Chemphyschem最新文献_第4页

Origin of Intrinsic Chirality in Cysteine-Passivated Metal Halide Perovskite Nanoclusters. 半胱氨酸钝化金属卤化物钙钛矿纳米团簇中固有手性的来源。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-21 DOI: 10.1002/cphc.202500061

Celia F Todd, David Zeitz, Jin Z Zhang

引用次数: 0

Nanostructuring of AlCu alloy NPs obtained by FLASiS†. FLASiS法制备AlCu合金NPs的纳米结构。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-18 DOI: 10.1002/cphc.202400932

Jesica María José Santillán, David Muñetón Arboleda, Osvaldo Fornaro, Marcelo Lester, Daniel C Schinca, Lucía B Scaffardi

{"title":"Nanostructuring of AlCu alloy NPs obtained by FLASiS†.","authors":"Jesica María José Santillán, David Muñetón Arboleda, Osvaldo Fornaro, Marcelo Lester, Daniel C Schinca, Lucía B Scaffardi","doi":"10.1002/cphc.202400932","DOIUrl":"https://doi.org/10.1002/cphc.202400932","url":null,"abstract":"In the nanometric scale, alloy nanomaterials behave as new materials since they are able to display structures and properties which are different from those of the pure metal nanostructures or bulk alloys. In this work, the compositional characteristics of AlCu alloy nanoparticles (NPs) obtained by †Femtosecond Laser Ablation Synthesis in Solution (FLASiS) on solid targets with different percentages of Al and Cu were studied, motivated by their increasing importance in the construction, aerospace and transportation industrial areas, as well as catalytic activity, and antibacterial effects. Morphology, structure, composition and plasmonic behaviour of the NPs were analysed by SEM, TEM, EDS, XRD and OES. From the obtained results, a configuration model of a host alumina matrix with Cu inclusions, together with a possible kinetic formation mechanism of these nanostructures are both proposed. Analysis of the plasmonic resonance in the experimental optical extinction spectra of the synthesized colloids using this model shows that the nanoparticles in the colloid have Cu filling factors in the range 0.002 - 0.005. Results from TEM images on selected NPs are compared with those obtained independently from the fitting of experimental spectra using the proposed model. Deviation from bulk stoichiometry in the alloy NPs is discussed.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400932"},"PeriodicalIF":2.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143974008","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

Red- and Blue-shifting Hydrogen Bonds of Cyclic Ketones of Varying Ring Sizes with HF and CHF₃: Comparison of the Results of B3LYP, O3LYP, and M06-2X Functionals. 不同环尺寸环酮与HF和CHF3的红移和蓝移氢键：B3LYP、O3LYP和M06-2X官能团结果的比较

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-18 DOI: 10.1002/cphc.202500057

Bijan K Paul

{"title":"Red- and Blue-shifting Hydrogen Bonds of Cyclic Ketones of Varying Ring Sizes with HF and CHF3: Comparison of the Results of B3LYP, O3LYP, and M06-2X Functionals.","authors":"Bijan K Paul","doi":"10.1002/cphc.202500057","DOIUrl":"https://doi.org/10.1002/cphc.202500057","url":null,"abstract":"The density functionals B3LYP, O3LYP, and M06-2X are employed to characterize and compare the properties of hydrogen bonds (HBs) between cyclic ketones of increasing ring size (cyclopropanone to cyclohexanone) and HF and CHF3. Herein, HF forms the classical red-shifting HBs whereas CHF3 forms the unconventional blue-shifting HBs with the cyclic ketones. The red-shifting FH···O HBs are found to be characterized by predominantly shared-shell interaction as contrary to the closed-shell (electrostatic) interaction governing the blue-shifting F3CH···O HBs. This is seen to be consistent with the dominance of hyperconjugative ( <math> <semantics><mrow><mi>n</mi> <mrow><mo>(</mo> <mi>O</mi> <mo>)</mo></mrow> <mo>→</mo> <msup><mi>σ</mi> <mo>*</mo></msup> <mrow><mo>(</mo> <mrow><mtext>HF</mtext></mrow> <mo>)</mo></mrow> </mrow> <annotation>$n left(right. text{O} left.right) rightarrow left(sigmaright)^{star} left(right. text{HF} left.right)$</annotation></semantics> </math> charge transfer) effect over the rehybridization effect underlying the redshifting FH···O HBs, while the reverse situation prevails for blueshifting F3CH···O HBs. The geometry and electronic structure parameters of the cyclic ketones (HB acceptors) show that the polarity of the carbonyl (CO) moiety can be correlated with the ring size to rationalize the electrostatic stabilization of the HBs. The performance of the three density functionals is compared for characterizing the HBs in combination with the triple-ζ basis set 6-311++g(d,p).","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500057"},"PeriodicalIF":2.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143965705","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

Octahedral Distortion-Induced Photoluminescence in Cs₂NaIn_xBi_1-xCl₆ Halide Double Perovskites. 八面体畸变诱导Cs2NaInxBi1-xCl6卤化物双钙钛矿的光致发光。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-18 DOI: 10.1002/cphc.202401036

Poonam Sikarwar, Abhishek Anand, Aravind Kumar Chandiran

引用次数: 0

Thermal Isomerization Rates of New Azoquinoline-Functionalized Copolymers as a Function of Substitution Patterns. 新型偶氮喹啉功能化共聚物的热异构化速率与取代模式的关系。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-18 DOI: 10.1002/cphc.202401155

Dariusz Chomicki, Oksana Kharchenko, Anna Kaczmarek-Kędziera, Robert Czaplicki, Oksana Krupka, Dorota Kowalska, Seyedeh Arasteh Jahani, Vitaliy Smokal, Beata Derkowska-Zielinska

{"title":"Thermal Isomerization Rates of New Azoquinoline-Functionalized Copolymers as a Function of Substitution Patterns.","authors":"Dariusz Chomicki, Oksana Kharchenko, Anna Kaczmarek-Kędziera, Robert Czaplicki, Oksana Krupka, Dorota Kowalska, Seyedeh Arasteh Jahani, Vitaliy Smokal, Beata Derkowska-Zielinska","doi":"10.1002/cphc.202401155","DOIUrl":"https://doi.org/10.1002/cphc.202401155","url":null,"abstract":"Herein, the impact of chromophore substitution patterns on the optical properties and material motions of newly synthesized side-chain methacrylic copolymers functionalized with azo dyes based on 8-hydroxyquinoline are investigated. The optical properties, specifically absorption spectra, are investigated using spectrometry and quantum-chemical time-dependent density functional theory calculations. Molecular-scale movements are observed by examining the thermal stability of cis isomers of chromophores. These findings reveal that the character of the substituents (electron-donating/withdrawing), as well as the substitution pattern, affects the difference in the excited and ground states dipole moments, the extent of the highest occupied molecular orbital-lowest unoccupied molecular orbital gap, and the parameters describing intramolecular charge transfer upon excitation. These factors contribute to the range of bathochromic shifts in the absorption spectrum. Additionally, the results reveal two species engaged in thermal isomerization, and the bathochromic shift of absorption correlates with their thermal isomerization rates and their contribution to the process. Understanding the dual role of substituents in shaping optical properties and thermal relaxation kinetics is giving perspectives for the design of azo-functionalized polymers with tailored photoresponsive behaviors for advanced applications in optoelectronics.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401155"},"PeriodicalIF":2.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143975234","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

Front Cover: RF Heating Effects in CEST NMR with Hyperpolarized 129Xe Considering Different Spin Exchange Kinetics and Saturation Schemes (ChemPhysChem 8/2025) 封面：考虑不同自旋交换动力学和饱和方案的超极化129Xe在CEST核磁共振中的射频加热效应（chemphyscheme 8/2025）

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-17 DOI: 10.1002/cphc.202580801

David Hernandez-Solarte, Prof. Dr. Leif Schröder

引用次数: 0

A Thermodynamic Scale of Multiple Bonds Reducibility Based on G4 Calculations. 基于G4计算的多键可约性热力学尺度。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-17 DOI: 10.1002/cphc.202500203

José Elguero, Ibon Alkorta

引用次数: 0

Metalized Borylene: A New Inorganic Cousin of Borylenes. 金属化硼炔：硼炔的一种新的无机表亲。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-15 DOI: 10.1002/cphc.202401163

Jin Hu, Xuefeng Wang

{"title":"Metalized Borylene: A New Inorganic Cousin of Borylenes.","authors":"Jin Hu, Xuefeng Wang","doi":"10.1002/cphc.202401163","DOIUrl":"https://doi.org/10.1002/cphc.202401163","url":null,"abstract":"Borylenes have become a heated topic of intense interest due to their fascinating transition metal-mimicking reactivity and their role as key intermediates in synthesizing complex boron-containing molecules. However, the practical utilization of borylenes has been limited by their instability and complicated methodologies. Very recently, metalized borylenes based on boron-metal covalent interactions and stabilization strategies involving boron-metal multicenter bonding have been proposed. Spectroscopic and theoretical evidence has substantiated that metal-stabilized metalized borylenes possess molecular activation abilities comparable to or even superior to those of classical organoborylenes; however, these species are yet to be isolated or realized experimentally. This brief concept presents an overview of the definition, structural and bonding characteristics, stabilization strategies, amphoteric reactivity, experimental cases, and future perspectives of metal-stabilized metalized borylene compounds. As a new member of the borylene family, metal-stabilized metalized borylenes unlock new access to hyperactive amphoteric borylene, paving the way for synthesizing novel chemicals and developing new catalytic reactions.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401163"},"PeriodicalIF":2.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143992471","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

Loop Nucleotide Chemical Shifts as a Tool to Characterize DNA G-Quadruplexes. 环核苷酸化学位移作为表征DNA g -四联体的工具。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-14 DOI: 10.1002/cphc.202401075

Rajesh Kumar Reddy Sannapureddi, Bharathwaj Sathyamoorthy

{"title":"Loop Nucleotide Chemical Shifts as a Tool to Characterize DNA G-Quadruplexes.","authors":"Rajesh Kumar Reddy Sannapureddi, Bharathwaj Sathyamoorthy","doi":"10.1002/cphc.202401075","DOIUrl":"https://doi.org/10.1002/cphc.202401075","url":null,"abstract":"DNA G-quadruplexes are known to play myriad functional roles in the cellular context and their structural diversity has diverse applications in various fields of science. Solution-state NMR spectroscopy has been instrumental in characterization of DNA G-quadruplexes across various fields, with recent advancements in the 13C/1H chemical shift-based approach affording rapid and reliable backbone topology identification. In addition to the backbone topology, for a complete 3D structural characterization, the conformational description of the loops is necessary. In this work, it is demonstrated that 13C/1H chemical shifts of propeller, lateral, and diagonal loop conformations provide an avenue towards topology discrimination within a given backbone fold. Nucleotide-based 1H shifts when evaluated using random forest and k-nearest neighbors machine learning methodologies provide a modest accuracy in predicting loop conformation. The predicted loop information when analyzed in conjunction with the traditional NMR methods allows for a complete characterization of DNA G-quadruplex folds in a convenient and reliable fashion. In addition, analysis of loop resonances highlights variable conformational flexibility motivating detailed characterization of loop dynamics.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401075"},"PeriodicalIF":2.3,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143961335","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

Experimental and Theoretical Studies on Reaction Kinetics, Mechanism, and Degradation of Quinoline-Based Herbicide with Hydroxyl Radical, Sulphate Radical Anion, and Hydrated Electron. 羟基自由基、硫酸盐自由基阴离子和水合电子对喹啉类除草剂反应动力学、机理及降解的实验与理论研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-11 DOI: 10.1002/cphc.202401135

Beena G Singh, Hari P Upadhyaya

{"title":"Experimental and Theoretical Studies on Reaction Kinetics, Mechanism, and Degradation of Quinoline-Based Herbicide with Hydroxyl Radical, Sulphate Radical Anion, and Hydrated Electron.","authors":"Beena G Singh, Hari P Upadhyaya","doi":"10.1002/cphc.202401135","DOIUrl":"https://doi.org/10.1002/cphc.202401135","url":null,"abstract":"The kinetic and mechanistic studies for the reaction of hydroxyl radical (•OH), sulfate radical anion ( <math> <semantics> <mrow> <msubsup><mrow><mtext>SO</mtext></mrow> <mn>4</mn> <mrow><mo>•</mo> <mo>-</mo></mrow> </msubsup> </mrow> <annotation>$text{SO}_{4}^{cdot -}$</annotation></semantics> </math> ), and hydrated electron <math> <semantics><mrow><mo>(</mo> <msubsup><mi>e</mi> <mrow><mtext>aq</mtext></mrow> <mo>-</mo></msubsup> <mo>)</mo></mrow> <annotation>$left(right. e_{text{aq}}^{-} left.right)$</annotation></semantics> </math> with quinoline-based herbicide, namely, 8-quinoline carboxylic acid (8QCA), have been performed using experimental and computational methods. Experimental studies are performed using pulse radiolysis technique at different pHs and corroborated with theoretical studies using ab initio molecular orbital calculations. At lower pH of 1, the 8QCA is protonated and reacts with •OH radical to generate transient spectrum with maxima at 340 and 420 nm. Similarly at higher pH of 9, the 8QCA is deprotonated and shows transient absorption maxima at 320 nm. At neutral pH, it exists as neutral species and reacts with •OH radical differently. Theoretically, individual rate coefficients for •OH radical addition reaction with each carbon atoms are evaluated including solvent effect and tunneling correction. Fukui index and individual rate constant determination confirm that C5 carbon atom is the most reactive site for the •OH radical addition reaction. The total rate constant evaluated theoretically and experimentally for the •OH radical reaction is equal to its diffusion-limit value. The ability of •OH radical to degrade 8QCA is found to be higher as compared to <math> <semantics> <mrow><msubsup><mi>e</mi> <mrow><mtext>aq</mtext></mrow> <mo>-</mo></msubsup> </mrow> <annotation>$e_{text{aq}}^{-}$</annotation></semantics> </math> .","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401135"},"PeriodicalIF":2.3,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143987384","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