Physical Chemistry Chemical Physics最新文献

{"title":"Oxidative stress via UVC irradiation on the structural rearrangement of Hen Egg White Lysozyme","authors":"Debdip Brahma, Amar Nath Gupta","doi":"10.1039/d4cp03653k","DOIUrl":"https://doi.org/10.1039/d4cp03653k","url":null,"abstract":"Oxidative stress is a physiological condition where oxygen radicals are responsible for the conformational restructuring and loss of functionality of important biomacromolecules. Among the various external agents, UV irradiation is one of the sources that can induce oxidative stress. Here, we report an in-vitro study to gauge the effect of ROS on the structural rearrangement of hen egg white lysozyme, a hydrolytic enzyme, via UVC exposure. Various biophysical techniques like UV-Vis absorption & photoluminescence spectroscopy, circular dichroism, FTIR, dynamic light scattering, and NMR techniques monitored the results. Rapid loss of helical structure of the protein was noted with an increase in β-sheet content as the helical structure decreased from ~34% to ~7% and the β-sheet increased from ~16% to ~34% in the first hour, beyond which there were minimal changes. UV-oxidation led to the thermal stability of the sample as compared to the partial reversibility of native lysozyme. Changes in the amide bands of the protein were noted, along with variations in the UV-vis & PL spectra of the samples. Loss of features with the increase in exposure was noted in the magnetic resonance spectrum. Lastly, with exposure, morphological changes were observed by cross-linking by generated radicals.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"83 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793516","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}

{"title":"Achieving efficiency above 30% with new inorganic cubic perovskites X2SnBr6 (X = Cs, Rb, K, Na) via DFT and SCAPS-1D","authors":"Md. Ferdous Rahman, Tanvir Al Galib, Md. Azizur Rahman, Md. Hafizur Rahman, Md. Harun-Or-Rashid, Md. Al Ijajul Islam, Md. Monirul Islam, N. Dhahri, Ahmad Irfan","doi":"10.1039/d4cp01883d","DOIUrl":"https://doi.org/10.1039/d4cp01883d","url":null,"abstract":"The solar sector is increasingly focusing on inorganic cubic halide perovskite materials without lead (Pb) because of their exceptional structural, electronic, and optoelectronic properties. At the first phase, we thoroughly examined the structural, electronic, and optical characteristics of X2SnBr6 (X = Cs, Rb, K, Na) in detail using FP-DFT in this manuscript. Additionally, we assessed their photovoltaic performance utilizing the SCAPS-1D simulator software. Based on our observations, it has been noted that each of the materials exhibits a direct band gap at the G (Gamma)-point, favorable tolerance factors, negligible losses, and outstanding absorption coefficients. Hence, their potential applications extend to photovoltaic cells and diverse optoelectronic devices. Consequently, we employed the SCAPS-1D simulator to conduct a thorough evaluation of the photovoltaic performance in solar cell configurations based on Cs2SnBr6, Rb2SnBr6, K2SnBr6, and Na2SnBr6 absorbers, incorporating a TiO2 ETL layer. This examination included altering the thickness, defect densities, and levels of doping. The top power conversion efficiencies (PCE) achieved were 29.22% for Cs2SnBr6, 27.25% for Rb2SnBr6, 30.62% for K2SnBr6, and 29.51% for Na2SnBr6 absorber layers, accompanied by VOC values of 1.0246, 0.8713, 0.8345, and 0.7741V; JSC values of 32.2656, 36.7150, 42.6921, and 45.484 mA/cm2; and FF values of 88.38, 85.18, 85.96, and 81.85%, respectively. Our findings indicate that changes in the size of the X-cation significantly impact the bandgap energy, band structure, and optoelectronic properties with the performance of solar cells. Therefore, this study contributes to the progress of lead-free hybrid solar cells and various other categories of optoelectronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"250 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793518","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}

{"title":"Electrochemical cycling stability of electrospun silicon/carbon nanofibers anode materials: A review","authors":"Xiaoru Feng, Fei Rong, Yibing Xie","doi":"10.1039/d4cp02819h","DOIUrl":"https://doi.org/10.1039/d4cp02819h","url":null,"abstract":"Silicon (Si) is regarded as the promissing anode material owing to its high specific capacity and low lithiation potential. The large volume change and the pulverization of silicon during the lithiation/delithiation process hinder its direct energy storage application. This review focuses on the electrospun silicon/carbon (Si/C) nanofibers anode material of lithium-ion battery for long-term stable energy storage. The silicon is completely embedded in electrospinning-based carbon nanofibers to form the electrospun Si/C nanofibers. It not only creates pore space to buffer silicon volume expansion, but also prevents direct contact between silicon and electrolyte, consequently forming a stable solid electrolyte interface film. The electrospun Si/C nanofibers solve the pulverization issue of silicon to achieve cycling stability. Furthermore, the electrospun carbon nanofibers form a flexible conductive network for surrounding silicon by facilely introducing sacrificial polymers or template agents. The electrospun Si/C nanofibers ultimately promote the lithium-ion transport to achieve rate stability. The silicon source selection and microstructure regulation of the electrospun Si/C nanofibers are overviewed. The silicon sources include the direct utilization of silicon or silicon oxide particles as well as the indirect conversion of silicon-based precursors. The cycle stability regulation of various metal- and metal oxide-modified silicon composites and heterogeneous carbon materials-decorated electrospun Si/C nanofibers are summarized. In addition, the microstructure designs of the electrospun Si/C nanofibers associated with the improvement of long-term capacity retention are overviewed. The main challenges of the electrospun Si/C nanofibers anode materials are summarized, and the future perspectives are also proposed.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"200 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793521","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}

{"title":"Improved Thermoelectric Efficiency of Sb2Si2Te6 Through Yttrium-Induced Nanocompositing","authors":"Kivanc Saglik, Xian Yi Tan, Jinfeng Dong, Ady Suwardi, Xi Zu Wang, Jianwei Xu, Qiang Zhu, Hongfei Liu, Cao Jing, Qingyu Yan","doi":"10.1039/d4cp04219k","DOIUrl":"https://doi.org/10.1039/d4cp04219k","url":null,"abstract":"Sb2Si2Te6 is a promising 2D material for medium-temperature thermoelectric applications, with a thermoelectric figure of merit zT approaching 1 at 823 K. However, its widespread use has been limited by relatively low power factor values. In this study, we successfully enhanced the performance of Sb2Si2Te6 by introducing Y nanocomposites. This modification fine-tuned the carrier concentration, electrical conductivity, and increased the power factor up to 946 μW/K at 570K. Jonker plot analysis revealed that increased carrier concentration did not affect the intrinsic electronic properties. SEM and TEM analyses revealed that Yttrium nano-compositing introduced secondary phases, reducing the lattice thermal conductivity to values close to simulated ones using the Debye Callaway model. Sb1.98Y0.02Si2Te6 exhibited the highest zT of 1.49 at 773K due to the ultralow lattice thermal conductivity of 0.29 W/mK and moderate power factor of 858 μW/K at the same temperature. Single Parabolic Band (SPB) model suggests that with further optimization of the Fermi level and additional reduction in lattice thermal conductivity, the zT value could potentially increase to 1.55. These results demonstrate the potential of Yttrium nanocompositing for enhancing Sb2Si2Te6 as an efficient medium-temperature thermoelectric material.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"28 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793522","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}

{"title":"Molecular Insights on Kinetic Stabilization of Amorphous Solid Dispersion of Pharmaceuticals","authors":"Vladislav Aulich, Jan Ludik, Michal Fulem, Ctirad Cervinka","doi":"10.1039/d4cp03557g","DOIUrl":"https://doi.org/10.1039/d4cp03557g","url":null,"abstract":"Poor aqueous solubility of crystalline active pharmaceutical ingredients (API) restricts their bioavailability. Amorphous solid dispersions with biocompatible polymer excipients offers a solution to overcome this problem, potentially enabling a broader use of many drug candidate molecules. This work addresses various aspects of in silico design of a suitable combination of an API and a polymer to form such a binary solid dispersion. Molecular interactions in such bulk systems are tracked at full atomic resolution within molecular-dynamics (MD) simulations, enabling to identify API – polymer pairs that exhibit the most beneficial interactions. Importance of those interactions is manifold: increasing the mutual miscibility, kinetic stabilization of their amorphous dispersions and impedance of the spurious recrystallization of the API component. MD tools are used to investigate the structural and cohesive properties of pure compounds and mixtures, with a special emphasis on molecular interactions, microscopic structure and internal dynamics. This analysis is then accompanied by a macroscopic image of the energetic compatibility and vitrification tendency of the mixtures in terms of their excess enthalpies and glass transition temperatures. Density-functional theory (DFT) and non-covalent interaction (NCI) analysis fortify our computational conclusions and enable us to map intensities of particular NCI among the individual target materials and relevant molecular sites therein. Three archetypal polymer excipients and four API molecules are included in this study. Results of our computational analysis of molecular interactions in bulk systems agree with the experimentally observed trends of solubility of the given API in polymers. Our calculations confirm PVP as the most potent acceptor of hydrogen bonding among the considered polymer excipients, whereas ibuprofen molecules are predicted to be the most efficient hydrogen bond donors among our target API. Our simulations also suggest that carbamazepine does not exhibit particularly strong interactions with the considered polymer excipients. Although current MD cannot offer quantitative accuracy of many of the discussed descriptors, current computational models focusing on NCI of API with polymer excipients contributes to understanding of the behavior of these materials at the molecular level, and thus also to the rational design of novel efficient drug formulations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793662","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}

{"title":"Singlet (1∆g) O2 initiated gas phase oxidation as a potential tropospheric decay channel for ketene","authors":"Saptarshi Sarkar, Ashray Dhiman, Biman Bandyopadhyay","doi":"10.1039/d4cp04026k","DOIUrl":"https://doi.org/10.1039/d4cp04026k","url":null,"abstract":"The oxidation of CH2CO by (1Δg) O2 has been investigated by means of high level quantum chemical and chemical kinetic calculations. The reaction was found to proceed through a four membered cyclic transition state resulting from the addition of O2 to the C=C bond of ketene. The reaction energetics has been calculated employing post-CCSD(T) corrections. The energy of the transition state was found to be 33.6 kcal mol−1 below that of the isolated reactants. The rate coefficient, calculated using master equation under tropospheric conditions, was found to be 5.1 × 10−15 cm3 molecule−1s−1 at 298 K and 1 bar. Atmospheric implications of the title reaction has been estimated by comparing the atmospheric lifetime of ketene for the title reaction against reactions with •OH, H2O and NH3. On a global scale, lifetime for the title reaction was found to be almost 70 times to that for the reaction with •OH. However, under special conditions, where the local concentration of singlet O2 is significantly higher and/or the same of •OH is significantly lower, 1O2 initiated oxidation could become the most significant tropospheric loss mechanism of CH2CO.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"69 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793517","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}

{"title":"GOCIA: grand canonical Global Optimizer for Clusters, Interfaces, and Adsorbates","authors":"Zisheng Zhang, Winston Gee, Robert H Lavroff, Anastassia Alexandrova","doi":"10.1039/d4cp03801k","DOIUrl":"https://doi.org/10.1039/d4cp03801k","url":null,"abstract":"Restructuring of surfaces and interfaces underlie the activation and/or deactivation of a wide spectrum of heterogeneous catalysts and functional materials. The statistical ensemble representation can provide unique atomistic insights into this fluxional and metastable realm, but constructing the ensemble is very challenging, especially for the systems with off-stoichiometric reconstruction and varying coverage of mixed adsorbates. Here we report GOCIA, a general-purpose global optimizer for exploring the chemical space of these systems. It features the grand canonical genetic algorithm (GCGA), which bases the target function on the grand potential and evolves across the compositional space, as well as many useful functionalities and implementation details. GOCIA has been applied to various systems in catalysis, from cluster to surfaces, and from thermal to electro-catalysis.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"9 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797699","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}

{"title":"First-principles investigation of high capacity, rechargeable CFx cathode batteries based on graphdiyne and 'holey'' graphene carbon allotropes","authors":"Quinn Campbell, Nirajan Paudel, Krishna Acharya, Bryan R Wygant, Igor Vasiliev, Timothy N. Lambert","doi":"10.1039/d4cp03643c","DOIUrl":"https://doi.org/10.1039/d4cp03643c","url":null,"abstract":"Batteries composed of CF<small>_x</small> cathodes have high theoretical specific capacities (&gt; 860 mAh/g). Attempts at realizing such batteries coupled with Li anodes have failed to deliver on this promise, however, due to a discharge voltage plateau below the theoretical maximum lowering the realized energy density and difficulties with recharging the system. In this study, we use first-principles calculations to investigate novel carbon allotropes for these battery systems: graphdiyne and \"holey'' graphene. We first identify stable flourination structures and calculate their band gaps. We demonstrate that the holes in these carbon allotropes can induce the formation of an amorphous LiF network within the carbon and that this formation may, in fact, be kinetically favored. For structures where amorphous LiF forms within the carbon, we predict it is easier to recharge and higher discharge voltages can be achieved. If the LiF forms outside the carbon product, however, it will be crystalline in form and lead to lower discharge voltages and more difficulty in recharging the systems. Finally, we simulate XPS spectra of representative cases, demonstrating an experimental pathway for determining the reaction pathway of these systems. Our work suggests CF<small>_x</small> allotropes with holes in them as potential targets for high capacity, rechargable cathodes for Li batteries, provided they lead to the formation of amorphous LiF within the C structure.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797316","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}

{"title":"Effects of polymer network flexibility on the kinetics of DEZ vapor phase infiltration into photo-polymerized polyacrylates†","authors":"Lisanne Demelius, Anna Maria Coclite and Mark D. Losego","doi":"10.1039/D4CP02864C","DOIUrl":"10.1039/D4CP02864C","url":null,"abstract":"<p >Vapor phase infiltration (VPI) enables the fabrication of novel organic–inorganic hybrid materials with distinctive properties by infiltrating polymers with inorganic species through a top-down approach. However, understanding the process kinetics is challenging due to the complex interplay of sorption, diffusion and reaction processes. This study examines how polymer network flexibility affects the kinetics of diethylzinc (DEZ) infiltration into a highly crosslinked polyacrylate copolymer system composed of two monomers: trimethylolpropane triacrylate (TMPTA) and ethoxylated trimethylolpropane triacrylate (ETPTA). The findings show that increasing the ratio of ETPTA, which enhances network flexibility, facilitates precursor diffusion, resulting in deeper infiltration and faster saturation. A reaction–diffusion transport model is employed to qualitatively interpret the experimental results and gain insights into the underlying process mechanisms, thus contributing to a better understanding of VPI kinetics.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 498-512"},"PeriodicalIF":2.9,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d4cp02864c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797700","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}

{"title":"An ab initio study of the rovibronic spectra of CH†","authors":"Zhenlu Hou and Linhua Liu","doi":"10.1039/D4CP03298E","DOIUrl":"10.1039/D4CP03298E","url":null,"abstract":"<p >CH is one of the most spectroscopically studied diatomic molecules. The rovibronic spectra of the methylidyne radical (CH) in adiabatic and diabatic representations are obtained based on <em>ab initio</em> data, including 12 potential energy curves, 38 dipole moment curves, 79 spin–orbit coupling curves, and 18 electronic angular momentum coupling curves. We employed the internally contracted multireference configuration interaction method including the Davidson correction with the aug-cc-pV(5+d)Z basis set for the C atom and the aug-cc-pV5Z basis set for the H atom. The diabatic transformations are performed based on a property-based diabatisation method to remove the avoided crossings for the E <small>²</small>Π–F <small>²</small>Π and F <small>²</small>Π–H <small>²</small>Π pairs. The coupled nuclear motion Schrödinger equations are then solved using the Duo nuclear motion program to obtain the rovibronic spectra of CH for wavenumbers from 0 to 80 000 cm<small>⁻¹</small> at 5000 K. An overall prediction of the rovibronic spectra of CH is provided in this work. Our results could be beneficial for future calculations of rovibronic spectra of CH and contribute to improving astronomical, chemical, and physical models.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 367-375"},"PeriodicalIF":2.9,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782928","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}