Alevtina L Makhamatkhanova,Ekaterina Y Bulykina,Tatyana V Tyumkina
An efficient atom-economical synthetic method has been proposed for the synthesis of stereoisomeric 3-alkyl-1-(α-hydroxydialkyl(diphenyl))phospholane oxides and 3-alkyl-1-(α-hydroxyalkylphenyl)phospholane oxides via the reaction of 3-alkyl-1H-phospholane oxides with aliphatic and aromatic ketones under mild conditions (20-22 °C, 12 h), conducted without the use of solvents or catalysts, achieving yields of 85-98%. Phosphorylation of acetylacetone by 3-alkyl-1H-phospholane oxides has been successfully achieved at both carbonyl groups. The mechanism of the addition of cyclic secondary phosphine oxides to ketones is discussed.
{"title":"Addition of Ketones to 3-Alkyl-1H-phospholane Oxides in the Synthesis of Tetrasubstituted α-Hydroxyphospholane Oxides.","authors":"Alevtina L Makhamatkhanova,Ekaterina Y Bulykina,Tatyana V Tyumkina","doi":"10.1021/acs.joc.5c02403","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02403","url":null,"abstract":"An efficient atom-economical synthetic method has been proposed for the synthesis of stereoisomeric 3-alkyl-1-(α-hydroxydialkyl(diphenyl))phospholane oxides and 3-alkyl-1-(α-hydroxyalkylphenyl)phospholane oxides via the reaction of 3-alkyl-1H-phospholane oxides with aliphatic and aromatic ketones under mild conditions (20-22 °C, 12 h), conducted without the use of solvents or catalysts, achieving yields of 85-98%. Phosphorylation of acetylacetone by 3-alkyl-1H-phospholane oxides has been successfully achieved at both carbonyl groups. The mechanism of the addition of cyclic secondary phosphine oxides to ketones is discussed.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"298 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1021/acs.jpcc.5c06574
Lin Liu, Jinhua Sun
Single-particle impedance measurements (SPIMs) have emerged as powerful tools for probing fundamental electrode processes in lithium-ion batteries. However, electrical circuit models used to interpret impedance data are often vague in their physical meaning. In this paper, we develop a physics-based impedance model for primary intercalation particles with the absence or the existence of the solid–electrolyte interphase (SEI). The model considers multiple physicochemical processes, including solid-phase diffusion, interfacial transfer, double-layer charging, and ion transport in a solid-electrolyte interphase and electrolyte solution. Electrical double-layer effects on the interfacial transfer kinetics are considered. Analytical expressions for the impedance are derived and approximated into two equivalent circuits with each element mapped to a specific physical process. Our study shows that two coupled semicircles emerge when the ratio of the ion-transfer time constant to the SEI-transport time constant exceeds a critical threshold. The high-frequency semicircle should be attributed to interfacial transfer and the mid- to high-frequency semicircle to ion transport within the compact layer of SEI. When the ratio of two time constants is lower than the threshold, a semicardicircle extending partially into the second quadrant appears, consistent with recent experimental observations. We introduce a time-constant space framework to explain the result, which enables the clear assignment of individual semicircles to their governing processes. Finally, a comparison with experimental SPIM data validates the model.
{"title":"Impedance of Battery Primary Particles with a Solid–Electrolyte Interphase: Physical Models and Electrical Circuit Analogs","authors":"Lin Liu, Jinhua Sun","doi":"10.1021/acs.jpcc.5c06574","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06574","url":null,"abstract":"Single-particle impedance measurements (SPIMs) have emerged as powerful tools for probing fundamental electrode processes in lithium-ion batteries. However, electrical circuit models used to interpret impedance data are often vague in their physical meaning. In this paper, we develop a physics-based impedance model for primary intercalation particles with the absence or the existence of the solid–electrolyte interphase (SEI). The model considers multiple physicochemical processes, including solid-phase diffusion, interfacial transfer, double-layer charging, and ion transport in a solid-electrolyte interphase and electrolyte solution. Electrical double-layer effects on the interfacial transfer kinetics are considered. Analytical expressions for the impedance are derived and approximated into two equivalent circuits with each element mapped to a specific physical process. Our study shows that two coupled semicircles emerge when the ratio of the ion-transfer time constant to the SEI-transport time constant exceeds a critical threshold. The high-frequency semicircle should be attributed to interfacial transfer and the mid- to high-frequency semicircle to ion transport within the compact layer of SEI. When the ratio of two time constants is lower than the threshold, a semicardicircle extending partially into the second quadrant appears, consistent with recent experimental observations. We introduce a time-constant space framework to explain the result, which enables the clear assignment of individual semicircles to their governing processes. Finally, a comparison with experimental SPIM data validates the model.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"19 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718416","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}
Saurabh S Satpute,Clayton T West,Hannah C Wendlandt,Ryan S Storteboom,Amol M Vibhute,Serhii Vasylevskyi,Cassandra E Callmann,Kami L Hull
The established conditions for the oxidative aminoboration of α-olefins employ O2, a combustion accelerator, as the terminal oxidant. Herein, we report an efficient Pd- and Cu-cocatalyzed aminoboration of unactivated olefins, employing benzoquinone as the terminal oxidant. These conditions allow for enhanced turnover frequencies and an improved substrate scope relative to those of other Pd-catalyzed aminoboration reactions. These highly practical, selective, and high-yielding aminoboration conditions overcome many of the challenges associated with ligand-free oxidative Pd catalysis. The representative scope of the reaction includes 50 examples. α-Olefins, internal vinyl arenes, and strained cyclic olefins all participate along with a wide variety of amine nucleophiles. Mechanistic investigations support the idea that the rapid rate of oxidation by benzoquinone and Cu(II) prevents the aggregation of heterogeneous Pd(0) species, allowing the Pd to remain homogeneous throughout the aminoboration reaction. The scalability of the reaction and the synthetic utility of the products are demonstrated.
{"title":"Pd- and Cu-Cocatalyzed Anaerobic Olefin Aminoboration.","authors":"Saurabh S Satpute,Clayton T West,Hannah C Wendlandt,Ryan S Storteboom,Amol M Vibhute,Serhii Vasylevskyi,Cassandra E Callmann,Kami L Hull","doi":"10.1021/acs.joc.5c02524","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02524","url":null,"abstract":"The established conditions for the oxidative aminoboration of α-olefins employ O2, a combustion accelerator, as the terminal oxidant. Herein, we report an efficient Pd- and Cu-cocatalyzed aminoboration of unactivated olefins, employing benzoquinone as the terminal oxidant. These conditions allow for enhanced turnover frequencies and an improved substrate scope relative to those of other Pd-catalyzed aminoboration reactions. These highly practical, selective, and high-yielding aminoboration conditions overcome many of the challenges associated with ligand-free oxidative Pd catalysis. The representative scope of the reaction includes 50 examples. α-Olefins, internal vinyl arenes, and strained cyclic olefins all participate along with a wide variety of amine nucleophiles. Mechanistic investigations support the idea that the rapid rate of oxidation by benzoquinone and Cu(II) prevents the aggregation of heterogeneous Pd(0) species, allowing the Pd to remain homogeneous throughout the aminoboration reaction. The scalability of the reaction and the synthetic utility of the products are demonstrated.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1021/acs.jpcb.5c05850
Alyssa J Kranc, Ksenia B Bravaya
A complete mechanistic understanding of the excitation energy transfer in the Peridinin Chlorophyll Protein (PCP) complex has been a long sought after goal due to the protein's high light-harvesting efficacy. Multiple factors including the relative energies, electronic couplings, and the chromophores' interactions with the protein environment collectively contribute to the overall efficiency of the energy transfer in the PCP complex. Here we focus specifically on the energy ordering of the bright excited states of the eight peridinin chromophores in monomeric PCP. We provide a detailed analysis of the effects of the electrostatic interactions of peridinins with the protein matrix on excitation energies. Our results point to peridinins 611 and 621 as the lowest-energy excitation sites among the eight carotenoid chromophores. Despite the substantial transition dipole moment, the effects of the environment polarization on the computed excitation energies are found to be minor as compared to the effects of environment electrostatics. This conclusion is supported by both the perturbative state-specific and linear-response TDDFT/EFP polarizable embedding QM/MM calculations. Our simulations also indicate that methods beyond molecular dynamics with conventional molecular mechanics force fields should be used to sample the configurational space of the peridinins.
{"title":"Excited States of Peridinin in PCP: A Polarizable Embedding QM/MM Study.","authors":"Alyssa J Kranc, Ksenia B Bravaya","doi":"10.1021/acs.jpcb.5c05850","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c05850","url":null,"abstract":"<p><p>A complete mechanistic understanding of the excitation energy transfer in the Peridinin Chlorophyll Protein (PCP) complex has been a long sought after goal due to the protein's high light-harvesting efficacy. Multiple factors including the relative energies, electronic couplings, and the chromophores' interactions with the protein environment collectively contribute to the overall efficiency of the energy transfer in the PCP complex. Here we focus specifically on the energy ordering of the bright excited states of the eight peridinin chromophores in monomeric PCP. We provide a detailed analysis of the effects of the electrostatic interactions of peridinins with the protein matrix on excitation energies. Our results point to peridinins 611 and 621 as the lowest-energy excitation sites among the eight carotenoid chromophores. Despite the substantial transition dipole moment, the effects of the environment polarization on the computed excitation energies are found to be minor as compared to the effects of environment electrostatics. This conclusion is supported by both the perturbative state-specific and linear-response TDDFT/EFP polarizable embedding QM/MM calculations. Our simulations also indicate that methods beyond molecular dynamics with conventional molecular mechanics force fields should be used to sample the configurational space of the peridinins.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145740137","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}
Blood levels of the pollutants benzene, toluene, xylene (i.e., the sum of ortho-, meta-, and para-xylene isomers), and ethylbenzene (BTEX) are associated with an increased incidence of cardiovascular diseases. However, the underlying mechanisms are unknown. Here, we tested the hypothesis that BTEX accumulate in human atherosclerotic plaque, promoting local proinflammatory responses within atheroma tissues. To this aim, we retrospectively analyzed carotid plaque samples from 147 individuals from a cohort of people with asymptomatic carotid stenosis undergoing carotid endarterectomy. In atheroma specimens, we quantified BTEX and 1,4-benzoquinone, a benzene metabolite, through flame ionization detector gas chromatography and by high-performance liquid chromatography, respectively. We categorized individuals as BTEX-positive or BTEX-negative and compared the expression of plaque inflammatory markers in these two groups. To explore the mechanistic basis for our clinical observations, we also treated human monocytes with relevant concentrations of the four BTEX and evaluated their possible proinflammatory effect. Among the 147 plaques analyzed, 93 had evidence of at least one BTEX pollutant. Benzene was the most abundant, and its levels were positively correlated to those of 1,4-benzoquinone. Patients with evidence of BTEX within the atheroma, compared with those without, showed higher levels of CD68, MMP9, NLRP3, IL-1β, and TNF-α within the plaque but also of systemic markers of inflammation such as the white blood cell count and neutrophil-to-lymphocyte ratio. BTEX levels were positively correlated with NLRP3 and IL-1β levels as well as with triglyceride. BTEX levels were higher in people with a prior diagnosis of dyslipidemia and with a subsequent major cardiovascular event. Treatment of monocytes for 5 days with benzene, xylene, and ethylbenzene, but not toluene, fostered a consistent proinflammatory response, an effect observed in the absence of cytotoxicity and phenocopied by the treatment with 1,4-benzoquinone. BTEX and 1,4-benzoquinone also promoted foam cell formation in monocytes differentiated into macrophages. These data represent the first evidence that BTEX pollutants accumulate within the carotid plaque tissue. This phenomenon is associated with increased local inflammation, possibly suggesting the activation of proatherogenic pathways at the local level.
{"title":"Detection and Proinflammatory Effects of BTEX within the Human Atherosclerotic Plaque.","authors":"Raffaele Marfella,Francesca Carreras,Francesco Prattichizzo,Rosalba La Grotta,Valeria Pellegrini,Celestino Sardu,Nunzia D'Onofrio,Michelangela Barbieri,Maurizio Municinò,Mario Siniscalchi,Fabio Spinetti,Gennaro Vigliotti,Carmine Vecchione,Albino Carrizzo,Giulio Accarino,Antonio Squillante,Giuseppe Spaziano,Davida Mirra,Renata Esposito,Angelo Fenti,Simona Galoppo,Silvana Canzano,Ludovica Vittoria Marfella,Giovanni Falco,Maria Luisa Balestrieri,Ciro Mauro,Antonio Ceriello,Philip J Landrigan,Bruno D'Agostino,Pasquale Iovino,Giuseppe Paolisso","doi":"10.1021/acs.est.5c04941","DOIUrl":"https://doi.org/10.1021/acs.est.5c04941","url":null,"abstract":"Blood levels of the pollutants benzene, toluene, xylene (i.e., the sum of ortho-, meta-, and para-xylene isomers), and ethylbenzene (BTEX) are associated with an increased incidence of cardiovascular diseases. However, the underlying mechanisms are unknown. Here, we tested the hypothesis that BTEX accumulate in human atherosclerotic plaque, promoting local proinflammatory responses within atheroma tissues. To this aim, we retrospectively analyzed carotid plaque samples from 147 individuals from a cohort of people with asymptomatic carotid stenosis undergoing carotid endarterectomy. In atheroma specimens, we quantified BTEX and 1,4-benzoquinone, a benzene metabolite, through flame ionization detector gas chromatography and by high-performance liquid chromatography, respectively. We categorized individuals as BTEX-positive or BTEX-negative and compared the expression of plaque inflammatory markers in these two groups. To explore the mechanistic basis for our clinical observations, we also treated human monocytes with relevant concentrations of the four BTEX and evaluated their possible proinflammatory effect. Among the 147 plaques analyzed, 93 had evidence of at least one BTEX pollutant. Benzene was the most abundant, and its levels were positively correlated to those of 1,4-benzoquinone. Patients with evidence of BTEX within the atheroma, compared with those without, showed higher levels of CD68, MMP9, NLRP3, IL-1β, and TNF-α within the plaque but also of systemic markers of inflammation such as the white blood cell count and neutrophil-to-lymphocyte ratio. BTEX levels were positively correlated with NLRP3 and IL-1β levels as well as with triglyceride. BTEX levels were higher in people with a prior diagnosis of dyslipidemia and with a subsequent major cardiovascular event. Treatment of monocytes for 5 days with benzene, xylene, and ethylbenzene, but not toluene, fostered a consistent proinflammatory response, an effect observed in the absence of cytotoxicity and phenocopied by the treatment with 1,4-benzoquinone. BTEX and 1,4-benzoquinone also promoted foam cell formation in monocytes differentiated into macrophages. These data represent the first evidence that BTEX pollutants accumulate within the carotid plaque tissue. This phenomenon is associated with increased local inflammation, possibly suggesting the activation of proatherogenic pathways at the local level.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"148 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728472","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}
Adriana E Barni,Megan A George,Jacob R Pangborn,Brett N Hemric
A series of three divergent protocols for the copper-catalyzed azidation of 1,3-dienes using iodine(III) Zhdankin's reagent is reported. This strategy features protocols for 1,2-diazidation, two-component 1,2-azidooxygenation, and three-component 1,2-azidooxygenation of 1,3-dienes in highly chemo-, regio-, and site-selective fashion under mild conditions. Excellent to fair yields are reported for a variety of activated and unactivated 1,3-diene systems with a range of substitution patterns. Additionally, mechanistic investigations are included to provide insights into the underpinnings for the divergence of these protocols and the component requirements.
{"title":"Copper-Catalyzed 1,2-Diazidation and 1,2-Azidooxygenation of 1,3-Dienes: Three Divergent Protocols Using Zhdankin's Reagent.","authors":"Adriana E Barni,Megan A George,Jacob R Pangborn,Brett N Hemric","doi":"10.1021/acs.joc.5c02179","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02179","url":null,"abstract":"A series of three divergent protocols for the copper-catalyzed azidation of 1,3-dienes using iodine(III) Zhdankin's reagent is reported. This strategy features protocols for 1,2-diazidation, two-component 1,2-azidooxygenation, and three-component 1,2-azidooxygenation of 1,3-dienes in highly chemo-, regio-, and site-selective fashion under mild conditions. Excellent to fair yields are reported for a variety of activated and unactivated 1,3-diene systems with a range of substitution patterns. Additionally, mechanistic investigations are included to provide insights into the underpinnings for the divergence of these protocols and the component requirements.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.colsurfb.2025.115368
Zheng Zhang , Jing Zhang , Lihui Zheng , Wenjing Zhao , Tanglin Liu , Jiajing Wu , Wei Su , Yuchen Huang , Shijing Luo , Cong Wang , Mingfei Jin , Jing Huang
Recombinant production of collagen in Escherichia coli is pivotal for advancing biomedical applications, yet it is frequently hampered by critical challenges, notably endotoxin contamination and insufficient prolyl hydroxylation. To address these limitations, we engineered the probiotic bacterium E. coli Nissle 1917 (EcN) as a chassis for producing a hydroxylated human type III collagen-like protein named R8. Through the co-expression of R8 with Bacillus anthracis prolyl 4-hydroxylase (BaP4H) in EcN, we achieved a yield of 0.26 mg/mL for the hydroxylated collagen. A hydroxylation rate of 60 % was achieved, with LC–MS/MS mapping confirming modification at 33 out of 65 proline residues. Hydroxylated R8 exhibits enhanced thermal stability, maintaining the structural integrity of its triple helix and assembling into a porous fibrous network. Crucially, R8 from EcN showed reduced immunogenicity in macrophage activation assays, in stark contrast to material from conventional E. coli BL21(DE3). Moreover, hydroxylated R8 exhibits excellent biocompatibility, significantly promoting fibroblast proliferation and migration, and underscoring the critical role of this modification. This study establishes a strategy for producing bioactive collagen, whilst highlighting the critical importance of hydroxylation for collagen stability and function.
{"title":"A hydroxylated collagen-like construct with an integrin-binding motif produced in a probiotic chassis: Synthesis, structural stability, and in-vitro bioactivity","authors":"Zheng Zhang , Jing Zhang , Lihui Zheng , Wenjing Zhao , Tanglin Liu , Jiajing Wu , Wei Su , Yuchen Huang , Shijing Luo , Cong Wang , Mingfei Jin , Jing Huang","doi":"10.1016/j.colsurfb.2025.115368","DOIUrl":"10.1016/j.colsurfb.2025.115368","url":null,"abstract":"<div><div>Recombinant production of collagen in <em>Escherichia coli</em> is pivotal for advancing biomedical applications, yet it is frequently hampered by critical challenges, notably endotoxin contamination and insufficient prolyl hydroxylation. To address these limitations, we engineered the probiotic bacterium <em>E. coli</em> Nissle 1917 (EcN) as a chassis for producing a hydroxylated human type III collagen-like protein named R8. Through the co-expression of R8 with <em>Bacillus anthracis</em> prolyl 4-hydroxylase (BaP4H) in EcN, we achieved a yield of 0.26 mg/mL for the hydroxylated collagen. A hydroxylation rate of 60 % was achieved, with LC–MS/MS mapping confirming modification at 33 out of 65 proline residues. Hydroxylated R8 exhibits enhanced thermal stability, maintaining the structural integrity of its triple helix and assembling into a porous fibrous network. Crucially, R8 from EcN showed reduced immunogenicity in macrophage activation assays, in stark contrast to material from conventional <em>E. coli</em> BL21(DE3). Moreover, hydroxylated R8 exhibits excellent biocompatibility, significantly promoting fibroblast proliferation and migration, and underscoring the critical role of this modification. This study establishes a strategy for producing bioactive collagen, whilst highlighting the critical importance of hydroxylation for collagen stability and function.</div></div>","PeriodicalId":279,"journal":{"name":"Colloids and Surfaces B: Biointerfaces","volume":"259 ","pages":"Article 115368"},"PeriodicalIF":5.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mei Peng,Jun Jiang,Yao-Hui Wang,Ting Li,Zi Yang,Hai-Tao Zhu,Wei-Min He
Herein, we report a practical semiheterogeneous strategy for the photosynthesis of diverse selanyl phenanthrenes, employing CoS2 as a heterogeneous photocatalyst in combination with ferrocene (Cp2Fe) as a homogeneous redox catalyst. This synergistic system combines photogenerated electron-mediated reduction of selenyl cations into diselenide with photogenerated hole oxidation of Cp2Fe to its oxidized form, which not only oxidizes diselenide into selenyl radicals but also mediates oxidative dehydroaromatization, leading to high-yielding transformations with broad functional group compatibility. Notably, this method eliminates the need for stoichiometric oxidants or reductants and avoids sacrificial electron donors or acceptors.
{"title":"Semiheterogeneous Intrinsic CoS2-Photoredox/Cp2Fe Dual-Catalyzed Synthesis of Selenylated Phenanthrene.","authors":"Mei Peng,Jun Jiang,Yao-Hui Wang,Ting Li,Zi Yang,Hai-Tao Zhu,Wei-Min He","doi":"10.1021/acs.joc.5c02498","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02498","url":null,"abstract":"Herein, we report a practical semiheterogeneous strategy for the photosynthesis of diverse selanyl phenanthrenes, employing CoS2 as a heterogeneous photocatalyst in combination with ferrocene (Cp2Fe) as a homogeneous redox catalyst. This synergistic system combines photogenerated electron-mediated reduction of selenyl cations into diselenide with photogenerated hole oxidation of Cp2Fe to its oxidized form, which not only oxidizes diselenide into selenyl radicals but also mediates oxidative dehydroaromatization, leading to high-yielding transformations with broad functional group compatibility. Notably, this method eliminates the need for stoichiometric oxidants or reductants and avoids sacrificial electron donors or acceptors.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"146 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1021/acs.jpcc.5c07019
Kade Johnson, Kenneth Mikolaichik, David J. Gosztola, Gary P. Wiederrecht, Richard D. Schaller, Xuan Zhou
Extended conjugation of molecular π systems is of great significance for solar cells and organic light-emitting diodes as these can serve as new light absorbing and emitting chromophores. This research demonstrates the potential of using pressure and a solvent environment to create larger assemblies of molecular π-conjugated systems. We selected rhodamine 6G (Rh6G) to study the pressure-induced stacking of molecules in three different solvents: methanol (MeOH), isopropanol (IPA), and a 16:3:1 mixture of methanol:ethanol:water (MEW). Absorption, emission, and fluorescence lifetime were studied at pressures of up to 11.38 GPa. We found that pressure-induced stacking mechanisms can present solvent dependence: high pressures tend to create emissive H-aggregates in MeOH and MEW, but excimers in IPA. This work guides and demonstrates routes to stacking organic molecules using high pressures and provides fundamental insights into the formation of extended conjugation π systems.
{"title":"Pressure-Induced Stacking of Rhodamine 6G Molecules","authors":"Kade Johnson, Kenneth Mikolaichik, David J. Gosztola, Gary P. Wiederrecht, Richard D. Schaller, Xuan Zhou","doi":"10.1021/acs.jpcc.5c07019","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07019","url":null,"abstract":"Extended conjugation of molecular π systems is of great significance for solar cells and organic light-emitting diodes as these can serve as new light absorbing and emitting chromophores. This research demonstrates the potential of using pressure and a solvent environment to create larger assemblies of molecular π-conjugated systems. We selected rhodamine 6G (Rh6G) to study the pressure-induced stacking of molecules in three different solvents: methanol (MeOH), isopropanol (IPA), and a 16:3:1 mixture of methanol:ethanol:water (MEW). Absorption, emission, and fluorescence lifetime were studied at pressures of up to 11.38 GPa. We found that pressure-induced stacking mechanisms can present solvent dependence: high pressures tend to create emissive H-aggregates in MeOH and MEW, but excimers in IPA. This work guides and demonstrates routes to stacking organic molecules using high pressures and provides fundamental insights into the formation of extended conjugation π systems.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"49 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718440","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}
The development of high-performance Pt-based electrocatalysts with reduced metal loading is crucial for advancing proton exchange membrane fuel cell technology. Herein, we present a dual structure-directing agent approach for the precise formation of superstructures in uniform PtCoCu ternary alloy nanoparticles. Using zinc phthalocyanine for coordination-based composition control and dicyandiamide for carbon-mediated sintering suppression enabled molecular-level mixing and formation of an L10 face-centered cubic superstructure with exceptional uniformity and controlled electronic properties. The optimized L10-Pt45Co24Cu31 electrocatalyst exhibited remarkable oxygen reduction reaction activity with a mass activity of 2.13 A/mgPt at 0.9 V vs the reversible hydrogen electrode, representing a 7-fold improvement over commercial Pt/C and exceeding the DOE 2025 target by 483%. The electrocatalyst also demonstrated excellent durability, retaining more than 70% of its initial mass activity after 30 000 potential cycles. Comprehensive density functional theory calculations revealed that ternary alloying optimized the Pt and overall d-band centers, which were located at −2.87 and −2.50 eV, respectively, clarifying the electronic origin of the enhanced electrocatalytic performance. This dual structure-directing strategy overcomes the conventional trade-off between ordered phase formation and particle size control, demonstrating the potential of a tailored precursor design for developing next-generation electrocatalysts with precisely controlled superstructures.
开发高性能、低金属负载的pt基电催化剂是推进质子交换膜燃料电池技术的关键。在此，我们提出了一种双重结构导向剂的方法来精确形成均匀的PtCoCu三元合金纳米颗粒的超结构。使用酞菁锌进行配位控制，使用双氰胺进行碳介导的烧结抑制，使分子水平的混合和形成具有优异均匀性和可控电子性能的L10面心立方上层结构成为可能。优化后的L10-Pt45Co24Cu31电催化剂表现出显著的氧还原反应活性，相对于可逆氢电极，在0.9 V下的质量活性为2.13 a /mgPt，比商用Pt/C提高了7倍，超过DOE 2025目标483%。电催化剂也表现出优异的耐用性，在30 000次潜在循环后保持了70%以上的初始质量活性。综合密度泛函理论计算表明，三元合金优化了Pt和整体d带中心，分别位于- 2.87和- 2.50 eV，阐明了电催化性能增强的电子来源。这种双结构定向策略克服了传统的有序相形成和粒度控制之间的权衡，展示了定制前驱体设计的潜力，用于开发具有精确控制上层结构的下一代电催化剂。
{"title":"Dual Structure-Directing Agents for Superstructure Formation in PtCoCu Ternary Alloy Electrocatalysts","authors":"Pengfei Wang, Sangwoo Chae, Hojung Yun, Yuanyuan Liu, Zhuoya Deng, Seonjae Baek, Nutthira Pakkang, Garbis Atam Akceoglu, Yasuyuki Sawada, Nagahiro Saito","doi":"10.1021/acs.jpcc.5c06519","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06519","url":null,"abstract":"The development of high-performance Pt-based electrocatalysts with reduced metal loading is crucial for advancing proton exchange membrane fuel cell technology. Herein, we present a dual structure-directing agent approach for the precise formation of superstructures in uniform PtCoCu ternary alloy nanoparticles. Using zinc phthalocyanine for coordination-based composition control and dicyandiamide for carbon-mediated sintering suppression enabled molecular-level mixing and formation of an L1<sub>0</sub> face-centered cubic superstructure with exceptional uniformity and controlled electronic properties. The optimized L1<sub>0</sub>-Pt<sub>45</sub>Co<sub>24</sub>Cu<sub>31</sub> electrocatalyst exhibited remarkable oxygen reduction reaction activity with a mass activity of 2.13 A/mg<sub>Pt</sub> at 0.9 V vs the reversible hydrogen electrode, representing a 7-fold improvement over commercial Pt/C and exceeding the DOE 2025 target by 483%. The electrocatalyst also demonstrated excellent durability, retaining more than 70% of its initial mass activity after 30 000 potential cycles. Comprehensive density functional theory calculations revealed that ternary alloying optimized the Pt and overall d-band centers, which were located at −2.87 and −2.50 eV, respectively, clarifying the electronic origin of the enhanced electrocatalytic performance. This dual structure-directing strategy overcomes the conventional trade-off between ordered phase formation and particle size control, demonstrating the potential of a tailored precursor design for developing next-generation electrocatalysts with precisely controlled superstructures.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"15 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729139","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}
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