Chemphyschem最新文献_第8页

Controlling the Morphology and Orientation of the Helical Self-Assembly of Pyrazine Derivatives by Tuning Hydration Shells 通过调节水化壳控制吡嗪衍生物螺旋自组装的形态和取向。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-08 DOI: 10.1002/cphc.202400951

Samrat Sarkar, Anjana V. Mathath, Debashree Chakraborty

{"title":"Controlling the Morphology and Orientation of the Helical Self-Assembly of Pyrazine Derivatives by Tuning Hydration Shells","authors":"Samrat Sarkar, Anjana V. Mathath, Debashree Chakraborty","doi":"10.1002/cphc.202400951","DOIUrl":"10.1002/cphc.202400951","url":null,"abstract":"A combination of density functional theory (DFT) and classical molecular dynamics simulations is performed to unveil the guiding force in the self-assembly process of the pyrazine-based biopolymers to helical nanostructures. The highlight of the study shows the decisive role of the solvent-ligand H-bonding and the inter-molecular pi-pi stacking not only ensures the unidirectional packing of the helical structure but also the rotation of left-handed to the right-handed helical structure of the molecule. This transition is supported by the bulk release of the “ordered” water molecules. The extent of this bonding can be tuned by the temperature, concentration, and type of the metal ions. Smaller ions like Na+ and Al3+ destroy the structure, whereas bigger ions like Zn2+, Ni2+, and Au3+ preserve and rotate the structure according to their concentration. The interaction energy between the pyrazine derivatives is found to be high (−9000 kJ mol−1) for right-handed rotation of the helix, which increases further with the addition of D-histidine, forming a superhelical structure (−10300 kJ mol−1). The insights gained from this work can be used to generate nanostructures of desired morphology.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802637","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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All-Atom Quantum Mechanical Methodologies for One- and Two-Photon Absorption of Realistic Systems 实际系统单光子和双光子吸收的全原子量子力学方法。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-08 DOI: 10.1002/cphc.202401121

Sarah Löffelsender, Marilù G. Maraldi, Marc de Wergifosse

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Enhancing Vinyl Acetate Hydroformylation with La-Decorated Rh/TiO2 Nanotubes Catalysts la修饰的Rh/TiO2纳米管催化剂促进醋酸乙烯氢甲酰化。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202401016

Hongyuan Chuai, Baolin Zhu, Shoumin Zhang, WeiPing Huang

引用次数: 0

Structural Characteristics of Medium-Sized Sulfuric Acid–Ammonia Cluster Cations and Anions and their Atmospheric Implications 中型硫酸-氨簇阳离子和阴离子的结构特征及其大气意义。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202500066

Sijin Zhou, Yameng Hou, Kairui Yang, Xianglei Kong

{"title":"Structural Characteristics of Medium-Sized Sulfuric Acid–Ammonia Cluster Cations and Anions and their Atmospheric Implications","authors":"Sijin Zhou, Yameng Hou, Kairui Yang, Xianglei Kong","doi":"10.1002/cphc.202500066","DOIUrl":"10.1002/cphc.202500066","url":null,"abstract":"Sulfuric acid–ammonia clusters play important roles in atmospheric nucleation processes. However, experimental structural analysis of relative medium-sized or large-sized clusters at the molecular level has always been lacking. Herein, tandem mass spectrometry and IR photondissociation (IRPD) spectroscopy are applied to mass-selected medium-sized cluster ions that have diameters of 1.0–1.2 nm. The differences in their dissociation behaviors and IRPD spectra of the cluster cations and anions are attributed to their structural characteristics, which are further revealed by the combination of theoretical calculations. The protonated clusters can be treated as structures composed of ammonium cations and hydrogen sulfate anions with an alternate acid–base arrangement, which makes their dissociation characterized by the loss of the acid–base pair. For deprotonated clusters, the mobility of intra-cluster protons lowers energy barriers of isomerization, making their dissociation pathways more complicated. The differences and commonalities in the formation of organic acid– and inorganic acid–ammonia clusters are also discussed, as well as their impacts on nucleated orders and sizes. The method can be further extended to other clusters for obtaining the lacking information on relative key species in the formation of new particles in the atmosphere.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794759","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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Variation of Nucleophilicity N_HnA of Atoms A in Hydrides H_nA with the Group and Row of A in the Periodic Table. 氢化物中A原子亲核性NHnA随元素周期表中A族和A行的变化

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202500030

Ibon Alkorta, Anthony Legon

{"title":"Variation of Nucleophilicity NHnA of Atoms A in Hydrides HnA with the Group and Row of A in the Periodic Table.","authors":"Ibon Alkorta, Anthony Legon","doi":"10.1002/cphc.202500030","DOIUrl":"10.1002/cphc.202500030","url":null,"abstract":"Nucleophilicities NHnA of hydrides of atoms A acting as hydrogen-bond acceptors in complexes HnA···HX are reported. The HnA initially chosen are HB, H2C, H3N, H2O, and HF, that is from groups 13, 14, 15, 16, and 17, respectively, of row 1 of the Periodic Table. The Lewis acids HX involved are HF, HCl, HBr, HI, HCCH, and HCP. Nucleophilicities are determined from dissociation energies De for the process HnA···HX = HnA + HX by using De = cNHnA.EHX, where EHX are electrophilicities of the Lewis acids HX. This procedure is also followed for hydrides HnA in which the atoms A are from the same groups, but from rows 2, 3, and 4 of the Periodic Table. The order of NHnA values found is row 1 > row 2 ≈ row 3 ≈ row 4 in each of groups 13, 15, 15, 16, and 17, with a large decrease from row 1 to row 2 but with small decreases from rows 2 to 3 to 4. The series Rg···HX is similarly investigated to give the order of nucleophilicities Rg = Xe > Kr > Ar. > Ne, which is reversed from that in the hydrides of groups 13 to 17.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500030"},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794839","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

Structure and Optical Properties of Alkali-Metal Ion (Li+, Na+, K+, Rb+, and Cs+) Endohedral Cyclo[18]carbon 碱金属离子（Li+, Na+, K+, Rb+, Cs+）内嵌环[18]碳的结构与光学性质

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202500009

Yang Xiao, Xia Wang, Xiufen Yan, Zeyu Liu, Mengdi Zhao, Tian Lu

{"title":"Structure and Optical Properties of Alkali-Metal Ion (Li+, Na+, K+, Rb+, and Cs+) Endohedral Cyclo[18]carbon","authors":"Yang Xiao, Xia Wang, Xiufen Yan, Zeyu Liu, Mengdi Zhao, Tian Lu","doi":"10.1002/cphc.202500009","DOIUrl":"10.1002/cphc.202500009","url":null,"abstract":"With growing interest in carbon-based materials for energy storage and active research in the field of advanced optoelectronic devices, ten complexes are designed with cyclo[18]carbon (C18) inside and outside complexing alkali metal ion (M+ = Li+, Na+, K+, Rb+, and Cs+), respectively, referred to as M+@C18in and M+@C18out, and careful analysis of their structure, binding interaction between M+ and C18, as well as optical properties of stable endohedral complexes M+@C18in is performed. The effects of atomic number of alkali metals on structure, binding interaction, electronic absorption spectrum, and molecular (hyper)polarizability of the M+@C18in are studied using accurate (time-dependent) density functional theory calculations. The research suggests that the binding modes and strengths of different M+ with C18 are different but there is no evident difference in electronic absorption spectra of the complexes. The polarizability and second hyperpolarizability of M+@C18in containing different alkali-metal ions are close due to the similarity of ionic properties but their first hyperpolarizability differs greatly by reason of discrepancy in molecular symmetry. The similarities and differences in structure, fragment interaction, electronic absorption spectrum, and (hyper)polarizability of M+@C18in are explored using advanced wavefunction analysis methods.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 11","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794785","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

Spin-Crossover in a Dinuclear Iron(II) Complex on Highly Oriented Pyrolytic Graphite: An X-Ray Absorption Spectroscopy Study. HOPG上双核铁（II）配合物的自旋交叉：x射线吸收光谱研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202401081

Marcel Walter, Sebastien Elie Hadjadj, Clara Trommer, Jorge Torres, Jendrik Gördes, David Swerev, Tauqir Shinwari, Christian Lotze, Chen Luo, Florin Radu, Felix Tuczek, Sangeeta Thakur, Wolfgang Kuch

{"title":"Spin-Crossover in a Dinuclear Iron(II) Complex on Highly Oriented Pyrolytic Graphite: An X-Ray Absorption Spectroscopy Study.","authors":"Marcel Walter, Sebastien Elie Hadjadj, Clara Trommer, Jorge Torres, Jendrik Gördes, David Swerev, Tauqir Shinwari, Christian Lotze, Chen Luo, Florin Radu, Felix Tuczek, Sangeeta Thakur, Wolfgang Kuch","doi":"10.1002/cphc.202401081","DOIUrl":"10.1002/cphc.202401081","url":null,"abstract":"The spin-crossover (SCO) properties of the dinuclear complex <math> <semantics><mrow><mo>[</mo> <msub><mrow><mo>{</mo> <mtext>Fe</mtext> <msub> <mrow><mrow><mo>(</mo> <msub><mi>H</mi> <mn>2</mn></msub> <mi>B</mi> <msub><mrow><mo>(</mo> <mtext>pz</mtext> <mo>)</mo></mrow> <mn>2</mn></msub> <mo>)</mo></mrow> </mrow> <mn>2</mn></msub> <mo>}</mo></mrow> <mn>2</mn></msub> <mi>μ</mi> <mo>-</mo> <mo>(</mo> <msub><mrow><mtext>ac(bipy)</mtext></mrow> <mn>2</mn></msub> <mo>)</mo> <mo>]</mo></mrow> <annotation>$left[right. left{right. text{Fe} left(left(right. left(text{H}right)_{2} text{B} left(left(right. text{pz} left.right)right)_{2} left.right)right)_{2} left(left.right}right)_{2} mu - left(right. left(text{ac(bipy)}right)_{2} left.right) left]right.$</annotation></semantics> </math> are studied as (sub)-monolayer and thin film deposited by an ultrahigh vacuum liquid-jet deposition technique on highly oriented pyrolytic graphite (HOPG) by X-ray absorption spectroscopy. A comparison of the SCO properties of thin films and a dropcast sample indicates that the spin-switching probability of the thin films is limited due to substrate-molecule interactions. The maximum percentage of molecules in the low-spin (LS) state observed for 0.7 and 1.8 monolayers (ML) is ≈43% at a temperature of 80 K in comparison to the dropcast sample where ≈66% of the complex is in the LS state. The similar switching properties of the dropcast sample as of a bulk powder sample confirm that the SCO properties are not affected by the presence of solvent necessary for deposition. The soft-X-ray-induced excited spin-state trapping (SOXIESST) effect is pronounced in all samples, although the light-induced high-spin (HS) fraction of the dropcast and the thin-film samples on HOPG is higher as compared to the HS fraction attained by SOXIESST, which confirms the sensitivity of the complex to light.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401081"},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794753","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

Unfolding of the Villin Headpiece Domain: Revealing Structural Heterogeneity with Time-Resolved X-Ray Solution Scattering and Markov State Modeling Villin头饰域的展开：用时间分辨x射线溶液散射和马尔可夫态模型揭示结构非均质性。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202500049

Adam K. Nijhawan, Arnold M. Chan, Madeline B. Ho, Changmin Lee, Irina Kosheleva, Lin X. Chen, Kevin L. Kohlstedt

{"title":"Unfolding of the Villin Headpiece Domain: Revealing Structural Heterogeneity with Time-Resolved X-Ray Solution Scattering and Markov State Modeling","authors":"Adam K. Nijhawan, Arnold M. Chan, Madeline B. Ho, Changmin Lee, Irina Kosheleva, Lin X. Chen, Kevin L. Kohlstedt","doi":"10.1002/cphc.202500049","DOIUrl":"10.1002/cphc.202500049","url":null,"abstract":"Understanding protein folding pathways is crucial to deciphering the principles of protein structure and function. Here, the unfolding dynamics of the 35-residue villin headpiece (HP35) and a norleucine-substituted variant (2F4K) using a combination of experimental and computational techniques is investigated. Time-resolved X-ray solution scattering coupled with equilibrium molecular dynamics simulations and Markov state modeling reveals distinct unfolding mechanisms between the two variants: HP35 and 2F4K. Specifically, HP35 exhibits a two-state unfolding process, whereas an intermediate state is identified for the 2F4K mutant. A Markov state model constructed from simulations is used to map atomic-level transitions to experimental observations, providing insights into the role of sequence variations in modulating folding pathways. The findings underscore the importance of integrating experimental and computational approaches to unravel protein unfolding mechanisms between heterogenous structural ensembles.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500049","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794823","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

Reactions of 1,4-Diborinine Derivatives with CO2 1,4-二硼碱衍生物与CO2的反应。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202401049

Maxime Ferrer, Ibon Alkorta, José Elguero, Israel Fernández

引用次数: 0

QTAIM Analysis of a [2]Rotaxane Molecular Shuttle with a 2,2′-Bipyridyl Rigid Core 具有2,2'-联吡啶刚性核的[2]轮烷分子梭的QTAIM分析。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202500074

Costantino Zazza, Nico Sanna, Stefano Borocci, Felice Grandinetti

{"title":"QTAIM Analysis of a [2]Rotaxane Molecular Shuttle with a 2,2′-Bipyridyl Rigid Core","authors":"Costantino Zazza, Nico Sanna, Stefano Borocci, Felice Grandinetti","doi":"10.1002/cphc.202500074","DOIUrl":"10.1002/cphc.202500074","url":null,"abstract":"Chemical contacts responsible for the supramolecular assembly of a rigid H-shaped [2]rotaxane molecular shuttle composed of a 24-crown-8(24C8) macrocycle on a molecular thread containing two benzimidazole (Bzi) recognition sites and a central 2,2′-bipyridyl (Bipy) rigid core are analytically addressed by combining the Quantum Theory of Atoms in Molecules (QTAIM) with density functional theory (DFT). In this respect, the available crystallographic structure—CCDC number 2248267—is taken as a reference condition for addressing the nature of the chemical interactions finely modulating the shuttling of the 24C8 between Bzi stations. Moreover, previous DFT computations (Chem. Sci., 2023, 14, 7215) are extended over a supercomputing environment to address the proposed ligand exchange mechanism involving DMF solvent molecules and promoting the observed shuttling process upon the addition of Zn(II) cations. To this end, converged DFT wavefunctions are fully analyzed by means of electron density ρ(r) and local electronic energy density—H(r)—descriptors; interestingly, the derived covalent versus noncovalent interaction patterns shed some light on the mutual position of the macrocycle along the axle following the coordination of Zn(II) ions in DMF solvent.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500074","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771475","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