Chemphyschem最新文献_第9页

A Pericyclic Reaction in the Gas Phase Identified by Rotational Spectroscopy: Reaction of a Thiocarboxylic Acid with Sulfur Trioxide. 气相中通过旋转光谱确定的周环反应：硫代羧酸与三氧化硫的反应。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-22 DOI: 10.1002/cphc.202400844

Aaron J Reynolds, Kenneth J Koziol, Kenneth R Leopold

{"title":"A Pericyclic Reaction in the Gas Phase Identified by Rotational Spectroscopy: Reaction of a Thiocarboxylic Acid with Sulfur Trioxide.","authors":"Aaron J Reynolds, Kenneth J Koziol, Kenneth R Leopold","doi":"10.1002/cphc.202400844","DOIUrl":"10.1002/cphc.202400844","url":null,"abstract":"The reaction of sulfur trioxide (SO3) and thiobenzoic acid (C6H5COSH) is investigated in the gas phase under supersonic jet conditions. Rotational spectroscopy of the parent and several isotopically substituted derivatives, in conjunction with DFT calculations at the M06-2X/6-311++G(3df,3pd) level of theory, identify the product as thiobenzoic sulfuric anhydride, C6H5C(=S)OSO2OH. Single point CCSD(T)/CBS(D-T)//M06-2X/6-311++G(3df,3pd) calculations place the electronic energy of the product anhydride 114 kJ/mol lower than that of SO3+C6H5COSH at infinite separation. The calculations further indicate that the reaction proceeds through a cyclic transition state which lies 11.3 kJ/mol higher in energy than a C6H5COSH⋅SO3 complex, but 83.3 kJ/mol lower in energy than that of the separated reactants. The reaction is rapid under the experimental conditions of this study: based on the duration of the collisional phase of the supersonic expansion, it is clear that the product is formed within tens of microseconds after mixing. While the analogous reaction of carboxylic acids with SO3 has been demonstrated, the ability of a thiocarboxylic acid to undergo similar chemistry has not previously been established. Although rotational spectroscopy is best known for its precise interrogation of molecular and electronic structure, this work demonstrates its ability to study chemical transformations as well.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400844"},"PeriodicalIF":2.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142496016","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}

引用次数: 0

Multi-Layer Kesterite-Based Photocathodes for Nh₃ Photosynthesis from N₂ Reduction Reaction. 利用 N2 还原反应进行 NH3 光合作用的多层 Kesterite 基光电阴极。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-21 DOI: 10.1002/cphc.202400737

Juliana Ferreira de Brito, Marina Medina, Hugo Leandro Sousa Santos, Mileny Dos Santos Araujo, Marcos Antônio Santana Andrade, Lucia Helena Mascaro

{"title":"Multi-Layer Kesterite-Based Photocathodes for Nh3 Photosynthesis from N2 Reduction Reaction.","authors":"Juliana Ferreira de Brito, Marina Medina, Hugo Leandro Sousa Santos, Mileny Dos Santos Araujo, Marcos Antônio Santana Andrade, Lucia Helena Mascaro","doi":"10.1002/cphc.202400737","DOIUrl":"10.1002/cphc.202400737","url":null,"abstract":"The necessity of new methods to substitute the Haber-Bosch process in the NH3 synthesis, generating fewer greenhouse gases, and dispensing less energy, drove the investigation of the photoelectrocatalytic approach in the N2 reduction reaction (N2RR). For that, this work presents the synthesis and characterization of the layered CZTSSe/CdS/TiO2 photocathode decorated with Pt nanoparticles for application in NH3 production using the photoelectrocatalysis technique. The CZTSSe/CdS/TiO2-Pt characterization showed a well-designed and stable photocatalyst synthesized layer by layer with an important contribution of the Pt nanoparticles for the catalyst performance, improving the photocurrent density and the charge transfer. The N2RR in a two-compartment photochemical cell with 0.1 mol L-1 Na2SO3 and 0.05 mol L-1 H2SO4 in the cathodic and anodic chamber, respectively, using CZTSSe/CdS/TiO2-Pt and under 1 sun of light incidence and applied potential of -0.4 VAg/AgCl reached 0.22 mmol L-1 cm-2 NH3, a value 28 folds higher than using the catalyst without Pt modification. The superiority of N2RR under the photoelectrocatalysis technique was demonstrated compared to photocatalytic and electrocatalytic techniques, together with the investigation of the supporting electrolyte influence in the cathodic compartment. Additionally, that is the first time a kesterite-based photocathode has been applied to NH3 photosynthesis, showing excellent photoconversion capability.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400737"},"PeriodicalIF":2.3,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459192","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}

引用次数: 0

Unveiling the Inhibitory Effect of Magnolol in the Aggregation of Human Calcitonin (hCT): A Comprehensive In-Silico Study. 揭示木兰醇对人降钙素（hCT）聚集的抑制作用：一项综合体内研究

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-21 DOI: 10.1002/cphc.202400679

Mira Jhawar, Sandip Paul

{"title":"Unveiling the Inhibitory Effect of Magnolol in the Aggregation of Human Calcitonin (hCT): A Comprehensive In-Silico Study.","authors":"Mira Jhawar, Sandip Paul","doi":"10.1002/cphc.202400679","DOIUrl":"10.1002/cphc.202400679","url":null,"abstract":"Amyloid fibril formation by some peptides leads to several neurogenetic disorders. This limits their biological activity and increases cytotoxicity. Human calcitonin (hCT), 32 residue containing peptide, known for regulating calcium and phosphate concentration in the blood tends to form amyloids in aqueous medium. Polyphenols are very effective in inhibiting fibril formation. As part of our research, we have taken Magnolol (Mag), which is extracted from the Chinese herb Magnolia officinalis. To evaluate its effectiveness as an inhibitor in preventing hCT aggregation, we conducted an all-atom classical molecular dynamics simulation with varying concentrations of Mag. In presence of Mag, hCT maintains its helical conformation in higher order. Magnolol primarily interacts with hCT via van der Waals interaction. Asp15 residue of hCT, resides in the amyloid region (D15FNKF19) forms strong hydrogen bonding interaction with Mag. Moreover, aromatic residues of hCT interact with Mag through π-π stacking interactions. Our work gives insights into the molecular mechanism of Magnolol in the inhibition of hCT fibril formation to use it as a potential candidate for medicinal purpose.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400679"},"PeriodicalIF":2.3,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459198","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}

引用次数: 0

Microstructure Morphology of Chemical and Structural Phase Separation in Thermally Treated K_xFe_2-ySe₂ Superconductor. 热处理 KxFe2-ySe2 超导体中化学和结构相分离的微观结构形态学。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-21 DOI: 10.1002/cphc.202400363

G Campi, G Tomassucci, M Tanaka, H Takeya, Y Takano, T Mizokawa, N L Saini

{"title":"Microstructure Morphology of Chemical and Structural Phase Separation in Thermally Treated KxFe2-ySe2 Superconductor.","authors":"G Campi, G Tomassucci, M Tanaka, H Takeya, Y Takano, T Mizokawa, N L Saini","doi":"10.1002/cphc.202400363","DOIUrl":"10.1002/cphc.202400363","url":null,"abstract":"The iron-based KxFe2-ySe2 superconductor displays chemical, structural and electronic phase separation at nanoscale to microscale, leading to the coexisting metallic phase embedded in an antiferromagnetic host matrix. The metallic character of the system is believed to arise from a percolative granular network affecting its transport in the normal as well as in the superconducting state. This percolative network can be manipulated and controlled through thermal treatments. In this study, we have used scanning X-ray micro-fluorescence to visualize morphology of the chemical phase separation coupled to the percolation in KxFe2-ySe2, manipulated by two distinct thermal treatments, i. e., fast quenching and slow cooling. We find a differing spatial correlation between Fe and K distributions in the two samples, ascribed to a different degree of Fe vacancy ordering. We have also identified an intermediate phase that acts as an interface between the two main phases. The high temperature quenching produces directionally oriented clustered microstructure in which the percolation threshold is lower and hence a more effective transport networks. Instead, the slow cooling results in larger interfaces around the percolation threshold that seems to affect the superconducting properties of the system. The results provide a quantitative characterization of microstructural morphology of differently grown KxFe2-ySe2 showing potential for the design of electronic devices based on sub-micron scale chemical phase separation, thus opening avenues for further studies of complex heterogeneous functional structures.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400363"},"PeriodicalIF":2.3,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459191","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}

引用次数: 0

Size Effects of Gold Nanoparticles on Surface Plasmon Resonance Assays for DNA Hybridization. 金纳米粒子对 DNA 杂交表面等离子共振检测的尺寸效应

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-21 DOI: 10.1002/cphc.202400484

Zhen Li, Deming Yan, Tianbao Dong, Chaowei Han, Meng Jiang, Qing Kang, Pengcheng Wang, Yanhui Wang, Wenjuan Guo, Feimeng Zhou

{"title":"Size Effects of Gold Nanoparticles on Surface Plasmon Resonance Assays for DNA Hybridization.","authors":"Zhen Li, Deming Yan, Tianbao Dong, Chaowei Han, Meng Jiang, Qing Kang, Pengcheng Wang, Yanhui Wang, Wenjuan Guo, Feimeng Zhou","doi":"10.1002/cphc.202400484","DOIUrl":"10.1002/cphc.202400484","url":null,"abstract":"Recent advancements in signal amplifiers, such as biofunctionalized gold nanoparticles (AuNPs) have improved the surface plasmon resonance (SPR) performance. However, the correlation between the sizes of DNA-Au conjugates and the SPR chips remains elusive. We investigated how the size of AuNPs functioned with DNA detection probes (D-AuNPs) affect SPR signals in sandwich DNA hybridization assays. The effects of three sizes (5, 13, and 29 nm) of D-AuNPs with an equal surface probe density were systematically compared to delineate the relationship between signal amplification and steric hindrance. Sporadically adsorbed target DNA on sparse capture probe-coated chips led to a growth of signal amplification with larger D-AuNPs. In contrast, on dense capture probe-coated SPR chips, when the target DNA concentration was above 1.5 nM, the medium-sized 13 nm AuNPs displayed 1.7- and 1.3-fold enhancement factors than 5 nm and 29 nm ones, respectively. Our results indicate the steric hindrance disturbs the capture of D-AuNPs on dense target DNA-modified chips, rendering the surface density of captured D-AuNPs a determining factor of the sensor response. Alternatively, the sensor sensitivity to D-AuNP surface density is crucial on chips with sparse target DNA. These insights should stimulate and guide future research on surface functionalization toward SPR sensors and AuNPs.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400484"},"PeriodicalIF":2.3,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459196","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}

引用次数: 0

Converting Second-Order Saddle Points to Transition States: New Principles for the Design of 4π Photoswitches. 将二阶鞍点转换为过渡状态：设计 4π 光电开关的新原则。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-17 DOI: 10.1002/cphc.202400786

Amir Mirzanejad, Lukas Muechler

引用次数: 0

Unveiling Eco-Friendly Reverse Micelle Systems: Dimethyl Carbonate as a Novel Biocompatible Solvent. 揭开生态友好型反向胶束系统的神秘面纱：作为新型生物兼容溶剂的碳酸二甲酯。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-17 DOI: 10.1002/cphc.202400617

Alejandra González Herrera, N Mariano Correa, R Dario Falcone, Fernando Moyano

{"title":"Unveiling Eco-Friendly Reverse Micelle Systems: Dimethyl Carbonate as a Novel Biocompatible Solvent.","authors":"Alejandra González Herrera, N Mariano Correa, R Dario Falcone, Fernando Moyano","doi":"10.1002/cphc.202400617","DOIUrl":"10.1002/cphc.202400617","url":null,"abstract":"In this study, we systematically explored the characteristics of dimethyl carbonate (DMC)/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) reverse micelles (RMs) in the presence of water using dynamic light scattering (DLS), proton nuclear magnetic resonance (1H NMR), and molecular probes. DMC, a biocompatible solvent, enables the formulation of AOT RMs without the need for a co-surfactant. DLS revealed that as the water content increased, the droplet sizes grew larger. 1H NMR studies indicated that at low water content, water molecules interacted with DMC via hydrogen bonding. This interaction promoted the penetration of DMC toward the interface, affecting the solvation of AOT's sulfonate group. At higher water content, a competition for hydrogen bonding emerged between water-water and water-surfactant molecules, leading to distinct interfacial properties, as evidenced by molecular probes. The critical micellar concentration for DMC/AOT/water RMs was 7×10-3 M, similar to RMs formed with other biocompatible solvents. The presence of water facilitated the solvation of the surfactant's polar regions, promoting the RMs formation. The polarity of this system was measured using the ET(30) value. This novel micellar system holds significant potential in various fields, including catalysis, nanomaterials, and green chemistry.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400617"},"PeriodicalIF":2.3,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459197","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}

引用次数: 0

Chromium Complex of Macrocyclic Ligands as Precursor for Nitric Oxide Release: A Theoretical Study. 作为一氧化氮释放前体的大环配体铬复合物：理论研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-16 DOI: 10.1002/cphc.202400700

José Guadalupe Hernández, Pandiyan Thangarasu

{"title":"Chromium Complex of Macrocyclic Ligands as Precursor for Nitric Oxide Release: A Theoretical Study.","authors":"José Guadalupe Hernández, Pandiyan Thangarasu","doi":"10.1002/cphc.202400700","DOIUrl":"10.1002/cphc.202400700","url":null,"abstract":"Our research on the chromium complex of macrocyclic ligands as a precursor for nitric oxide release makes a significant contribution to the field of chemistry. We conduct a detailed analysis of nitrito chromium complexes, specifically trans-[M(III)L1-5(ONO)2]+, where M=Cr(III) and L1-L5 represent different ligands such as L1=1,4,8,11-tetraazacyclotetradecane, L2= (5,7-dimethyl-6-benzylcyclam), L3= (5,7-dimethyl-6-anthracylcyclam), L4= (5,7-dimethyl-6-(p-hydroxymethylbenzyl)-1,4, 8,11-cyclam) and L5= (5,7-dimethyl-6-(1¢-methyl-4'-(1\"-carboxymethylpyrene) benzyl)-1,4,8,11-tetraazacyclotetradecane). Our objective is to comprehensively understand the mechanism of NO release and identify the key factors influencing NO delivery. The optimized structure of the complexes at spin states S=1/2 or 3/2 indicates a decrease in the Cr(III)-O bond length (1.669-1.671 Å) along with an increase in the Cr(III)O-NO bond length (2.735-2.741 Å), which facilitates the release of NO. Furthermore, there is a significant change in the bond angle (Cr-O-NO), from 120.4° to 116.9°, to S=3/2, thus enlarging the O-NO bond and supporting the β-cleavage of NO from the complex. The calculated activation energy for the complexes reflects the energy difference between the low-spin doublet and high-spin quartet state due to spin crossover (SCO). Moreover, the Natural Transition Orbitals (NTOs) confirm the involvement of a hole-particle in the excitation. Additionally, TD-DFT reveals the pendant chromophore's role in generating NO, as the chromophore antenna effectively enhances light absorption.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400700"},"PeriodicalIF":2.3,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459186","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}

引用次数: 0

Halogen Substitution Strategy for Exploiting High-Performance Molecular Ferroelectrics. 开发高性能分子铁电的卤素置换策略。

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-16 DOI: 10.1002/cphc.202400801

Xingguang Chen, Haojie Xu, Wenjing Li, Junhua Luo, Zhihua Sun

引用次数: 0

Cover Feature: Molecular-Level Insight into the Chlorofluorocarbons Adsorption by Defective Covalent Organic Polymers (ChemPhysChem 20/2024) 封面专题：缺陷共价有机聚合物吸附氟氯化碳的分子级洞察（ChemPhysChem 20/2024）

IF 2.3 3区化学

Chemphyschem Pub Date : 2024-10-15 DOI: 10.1002/cphc.202482003

Jian Shen, Mohammad Wahiduzzaman, Abhishek Kumar, Dushyant Barpaga, B. Peter McGrail, Praveen K Thallapally, Guillaume Maurin, Radha Kishan Motkuri

{"title":"Cover Feature: Molecular-Level Insight into the Chlorofluorocarbons Adsorption by Defective Covalent Organic Polymers (ChemPhysChem 20/2024)","authors":"Jian Shen, Mohammad Wahiduzzaman, Abhishek Kumar, Dushyant Barpaga, B. Peter McGrail, Praveen K Thallapally, Guillaume Maurin, Radha Kishan Motkuri","doi":"10.1002/cphc.202482003","DOIUrl":"https://doi.org/10.1002/cphc.202482003","url":null,"abstract":"The Cover Feature shows modeling of a 1D Ising-like Hamiltonian chain for binuclear spin-crossover materials accounting for two-, three- and four-body intra- and inter-binuclear interactions. Exact treatment is carried out within the frame of the transfer matrix method. In the case of competing anti-ferroelastic intra-dinuclear and ferroelastic inter-dinuclear interactions, thermally induced two-, three- and four-step transitions are obtained. When interchain interactions are considered, multistep hysteretic transitions are generated, reproducing the experimental observations. More information can be found in the Research Article by K. Boukheddaden and co-workers (DOI: 10.1002/cphc.202400238).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture>\u0000 </div>\u0000 </figure>\u0000 ","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"25 20","pages":""},"PeriodicalIF":2.3,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202482003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142443417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0