The aim of our study is to provide a possible insight into blue-shifting and red-shifting hydrogen bonding complexes. For that, we have taken CHX3 (X F, Cl, Br) with hydrogen bond acceptors such as H2O, HCl, HCN, C2H2, NH3, H2S, PH3, CH3OH, C6H6 (Y O, N, Cl, P, S, ). In this work, we have optimized and computed the vibrational frequency by performing quantum chemical calculations on the systems utilizing B3LYP and MP2 levels of theory with 6-311++G(d, p) and aug-cc-pVDZ basis sets. Further, we compared the various calculated findings, such as geometrical parameters, interaction energies (E), hyper-conjugative interactions, second-order perturbation energies (E2), Laplacian electron densities () at the intermolecular bond critical point (BCP), vibrational shift (). The dependence of vibrational frequency on bond length and Mulliken charge was studied. Since NH3 has a highly negative Mulliken charge, it attracts the hydrogen (H) of CH having a positive Mulliken charge. This effect weakens the CH bond, leading to a red shift in the stretching frequency. In these complexes, NBO analysis revealed a higher value of second-order perturbation as a result of hyper-conjugative interaction from Lewis base to (CH), thus a higher redshift is observed.
{"title":"Comparative analysis of red and blue-shifting hydrogen bonds in 1:1 haloform complexes","authors":"Giridhar Baburao, Aishwaryavela Esakkimuthu, Gopi Ragupathy","doi":"10.1016/j.comptc.2024.114935","DOIUrl":"10.1016/j.comptc.2024.114935","url":null,"abstract":"<div><div>The aim of our study is to provide a possible insight into blue-shifting and red-shifting hydrogen bonding complexes. For that, we have taken CHX<sub>3</sub> (X <span><math><mo>=</mo></math></span> F, Cl, Br) with hydrogen bond acceptors such as H<sub>2</sub>O, HCl, HCN, C<sub>2</sub>H<sub>2</sub>, NH<sub>3</sub>, H<sub>2</sub>S, PH<sub>3</sub>, CH<sub>3</sub>OH, C<sub>6</sub>H<sub>6</sub> (Y <span><math><mo>=</mo></math></span> O, N, Cl, P, S, <span><math><mi>π</mi></math></span>). In this work, we have optimized and computed the vibrational frequency by performing quantum chemical calculations on the systems utilizing B3LYP and MP2 levels of theory with 6-311++G(d, p) and aug-cc-pVDZ basis sets. Further, we compared the various calculated findings, such as geometrical parameters, interaction energies (<span><math><mi>Δ</mi></math></span>E), hyper-conjugative interactions, second-order perturbation energies (E<sub>2</sub>), Laplacian electron densities (<span><math><mrow><msup><mrow><mo>∇</mo></mrow><mrow><mn>2</mn></mrow></msup><mi>ρ</mi></mrow></math></span>) at the intermolecular bond critical point (BCP), vibrational shift (<span><math><mrow><mi>Δ</mi><mi>ν</mi></mrow></math></span>). The dependence of vibrational frequency on bond length and Mulliken charge was studied. Since NH<sub>3</sub> has a highly negative Mulliken charge, it attracts the hydrogen (H) of C<img>H having a positive Mulliken charge. This effect weakens the C<img>H bond, leading to a red shift in the stretching frequency. In these complexes, NBO analysis revealed a higher value of second-order perturbation as a result of hyper-conjugative interaction from Lewis base to <span><math><msup><mrow><mi>σ</mi></mrow><mrow><mo>∗</mo></mrow></msup></math></span>(C<img>H), thus a higher redshift is observed.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114935"},"PeriodicalIF":3.0,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587481","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 : 2024-10-28DOI: 10.1016/j.comptc.2024.114943
Abdesslem Jedidi , Yasir Alzahrani , Saadullah G. Aziz , Osman I. Osman , Shaaban A. Elroby , Walid M.I. Hassan , Kamal A. Soliman
We used pentagonal boron nitride penta-BN2 (p-BN2) surface as a challenging material for the application as a gas sensor. The effect of applying a dopant on the surface was also studied, alongside the effect of decoration with a non-noble metal. Density Functional Theory (DFT) calculations were used to investigate the geometrical and electronic structures of the adsorbed H2S and SO2 gases on pristine (p-BN2) and doped carbon. They showed easy desorption processes from pristine surface and lead to high detection rates. This indicates that these surfaces are suitable for being used as sensors for H2S and SO2 gases. Additionally, pristine was decorated with nickel (Ni), iron (Fe), and cobalt (Co). The adsorption energies of the gases on the decorated metal pristine and their electronic properties were also performed. The results showed stronger adsorptions (chemisorption); that is, the charge transfers between the gas and the surface was considerably increased. These surfaces are, hence, more suitable for gases capture and removal by decomposition.
{"title":"The role of carbon doped and non-noble metal decorated p-BN2 for the adsorption of H2S and SO2 gases","authors":"Abdesslem Jedidi , Yasir Alzahrani , Saadullah G. Aziz , Osman I. Osman , Shaaban A. Elroby , Walid M.I. Hassan , Kamal A. Soliman","doi":"10.1016/j.comptc.2024.114943","DOIUrl":"10.1016/j.comptc.2024.114943","url":null,"abstract":"<div><div>We used pentagonal boron nitride penta-BN<sub>2</sub> (p-BN<sub>2</sub>) surface as a challenging material for the application as a gas sensor. The effect of applying a dopant on the surface was also studied, alongside the effect of decoration with a non-noble metal. Density Functional Theory (DFT) calculations were used to investigate the geometrical and electronic structures of the adsorbed H<sub>2</sub>S and SO<sub>2</sub> gases on pristine (p-BN<sub>2</sub>) and doped carbon. They showed easy desorption processes from pristine surface and lead to high detection rates. This indicates that these surfaces are suitable for being used as sensors for H<sub>2</sub>S and SO<sub>2</sub> gases. Additionally, pristine was decorated with nickel (Ni), iron (Fe), and cobalt (Co). The adsorption energies of the gases on the decorated metal pristine and their electronic properties were also performed. The results showed stronger adsorptions (chemisorption); that is, the charge transfers between the gas and the surface was considerably increased. These surfaces are, hence, more suitable for gases capture and removal by decomposition.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114943"},"PeriodicalIF":3.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572996","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 : 2024-10-28DOI: 10.1016/j.comptc.2024.114941
M. Kashif Masood , Wahidullah Khan , Shumaila Bibi , Niqab Khan , Redi Kristian Pingak , Kamran Tahir , Javed Rehman , Aboud Ahmed Awadh Bahajjaj
Perovskite hydrides are promising materials for hydrogen capacity application to achieve the US DOE on-board criteria. We have investigated novel perovskite hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for H2 storage and transportation applications. In this study we investigates the physical properties of XZrH3 light materials for solid-state hydrogen storage application by incorporating the DFT framework with the CASTEP code. We have theoretically examined the structural, mechanical, electronic, optical, and hydrogen storage properties of these materials. The selected compounds were fully relaxed and optimized in the cubic phase space group Pm-3 m. Structural phase stability was confirmed through thermodynamic, and mechanical analyses. Mechanical properties, evaluated based on Poisson’s ratio, the Puagh’s ratio, and Cauchy pressure, indicate the ductile behavior with a preference for ionic bonding. The electronic structure analysis reveals the metallic behavior of these materials. Optical calculations were also performed to provide additional insights into the physical properties of H2 compounds. The gravimetric hydrogen storage capacities were calculated as 2.55, 2.25, 1.66, and 1.31 wt% for MgZrH3, CaZrH3, SrZrH3, And BaZrH3 hydrides respectively. The identified properties of XZrH3 suggest that these materials could significantly enhance hydrogen storage systems, with potential integration into existing energy technologies, offering a pathway toward more efficient and sustainable hydrogen-based solutions.
{"title":"The structural, elastic, optoelectronic properties and hydrogen storage capability of lead-free hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for hydrogen storage application: A DFT study","authors":"M. Kashif Masood , Wahidullah Khan , Shumaila Bibi , Niqab Khan , Redi Kristian Pingak , Kamran Tahir , Javed Rehman , Aboud Ahmed Awadh Bahajjaj","doi":"10.1016/j.comptc.2024.114941","DOIUrl":"10.1016/j.comptc.2024.114941","url":null,"abstract":"<div><div>Perovskite hydrides are promising materials for hydrogen capacity application to achieve the US DOE on-board criteria. We have investigated novel perovskite hydrides XZrH<sub>3</sub> (X: Mg/Ca/Sr/Ba) for H<sub>2</sub> storage and transportation applications. In this study we investigates the physical properties of XZrH<sub>3</sub> light materials for solid-state hydrogen storage application by incorporating the DFT framework with the CASTEP code. We have theoretically examined the structural, mechanical, electronic, optical, and hydrogen storage properties of these materials. The selected compounds were fully relaxed and optimized in the cubic phase space group <em>Pm</em>-3 m. Structural phase stability was confirmed through thermodynamic, and mechanical analyses. Mechanical properties, evaluated based on Poisson’s ratio, the Puagh’s ratio, and Cauchy pressure, indicate the ductile behavior with a preference for ionic bonding. The electronic structure analysis reveals the metallic behavior of these materials. Optical calculations were also performed to provide additional insights into the physical properties of H<sub>2</sub> compounds. The gravimetric hydrogen storage capacities were calculated as 2.55, 2.25, 1.66, and 1.31 wt% for MgZrH<sub>3</sub>, CaZrH<sub>3</sub>, SrZrH<sub>3</sub>, And BaZrH<sub>3</sub> hydrides respectively. The identified properties of XZrH<sub>3</sub> suggest that these materials could significantly enhance hydrogen storage systems, with potential integration into existing energy technologies, offering a pathway toward more efficient and sustainable hydrogen-based solutions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114941"},"PeriodicalIF":3.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561276","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}
This study extensively examines the influence of pressure on several physical characteristics of cubic halide perovskites AZnF3 (A = Ga, In) in extreme conditions (up to 60 GPa hydrostatic pressure) via the use of the first principles approach. The reduction of the band gap of the chosen compounds under increasing pressure is comprehensively discussed through the band structure and density of states calculations. The strong hybridization between Ga-4p(In-5p) and F-2p states under pressure is responsible for lowering the electronic band gap. The ionic and covalent nature of Ga/In–F and Zn–F bonds, respectively, are confirmed by charge density mapping. The optical absorption shifts towards lower energy regions under pressure are advantageous for using AZnF3 (A = Ga, In) in photovoltaic applications. Furthermore, the comprehensive optical study demonstrates that the compound synthesized under pressure exhibits greater suitability for use in optoelectronic devices compared to systems formed under zero-pressure conditions. Interestingly, the brittleness of GaZnF3 is converted to ductile under the application of pressure.
{"title":"Stimulating band gap reduction of AZnF3 (A = Ga, In) perovskites under external pressure for improving optoelectronic performance","authors":"Md Saiduzzaman , Khandaker Monower Hossain , Arpon Biswas , Safin Alam , Aldina Sultana , Tanjun Ahmed , Jahid Kabir Rony , Sohail Ahmad , Mst.A. Khatun , S.K. Mitro","doi":"10.1016/j.comptc.2024.114940","DOIUrl":"10.1016/j.comptc.2024.114940","url":null,"abstract":"<div><div>This study extensively examines the influence of pressure on several physical characteristics of cubic halide perovskites AZnF<sub>3</sub> (A = Ga, In) in extreme conditions (up to 60 GPa hydrostatic pressure) via the use of the first principles approach. The reduction of the band gap of the chosen compounds under increasing pressure is comprehensively discussed through the band structure and density of states calculations. The strong hybridization between Ga-4p(In-5p) and F-2p states under pressure is responsible for lowering the electronic band gap. The ionic and covalent nature of Ga/In–F and Zn–F bonds, respectively, are confirmed by charge density mapping. The optical absorption shifts towards lower energy regions under pressure are advantageous for using AZnF<sub>3</sub> (A = Ga, In) in photovoltaic applications. Furthermore, the comprehensive optical study demonstrates that the compound synthesized under pressure exhibits greater suitability for use in optoelectronic devices compared to systems formed under zero-pressure conditions. Interestingly, the brittleness of GaZnF<sub>3</sub> is converted to ductile under the application of pressure.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114940"},"PeriodicalIF":3.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657636","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 : 2024-10-24DOI: 10.1016/j.comptc.2024.114926
Shuai Lian, Xiaoqiong Li , Xuefei Lv
Molnupiravir, a nucleoside analogue (EIDD-2801), is an RNA polymerase inhibitor that effectively treats infections caused by novel coronaviruses and can be administered orally. Therefore, it is necessary to monitor the distribution of Molnupiravir in vivo after oral administration. Surface-enhanced Raman spectroscopy (SERS) is a suitable detection method, so it is necessary to understand the interaction between Molnupiravir and noble metal nanoparticles in the SERS effect. Therefore, we used density functional theory combined with surface-enhanced Raman spectroscopy to investigate the interaction between Molnupiravir and noble metal/composite nanoparticles in the SERS effect. To study the interaction sites of Molnupiravir and the substrate in the SERS effect, the molecular electrostatic potential (MEP) of Molnupiravir was calculated. Considering the significant role of binding energy in studying molecular docking, the binding energy between Molnupiravir and Metal6 (Au6, Ag6, Au3Ag3) atomic clusters was calculated. The calculated results of the frontier orbitals and relevant molecular parameters of Molnupiravir and Molnupiravir-Metal6 complexes reveal the changes in the molecular properties of Molnupiravir in the SERS effect. Finally, the theoretical Raman spectra differences between Molnupiravir and complexes were compared and analyzed, and the adsorption structure of Molnupiravir on the substrate surface was determined based on the surface selection rules of SERS. The research results will provide insights into the interaction between Molnupiravir and the substrate in the SERS effect, and also offer theoretical support for the application of SERS methods in biomedical detection.
{"title":"Interaction between Molnupiravir and noble metal substrates in SERS detection: A DFT method and Raman characteristic study","authors":"Shuai Lian, Xiaoqiong Li , Xuefei Lv","doi":"10.1016/j.comptc.2024.114926","DOIUrl":"10.1016/j.comptc.2024.114926","url":null,"abstract":"<div><div>Molnupiravir, a nucleoside analogue (EIDD-2801), is an RNA polymerase inhibitor that effectively treats infections caused by novel coronaviruses and can be administered orally. Therefore, it is necessary to monitor the distribution of Molnupiravir in vivo after oral administration. Surface-enhanced Raman spectroscopy (SERS) is a suitable detection method, so it is necessary to understand the interaction between Molnupiravir and noble metal nanoparticles in the SERS effect. Therefore, we used density functional theory combined with surface-enhanced Raman spectroscopy to investigate the interaction between Molnupiravir and noble metal/composite nanoparticles in the SERS effect. To study the interaction sites of Molnupiravir and the substrate in the SERS effect, the molecular electrostatic potential (MEP) of Molnupiravir was calculated. Considering the significant role of binding energy in studying molecular docking, the binding energy between Molnupiravir and Metal<sub>6</sub> (Au<sub>6</sub>, Ag<sub>6</sub>, Au<sub>3</sub>Ag<sub>3</sub>) atomic clusters was calculated. The calculated results of the frontier orbitals and relevant molecular parameters of Molnupiravir and Molnupiravir-Metal<sub>6</sub> complexes reveal the changes in the molecular properties of Molnupiravir in the SERS effect. Finally, the theoretical Raman spectra differences between Molnupiravir and complexes were compared and analyzed, and the adsorption structure of Molnupiravir on the substrate surface was determined based on the surface selection rules of SERS. The research results will provide insights into the interaction between Molnupiravir and the substrate in the SERS effect, and also offer theoretical support for the application of SERS methods in biomedical detection.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114926"},"PeriodicalIF":3.0,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529109","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 : 2024-10-24DOI: 10.1016/j.comptc.2024.114939
Peter Škorňa , Sanam Bashir , Eva Scholtzová , Daniel Tunega
The theoretical DFT-D3 approach was used in the model study of the immobilisation of the toxic selenate oxyanion, with montmorillonite clay modified by poly(2-methyl-2-oxazoline) polymer represented by a pentamer unit, and tetrabutylphosphonium cation. The calculated basal spacing for Se-POx-Mt and Se-TBP-Mt models provided similar results differing by 0.2 Å (18.3 Å for Se-POx-Mt and/or 18.5 Å for Se-TBP-Mt, respectively). The calculated intercalation energy, ΔEint, showed a suitability of both modified Mts for trapping of (SeO4)2– oxyanions favouring the Se-TBP-Mt (–210.7 kJ/mol) system compared to Se-POx-Mt (–124.5 kJ/mol). The main interactions in both models were classified as hydrogen bonds of weak (CH···O) and moderate-to-strong (OH···O) strength. The calculated total and projected vibrational density of states of the Se-POx-Mt and Se‑TBP‑Mt models, obtained from the ab initio molecular dynamics simulations, were used for distinct identification of vibrational modes of the intercalated (SeO4)2– ion in the interlayer space of both models.
{"title":"Model study on potential removal of toxic Se(VI) by organically modified montmorillonite","authors":"Peter Škorňa , Sanam Bashir , Eva Scholtzová , Daniel Tunega","doi":"10.1016/j.comptc.2024.114939","DOIUrl":"10.1016/j.comptc.2024.114939","url":null,"abstract":"<div><div>The theoretical DFT-D3 approach was used in the model study of the immobilisation of the toxic selenate oxyanion, with montmorillonite clay modified by poly(2-methyl-2-oxazoline) polymer represented by a pentamer unit, and tetrabutylphosphonium cation. The calculated basal spacing for Se-POx-Mt and Se-TBP-Mt models provided similar results differing by 0.2 Å (18.3 Å for Se-POx-Mt and/or 18.5 Å for Se-TBP-Mt, respectively). The calculated intercalation energy, Δ<em>E</em><sub>int,</sub> showed a suitability of both modified Mts for trapping of (SeO<sub>4</sub>)<sup>2–</sup> oxyanions favouring the Se-TBP-Mt (–210.7 kJ/mol) system compared to Se-POx-Mt (–124.5 kJ/mol). The main interactions in both models were classified as hydrogen bonds of weak (C<img>H···O) and moderate-to-strong (O<img>H···O) strength. The calculated total and projected vibrational density of states of the Se-POx-Mt and Se‑TBP‑Mt models, obtained from the <em>ab initio</em> molecular dynamics simulations, were used for distinct identification of vibrational modes of the intercalated (SeO<sub>4</sub>)<sup>2–</sup> ion in the interlayer space of both models.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114939"},"PeriodicalIF":3.0,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561275","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 : 2024-10-24DOI: 10.1016/j.comptc.2024.114938
Rebaz Obaid Kareem , Rebaz Anwar Omer , Yousif Hussein Azeez , Lana Omer Ahmed , Othman Abdulrahman Hamad
Since corrosion causes significant economic and environmental damage, sustainable corrosion inhibitors are essential. This work examined the corrosion prevention properties of a series of closely related compounds with names: Chloroquine (S1) Hydroxychloroquine (S2) Desethylchloroquine (S3) Desethylhydroxychloeoquine (S4) Bisdesethylchloroquine (S5). With applying DFT/B3LYP/6-31+G(d,p) foundation, also Monte Carlo simulations showed compound adsorption on Fe(1 1 0). The HOMO-LUMO, refractive index, dielectric constant, and electrical conductivity, the results for S1 and S2 indicate that all inhibitors were bound to Fe (1 1 0), as predicted by the Monte Carlo simulation.
{"title":"A study on the properties of chloroquine and hydroxychloroquine derivatives as biomass corrosion inhibitors","authors":"Rebaz Obaid Kareem , Rebaz Anwar Omer , Yousif Hussein Azeez , Lana Omer Ahmed , Othman Abdulrahman Hamad","doi":"10.1016/j.comptc.2024.114938","DOIUrl":"10.1016/j.comptc.2024.114938","url":null,"abstract":"<div><div>Since corrosion causes significant economic and environmental damage, sustainable corrosion inhibitors are essential. This work examined the corrosion prevention properties of a series of closely related compounds with names: Chloroquine (<strong>S1</strong>) Hydroxychloroquine (<strong>S2</strong>) Desethylchloroquine (<strong>S3</strong>) Desethylhydroxychloeoquine (<strong>S4</strong>) Bisdesethylchloroquine (<strong>S5</strong>). With applying DFT/B3LYP/6-31+G(d,p) foundation, also Monte Carlo simulations showed compound adsorption on Fe(1 1 0). The HOMO-LUMO, refractive index, dielectric constant, and electrical conductivity, the results for <strong>S1</strong> and <strong>S2</strong> indicate that all inhibitors were bound to Fe (1 1 0), as predicted by the Monte Carlo simulation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114938"},"PeriodicalIF":3.0,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529108","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 : 2024-10-23DOI: 10.1016/j.comptc.2024.114937
Xuliang Zhu , Guangyong Zhu
As an aroma material, beta-ionone also has a range of pharmacological activities. To solve its problems such as low bioavailability, water-immiscibility, thermo-instability, and volatility, beta-ionone was successfully encapsulated in 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD) in our previous work. However, the structure of the product, the interaction between beta-ionone and HP-beta-CD, and the mechanism of action were not clear. In this paper, in order to gain a more profound understanding of the structure and chemical behavior of beta-ionone-HP-beta-CD inclusion complex, the interaction between beta-ionone and HP-beta-CD was investigated by molecular simulation. The optimized structures, binding energy, deformation energy, charge transfer, frontier orbital energy gap, chemical hardness, chemical potential, and electrophilicity index were obtained. In the complex, beta-ionone denotes electrons to HP-beta-CD and carries a positive charge. The negative chemical potential of inclusion complex indicates that complex process is spontaneous. The complex shows a relatively higher reactivity and electrophilicity than beta-ionone and HP-beta-CD.
{"title":"The interaction between beta-ionone and 2-hydroxypropyl-beta-cyclodextrin during the formation of the inclusion complex","authors":"Xuliang Zhu , Guangyong Zhu","doi":"10.1016/j.comptc.2024.114937","DOIUrl":"10.1016/j.comptc.2024.114937","url":null,"abstract":"<div><div>As an aroma material, beta-ionone also has a range of pharmacological activities. To solve its problems such as low bioavailability, water-immiscibility, thermo-instability, and volatility, beta-ionone was successfully encapsulated in 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD) in our previous work. However, the structure of the product, the interaction between beta-ionone and HP-beta-CD, and the mechanism of action were not clear. In this paper, in order to gain a more profound understanding of the structure and chemical behavior of beta-ionone-HP-beta-CD inclusion complex, the interaction between beta-ionone and HP-beta-CD was investigated by molecular simulation. The optimized structures, binding energy, deformation energy, charge transfer, frontier orbital energy gap, chemical hardness, chemical potential, and electrophilicity index were obtained. In the complex, beta-ionone denotes electrons to HP-beta-CD and carries a positive charge. The negative chemical potential of inclusion complex indicates that complex process is spontaneous. The complex shows a relatively higher reactivity and electrophilicity than beta-ionone and HP-beta-CD.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114937"},"PeriodicalIF":3.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529112","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 : 2024-10-23DOI: 10.1016/j.comptc.2024.114934
Pengcheng Zhang , Chunxiang Zhao , Hongyu Chen , Han Zhang , Huijie Ni , Yubing Si
Al3+ detection is crucial for food safety, environmental monitoring, and biological assays. This work investigated the fluorescent properties of the probe VN62 and its sensing mechanism for the detection of Al3+ ion in detail. The ground- and excited-state properties such as isomerization geometries and absorption spectra, as well as the photophysical processes of transitions in PES have been studied. There are few fluorescent S1 states (PT*, TICT) of the VN62 molecule, and the conical intersections (CIs) have key importance in the fluorescent process. By comparing the radiative rate (kr) and the rate of transition to CI, we deduce that these fluorescent states are lack of stability for light emission. Therefore, the fluorescence of probe alone can be quenched by CI pathways. After coordination with Al3+, the CI pathways will be suppressed, resulting in enhanced fluorescence. This sensing mechanism is different from the previously proposed mechanisms, such as the dark state of TICT or ESIPT. We anticipate that our research would shed some light on the design of turn-on sensors.
Al3+ 检测对食品安全、环境监测和生物检测至关重要。这项工作详细研究了探针 VN62 的荧光特性及其检测 Al3+ 离子的传感机制。研究了 PES 的基态和激发态特性，如异构化几何形状和吸收光谱，以及跃迁的光物理过程。VN62 分子中存在少数荧光 S1 态（PT*、TICT），而锥形交叉点（CI）在荧光过程中具有关键意义。通过比较辐射率（kr）和向 CI 过渡的速率，我们推断出这些荧光态缺乏光发射的稳定性。因此，探针本身的荧光可以通过 CI 途径被淬灭。与 Al3+ 配位后，CI 途径将被抑制，从而导致荧光增强。这种传感机制不同于之前提出的机制，如 TICT 或 ESIPT 的暗态。我们希望我们的研究能为开启传感器的设计提供一些启示。
{"title":"Computational insights into the photophysical processes of an acylhydrazone fluorescent probe based on conical intersection and sensing mechanism for Al3+ detection","authors":"Pengcheng Zhang , Chunxiang Zhao , Hongyu Chen , Han Zhang , Huijie Ni , Yubing Si","doi":"10.1016/j.comptc.2024.114934","DOIUrl":"10.1016/j.comptc.2024.114934","url":null,"abstract":"<div><div>Al<sup>3+</sup> detection is crucial for food safety, environmental monitoring, and biological assays. This work investigated the fluorescent properties of the probe VN62 and its sensing mechanism for the detection of Al<sup>3+</sup> ion in detail. The ground- and excited-state properties such as isomerization geometries and absorption spectra, as well as the photophysical processes of transitions in PES have been studied. There are few fluorescent S<sub>1</sub> states (PT*, TICT) of the VN62 molecule, and the conical intersections (CIs) have key importance in the fluorescent process. By comparing the radiative rate (<em>k<sub>r</sub></em>) and the rate of transition to CI, we deduce that these fluorescent states are lack of stability for light emission. Therefore, the fluorescence of probe alone can be quenched by CI pathways. After coordination with Al<sup>3+</sup>, the CI pathways will be suppressed, resulting in enhanced fluorescence. This sensing mechanism is different from the previously proposed mechanisms, such as the dark state of TICT or ESIPT. We anticipate that our research would shed some light on the design of turn-on sensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114934"},"PeriodicalIF":3.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529111","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 : 2024-10-22DOI: 10.1016/j.comptc.2024.114932
Pengfei Ma , Rui Wang , Chengsong Liu , Pengfei Liu , Chaozheng He , Wei Song , Tao Zhang
NH3 is considered one of the most important chemicals, not only as an industrial feedstock for the production of fertilizers, but also as renewable carbon-free energy carrier. In recent years, electrocatalytic nitrogen reduction reaction (NRR), which uses N2 and H2O as raw materials to synthesize NH3, is considered as one of the most promising methods for N2 fixation. Therefore, the design and synthesis of NRR electrocatalysts with high catalytic performance is very important. Herein, using density functional theory method, 3d transition metal single atom anchored to g-C3N4 as single-atom catalysts was studied for the catalytic reduction of N2. The results found that V@g-C3N4 exhibited high electrocatalytic activity and good catalytic selectivity. The limiting potential was only –0.115 V. Furthermore, the relevant electronic properties of V@g-C3N4 were also analyzed. Our work can provide ideas and help to understand the reaction mechanism of single atom doped g-C3N4 as NRR electrocatalysts with excellent catalytic performance.
{"title":"Theoretical insights into efficient electrocatalysts for nitrogen reduction reaction by transition metal atoms supported on g-C3N4","authors":"Pengfei Ma , Rui Wang , Chengsong Liu , Pengfei Liu , Chaozheng He , Wei Song , Tao Zhang","doi":"10.1016/j.comptc.2024.114932","DOIUrl":"10.1016/j.comptc.2024.114932","url":null,"abstract":"<div><div>NH<sub>3</sub> is considered one of the most important chemicals, not only as an industrial feedstock for the production of fertilizers, but also as renewable carbon-free energy carrier. In recent years, electrocatalytic nitrogen reduction reaction (NRR), which uses N<sub>2</sub> and H<sub>2</sub>O as raw materials to synthesize NH<sub>3</sub>, is considered as one of the most promising methods for N<sub>2</sub> fixation. Therefore, the design and synthesis of NRR electrocatalysts with high catalytic performance is very important. Herein, using density functional theory method, 3d transition metal single atom anchored to g-C<sub>3</sub>N<sub>4</sub> as single-atom catalysts was studied for the catalytic reduction of N<sub>2</sub>. The results found that V@g-C<sub>3</sub>N<sub>4</sub> exhibited high electrocatalytic activity and good catalytic selectivity. The limiting potential was only –0.115 V. Furthermore, the relevant electronic properties of V@g-C<sub>3</sub>N<sub>4</sub> were also analyzed. Our work can provide ideas and help to understand the reaction mechanism of single atom doped g-C<sub>3</sub>N<sub>4</sub> as NRR electrocatalysts with excellent catalytic performance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114932"},"PeriodicalIF":3.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529105","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号