Pub Date : 2024-09-27DOI: 10.1016/j.chemphys.2024.112462
H. Tamagawa , D.L. Anh , M. Sasaki , W. Lin , B. Delalande
Although continuous mobile ion passage across the plasma membrane is responsible for the generation of the membrane potential, some experiments suggest that the membrane potential can be generated even without the ion passage across the membrane. This potential could be due to the ion adsorption–desorption phenomenon, and it is even possible to derive a potential formula under such a mechanism. This potential formula is somehow identical to the well-known Nernst equation. We investigated this potential formula in depth and found that the profile of “the membrane surface potential versus the logarithm of ion concentration” exhibits the Nernst slope, and this Nernst slope is the key to the identical potential formula to the Nernst equation even for the system without the passage of ions across the membrane. This work may trigger new information about the membrane potential generation mechanism.
{"title":"Nernst slope and the constant surface charge density behind the ion adsorption-origin membrane potential","authors":"H. Tamagawa , D.L. Anh , M. Sasaki , W. Lin , B. Delalande","doi":"10.1016/j.chemphys.2024.112462","DOIUrl":"10.1016/j.chemphys.2024.112462","url":null,"abstract":"<div><div>Although continuous mobile ion passage across the plasma membrane is responsible for the generation of the membrane potential, some experiments suggest that the membrane potential can be generated even without the ion passage across the membrane. This potential could be due to the ion adsorption–desorption phenomenon, and it is even possible to derive a potential formula under such a mechanism. This potential formula is somehow identical to the well-known Nernst equation. We investigated this potential formula in depth and found that the profile of “the membrane surface potential versus the logarithm of ion concentration” exhibits the Nernst slope, and this Nernst slope is the key to the identical potential formula to the Nernst equation even for the system without the passage of ions across the membrane. This work may trigger new information about the membrane potential generation mechanism.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112462"},"PeriodicalIF":2.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142356858","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}
Pub Date : 2024-09-26DOI: 10.1016/j.chemphys.2024.112470
Jiale Kang , Daohan Liu , Wenxiu Ji , Chunxiao Lv , Shiming Liang , Xiumei Ma , Zhengyou Zhu
Facile synthesis of metal oxide semiconductors (MOSs) nanoparticles with ultrafine size is quite promising to improve gas sensing performance due to the large effect of the particle size on the electron depletion layer (EDL), however, which is currently difficult to realize. In this work, we synthesized ultrafine WO3 nanoparticles of 20 ∼ 30 nm via room-temperature hydrolysis with following annealing and investigated the gas sensing performance of the WO3 nanoparticles towards acetoin biomarker released by Listeria monocytogenes (LMs). The WO3 gas sensor displays high response (Ra/Rg = 32.0@5 ppm), excellent selectivity and low detection limit at 140 °C. The ultrafine size of WO3 comparable to its Debye length can lead to a larger variation of EDL thus a higher sensor response. Our work has provided a facile, low cost and large-scale synthetic route to constructing high-performance acetoin biomarker gas sensors and might contribute to the development for LMs detection.
{"title":"Facile synthesis of ultrafine WO3 nanoparticles for highly sensitive acetoin biomarker gas detection","authors":"Jiale Kang , Daohan Liu , Wenxiu Ji , Chunxiao Lv , Shiming Liang , Xiumei Ma , Zhengyou Zhu","doi":"10.1016/j.chemphys.2024.112470","DOIUrl":"10.1016/j.chemphys.2024.112470","url":null,"abstract":"<div><div>Facile synthesis of metal oxide semiconductors (MOSs) nanoparticles with ultrafine size is quite promising to improve gas sensing performance due to the large effect of the particle size on the electron depletion layer (EDL), however, which is currently difficult to realize. In this work, we synthesized ultrafine WO<sub>3</sub> nanoparticles of 20 ∼ 30 nm via room-temperature hydrolysis with following annealing and investigated the gas sensing performance of the WO<sub>3</sub> nanoparticles towards acetoin biomarker released by <em>Listeria monocytogenes</em> (LMs). The WO<sub>3</sub> gas sensor displays high response (R<sub>a</sub>/R<sub>g</sub> = 32.0@5 ppm), excellent selectivity and low detection limit at 140 °C. The ultrafine size of WO<sub>3</sub> comparable to its Debye length can lead to a larger variation of EDL thus a higher sensor response. Our work has provided a facile, low cost and large-scale synthetic route to constructing high-performance acetoin biomarker gas sensors and might contribute to the development for LMs detection.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112470"},"PeriodicalIF":2.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142427944","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}
Pub Date : 2024-09-25DOI: 10.1016/j.chemphys.2024.112469
M. Musa Saad H.-E. , B.O. Alsobhi
The structural, mechanical, optical, and electronic properties of half-Heuslers MTiSn (M = Pd and Pt) are investigated using FP-LAPW incorporating the GGA-PBE. MTiSn crystallize in ferromagnetic (FM) and cubic structure (F-43m; C1b) with lattice constants of 6.216 Å and 6.241 Å, respectively, in good agreement with the available data. Elastic constants reveal that MTiSn meet the mechanical stability criteria with notable thermodynamic properties. Also, we have conducted a detailed analysis of optical properties, encompassing the dielectric function, absorption coefficient, optical conductivity, optical refractivity, and extinction coefficient. It is found that PtTiSn shows higher optical responses than PdTiSn at low and high energy ranges. In terms of electronic properties, MTiSn demonstrate narrow bandgap semiconductor characteristics with an indirect bandgap of = 0.507 eV (M = Pd) and = 0.782 eV (M = Pt). The notable optoelectronic responses have also been examined, indicating the high potential of MTiSn materials for optoelectronic applications.
{"title":"First-principles calculations to investigate optoelectronic of transition-metal half-Heusler alloys MTiSn (M = Pd and Pt) for optoelectronics applications","authors":"M. Musa Saad H.-E. , B.O. Alsobhi","doi":"10.1016/j.chemphys.2024.112469","DOIUrl":"10.1016/j.chemphys.2024.112469","url":null,"abstract":"<div><div>The structural, mechanical, optical, and electronic properties of half-Heuslers MTiSn (M = Pd and Pt) are investigated using FP-LAPW incorporating the GGA-PBE. MTiSn crystallize in ferromagnetic (FM) and cubic structure (<em>F</em>-43<em>m</em>; C1<sub>b</sub>) with lattice constants of 6.216 Å and 6.241 Å, respectively, in good agreement with the available data. Elastic constants <span><math><msub><mi>C</mi><mrow><mi>ij</mi></mrow></msub></math></span> reveal that MTiSn meet the mechanical stability criteria with notable thermodynamic properties. Also, we have conducted a detailed analysis of optical properties, encompassing the dielectric function, absorption coefficient, optical conductivity, optical refractivity, and extinction coefficient. It is found that PtTiSn shows higher optical responses than PdTiSn at low and high energy ranges. In terms of electronic properties, MTiSn demonstrate narrow bandgap semiconductor characteristics with an indirect bandgap of <span><math><msub><mi>E</mi><mi>g</mi></msub></math></span> = 0.507 eV (M = Pd) and <span><math><msub><mi>E</mi><mi>g</mi></msub></math></span> = 0.782 eV (M = Pt). The notable optoelectronic responses have also been examined, indicating the high potential of MTiSn materials for optoelectronic applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112469"},"PeriodicalIF":2.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142327328","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}
Pub Date : 2024-09-22DOI: 10.1016/j.chemphys.2024.112464
Constantinos D. Zeinalipour-Yazdi
The tailored design of nanoparticles becomes more important with the advancement of heterogeneous catalysis and materials science. The formation of nanoparticles in catalysts with a specific geometry of the active site becomes necessary to improve activity and selectivity in catalysis. Here we have used physical sphere-in-contact models of various nanoparticles with hexagonal, square and trigonal geometries on flat close-packed surfaces to understand how the distribution of (100) and (111) sites changes as a function of nanoparticle (NP) size in a simplified model of nanoparticle supported metals. The results from this approach clearly show that in 2-layer NPs that have a hexagonal base have 2–3 times more (100) sites than the square and trigonal base NPs as a function of the number of atoms in the NP. In 3D isotropic NPs, this phenomenon is even more pronounced than the 2-layer NPs. We derive equations that estimate the number of (100), (111), the number of atoms and the aspect ratio as a function of n. These equations are important in tailoring the properties of NPs supported on close-packed metal surfaces, which may find applications in materials science, nanotechnology and catalysis.
{"title":"A study using physical sphere-in-contact models to investigate the structure of close-packed nanoparticles supported on flat hexagonal, square and trigonal lattices","authors":"Constantinos D. Zeinalipour-Yazdi","doi":"10.1016/j.chemphys.2024.112464","DOIUrl":"10.1016/j.chemphys.2024.112464","url":null,"abstract":"<div><div>The tailored design of nanoparticles becomes more important with the advancement of heterogeneous catalysis and materials science. The formation of nanoparticles in catalysts with a specific geometry of the active site becomes necessary to improve activity and selectivity in catalysis. Here we have used physical sphere-in-contact models of various nanoparticles with hexagonal, square and trigonal geometries on flat close-packed surfaces to understand how the distribution of (100) and (111) sites changes as a function of nanoparticle (NP) size in a simplified model of nanoparticle supported metals. The results from this approach clearly show that in 2-layer NPs that have a hexagonal base have 2–3 times more (100) sites than the square and trigonal base NPs as a function of the number of atoms in the NP. In 3D isotropic NPs, this phenomenon is even more pronounced than the 2-layer NPs. We derive equations that estimate the number of (100), (111), the number of atoms and the aspect ratio as a function of n. These equations are important in tailoring the properties of NPs supported on close-packed metal surfaces, which may find applications in materials science, nanotechnology and catalysis.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112464"},"PeriodicalIF":2.0,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142322454","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}
Pub Date : 2024-09-21DOI: 10.1016/j.chemphys.2024.112463
Muhammad Jawad , Amin Ur Rahman , Shafaat Hussain Mirza , Noor ul Amin , Muhammad Faizan , Abdullah Saad Alsubaie , Salah M. El-Bahy
In this work, the structural, electronic, optical and thermoelectric properties of Cs2AlAgBr6, K2AlAgBr6 and Rb2AlAgBr6 have been investigated using WIEN2k code. All the three double perovskites show stability. The stability is confirmed by calculating their formation energy, tolerance factor and molecular dynamic simulations. The electronic properties revealed the understudy compounds as semiconductors of direct band gap of 2.62, 2.61 and 2.59 eV for Cs2AlAgBr6, K2AlAgBr6 and Rb2AlAgBr6, respectively. The absorption band of our compounds is mostly in the ultraviolet energy range which is particularly significant for optoelectronic devices. The studied double perovskites exhibit a large Seebeck coefficient and electrical conductivity, which is significant for the high figure of merit. These properties make them particularly suitable for thermoelectric (TE) devices and other photovoltaic applications, as their high figure of merit at low temperatures opens up new possibilities for these materials.
{"title":"First-principles investigation of structural, electronic, optical and thermoelectric performance of stable inorganic double perovskites A2AlAgBr6 (A=K, Rb, Cs) for energy harvesting","authors":"Muhammad Jawad , Amin Ur Rahman , Shafaat Hussain Mirza , Noor ul Amin , Muhammad Faizan , Abdullah Saad Alsubaie , Salah M. El-Bahy","doi":"10.1016/j.chemphys.2024.112463","DOIUrl":"10.1016/j.chemphys.2024.112463","url":null,"abstract":"<div><div>In this work, the structural, electronic, optical and thermoelectric properties of Cs<sub>2</sub>AlAgBr<sub>6</sub>, K<sub>2</sub>AlAgBr<sub>6</sub> and Rb<sub>2</sub>AlAgBr<sub>6</sub> have been investigated using WIEN2k code. All the three double perovskites show stability. The stability is confirmed by calculating their formation energy, tolerance factor and molecular dynamic simulations. The electronic properties revealed the understudy compounds as semiconductors of direct band gap of 2.62, 2.61 and 2.59 eV for Cs<sub>2</sub>AlAgBr<sub>6</sub>, K<sub>2</sub>AlAgBr<sub>6</sub> and Rb<sub>2</sub>AlAgBr<sub>6</sub>, respectively. The absorption band of our compounds is mostly in the ultraviolet energy range which is particularly significant for optoelectronic devices. The studied double perovskites exhibit a large Seebeck coefficient and electrical conductivity, which is significant for the high figure of merit. These properties make them particularly suitable for thermoelectric (TE) devices and other photovoltaic applications, as their high figure of merit at low temperatures opens up new possibilities for these materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112463"},"PeriodicalIF":2.0,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142322455","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}
Pub Date : 2024-09-21DOI: 10.1016/j.chemphys.2024.112468
Pasar Nizar Saeed, Muhammet Guler
Herein, a novel carboxylated multi-walled carbon nanotubes-carboxylated graphene oxide coated glassy carbon electrode (f-MWCNTs/f-GO/GCE) was prepared for electrochemical determination of 4-nitropehenol (4-NP). The sensor was characterized using fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), raman spectroscopy, and powder x-ray diffraction (XRD). Electrochmical experiments were performed using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and amperometry. The resulting f-MWCNTs/f-GO/GCE could be performed for quick, sensitive, and selective determination of 4-NP in the presence of other electroactive compounds. 4-NP was electrochemically detected depending on the reduction of 4-NP at −0.65 V potential using amperometric method. Under the optimum condutions, the sensor showed excellent response to the determination of 4-NP with three linear detection ranges from 0.018 to 700 µM. The sensor exhibited extremely low limit of detection (5.4 nM). Also, the fabricated sensor was used for detection of 4-NP in different water samples.
{"title":"Electrochemical determination of 4-nitrophenol using functionalized graphene oxide/functionalized multi-walled carbon nanotubes hybrid material modified glassy carbon electrode","authors":"Pasar Nizar Saeed, Muhammet Guler","doi":"10.1016/j.chemphys.2024.112468","DOIUrl":"10.1016/j.chemphys.2024.112468","url":null,"abstract":"<div><div>Herein, a novel carboxylated multi-walled carbon nanotubes-carboxylated graphene oxide coated glassy carbon electrode (f-MWCNTs/f-GO/GCE) was prepared for electrochemical determination of 4-nitropehenol (4-NP). The sensor was characterized using fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), raman spectroscopy, and powder x-ray diffraction (XRD). Electrochmical experiments were performed using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and amperometry. The resulting f-MWCNTs/f-GO/GCE could be performed for quick, sensitive, and selective determination of 4-NP in the presence of other electroactive compounds. 4-NP was electrochemically detected depending on the reduction of 4-NP at −0.65 V potential using amperometric method. Under the optimum condutions, the sensor showed excellent response to the determination of 4-NP with three linear detection ranges from 0.018 to 700 µM. The sensor exhibited extremely low limit of detection (5.4 nM). Also, the fabricated sensor was used for detection of 4-NP in different water samples.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112468"},"PeriodicalIF":2.0,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319167","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}
Pub Date : 2024-09-19DOI: 10.1016/j.chemphys.2024.112465
Yu Xiao , Feng-Yi Zhang , Ming-Jun Ma , Si-Jun Lu , Yong-Jun Zhang , Xiao-Yu Zhao , Ya-Xin Wang , Kun Zhang , Hong-Liang Xu
Hoogsteen (HG) and Watson-Crick (WC) adenine–thymine (A-T) base pairs are fundamental to gene expression and genomic stability. Our research applied density functional theory (DFT) calculations to analyze these base pairs, demonstrating that linking them with ribose or deoxyribose and their immersion in solvents markedly enhances the distinctions in their optical properties. DFT results reveal that N···HN hydrogen bonds in both HG and WC pairs exhibit characteristics of both ionic and covalent bonds, playing a crucial role in their stability. While WC base pairs demonstrate stronger orbital interactions, they also experience greater repulsion than HG pairs. This repulsion offsets the positive interactions to a degree, making the interaction energy of WC pairs slightly lower than that of HG pairs. Furthermore, the distinct conformations of these base pairs result in different vibrational modes, suggesting Raman spectroscopy as an effective method for distinguishing between WC and HG base pairs.
{"title":"Theoretical Investigation of the structure and Raman scattering properties of Hoogsteen- and Watson-Crick-type Adenine-Thymine base pair","authors":"Yu Xiao , Feng-Yi Zhang , Ming-Jun Ma , Si-Jun Lu , Yong-Jun Zhang , Xiao-Yu Zhao , Ya-Xin Wang , Kun Zhang , Hong-Liang Xu","doi":"10.1016/j.chemphys.2024.112465","DOIUrl":"10.1016/j.chemphys.2024.112465","url":null,"abstract":"<div><div>Hoogsteen (HG) and Watson-Crick (WC) adenine–thymine (A-T) base pairs are fundamental to gene expression and genomic stability. Our research applied density functional theory (DFT) calculations to analyze these base pairs, demonstrating that linking them with ribose or deoxyribose and their immersion in solvents markedly enhances the distinctions in their optical properties. DFT results reveal that N···H<img>N hydrogen bonds in both HG and WC pairs exhibit characteristics of both ionic and covalent bonds, playing a crucial role in their stability. While WC base pairs demonstrate stronger orbital interactions, they also experience greater repulsion than HG pairs. This repulsion offsets the positive interactions to a degree, making the interaction energy of WC pairs slightly lower than that of HG pairs. Furthermore, the distinct conformations of these base pairs result in different vibrational modes, suggesting Raman spectroscopy as an effective method for distinguishing between WC and HG base pairs.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112465"},"PeriodicalIF":2.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142311127","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}
Pub Date : 2024-09-19DOI: 10.1016/j.chemphys.2024.112467
Shuyan Liu , Yuxin Jiang , Peng Zhao , Xianzhen Xu , Xiaohui Liu , Yu Zhou
Ester-functionalized ionic liquids (ILs) are widely applied in electrochemistry, separation, reduction and extraction, but there are few basic researches on them. This study investigates the hydrogen bonding interactions between the ester-functionalized ILs and dimethyl sulfoxide (DMSO), as well as compares it to the ethyl acetate–DMSO (CH3COOCH2CH3–DMSO) system. Experimental and quantum chemical calculation sections were employed for this purpose. The results demonstrate that: (1) The hydrogen bonding interactions in the 1-acetoxymethyl-3-methylimidazolium tetrafluoroborate (AOMMIMBF4–DMSO) and 1-acetoxyethyl-3-methylimidazolium tetrafluoroborate (AOEMIMBF4–DMSO) systems are stronger than that in CH3COOCH2CH3–DMSO system. (2) AOMMIMBF4–DMSO and AOEMIMBF4–DMSO systems exhibit comparable interaction strengths. (3) The complexes were identified by the excess spectra and quantum chemical calculations, which are 2AOMMIMBF4, 2AOMMIMBF4–DMSO, AOMMIMBF4–DMSO and [AOMMIM]+−DMSO complexes, respectively. This study enhances understanding of hydrogen bonding interactions between ester-functionalized IL and DMSO, and provides a theoretical basis for further applications of ester-functionalized ILs.
{"title":"Molecular behavior of 1-acetoxymethyl-3-methylimidazolium tetrafluoroborate and DMSO binary system","authors":"Shuyan Liu , Yuxin Jiang , Peng Zhao , Xianzhen Xu , Xiaohui Liu , Yu Zhou","doi":"10.1016/j.chemphys.2024.112467","DOIUrl":"10.1016/j.chemphys.2024.112467","url":null,"abstract":"<div><p>Ester-functionalized ionic liquids (ILs) are widely applied in electrochemistry, separation, reduction and extraction, but there are few basic researches on them. This study investigates the hydrogen bonding interactions between the ester-functionalized ILs and dimethyl sulfoxide (DMSO), as well as compares it to the ethyl acetate–DMSO (CH<sub>3</sub>COOCH<sub>2</sub>CH<sub>3</sub>–DMSO) system. Experimental and quantum chemical calculation sections were employed for this purpose. The results demonstrate that: (1) The hydrogen bonding interactions in the 1-acetoxymethyl-3-methylimidazolium tetrafluoroborate (AOMMIMBF<sub>4</sub>–DMSO) and 1-acetoxyethyl-3-methylimidazolium tetrafluoroborate (AOEMIMBF<sub>4</sub>–DMSO) systems are stronger than that in CH<sub>3</sub>COOCH<sub>2</sub>CH<sub>3</sub>–DMSO system. (2) AOMMIMBF<sub>4</sub>–DMSO and AOEMIMBF<sub>4</sub>–DMSO systems exhibit comparable interaction strengths. (3) The complexes were identified by the excess spectra and quantum chemical calculations, which are 2AOMMIMBF<sub>4</sub>, 2AOMMIMBF<sub>4</sub>–DMSO, AOMMIMBF<sub>4</sub>–DMSO and [AOMMIM]<sup>+</sup>−DMSO complexes, respectively. This study enhances understanding of hydrogen bonding interactions between ester-functionalized IL and DMSO, and provides a theoretical basis for further applications of ester-functionalized ILs.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112467"},"PeriodicalIF":2.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142272952","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}
Pub Date : 2024-09-19DOI: 10.1016/j.chemphys.2024.112466
Shuangfei Zhu , Chaowen Yang , Junjun Zhao , Shuhai Zhang , Ruijun Gou , Yang Liu , Yahong Chen
The decomposition mechanisms of crystalline and amorphous TNT were studied through ReaxFF-lg simulations under the heat-loaded and shock-loaded. Their differences were elucidated from the initial decay reactions, activation energy, products and the clusters. Results showed that the heat-induced pyrolysis of two systems differed slight, but the shock-induced pyrolysis differed large. The decomposition reactions of amorphous and crystalline models are similar, but the nitro oxidation of TNT is only found in amorphous. Dimerization and intermolecular H-transfer were found at the constant temperature and MSST simulations, and intermolecular O-transfer were only found at the constant temperature simulations. For MSST simulation, products in crystalline formed later than in amorphous, and the number of clusters in crystalline is much larger than in amorphous, which indicating crystalline TNT would be induced early through shock wave. These findings could help to increase the understanding for the thermolysis behavior and safety of crystalline and amorphous energetic materials.
通过 ReaxFF-lg 模拟研究了晶体和无定形 TNT 在热负荷和冲击负荷下的分解机理。从初始衰变反应、活化能、产物和团聚体等方面阐明了它们之间的差异。结果表明，两种体系的热诱导热分解差异较小，但冲击诱导热分解差异较大。无定形模型和晶体模型的分解反应相似，但 TNT 的硝基氧化反应只出现在无定形模型中。在恒温模拟和 MSST 模拟中发现了二聚化和分子间 H 转移，而分子间 O 转移只在恒温模拟中发现。在MSST模拟中，晶体中产物的形成晚于非晶体，且晶体中簇的数量远大于非晶体，这表明晶体TNT通过冲击波诱导的时间较早。这些发现有助于加深对晶体和非晶态高能材料热分解行为和安全性的理解。
{"title":"Heat- and shock-induced pyrolysis of crystalline and amorphous TNT revealed by ReaxFF-lg simulations","authors":"Shuangfei Zhu , Chaowen Yang , Junjun Zhao , Shuhai Zhang , Ruijun Gou , Yang Liu , Yahong Chen","doi":"10.1016/j.chemphys.2024.112466","DOIUrl":"10.1016/j.chemphys.2024.112466","url":null,"abstract":"<div><p>The decomposition mechanisms of crystalline and amorphous TNT were studied through ReaxFF-lg simulations under the heat-loaded and shock-loaded. Their differences were elucidated from the initial decay reactions, activation energy, products and the clusters. Results showed that the heat-induced pyrolysis of two systems differed slight, but the shock-induced pyrolysis differed large. The decomposition reactions of amorphous and crystalline models are similar, but the nitro oxidation of TNT is only found in amorphous. Dimerization and intermolecular H-transfer were found at the constant temperature and MSST simulations, and intermolecular O-transfer were only found at the constant temperature simulations. For MSST simulation, products in crystalline formed later than in amorphous, and the number of clusters in crystalline is much larger than in amorphous, which indicating crystalline TNT would be induced early through shock wave. These findings could help to increase the understanding for the thermolysis behavior and safety of crystalline and amorphous energetic materials.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112466"},"PeriodicalIF":2.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142272951","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}
Pub Date : 2024-09-17DOI: 10.1016/j.chemphys.2024.112460
Swera Khalid , Sawera Ramzan , Saleh S Alarfaji , Saeed Ahmad Buzdar , Muhammad Isa Khan
While effective targeted delivery is a challenge in nanomedicine for the delivery of anti-cancer drugs, this work focuses on the potential use of Bismuthene and antimonene nanosheets as nanocarriers for cisplatin anti-cancer using DFT methods. The results indicate that, compared to antimonene, bismuthene demonstrates significantly better physical stability, drug release rate, solubility, and biocompatibility, making it an excellent candidate for drug delivery systems. The parallel and perpendicular orientations of the anticancer drug were adsorbed on both nanosheets; the parallel configuration was the most energetically favored with an adsorption energy of −0.79 eV at the parallel site. A charge transfer from the drug to the bismuthene sheet is also revealed by the electronic charge analysis and DOS calculation, thus confirming efficient drug adsorption. Modeling a proton attack on the drug and the carrier surface near the adsorption sites was performed to model drug release, showing the stability and potential of bismuthene in this aspect of drug release mechanisms. Further, with an approach to studying its interactions with biomolecules, interactions of the drug molecule have been analyzed with amino acids, showing that drugs interact efficiently. Further assessments concerning work function, recovery time, electron localization function, and frontier molecular orbital analyses leave no doubt that bismuthene has beneficial features over antimonene. These thorough assessments present bismuthene as a more promising nanocarrier for the delivery of anti-cancer drugs and open a potential pathway to enhance the efficacy of strategies against cancer treatment.
有效的靶向给药是纳米医学中抗癌药物给药的一项挑战，本研究利用 DFT 方法重点研究了双钌和锑纳米片作为顺铂抗癌纳米载体的潜在用途。研究结果表明，与锑相比，双钌在物理稳定性、药物释放率、溶解性和生物相容性方面都明显优于锑，是药物输送系统的理想候选材料。两种纳米片上都吸附了平行和垂直取向的抗癌药物；平行构型的能量最高，平行位点的吸附能为-0.79 eV。电子电荷分析和 DOS 计算也揭示了从药物到双钌片的电荷转移，从而证实了药物的高效吸附。通过模拟质子对药物和吸附位点附近载体表面的攻击，建立了药物释放模型，显示出双丁烯在药物释放机制方面的稳定性和潜力。此外，为了研究其与生物分子的相互作用，还分析了药物分子与氨基酸的相互作用，结果表明药物能有效地相互作用。有关功函数、恢复时间、电子定位函数和前沿分子轨道分析的进一步评估表明，与锑烯相比，双钌无疑具有有益的特性。这些全面的评估表明，双丁烯是一种更有前景的抗癌药物纳米载体，并为提高癌症治疗策略的有效性开辟了一条潜在的途径。
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