Pub Date : 2025-03-03DOI: 10.1016/j.comptc.2025.115158
Hazem Abdelsalam , Mahmoud A.S. Sakr , Nahed H. Teleb , Ghada M. Abdelrazek , Omar H. Abd-Elkader , Qinfang Zhang
This study investigates finite-length boron nitride nanotubes (4ZHBN-NTs) constructed from quantum dots for selective gas sensing, focusing on NO, NO₂, SO₂, and SO₃. Adsorption energy calculations showed stable interactions, especially with SO₃ (−2.805 eV). Natural bond orbital (NBO) analysis revealed significant charge transfer during adsorption, with NO₂ and SO₃ causing the highest electronic perturbations. Density of states (DOS) analysis confirmed strong gas-nanotube interactions through noticeable shifts in peak positions. Optical studies highlighted redshifts in absorption spectra, particularly for NO₂, with wavelengths extending up to 418 nm. Recovery time analysis revealed fast desorption for NO and NO₂, while SO₃ exhibited prolonged retention due to its higher adsorption energy. These findings demonstrate the high sensitivity of 4ZHBN-NTs to gas adsorption, with distinct electronic and optical signatures for each gas, showcasing their potential as efficient sensors for environmental monitoring.
{"title":"The role of quantum-confined boron nitride nanotubes in gas monitoring: Adsorption and detection of NO, NO₂, SO₂, and SO₃.","authors":"Hazem Abdelsalam , Mahmoud A.S. Sakr , Nahed H. Teleb , Ghada M. Abdelrazek , Omar H. Abd-Elkader , Qinfang Zhang","doi":"10.1016/j.comptc.2025.115158","DOIUrl":"10.1016/j.comptc.2025.115158","url":null,"abstract":"<div><div>This study investigates finite-length boron nitride nanotubes (4ZHBN-NTs) constructed from quantum dots for selective gas sensing, focusing on NO, NO₂, SO₂, and SO₃. Adsorption energy calculations showed stable interactions, especially with SO₃ (−2.805 eV). Natural bond orbital (NBO) analysis revealed significant charge transfer during adsorption, with NO₂ and SO₃ causing the highest electronic perturbations. Density of states (DOS) analysis confirmed strong gas-nanotube interactions through noticeable shifts in peak positions. Optical studies highlighted redshifts in absorption spectra, particularly for NO₂, with wavelengths extending up to 418 nm. Recovery time analysis revealed fast desorption for NO and NO₂, while SO₃ exhibited prolonged retention due to its higher adsorption energy. These findings demonstrate the high sensitivity of 4ZHBN-NTs to gas adsorption, with distinct electronic and optical signatures for each gas, showcasing their potential as efficient sensors for environmental monitoring.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115158"},"PeriodicalIF":3.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143534928","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 : 2025-03-03DOI: 10.1016/j.comptc.2025.115161
Yousif Hussein Azeez , Rebaz Obaid Kareem , Rebaz Anwar Omer , Lana Omer Ahmed , Ibrahim Nazem Qader , Karukh Ali Babakr
This study explores the corrosion inhibition properties of ten chalcone derivatives (Ch1–Ch10) using advanced computational techniques. Density Functional Theory (DFT) calculations were conducted using the B3LYP functional with the 6–311 + G(d,p) basis set to evaluate the electronic properties of the molecules. In addition, Monte Carlo simulations were used to model the adsorption behavior of the chalcone derivatives on Fe (110) and Cu (111) surfaces. Among the derivatives, Ch1 displayed the largest HOMO-LUMO energy gap (3.066 eV) and the highest hardness (1.553 eV), indicating significant molecular stability and low chemical reactivity. Its optical properties, including a refractive index of 2.0388 and a dielectric constant of 4.1568, suggested low polarizability. However, despite these stable and inert characteristics, Ch1 showed limited potential as a corrosion inhibitor. In contrast, Ch7 and Ch10 exhibited the strongest adsorption interactions in the Monte Carlo simulations, suggesting that these compounds have the greatest potential as effective corrosion inhibitors on both Fe (110) and Cu (111) surfaces.
{"title":"DFT and Monte Carlo Study of Chalcone Compounds as Corrosion Inhibitors: Influence of Various Substituents (R = Cl, Br, CH3, OCH3, NH2, OH, N(CH3)2, H, COOH)","authors":"Yousif Hussein Azeez , Rebaz Obaid Kareem , Rebaz Anwar Omer , Lana Omer Ahmed , Ibrahim Nazem Qader , Karukh Ali Babakr","doi":"10.1016/j.comptc.2025.115161","DOIUrl":"10.1016/j.comptc.2025.115161","url":null,"abstract":"<div><div>This study explores the corrosion inhibition properties of ten chalcone derivatives (Ch1–Ch10) using advanced computational techniques. Density Functional Theory (DFT) calculations were conducted using the B3LYP functional with the 6–311 + G(d,p) basis set to evaluate the electronic properties of the molecules. In addition, Monte Carlo simulations were used to model the adsorption behavior of the chalcone derivatives on Fe (110) and Cu (111) surfaces. Among the derivatives, Ch1 displayed the largest HOMO-LUMO energy gap (3.066 eV) and the highest hardness (1.553 eV), indicating significant molecular stability and low chemical reactivity. Its optical properties, including a refractive index of 2.0388 and a dielectric constant of 4.1568, suggested low polarizability. However, despite these stable and inert characteristics, Ch1 showed limited potential as a corrosion inhibitor. In contrast, Ch7 and Ch10 exhibited the strongest adsorption interactions in the Monte Carlo simulations, suggesting that these compounds have the greatest potential as effective corrosion inhibitors on both Fe (110) and Cu (111) surfaces.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115161"},"PeriodicalIF":3.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552139","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 : 2025-03-02DOI: 10.1016/j.comptc.2025.115168
Ali Zamani , Fadhel F. Sead , Irwanjot Kaur , Aziz Kubaev , Seyedeh Tahereh Hamedani , Halimeh Majedi
This study investigates Dimethyl fumarate (DMF) interactions with B12N12 and B24 nanoclusters in gas and aqueous environments using density functional theory (DFT) to assess structural, electronic, and thermodynamic properties. DMF adsorption on B12N12 significantly reduces the energy gap (from 11.14 eV to 7.46 eV in gas and 11.19 eV to 7.96 eV in water), enhancing conductivity and suggesting improved suitability for controlled drug release. Fermi levels shift from −4.35 eV in the pristine state to −5.30 eV upon adsorption, indicating increased electronic stability. In contrast, DMF chemisorption on B24 in water results in minimal energy gap changes (from 6.19 eV to 5.91 eV) and strong, stable binding (adsorption energies up to −124.51 kJ/mol), which may impede controlled release but support prolonged attachment. These results suggest that B12N12 suits applications requiring precise drug release, while B24 may be a stable carrier for sustained delivery.
{"title":"DFT analysis of dimethyl fumarate interactions with B12N12 and B24 nanoclusters for enhanced anticancer drug delivery","authors":"Ali Zamani , Fadhel F. Sead , Irwanjot Kaur , Aziz Kubaev , Seyedeh Tahereh Hamedani , Halimeh Majedi","doi":"10.1016/j.comptc.2025.115168","DOIUrl":"10.1016/j.comptc.2025.115168","url":null,"abstract":"<div><div>This study investigates Dimethyl fumarate (DMF) interactions with B<sub>12</sub>N<sub>12</sub> and B<sub>24</sub> nanoclusters in gas and aqueous environments using density functional theory (DFT) to assess structural, electronic, and thermodynamic properties. DMF adsorption on B<sub>12</sub>N<sub>12</sub> significantly reduces the energy gap (from 11.14 eV to 7.46 eV in gas and 11.19 eV to 7.96 eV in water), enhancing conductivity and suggesting improved suitability for controlled drug release. Fermi levels shift from −4.35 eV in the pristine state to −5.30 eV upon adsorption, indicating increased electronic stability. In contrast, DMF chemisorption on B<sub>24</sub> in water results in minimal energy gap changes (from 6.19 eV to 5.91 eV) and strong, stable binding (adsorption energies up to −124.51 kJ/mol), which may impede controlled release but support prolonged attachment. These results suggest that B<sub>12</sub>N<sub>12</sub> suits applications requiring precise drug release, while B<sub>24</sub> may be a stable carrier for sustained delivery.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115168"},"PeriodicalIF":3.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552138","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 : 2025-03-02DOI: 10.1016/j.comptc.2025.115169
Vitaly V. Chaban
Hydrogen bonding is an omnipresent phenomenon in room-temperature ionic liquids (RTILs). The presence or absence of the hydrogen bond drastically alternates self-diffusion, shear viscosity, phase transition points, and other physicochemical properties of a pure substance. For electrochemical applications, the presence of cation-anion hydrogen bonding is undesirable because the latter suppresses ionic mobility. In the present paper, we investigate the implication of removing the hydrogen…fluorine interionic attraction in the imidazolium organic borates, being the strongest non-covalent interaction in the [C2IM][BF4] salt. Suppression of fluorine interaction centers cancels H-bonding. Furthermore, it changes the most thermodynamically preferable orientation of the cation in the vicinity of the anion. The most acidic hydrogen atom of the imidazole ring remains the paramount electrophilic center of the cation. However, it does not give rise to strong electrostatically driven coordination patterns. The reported structural parameters and electronic density distributions characterize the new regularities of ion-ion coupling. The reported new insights may inspire synthetic efforts to design novel RTILs exhibiting lower electrostatic energies and adjusted solvation properties.
{"title":"Bulkier anions versus hydrogen bonding in imidazolium ionic liquids: Stationary point analysis","authors":"Vitaly V. Chaban","doi":"10.1016/j.comptc.2025.115169","DOIUrl":"10.1016/j.comptc.2025.115169","url":null,"abstract":"<div><div>Hydrogen bonding is an omnipresent phenomenon in room-temperature ionic liquids (RTILs). The presence or absence of the hydrogen bond drastically alternates self-diffusion, shear viscosity, phase transition points, and other physicochemical properties of a pure substance. For electrochemical applications, the presence of cation-anion hydrogen bonding is undesirable because the latter suppresses ionic mobility. In the present paper, we investigate the implication of removing the hydrogen…fluorine interionic attraction in the imidazolium organic borates, being the strongest non-covalent interaction in the [C<sub>2</sub>IM][BF<sub>4</sub>] salt. Suppression of fluorine interaction centers cancels H-bonding. Furthermore, it changes the most thermodynamically preferable orientation of the cation in the vicinity of the anion. The most acidic hydrogen atom of the imidazole ring remains the paramount electrophilic center of the cation. However, it does not give rise to strong electrostatically driven coordination patterns. The reported structural parameters and electronic density distributions characterize the new regularities of ion-ion coupling. The reported new insights may inspire synthetic efforts to design novel RTILs exhibiting lower electrostatic energies and adjusted solvation properties.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115169"},"PeriodicalIF":3.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535008","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 : 2025-03-01DOI: 10.1016/j.comptc.2025.115166
Marija Baranac-Stojanović
BN/CC isosterism has emerged as a useful strategy for modulating chemical and physical properties of PAHs, which find applications in organic electronics. For such applications, it is important to predict and understand fundamental properties, such as HOMO-LUMO and S0-T1 energy gaps, influenced by the ground and triplet state aromaticity. The subject of this work is the influence of BN unit(s) on the aforementioned properties of coronene, studied using DFT. Structures include positional isomers with one BN unit in the central ring and orientational isomers with two BN units in the spoke bonds. Calculations show that the positional isomers have different HOMO-LUMO and S0-T1 gaps, smaller than coronene. They have different aromaticity topologies in both electronic states. Orientational isomers have the same aromaticity topology in both electronic states, similar HOMO-LUMO and S0-T1 gaps, also similar to those of coronene. All molecules contain Hückel aromatic carbocyclic subunits in their triplet state.
{"title":"BN- and B2N2-coronenes: Singlet and triplet state aromaticity, HOMO-LUMO and S0-T1 energy gap","authors":"Marija Baranac-Stojanović","doi":"10.1016/j.comptc.2025.115166","DOIUrl":"10.1016/j.comptc.2025.115166","url":null,"abstract":"<div><div>BN/CC isosterism has emerged as a useful strategy for modulating chemical and physical properties of PAHs, which find applications in organic electronics. For such applications, it is important to predict and understand fundamental properties, such as HOMO-LUMO and S<sub>0</sub>-T<sub>1</sub> energy gaps, influenced by the ground and triplet state aromaticity. The subject of this work is the influence of BN unit(s) on the aforementioned properties of coronene, studied using DFT. Structures include positional isomers with one BN unit in the central ring and orientational isomers with two BN units in the spoke bonds. Calculations show that the positional isomers have different HOMO-LUMO and S<sub>0</sub>-T<sub>1</sub> gaps, smaller than coronene. They have different aromaticity topologies in both electronic states. Orientational isomers have the same aromaticity topology in both electronic states, similar HOMO-LUMO and S<sub>0</sub>-T<sub>1</sub> gaps, also similar to those of coronene. All molecules contain Hückel aromatic carbocyclic subunits in their triplet state.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115166"},"PeriodicalIF":3.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535009","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 : 2025-02-27DOI: 10.1016/j.comptc.2025.115157
Kai Wang , Chaoyong Wang , Yabing Du , Renqi Zhang , Yan Zhang
The global minimum structures and electronic properties of anionic and neutral Gan−/0 (n = 2–15) clusters were studied through a hybrid particle swarm optimization and genetic algorithm in combination with density functional theory (DFT) calculations. The correctness of the structures of Gan− (n = 2–15) has been determined through the comparison of experimental and simulated photoelectron spectra (PESs). Both of anionic and neutral states share the same geometric configurations, which are similar to those of the Inn clusters, but different from Aln clusters. It is found that the Ga clusters gradually grow to a distorted cubic structure from n = 2–8, and then form an elongated pentagonal bipyramid at n = 13. By adding an extra Ga atom to one of the square faces of Ga13 can obtain the structure of Ga14, while Ga15 takes a completely different prolate structure. Among these anionic and neutral clusters, Ga13− cluster possesses the largest vertical detachment energy, adiabatic detachment energy, HOMO-LUMO gap, average binding energies, and second order energy difference values, which can be attributed to its being a superatom with the electronic configuration of (1S)2(1P)6(1D)10(2S)2(1F)14(2P)6. The constructed alkali-halide AMGa13 (AM = Li, Na, K, Rb, Cs) clusters also exhibit superatomic characteristics with the same electronic configuration as that of Ga13−.
{"title":"Determination of the ground state structures of anionic Gan (n = 2–15) clusters","authors":"Kai Wang , Chaoyong Wang , Yabing Du , Renqi Zhang , Yan Zhang","doi":"10.1016/j.comptc.2025.115157","DOIUrl":"10.1016/j.comptc.2025.115157","url":null,"abstract":"<div><div>The global minimum structures and electronic properties of anionic and neutral Ga<sub><em>n</em></sub><sup>−/0</sup> (<em>n</em> = 2–15) clusters were studied through a hybrid particle swarm optimization and genetic algorithm in combination with density functional theory (DFT) calculations. The correctness of the structures of Ga<sub><em>n</em></sub><sup>−</sup> (<em>n</em> = 2–15) has been determined through the comparison of experimental and simulated photoelectron spectra (PESs). Both of anionic and neutral states share the same geometric configurations, which are similar to those of the In<sub><em>n</em></sub> clusters, but different from Al<sub><em>n</em></sub> clusters. It is found that the Ga clusters gradually grow to a distorted cubic structure from <em>n</em> = 2–8, and then form an elongated pentagonal bipyramid at <em>n</em> = 13. By adding an extra Ga atom to one of the square faces of Ga<sub>13</sub> can obtain the structure of Ga<sub>14</sub>, while Ga<sub>15</sub> takes a completely different prolate structure. Among these anionic and neutral clusters, Ga<sub>13</sub><sup>−</sup> cluster possesses the largest vertical detachment energy, adiabatic detachment energy, HOMO-LUMO gap, average binding energies, and second order energy difference values, which can be attributed to its being a superatom with the electronic configuration of (1S)<sup>2</sup>(1P)<sup>6</sup>(1D)<sup>10</sup>(2S)<sup>2</sup>(1F)<sup>14</sup>(2P)<sup>6</sup>. The constructed alkali-halide AMGa<sub>13</sub> (AM = Li, Na, K, Rb, Cs) clusters also exhibit superatomic characteristics with the same electronic configuration as that of Ga<sub>13</sub><sup>−</sup>.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115157"},"PeriodicalIF":3.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143520635","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 : 2025-02-19DOI: 10.1016/j.comptc.2025.115147
Haniyeh Baluch, Ali Ebrahimi, Najmeh Mostafavi
In this study, we identified seven minimum stationary points on the potential energy surface of the benzimidazolium ionophore (BII) using quantum mechanical methods. These minima were further analyzed through energy decomposition analysis employing the sobEDA method, alongside population analysis utilizing the atoms in molecules (AIM) and natural bond orbital (NBO) approaches. Notably, the most stable conformer of BII remains unchanged in the presence of a counterion and its interaction with a cation; however, the optimal positioning of the counterion varies in the presence of a cation. Interactions that influence the binding of the counterion to the BII were identified through AIM analysis. The nature of these interactions was evaluated by establishing a linear relationship between the electron density (ρ), calculated at bond critical points (BCPs) between the two components of the ion pair, and their corresponding interaction energies. The interaction with the benzimidazolium skeleton (BIS) is primarily electrostatic, while both attractive and repulsive weak interactions are observed with the side chains (SC). These interactions are strongly supported by reduced density gradient (RDG) scatter plots and low RDG isosurfaces. Furthermore, sobEDA analysis, utilizing model systems that focus solely on the BIS. X and SC. X interactions, indicates that the nature of the predominant interaction is dependent on the specific anion involved. Charge transfer occurs from the anion to the BS and from the side chains to the anion, as demonstrated by NBO analysis in conjunction with the aforementioned model systems. This comprehensive evaluation enhances our understanding of the binding mechanisms within this system.
{"title":"Quantum mechanical insights into the structural and conformational features of benzimidazolium ionophore and its ion pairs","authors":"Haniyeh Baluch, Ali Ebrahimi, Najmeh Mostafavi","doi":"10.1016/j.comptc.2025.115147","DOIUrl":"10.1016/j.comptc.2025.115147","url":null,"abstract":"<div><div>In this study, we identified seven minimum stationary points on the potential energy surface of the benzimidazolium ionophore (<strong>BII</strong>) using quantum mechanical methods. These minima were further analyzed through energy decomposition analysis employing the sobEDA method, alongside population analysis utilizing the atoms in molecules (AIM) and natural bond orbital (NBO) approaches. Notably, the most stable conformer of <strong>BII</strong> remains unchanged in the presence of a counterion and its interaction with a cation; however, the optimal positioning of the counterion varies in the presence of a cation. Interactions that influence the binding of the counterion to the <strong>BII</strong> were identified through AIM analysis. The nature of these interactions was evaluated by establishing a linear relationship between the electron density (ρ), calculated at bond critical points (BCPs) between the two components of the ion pair, and their corresponding interaction energies. The interaction with the benzimidazolium skeleton (BIS) is primarily electrostatic, while both attractive and repulsive weak interactions are observed with the side chains (SC). These interactions are strongly supported by reduced density gradient (RDG) scatter plots and low RDG isosurfaces. Furthermore, sobEDA analysis, utilizing model systems that focus solely on the BIS. X and SC. X interactions, indicates that the nature of the predominant interaction is dependent on the specific anion involved. Charge transfer occurs from the anion to the BS and from the side chains to the anion, as demonstrated by NBO analysis in conjunction with the aforementioned model systems. This comprehensive evaluation enhances our understanding of the binding mechanisms within this system.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115147"},"PeriodicalIF":3.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143480686","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 : 2025-02-17DOI: 10.1016/j.comptc.2025.115146
Yang Zeng , Xue Jiang , Yujun Si , Lijun Yang
Iron(IV)-oxo porphyrin (Cpd I) is the main catalytically active intermediate in the cytochrome P450 enzymatic cycle. During the C(sp3)-H bond activation, the Cpd I abstracts hydrogen atom from substrate, forming a transient Fe(III)-hydroxo (Cpd II) species and substrate radical. In this study, DFT reported the regioselectivity of CH activation and the effect of axial ligand, using experimentally characterized hemes containing L = none, imidazole, SCH3, OCH3, Cl, and CN to simulate no axial ligand, His, Cys, Ser, and inorganic ligands for comparison. The results show that axial ligands can affect the spin density of complex and exhibit lower energy barrier for C2H activation compared to C4H in lidocaine. Ligands OCH3 and SCH3 demonstrate superior regioselectivity for C2H activation. For Cpd II, the ligands CN, SCH3 and OCH3 are advantageous for C1H abstraction. The findings enhance understanding of the ligand effect in Cpd I and provide novel insights into P450 enzyme catalytic mechanisms.
{"title":"Mechanistic insights into axial ligation effects on electron transfer and selective C−H activation catalyzed by iron-oxo analogues","authors":"Yang Zeng , Xue Jiang , Yujun Si , Lijun Yang","doi":"10.1016/j.comptc.2025.115146","DOIUrl":"10.1016/j.comptc.2025.115146","url":null,"abstract":"<div><div>Iron(IV)-oxo porphyrin (Cpd I) is the main catalytically active intermediate in the cytochrome P450 enzymatic cycle. During the C(sp<sup>3</sup>)-H bond activation, the Cpd I abstracts hydrogen atom from substrate, forming a transient Fe(III)-hydroxo (Cpd II) species and substrate radical. In this study, DFT reported the regioselectivity of C<img>H activation and the effect of axial ligand, using experimentally characterized hemes containing L = none, imidazole, SCH<sub>3</sub>, OCH<sub>3</sub>, Cl, and CN to simulate no axial ligand, His, Cys, Ser, and inorganic ligands for comparison. The results show that axial ligands can affect the spin density of complex and exhibit lower energy barrier for C2<img>H activation compared to C4<img>H in lidocaine. Ligands OCH<sub>3</sub> and SCH<sub>3</sub> demonstrate superior regioselectivity for C2<img>H activation. For Cpd II, the ligands CN, SCH<sub>3</sub> and OCH<sub>3</sub> are advantageous for C1<img>H abstraction. The findings enhance understanding of the ligand effect in Cpd I and provide novel insights into P450 enzyme catalytic mechanisms.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115146"},"PeriodicalIF":3.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444684","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 : 2025-02-15DOI: 10.1016/j.comptc.2025.115138
Maria Milena Regina E. Cavalcante , Rosemarie B. Marques , Ricardo R. Martins , Evandro Paulo S. Martins , Agmael M. Silva , Marcelo L. Pereira Jr. , Antonio de Macedo-Filho
The monoterpene hydrocarbons limonene, sabinene, -phellandrene, and -phellandrene are organic compounds produced by plants during adaptation, defense, and reproduction processes, with their concentrations varying according to physical and chemical factors. These compounds were identified as the group with the highest percentage in the essential oil of the leaves of Croton heliotropiifolius Kunth, whose extract shows potential as a drug candidate. To better understand these compounds’ properties, we studied the quantum-chemical descriptors of these four molecules. In addition, thermodynamic and electronic properties of the chemical structures of the monoterpene hydrocarbons were obtained using the Density Functional Theory (DFT) formalism. This study provides new insights into the analyzed systems. It establishes correlations between structure, property, and activity, allowing the investigated monoterpene compounds to be screened and selected for the design of future drugs based on essential oils derived from these molecules. It also assists in identifying ideal preparation and administration methods for your products suitable for outpatient, hospital, and home use.
{"title":"Quantum-chemical insights into the thermodynamic and electronic characteristics of monoterpene hydrocarbons","authors":"Maria Milena Regina E. Cavalcante , Rosemarie B. Marques , Ricardo R. Martins , Evandro Paulo S. Martins , Agmael M. Silva , Marcelo L. Pereira Jr. , Antonio de Macedo-Filho","doi":"10.1016/j.comptc.2025.115138","DOIUrl":"10.1016/j.comptc.2025.115138","url":null,"abstract":"<div><div>The monoterpene hydrocarbons limonene, sabinene, <span><math><mi>α</mi></math></span>-phellandrene, and <span><math><mi>β</mi></math></span>-phellandrene are organic compounds produced by plants during adaptation, defense, and reproduction processes, with their concentrations varying according to physical and chemical factors. These compounds were identified as the group with the highest percentage in the essential oil of the leaves of <em>Croton heliotropiifolius</em> Kunth, whose extract shows potential as a drug candidate. To better understand these compounds’ properties, we studied the quantum-chemical descriptors of these four molecules. In addition, thermodynamic and electronic properties of the chemical structures of the monoterpene hydrocarbons were obtained using the Density Functional Theory (DFT) formalism. This study provides new insights into the analyzed systems. It establishes correlations between structure, property, and activity, allowing the investigated monoterpene compounds to be screened and selected for the design of future drugs based on essential oils derived from these molecules. It also assists in identifying ideal preparation and administration methods for your products suitable for outpatient, hospital, and home use.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115138"},"PeriodicalIF":3.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143453281","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 : 2025-02-14DOI: 10.1016/j.comptc.2025.115139
A.C.L. Moreira, J.A.B. Silva, A.J.L. Oliveira
In this work we propose a theoretical study of an interplay between impurities effects and transversal electric field (TEF) in charge transport through a two terminals device composed by a pure anthracene and a doped one. We use the Landauer approach, with the electronic structure treated at a density functional theory (DFT) level and model the self-energy with complex absorbing potentials. For the pure anthracene, the effect of the applied TEF is less significant than for the doped anthracene, where the dipole moment is high and the transverse field trends to rotate it. The changes in the geometry of the system alter the electronic structure in such manner that delocalized molecular orbitals can appear, thus opening transport channels. Our results reveal how the impurity on the anthracene island facilitates the control of the electrical current.
{"title":"Transverse electric field as a controller of the magnitude of electric current through a doped anthracene island","authors":"A.C.L. Moreira, J.A.B. Silva, A.J.L. Oliveira","doi":"10.1016/j.comptc.2025.115139","DOIUrl":"10.1016/j.comptc.2025.115139","url":null,"abstract":"<div><div>In this work we propose a theoretical study of an interplay between impurities effects and transversal electric field (TEF) in charge transport through a two terminals device composed by a pure anthracene and a doped one. We use the Landauer approach, with the electronic structure treated at a density functional theory (DFT) level and model the self-energy with complex absorbing potentials. For the pure anthracene, the effect of the applied TEF is less significant than for the doped anthracene, where the dipole moment is high and the transverse field trends to rotate it. The changes in the geometry of the system alter the electronic structure in such manner that delocalized molecular orbitals can appear, thus opening transport channels. Our results reveal how the impurity on the anthracene island facilitates the control of the electrical current.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115139"},"PeriodicalIF":3.0,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427597","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