10k cycles. The FeNC/CeO<sub>2</sub>-based zinc-air battery also shows minimal voltage decay over 140 h in galvanostatic discharge-charge cycling tests, outperforming FeNC and commercial Pt/C.</p>","PeriodicalId":53,"journal":{"name":"Nano Letters","volume":null,"pages":null},"PeriodicalIF":9.6,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Liam R Carson, Megan Beaudry, Caterina Valeo, Jianxun He, Graham Banting, Bert van Duin, Clint Goodman, Candis Scott, Norman F Neumann
A. butzleri is an underappreciated emerging global pathogen, despite growing evidence that it is a major contributor of diarrheal illness. Few studies have investigated the occurrence and public health risks that this organism possesses from waterborne exposure routes including through stormwater use. In this study, we assessed the prevalence, virulence potential, and primary sources of stormwater-isolated A. butzleri in fecally contaminated urban stormwater systems. Based on qPCR, A. butzleri was the most common enteric bacterial pathogen [25%] found in stormwater among a panel of pathogens surveyed, including Shiga-toxin producing Escherichia coli (STEC) [6%], Campylobacter spp. [4%], and Salmonella spp. [<1%]. Concentrations of the bacteria, based on qPCR amplification of the single copy gene hsp60, were as high as 6.2 log10 copies/100 mL, suggesting significant loading of this pathogen in some stormwater systems. Importantly, out of 73 unique stormwater culture isolates, 90% were positive for the putative virulence genes cadF, ciaB, tlyA, cjl349, pldA, and mviN, while 50-75% of isolates also possessed the virulence genes irgA, hecA, and hecB. Occurrence of A. butzleri was most often associated with the human fecal pollution marker HF183 in stormwater samples. These results suggest that A. butzleri may be an important bacterial pathogen in stormwater, warranting further study on the risks it represents to public health during stormwater use.
{"title":"Occurrence, Sources and Virulence Potential of <i>Arcobacter butzleri</i> in Urban Municipal Stormwater Systems.","authors":"Liam R Carson, Megan Beaudry, Caterina Valeo, Jianxun He, Graham Banting, Bert van Duin, Clint Goodman, Candis Scott, Norman F Neumann","doi":"10.1021/acs.est.4c01358","DOIUrl":"https://doi.org/10.1021/acs.est.4c01358","url":null,"abstract":"<p><p><i>A. butzleri</i> is an underappreciated emerging global pathogen, despite growing evidence that it is a major contributor of diarrheal illness. Few studies have investigated the occurrence and public health risks that this organism possesses from waterborne exposure routes including through stormwater use. In this study, we assessed the prevalence, virulence potential, and primary sources of stormwater-isolated <i>A. butzleri</i> in fecally contaminated urban stormwater systems. Based on qPCR, <i>A. butzleri</i> was the most common enteric bacterial pathogen [25%] found in stormwater among a panel of pathogens surveyed, including Shiga-toxin producing <i>Escherichia coli</i> (STEC) [6%], <i>Campylobacter</i> spp. [4%], and <i>Salmonella</i> spp. [<1%]. Concentrations of the bacteria, based on qPCR amplification of the single copy gene <i>hsp60</i>, were as high as 6.2 log<sub>10</sub> copies/100 mL, suggesting significant loading of this pathogen in some stormwater systems. Importantly, out of 73 unique stormwater culture isolates, 90% were positive for the putative virulence genes <i>cadF, ciaB, tlyA, cjl349, pldA</i>, and <i>mviN</i>, while 50-75% of isolates also possessed the virulence genes <i>irgA</i>, <i>hecA</i>, and <i>hecB</i>. Occurrence of <i>A</i>. <i>butzleri</i> was most often associated with the human fecal pollution marker HF183 in stormwater samples. These results suggest that <i>A. butzleri</i> may be an important bacterial pathogen in stormwater, warranting further study on the risks it represents to public health during stormwater use.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":null,"pages":null},"PeriodicalIF":10.8,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578241","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 : 2024-07-11Epub Date: 2024-06-22DOI: 10.1021/acs.jmedchem.4c00610
Paolo Bruno, Alessandra Micoli, Mauro Corsi, Daniele Pala, Sara Guariento, Claudio Fiorelli, Paolo Ronchi, Alessandro Fioni, Paola Maria Gallo, Giulia Marenghi, Serena Bertolini, Silvia Capacchi, Valentina Mileo, Matteo Biagetti, Anna Maria Capelli
A hit-to-lead campaign pursuing the identification of novel inhalant small-molecule phosphatidylinositol 3-kinase (PI3K) inhibitors for the treatment of inflammatory respiratory diseases is disclosed. A synthetically versatile pyridazin-3(2H)-one scaffold was designed, and three exit vectors on the core moiety were used to explore chemical diversity and optimize pharmacological and absorption, distribution, metabolism, and excretion (ADME) properties. Desired modulation of PI3Kδ selectivity and cellular potency as well as ADME properties in view of administration by inhalation was achieved. Intratracheal administration of lead compound 26 resulted in a promising pharmacokinetic profile, thus demonstrating that the optimization strategy of in vitro profiles successfully translated to an in vivo setting.
{"title":"Discovery and Optimization of Pyridazinones as PI3Kδ Selective Inhibitors for Administration by Inhalation.","authors":"Paolo Bruno, Alessandra Micoli, Mauro Corsi, Daniele Pala, Sara Guariento, Claudio Fiorelli, Paolo Ronchi, Alessandro Fioni, Paola Maria Gallo, Giulia Marenghi, Serena Bertolini, Silvia Capacchi, Valentina Mileo, Matteo Biagetti, Anna Maria Capelli","doi":"10.1021/acs.jmedchem.4c00610","DOIUrl":"10.1021/acs.jmedchem.4c00610","url":null,"abstract":"<p><p>A hit-to-lead campaign pursuing the identification of novel inhalant small-molecule phosphatidylinositol 3-kinase (PI3K) inhibitors for the treatment of inflammatory respiratory diseases is disclosed. A synthetically versatile pyridazin-3(2<i>H</i>)-one scaffold was designed, and three exit vectors on the core moiety were used to explore chemical diversity and optimize pharmacological and absorption, distribution, metabolism, and excretion (ADME) properties. Desired modulation of PI3Kδ selectivity and cellular potency as well as ADME properties in view of administration by inhalation was achieved. Intratracheal administration of lead compound <b>26</b> resulted in a promising pharmacokinetic profile, thus demonstrating that the optimization strategy of <i>in vitro</i> profiles successfully translated to an <i>in vivo</i> setting.</p>","PeriodicalId":46,"journal":{"name":"Journal of Medicinal Chemistry","volume":null,"pages":null},"PeriodicalIF":6.8,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141440061","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-11Epub Date: 2024-06-25DOI: 10.1021/acs.jpca.4c02687
Caroline Smith Lewin, Avinash Kumar, Olivier Herbinet, Philippe Arnoux, Rabbia Asgher, Shawon Barua, Frédérique Battin-Leclerc, Sana Farhoudian, Gustavo A Garcia, Luc-Sy Tran, Guillaume Vanhove, Laurent Nahon, Matti Rissanen, Jérémy Bourgalais
This study investigates the complex interaction between ozone and the autoxidation of 1-hexene over a wide temperature range (300-800 K), overlapping atmospheric and combustion regimes. It is found that atmospheric molecular mechanisms initiate the oxidation of 1-hexene from room temperature up to combustion temperatures, leading to the formation of highly oxygenated organic molecules. As temperature rises, the highly oxygenated organic molecules contribute to radical-branching decomposition pathways inducing a high reactivity in the low-temperature combustion region, i.e., from 550 K. Above 650 K, the thermal decomposition of ozone into oxygen atoms becomes the dominant process, and a remarkable enhancement of the conversion is observed due to their diradical nature, counteracting the significant negative temperature coefficient behavior usually observed for 1-hexene. In order to better characterize the formation of heavy oxygenated organic molecules at the lowest temperatures, two analytical performance methods have been combined for the first time: synchrotron-based mass-selected photoelectron spectroscopy and orbitrap chemical ionization mass spectrometry. At the lowest studied temperatures (below 400 K), this analytical work has demonstrated the formation of the ketohydroperoxides usually found during the LTC oxidation of 1-hexene, as well as of molecules containing up to nine O atoms.
本研究调查了臭氧与 1-hexene 自氧化之间在宽温度范围(300-800 K)内的复杂相互作用,以及大气和燃烧状态的重叠。研究发现,从室温到燃烧温度,大气分子机制启动了 1-己烯的氧化,从而形成高含氧有机分子。随着温度的升高,高含氧有机分子有助于自由基支化分解途径,从而在低温燃烧区域(即从 550 K 开始)产生高反应性。超过 650 K 后,臭氧热分解为氧原子的过程成为主要过程,由于其二元对立性质,转化率显著提高,抵消了通常在 1-己烯中观察到的显著负温度系数行为。为了更好地描述重含氧有机分子在最低温度下的形成过程,我们首次将两种分析性能方法结合在一起:同步辐射质量选择光电子能谱和轨道阱化学电离质谱。在研究的最低温度(低于 400 K)下,这项分析工作证明了在 1-hexene 的 LTC 氧化过程中通常发现的酮氢过氧化物以及含有多达 9 个 O 原子的分子的形成。
{"title":"1-Hexene Ozonolysis across Atmospheric and Combustion Temperatures via Synchrotron-Based Photoelectron Spectroscopy and Chemical Ionization Mass Spectrometry.","authors":"Caroline Smith Lewin, Avinash Kumar, Olivier Herbinet, Philippe Arnoux, Rabbia Asgher, Shawon Barua, Frédérique Battin-Leclerc, Sana Farhoudian, Gustavo A Garcia, Luc-Sy Tran, Guillaume Vanhove, Laurent Nahon, Matti Rissanen, Jérémy Bourgalais","doi":"10.1021/acs.jpca.4c02687","DOIUrl":"10.1021/acs.jpca.4c02687","url":null,"abstract":"<p><p>This study investigates the complex interaction between ozone and the autoxidation of 1-hexene over a wide temperature range (300-800 K), overlapping atmospheric and combustion regimes. It is found that atmospheric molecular mechanisms initiate the oxidation of 1-hexene from room temperature up to combustion temperatures, leading to the formation of highly oxygenated organic molecules. As temperature rises, the highly oxygenated organic molecules contribute to radical-branching decomposition pathways inducing a high reactivity in the low-temperature combustion region, i.e., from 550 K. Above 650 K, the thermal decomposition of ozone into oxygen atoms becomes the dominant process, and a remarkable enhancement of the conversion is observed due to their diradical nature, counteracting the significant negative temperature coefficient behavior usually observed for 1-hexene. In order to better characterize the formation of heavy oxygenated organic molecules at the lowest temperatures, two analytical performance methods have been combined for the first time: synchrotron-based mass-selected photoelectron spectroscopy and orbitrap chemical ionization mass spectrometry. At the lowest studied temperatures (below 400 K), this analytical work has demonstrated the formation of the ketohydroperoxides usually found during the LTC oxidation of 1-hexene, as well as of molecules containing up to nine O atoms.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141449058","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}