Chemphyschem最新文献_第5页

Conductivity-Viscosity Decoupling in Concentrated LiTFSI and LiCl Electrolytes. 浓缩LiTFSI和LiCl电解质的电导率-粘度解耦。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-11 DOI: 10.1002/cphc.202400981

Yuchen Sun, Liqi Kang, Yuanxi Yu, Liang Hong, Zhuo Liu

{"title":"Conductivity-Viscosity Decoupling in Concentrated LiTFSI and LiCl Electrolytes.","authors":"Yuchen Sun, Liqi Kang, Yuanxi Yu, Liang Hong, Zhuo Liu","doi":"10.1002/cphc.202400981","DOIUrl":"https://doi.org/10.1002/cphc.202400981","url":null,"abstract":"Water-in-salt (WiS) electrolytes are increasingly recognized for their superior electrochemical stability and advantageous transport properties in energy storage applications. These electrolytes, formulated with various anions, such as halogen-containing organic anions and halogen-inorganic anions, exhibit distinct characteristics. While the mechanisms governing conductivity-viscosity decoupling in concentrated electrolytes with halogen-containing organic anion salts have been extensively investigated, the decoupling behavior in concentrated electrolytes with halogen-inorganic anion salts remains inadequately characterized. Herein, clear differences in decoupling behavior between concentrated LiTFSI and LiCl electrolytes, with the decoupling parameter α being less than unity for LiTFSI but greater than unity for LiCl are presented. Structural analysis reveals ordered arrangements at ≈6 Å and 13 Å in the concentrated LiTFSI electrolyte, in contrast to the lack of such ordered structures in concentrated LiCl electrolyte. Additionally, the molecular dynamics simulations indicate that the decoupling in concentrated LiTFSI results from the counteractive movements of TFSI- nanoclusters, whereas the decoupling observed in concentrated LiCl is attributable to the cooperative motion of undissociated Li+-Cl- pairs. This work elucidates the conduction mechanism in LiCl-based WiS electrolyte, contributing to a deeper understanding of the conductivity-viscosity relationship and guiding the design of electrolytes for enhanced performance in lithium-ion batteries and supercapacitors.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2400981"},"PeriodicalIF":2.3,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143978388","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

Heteronuclear Parahydrogen-Induced Hyperpolarization via Side Arm Hydrogenation. 异核对氢诱导的侧臂氢化超极化。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-10 DOI: 10.1002/cphc.202401119

Oleg G Salnikov, Nikita V Chukanov, Andrey N Pravdivtsev, Dudari B Burueva, Sergey V Sviyazov, Kolja Them, Jan-Bernd Hövener, Igor V Koptyug

{"title":"Heteronuclear Parahydrogen-Induced Hyperpolarization via Side Arm Hydrogenation.","authors":"Oleg G Salnikov, Nikita V Chukanov, Andrey N Pravdivtsev, Dudari B Burueva, Sergey V Sviyazov, Kolja Them, Jan-Bernd Hövener, Igor V Koptyug","doi":"10.1002/cphc.202401119","DOIUrl":"https://doi.org/10.1002/cphc.202401119","url":null,"abstract":"Nuclear spin hyperpolarization dramatically enhances the sensitivity of nuclear magnetic resonance spectroscopy and imaging. Hyperpolarization of biomolecules (e.g., pyruvate) is of particular interest as it allows one to follow their metabolism, providing a diagnostic tool for various pathologies, including cancer. In this regard, the hyperpolarization of 13C nuclei is especially beneficial due to its typically relatively long hyperpolarization lifetime and the absence of a background signal. Parahydrogen-induced polarization (PHIP) is arguably the most affordable hyperpolarization technique. PHIP exploits the pairwise addition of parahydrogen to an unsaturated substrate. This sets limitations on the range of compounds amenable to direct PHIP hyperpolarization. The range of molecules that can be hyperpolarized with PHIP significantly expanded in 2015 when PHIP by means of side arm hydrogenation (PHIP-SAH) was introduced. Herein, parahydrogen is added to an unsaturated alcoholic moiety of an ester followed by polarization transfer to carboxylate 13C nuclei with a subsequent side arm cleavage. In this review, the recent advances in PHIP-SAH are discussed, including the synthetic methodology to produce isotopically labeled precursors, peculiarities of pairwise addition of parahydrogen to PHIP-SAH precursors, polarization transfer approaches, hyperpolarization lifetime, side arm cleavage, purification of hyperpolarized solution, and, finally, in vitro and in vivo applications.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401119"},"PeriodicalIF":2.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143976074","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

Bromo-Heptahelicene-Bis-Thiadiazole: Photophysics, Chiroptics, and Excited-State Dynamics. 溴-七螺旋烯-双噻二唑：光物理、热力学和激发态动力学。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-09 DOI: 10.1002/cphc.202500176

Debsouri Kundu, Rituparno Chowdhury, Natalia Del Rio, Marie Cordier, Nicolas Vanthuyne, Richard H Friend, Monika Srebro-Hooper, Jeanne Crassous

{"title":"Bromo-Heptahelicene-Bis-Thiadiazole: Photophysics, Chiroptics, and Excited-State Dynamics.","authors":"Debsouri Kundu, Rituparno Chowdhury, Natalia Del Rio, Marie Cordier, Nicolas Vanthuyne, Richard H Friend, Monika Srebro-Hooper, Jeanne Crassous","doi":"10.1002/cphc.202500176","DOIUrl":"https://doi.org/10.1002/cphc.202500176","url":null,"abstract":"The synthesis of a [7]helicene bromide derivative with two fused 2,1,3-thiadiazole heterocycles (TD[7]Br) and a comprehensive study of its photophysical and chiroptical characteristics are presented along with a comparison with 9-bromo-carbo[7]helicene ([7]Br) and 2,15-dibromo-carbo[6]helicene ([6]Br). The integration of a bromine heavy atom onto the helicene backbone facilitates efficient singlet-to-triplet conversion allowing to investigate the resulting fluorescence and phosphorescence properties. The steady-state chiroptical features of the systems are demonstrated through electronic circular dichroism and circularly polarized luminescence. Interestingly, a fluorescence quantum yield of 14% is obtained, a 17-fold increase compared to the corresponding bromo-heptacarbohelicene, and phosphorescence dissymmetry factors reach ±1.2 × 10-2 at 580 nm at low temperature. Finally, the exploration of various excited states generated during the excitation process and their dynamics is delved into by employing nonpolarized transient absorption and emission spectroscopies, thus, highlighting the fruitful combination of heavy-atom effect and charge transfer. The experimental results are understood through time-dependent density functional theory computations.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500176"},"PeriodicalIF":2.3,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144062504","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

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":" ","pages":"e2400951"},"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}

引用次数: 0

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

引用次数: 0

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":" ","pages":"e2500066"},"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}

引用次数: 0

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+@C18 in and M+@C18 out, and careful analysis of their structure, binding interaction between M+ and C18, as well as optical properties of stable endohedral complexes M+@C18 in is performed. The effects of atomic number of alkali metals on structure, binding interaction, electronic absorption spectrum, and molecular (hyper)polarizability of the M+@C18 in 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+@C18 in 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+@C18 in are explored using advanced wavefunction analysis methods.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500009"},"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

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":"https://doi.org/10.1002/cphc.202500049","url":null,"abstract":"Understanding protein folding pathways is crucial to deciphering the principles of protein structure and function. Here, we investigate the unfolding dynamics of the 35-residue villin headpiece (HP35) and a norleucine-substituted variant (2F4K) using a combination of experimental and computational techniques. Time-resolved X-ray solution scattering (TRXSS) coupled with equilibrium Molecular Dynamics (MD) 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 was identified for the 2F4K mutant. A Markov state model constructed from simulations was used to map atomic-level transitions to experimental observations, providing insights into the role of sequence variations in modulating folding pathways. Our 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":" ","pages":"e202500049"},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0