Feddro Gilbert Wijaya, Sopan Pralhad Khandare, Dániel Csókás, Raghunath O. Ramabhadran, Roderick W. Bates
A synthesis of (−)-viriditin A and (−)-viriditin B has been completed sequentially using a Suzuki coupling and a Heck reaction of trans-1,2-dichloroethylene. The selectivity for monocoupling of trans-1,2-dichloroethylene is attributed to a lower-energy transition state for the oxidative addition step.
{"title":"Synthesis of Viriditins A and B by Selective Coupling of Trans-1,2-Dichloroethylene","authors":"Feddro Gilbert Wijaya, Sopan Pralhad Khandare, Dániel Csókás, Raghunath O. Ramabhadran, Roderick W. Bates","doi":"10.1021/acs.joc.4c02975","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02975","url":null,"abstract":"A synthesis of (−)-viriditin A and (−)-viriditin B has been completed sequentially using a Suzuki coupling and a Heck reaction of <i>trans</i>-1,2-dichloroethylene. The selectivity for monocoupling of <i>trans</i>-1,2-dichloroethylene is attributed to a lower-energy transition state for the oxidative addition step.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"26 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827282","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}
Min Liu, Shenhong Wang, Xing Chen, Mengjing Wang, Haoduo Zhao, Fanrong Zhao, Shixuan Cui, Li Li, Mingliang Fang
The gastrointestinal tract (GIT) is crucial in the absorption and metabolism of xenobiotics, including phthalates─widespread environmental contaminants associated with various health risks. Estimating human exposure to phthalates via biomonitoring is challenging due to their complex metabolic pathways, resulting in a mass-balance gap between internal and external exposure. The relative contributions of the GIT and liver to phthalate metabolism remain underexplored. This study investigated the metabolism of three representative phthalate diesters─dibutyl phthalate (DBP), di(2-ethylhexyl)phthalate (DEHP), and diethyl phthalate (DEP) in GIT. We first incubated these diesters in simulated stomach and small intestine fluids to identify the primary enzyme responsible for their hydrolysis. The kinetics were further investigated under varying pH conditions (4.0, 5.0, 6.0, 7.0 or 7.5) to mimic the small intestine environment. Next, using a refined human physiologically based toxicokinetic model, we quantified the relative contributions of preabsorption intestinal versus postabsorption hepatic biotransformation to the body burden of phthalates. Our results suggested that DBP and DEHP were extensively metabolized (>90%) in the GIT by lipase, with comparatively lower hepatic involvement, while DEP underwent minimal preadsorption metabolism (13%) in the GIT, highlighting the influence of structure-dependent differences on metabolic rates. This study emphasized the importance of incorporating both intestinal and hepatic metabolism into toxicokinetic analyses. The findings demonstrate the GIT’s critical role in limiting phthalate bioavailability, underscoring the need to account for the intestinal first-pass effect in toxicokinetic models to enhance predictions of phthalate pharmacokinetics and health impacts.
{"title":"Separating the Role of Gut Enzymatic Transformation in Modulating Internal Exposure to Three Major Phthalates","authors":"Min Liu, Shenhong Wang, Xing Chen, Mengjing Wang, Haoduo Zhao, Fanrong Zhao, Shixuan Cui, Li Li, Mingliang Fang","doi":"10.1021/acs.est.4c12870","DOIUrl":"https://doi.org/10.1021/acs.est.4c12870","url":null,"abstract":"The gastrointestinal tract (GIT) is crucial in the absorption and metabolism of xenobiotics, including phthalates─widespread environmental contaminants associated with various health risks. Estimating human exposure to phthalates via biomonitoring is challenging due to their complex metabolic pathways, resulting in a mass-balance gap between internal and external exposure. The relative contributions of the GIT and liver to phthalate metabolism remain underexplored. This study investigated the metabolism of three representative phthalate diesters─dibutyl phthalate (DBP), di(2-ethylhexyl)phthalate (DEHP), and diethyl phthalate (DEP) in GIT. We first incubated these diesters in simulated stomach and small intestine fluids to identify the primary enzyme responsible for their hydrolysis. The kinetics were further investigated under varying pH conditions (4.0, 5.0, 6.0, 7.0 or 7.5) to mimic the small intestine environment. Next, using a refined human physiologically based toxicokinetic model, we quantified the relative contributions of preabsorption intestinal versus postabsorption hepatic biotransformation to the body burden of phthalates. Our results suggested that DBP and DEHP were extensively metabolized (>90%) in the GIT by lipase, with comparatively lower hepatic involvement, while DEP underwent minimal preadsorption metabolism (13%) in the GIT, highlighting the influence of structure-dependent differences on metabolic rates. This study emphasized the importance of incorporating both intestinal and hepatic metabolism into toxicokinetic analyses. The findings demonstrate the GIT’s critical role in limiting phthalate bioavailability, underscoring the need to account for the intestinal first-pass effect in toxicokinetic models to enhance predictions of phthalate pharmacokinetics and health impacts.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"25 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832214","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 : 2025-04-14DOI: 10.1021/acs.jpclett.5c00408
Ivan Tambovtsev, Yorick L. A. Schmerwitz, Gianluca Levi, Darina D. Darmoroz, Pavel V. Nesterov, Tetiana Orlova, Hannes Jónsson
The elementary steps in the rotation of several second-generation molecular motors are analyzed by finding the minimum energy path between the metastable and stable states and evaluating the transition rate within harmonic transition state theory based on energetics obtained from density functional theory. Comparison with published experimental data shows remarkably good agreement and demonstrates the predictive capability of this approach. While previous measurements by Feringa and co-workers have shown that a replacement of the hydrogen atom at the stereogenic center by a fluorine atom can slow down the rate-limiting thermal helix inversion (THI) step by raising the energy of the transition state, even to the extent that the backreaction in the ground state becomes preferred in some cases, we find that a replacement of a CH3 group by CF3 at the same site accelerates the THI by elevating the energy of the metastable state without affecting the transition state significantly. Since these two fluorine substitutions have an opposite effect on the rate of the THI, the combination of both can provide ways to fine-tune the rotational speed of molecular motors.
{"title":"Fine Tuning of the Rotational Speed of Light-Driven, Second-Generation Molecular Motors by Fluorine Substitution","authors":"Ivan Tambovtsev, Yorick L. A. Schmerwitz, Gianluca Levi, Darina D. Darmoroz, Pavel V. Nesterov, Tetiana Orlova, Hannes Jónsson","doi":"10.1021/acs.jpclett.5c00408","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00408","url":null,"abstract":"The elementary steps in the rotation of several second-generation molecular motors are analyzed by finding the minimum energy path between the metastable and stable states and evaluating the transition rate within harmonic transition state theory based on energetics obtained from density functional theory. Comparison with published experimental data shows remarkably good agreement and demonstrates the predictive capability of this approach. While previous measurements by Feringa and co-workers have shown that a replacement of the hydrogen atom at the stereogenic center by a fluorine atom can slow down the rate-limiting thermal helix inversion (THI) step by raising the energy of the transition state, even to the extent that the backreaction in the ground state becomes preferred in some cases, we find that a replacement of a CH<sub>3</sub> group by CF<sub>3</sub> at the same site accelerates the THI by elevating the energy of the metastable state without affecting the transition state significantly. Since these two fluorine substitutions have an opposite effect on the rate of the THI, the combination of both can provide ways to fine-tune the rotational speed of molecular motors.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"25 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832373","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}
Perovskites have attracted considerable attention in materials science due to their promising applications in photovoltaics and photocatalysis. Accurate prediction of their electronic band gap is essential for optimizing the performance. Traditional computational methods for band gap prediction often face a trade-off between accuracy and computational efficiency. General density functional theory (DFT) calculations typically underestimate band gap values, while the more accurate quasi-particle method demands substantial computational resources. In this study, a multistep machine learning framework was developed for efficient screening of semiconductor double perovskites. Furthermore, we proposed an interpretable descriptor that can predict quasi-particle band gaps of perovskites with a precision of over 90% accuracy. Using this approach, we screened 4,507 perovskite candidates and identified 94 structures that have suitable band gaps and are lead-free. Among these, six candidate structures were selected for further verification based on their photocatalytic potential and thermal stability.
{"title":"Efficient and Accurate Prediction of Double Perovskite Quasiparticle Band Gaps via Machine Learning and a Descriptor","authors":"Guangcheng Niu, Yilei Wu, Xinyu Chen, Yehui Zhang, Shijun Yuan, Jinlan Wang","doi":"10.1021/acs.jpclett.5c00173","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00173","url":null,"abstract":"Perovskites have attracted considerable attention in materials science due to their promising applications in photovoltaics and photocatalysis. Accurate prediction of their electronic band gap is essential for optimizing the performance. Traditional computational methods for band gap prediction often face a trade-off between accuracy and computational efficiency. General density functional theory (DFT) calculations typically underestimate band gap values, while the more accurate quasi-particle method demands substantial computational resources. In this study, a multistep machine learning framework was developed for efficient screening of semiconductor double perovskites. Furthermore, we proposed an interpretable descriptor that can predict quasi-particle band gaps of perovskites with a precision of over 90% accuracy. Using this approach, we screened 4,507 perovskite candidates and identified 94 structures that have suitable band gaps and are lead-free. Among these, six candidate structures were selected for further verification based on their photocatalytic potential and thermal stability.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"60 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827338","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}
In this work, a series of high-performance organic light-emitting devices based on blue thermally activated delayed fluorescence material DBA-DI were designed and fabricated by utilizing the gadolinium(III) complex as a hole trapper. After optimizing the doping concentration of the blue emitter, the Gd complex was codoped into the emitting layer (EML). Due to the high-lying highest occupied molecular orbital level (HOMO) of the Gd complex, superfluous holes within EML were effectively captured, thus improving carrier balance and broadening the recombination zone. Experimental results demonstrated that the codoped devices obtained significantly elevated electroluminescent (EL) performance by regulating carrier distribution and suppressing exciton quenching. Compared with nonco-doped devices, codoped devices displayed higher external quantum efficiency (EQE) and brightness with increased ratios of nearly 20% and over 30%, respectively. Eventually, the optimal codoped double-EML device obtained the maximum EQE, brightness, current efficiency, and power efficiency as high as 15.82%, 12,170 cd m–2, 27.47 cd A–1, and 31.96 lm W–1, respectively. In addition, by further optimizing the thickness of the electron transport layer, a maximum EQE as high as 17.49% was realized.
{"title":"Blue Thermally Activated Delayed Fluorescence Organic Electroluminescent Devices with Carriers Regulating Structure by Employing the Gadolinium(III) Complex as a Hole Trapper","authors":"Guodong Sun, Yue Xu, Haoran Yang, Xiaoyang Xia, Jiuqi Wang, Liang Zhou, Quanguo Zhou","doi":"10.1021/acs.jpcc.5c01184","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01184","url":null,"abstract":"In this work, a series of high-performance organic light-emitting devices based on blue thermally activated delayed fluorescence material DBA-DI were designed and fabricated by utilizing the gadolinium(III) complex as a hole trapper. After optimizing the doping concentration of the blue emitter, the Gd complex was codoped into the emitting layer (EML). Due to the high-lying highest occupied molecular orbital level (HOMO) of the Gd complex, superfluous holes within EML were effectively captured, thus improving carrier balance and broadening the recombination zone. Experimental results demonstrated that the codoped devices obtained significantly elevated electroluminescent (EL) performance by regulating carrier distribution and suppressing exciton quenching. Compared with nonco-doped devices, codoped devices displayed higher external quantum efficiency (EQE) and brightness with increased ratios of nearly 20% and over 30%, respectively. Eventually, the optimal codoped double-EML device obtained the maximum EQE, brightness, current efficiency, and power efficiency as high as 15.82%, 12,170 cd m<sup>–2</sup>, 27.47 cd A<sup>–1</sup>, and 31.96 lm W<sup>–1</sup>, respectively. In addition, by further optimizing the thickness of the electron transport layer, a maximum EQE as high as 17.49% was realized.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"24 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Azobenzenes are promising materials for energy storage due to their reversible photoisomerization and redox properties. Given the critical role of redox behavior in the latter application, an investigation of their redox processes is essential. We propose a classification of azobenzenes into two categories: benzenoid-type and quinoid-type, based on the mechanism of their oxidation. Benzenoid-type compounds have been extensively studied due to their reversible reduction. Quinoid-type compounds exhibit oxidative and reductive versatility, making them promising for further research in energy storage.
{"title":"Electrochemistry of Azobenzenes and Its Potential for Energy Storage","authors":"Dominic Schatz, Hermann A. Wegner","doi":"10.1021/acs.joc.5c00315","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00315","url":null,"abstract":"Azobenzenes are promising materials for energy storage due to their reversible photoisomerization and redox properties. Given the critical role of redox behavior in the latter application, an investigation of their redox processes is essential. We propose a classification of azobenzenes into two categories: <i>benzenoid</i>-type and <i>quinoid</i>-type, based on the mechanism of their oxidation. <i>Benzenoid</i>-type compounds have been extensively studied due to their reversible reduction. <i>Quinoid</i>-type compounds exhibit oxidative and reductive versatility, making them promising for further research in energy storage.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"40 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832544","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}
Qianqian Xie, Weihua Chen, Bin Yuan, Yibo Huangfu, Xianjun He, Liqing Wu, Mingkai Liu, Yingchang You, Min Shao, Xuemei Wang
Recent observations have revealed unexpectedly high concentrations of monoterpenes (MT) in urban areas, frequently surpassing those in forested regions. These findings suggest significant anthropogenic contributions (MTANT), challenging the traditional view that MT emissions are predominantly natural (MTNAT) in current inventories. This oversight likely results in a substantial underestimation of MT’s role in urban ozone (O3) production. Therefore, we developed a novel approach to generate a gridded emission inventory (EI) of MTANT, integrating flux measurements of MT and carbon monoxide (CO). Results show that MTANT emission rate in Beijing core areas exceeds MTNAT by a factor of 1.83, with household volatile chemical products (VCPs) contributing 56% of total MTANT emissions. Incorporating MTANT emissions into the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) model significantly improved the simulation of diurnal MT variations (correlation coefficient, r = 0.985) and reduced the normalized mean bias (NMB) in surface MT concentration predictions by 53%. Notably, the combined effects of anthropogenic and biogenic MT emissions increased summertime maximum daily 8-h average (MDA8) O3 levels by 12.8 ppb in Beijing core areas, with MT from household VCPs (MTVCP) accounting for 62% of the MTANT-driven O3 increase. This study provides a robust quantitative foundation for assessing the impact of anthropogenic MT emissions on urban air quality and highlights the urgent need for targeted regulatory measures to mitigate their growing contribution to O3 pollution.
{"title":"Significant but Overlooked: The Role of Anthropogenic Monoterpenes in Ozone Formation in a Chinese Megacity","authors":"Qianqian Xie, Weihua Chen, Bin Yuan, Yibo Huangfu, Xianjun He, Liqing Wu, Mingkai Liu, Yingchang You, Min Shao, Xuemei Wang","doi":"10.1021/acs.est.5c00001","DOIUrl":"https://doi.org/10.1021/acs.est.5c00001","url":null,"abstract":"Recent observations have revealed unexpectedly high concentrations of monoterpenes (MT) in urban areas, frequently surpassing those in forested regions. These findings suggest significant anthropogenic contributions (MT<sub>ANT</sub>), challenging the traditional view that MT emissions are predominantly natural (MT<sub>NAT</sub>) in current inventories. This oversight likely results in a substantial underestimation of MT’s role in urban ozone (O<sub>3</sub>) production. Therefore, we developed a novel approach to generate a gridded emission inventory (EI) of MT<sub>ANT</sub>, integrating flux measurements of MT and carbon monoxide (CO). Results show that MT<sub>ANT</sub> emission rate in Beijing core areas exceeds MT<sub>NAT</sub> by a factor of 1.83, with household volatile chemical products (VCPs) contributing 56% of total MT<sub>ANT</sub> emissions. Incorporating MT<sub>ANT</sub> emissions into the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) model significantly improved the simulation of diurnal MT variations (correlation coefficient, <i>r</i> = 0.985) and reduced the normalized mean bias (<i>NMB</i>) in surface MT concentration predictions by 53%. Notably, the combined effects of anthropogenic and biogenic MT emissions increased summertime maximum daily 8-h average (MDA8) O<sub>3</sub> levels by 12.8 ppb in Beijing core areas, with MT from household VCPs (MT<sub>VCP</sub>) accounting for 62% of the MT<sub>ANT</sub>-driven O<sub>3</sub> increase. This study provides a robust quantitative foundation for assessing the impact of anthropogenic MT emissions on urban air quality and highlights the urgent need for targeted regulatory measures to mitigate their growing contribution to O<sub>3</sub> pollution.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"42 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827162","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 : 2025-04-14DOI: 10.1016/j.bios.2025.117477
Yongbin Cao , Yaxiong Tang , Jianzhong Ai , Jian Peng
To enhance the accuracy of early prostate cancer diagnosis, we developed an electrochemical sensor based on synthesized mesoporous carbon nanospheres functionalized with ferrocenecarboxylic acid and encapsulated hemoglobin (HMCNs-FCA-Hb). This sensor enables the simultaneous detection of prostate-specific antigen (PSA) and sarcosine (SAR) as dual biomarkers. Unlike traditional electrochemical detection methods that frequently necessitate multiple electrode modifications, our sensor operates without the need for such modifications, thereby significantly simplifying the detection process. Under alkaline conditions, HMCNs-FCA-Hb can release ferrocenecarboxylic acid to generate an electrical signal for PSA detection. The linear range for PSA detection is from 0.001 to 30 ng/mL, with a detection limit of 0.11 pg mL−1 (S/N = 3). Additionally, HMCNs-FCA-Hb with excellent peroxidase-like activity allows for indirect detection of SAR with the linear range of 0.01–25 μM and a detection limit of 0.003 μM (S/N = 3). Specifically, we have integrated a micro electrochemical workstation and mobile smart devices to achieve portable and wireless detection of PSA and SAR in clinical serum samples with satisfactory results. The results can be visually and promptly displayed, highlighting the sensor's potential for clinical application in the early diagnosis of prostate cancer.
{"title":"Wireless detection of dual prostate cancer biomarkers using ferrocenecarboxylic acid-functionalized mesoporous carbon nanospheres without electrode modifications","authors":"Yongbin Cao , Yaxiong Tang , Jianzhong Ai , Jian Peng","doi":"10.1016/j.bios.2025.117477","DOIUrl":"10.1016/j.bios.2025.117477","url":null,"abstract":"<div><div>To enhance the accuracy of early prostate cancer diagnosis, we developed an electrochemical sensor based on synthesized mesoporous carbon nanospheres functionalized with ferrocenecarboxylic acid and encapsulated hemoglobin (HMCNs-FCA-Hb). This sensor enables the simultaneous detection of prostate-specific antigen (PSA) and sarcosine (SAR) as dual biomarkers. Unlike traditional electrochemical detection methods that frequently necessitate multiple electrode modifications, our sensor operates without the need for such modifications, thereby significantly simplifying the detection process. Under alkaline conditions, HMCNs-FCA-Hb can release ferrocenecarboxylic acid to generate an electrical signal for PSA detection. The linear range for PSA detection is from 0.001 to 30 ng/mL, with a detection limit of 0.11 pg mL<sup>−1</sup> (S/N = 3). Additionally, HMCNs-FCA-Hb with excellent peroxidase-like activity allows for indirect detection of SAR with the linear range of 0.01–25 μM and a detection limit of 0.003 μM (S/N = 3). Specifically, we have integrated a micro electrochemical workstation and mobile smart devices to achieve portable and wireless detection of PSA and SAR in clinical serum samples with satisfactory results. The results can be visually and promptly displayed, highlighting the sensor's potential for clinical application in the early diagnosis of prostate cancer.</div></div>","PeriodicalId":259,"journal":{"name":"Biosensors and Bioelectronics","volume":"281 ","pages":"Article 117477"},"PeriodicalIF":10.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143833711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Understanding how anion adsorption and crystallographic orientation affect the oxygen reduction reaction (ORR) activity is important for designing efficient Pt-based catalysts for fuel cell cathodes. In this study, we used scanning electrochemical cell microscopy (SECCM) to investigate the relationship between anion adsorption and the crystallographic orientation for the ORR activity on polycrystalline Pt electrodes. The ORR is sensitive to surface contamination, so it is important to clean the electrode surface prior to measurement. Therefore, we proposed a method to measure the ORR current using SECCM by linear sweep voltammetry after cyclic-voltammetry-based electrochemical cleaning. A comparative analysis of grains with different crystallographic orientations showed that the ORR activity was higher in the HClO4 solution than in the H2SO4 solution for grains oriented close to (111). This difference is probably due to the specific adsorption of (bi)sulfate anions on Pt(111) terrace, which inhibits the oxygen adsorption and thereby reduces the ORR activity. These results demonstrated the applicability of SECCM in studying the anion adsorption effect on the ORR activity at the polycrystalline Pt electrode. The insights gained are valuable for understanding how the solution composition influences the electrochemical behavior at different crystallographic orientations, providing important guidance for optimizing catalyst design.
{"title":"Evaluation of the Effect of Anions on Oxygen Reduction Reactions at Polycrystalline Platinum Electrodes Using Scanning Electrochemical Cell Microscopy","authors":"Yusuke Kawabe, Fumiya Ito, Kaito Hirata, Naoto Todoroki, Yasufumi Takahashi","doi":"10.1021/acs.jpcc.4c07227","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07227","url":null,"abstract":"Understanding how anion adsorption and crystallographic orientation affect the oxygen reduction reaction (ORR) activity is important for designing efficient Pt-based catalysts for fuel cell cathodes. In this study, we used scanning electrochemical cell microscopy (SECCM) to investigate the relationship between anion adsorption and the crystallographic orientation for the ORR activity on polycrystalline Pt electrodes. The ORR is sensitive to surface contamination, so it is important to clean the electrode surface prior to measurement. Therefore, we proposed a method to measure the ORR current using SECCM by linear sweep voltammetry after cyclic-voltammetry-based electrochemical cleaning. A comparative analysis of grains with different crystallographic orientations showed that the ORR activity was higher in the HClO<sub>4</sub> solution than in the H<sub>2</sub>SO<sub>4</sub> solution for grains oriented close to (111). This difference is probably due to the specific adsorption of (bi)sulfate anions on Pt(111) terrace, which inhibits the oxygen adsorption and thereby reduces the ORR activity. These results demonstrated the applicability of SECCM in studying the anion adsorption effect on the ORR activity at the polycrystalline Pt electrode. The insights gained are valuable for understanding how the solution composition influences the electrochemical behavior at different crystallographic orientations, providing important guidance for optimizing catalyst design.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"40 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yoshihara, Hiroki, Yagi, and Itami utilized an unusual Friedel–Crafts-like alkylation in the synthesis of an adamantane-annulated arene. The precursor was a 3° carbocation, which they proposed undergoes a Wagner–Meerwein shift to a 2° carbocation, which subsequently alkylates a benzene ring. This mechanism was supported by their DFT calculations. However, their choice of the B3LYP functional often finds false transition structures. A more appropriate functional showed that the alkylation occurs via a concerted reaction.
{"title":"An Unusual Friedel–Crafts Reaction and Violation of the Markovnikov Rule in the Formation of an Adamantyl Arene","authors":"B. Andes Hess, Jr, Lidia Smentek","doi":"10.1021/acs.joc.5c00215","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00215","url":null,"abstract":"Yoshihara, Hiroki, Yagi, and Itami utilized an unusual Friedel–Crafts-like alkylation in the synthesis of an adamantane-annulated arene. The precursor was a 3° carbocation, which they proposed undergoes a Wagner–Meerwein shift to a 2° carbocation, which subsequently alkylates a benzene ring. This mechanism was supported by their DFT calculations. However, their choice of the B3LYP functional often finds false transition structures. A more appropriate functional showed that the alkylation occurs via a concerted reaction.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832543","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}
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