Computational and Theoretical Chemistry最新文献

{"title":"A first principle study of Nitrogen/Carbon replacement in a set of β-aminoacrolein/β-thioaminoacrolein derivatives","authors":"Malihe Shahraki,&nbsp;Alireza Nowroozi,&nbsp;Ebrahim Nakhaei","doi":"10.1016/j.comptc.2024.115053","DOIUrl":"10.1016/j.comptc.2024.115053","url":null,"abstract":"<div><div>This study systematically investigates the impact of N/C substitution in β-aminoacrolein/β-thioaminoacrolein derivatives at various theoretical levels. Key electronic energy components, including electron configuration, nitrogen atom positioning, lone pair-lone pair (Lp-Lp) repulsion, and resonance-assisted hydrogen bonding (RAHB), are evaluated. Results reveal that electron configuration contributes the most stabilizing energy (∼-16 Hartree), while nitrogen positioning and Lp-Lp repulsions destabilizes structures, following the trend: N2 &lt; N1 &lt; N3. RAHB energies are strongly influenced by nitrogen count, with stability improving in the order: N1 (−0.0145) &lt; N2 (−0.0273) &lt; N3 (−0.0370) &lt; N1N2 (−0.0418) &lt; N1N3 (−0.0515) &lt; N2N3 (−0.0643) &lt; N1N2N3 (-0.0788H). Furthermore, energetic, structural, spectral, and topological descriptors support these findings. Interestingly, the aromaticity index indicates a slight reduction in π-electron delocalization (π-ED) with N/C substitution, challenging conventional RAHB theory.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115053"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of external electric field regulating hydrogen adsorption on graphene quantum dots, graphene quantum dots with defects, and metal-ion-doped graphene quantum dots","authors":"Thanawit Kuamit ,&nbsp;Fadjar Mulya ,&nbsp;Sirilak Kongkaew ,&nbsp;Vudhichai Parasuk","doi":"10.1016/j.comptc.2024.115050","DOIUrl":"10.1016/j.comptc.2024.115050","url":null,"abstract":"<div><div>Hydrogen storage is crucial for efficient hydrogen energy utilization, but current materials often require extreme conditions, such as low temperatures (&lt;20.15 K) or high pressures (350–700 atm), and an ideal adsorption energy between −0.2 and −0.6 eV. This study employs density functional theory (DFT) to explore hydrogen adsorption on graphene quantum dots (GQDs), including pristine GQDs, nitrogen-substituted divacancy defect GQDs (4N-GQDs), and metal-ion-doped 4N-GQDs (M-4N-GQDs, M = Ti²⁺, Fe²⁺, Cu²⁺, Zn²⁺). Pristine and 4N-GQDs show comparable adsorption energies (−0.02 eV), while M-4N-GQDs exhibit stronger adsorption, ranging from −0.221 to −0.025 eV. Ti²⁺-4N-GQD achieves an optimal adsorption energy of −0.221 eV, making it highly suitable for hydrogen storage. The metal center’s charge transfer upon hydrogen adsorption influences binding strength. An external electric field (EEF) further reduces adsorption energy, promoting H₂ desorption. These results highlight Ti²⁺-4N-GQD’s potential for regulating H₂ adsorption and desorption in hydrogen storage applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115050"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic insights into the role of Glu103-mediated hydrogen bond shift in quercetin catalysis by Pirin homologs","authors":"Chang Yuan ,&nbsp;Guangju Chen ,&nbsp;Hongwei Tan ,&nbsp;Zongchao Jia","doi":"10.1016/j.comptc.2024.115047","DOIUrl":"10.1016/j.comptc.2024.115047","url":null,"abstract":"<div><div>YhhW and hPirin, as Pirin homologs, catalyze the conversion of quercetin to 2-protocatechuoyl-phloroglucinol carboxylic acid and CO. Compared to hPirin, YhhW exhibits lower catalytic efficiency in quercetin oxygenolysis and lacks C-terminal α-helix and Metal-Glu103 coordination. In this work, combined QM/MM calculations and MD simulations are utilized to investigate the detailed mechanisms of quercetin oxygenolysis by YhhW and hpirin. MD simulations reveal that the C-terminal helix in hPirin is crucial for stabilizing Metal-Glu103 coordination. QM/MM calculations further reveal that this coordination not only stabilizes the intermediate but also facilitates hydrogen bond shifts between Glu103 and the carbonyl group of quercetin, optimizing charge distribution and promoting the final ring formation. In contrast, the distal positioning of Glu103 in YhhW disrupts efficient hydrogen bond switching, leading to diminished activity. This work provides deeper insights into quercetin oxygenolysis mechanisms by Pirin homologs and sheds light on the role of hydrogen bond in enzymatic reactions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115047"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"ReaxFF molecular dynamics investigation of hot spot under electric field in RDX embedded with carbon nanotube","authors":"Feng Miao ,&nbsp;Lilai Wei ,&nbsp;Min Xu ,&nbsp;Xinlu Cheng ,&nbsp;Zheng Wang ,&nbsp;Shiquan Feng","doi":"10.1016/j.comptc.2025.115083","DOIUrl":"10.1016/j.comptc.2025.115083","url":null,"abstract":"<div><div>Artificial defects in energetic materials can alter their hotspot formation and decomposition processes. In this paper, we set up the RDX model embedded with carbon nanotube (CNT) and investigate the process of the hot spot formation and propagation in the CNT-embedded RDX composite under the applied external electric field using ReaxFF molecular dynamics. The early inter-molecular reactions were also analyzed. Results show that the hot spot is formed around CNT due to the conversion of strain energy of the embedded CNT in the applied electric field. And as the hot spot grows, a combustion layer is generated. During the propagation of the hot spot, the speed of combustion front increases with the time. By analyzing the types and quantities of the main intermediate products during the early decomposition reaction, we found that the presence of an electric field promotes inter-molecular decomposition reactions of CNT-embedded RDX composite.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115083"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect on Au adatom of the different configurations of BnNn (n = 1–3) co-doped graphene","authors":"Yan-ni Wen ,&nbsp;Chuan Zhang ,&nbsp;Pan Zhao ,&nbsp;Quan Zhang ,&nbsp;You Xie","doi":"10.1016/j.comptc.2024.115007","DOIUrl":"10.1016/j.comptc.2024.115007","url":null,"abstract":"<div><div>The effects of different amounts of B<img>N atom pairs on the structural and electronic properties of doped graphene, as well as the adsorption of Au atoms, were studied by first-principles calculations. The results show that the first-nearest-neighbor structure of B and N atoms was the most stable, and perfect B<img>N hexagon rings can be substituted for B<img>N<img>C ones with increasing number of B<img>N atom pairs in B<img>N co-doped graphene. In the co-doped graphene, the optimal adsorption site for Au atoms was on top of a B atom. The site on the B atom between N and C atoms was more stable than that between N and N atoms. All optimal configurations of B_nN_n co-doped graphene were semiconductors, which turned into metals when an Au atom was adsorbed. These results are of great significance in guiding new research on the adsorption of B<img>N co-doped graphene with the selection of doping configurations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115007"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143161362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigation of surface modified armchair type (5,5) single walled carbon nanotube with Si and B dopant atoms towards the evaluation of selective delivery of aceclidine drug: A DFT approach","authors":"Özge Bağlayan ,&nbsp;Emrah Akan","doi":"10.1016/j.comptc.2024.115035","DOIUrl":"10.1016/j.comptc.2024.115035","url":null,"abstract":"<div><div>Controlled drug delivery studies based on single walled carbon nanotubes (SWCNTs) have become an important research field. In the scope of this work, computational considerations based on the density functional theory, the controlled and selective delivery attempts of silicon and boron decorated SWCNTs towards the aceclidine drug molecule were investigated. The structure and reactivity relationship together with some important diagnostic vibrational bands of double Si-B doped SWCNT and its interacted form with the aceclidine were investigated. It was observed that by selective determination of the interaction sites of aceclidine molecule, it is possible to produce stable systems with Si and B-modified SWCNTs with acceptable recovery times for possible extended and selective drug delivery assessments.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115035"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143161374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of SiC monolayer for detection of SO3 and NF3 hazardous gases based on DFT calculations","authors":"Maher Ali Rusho ,&nbsp;Prakash Kanjariya ,&nbsp;Asha Rajiv ,&nbsp;Amina Dawood Suleman ,&nbsp;Radhwan Abdul Kareem ,&nbsp;Hayder Saadoon Abdulaali ,&nbsp;Ameer Hassan Idan ,&nbsp;Aman Shankhyan ,&nbsp;Alaa A. Omran","doi":"10.1016/j.comptc.2024.115045","DOIUrl":"10.1016/j.comptc.2024.115045","url":null,"abstract":"<div><div>Identifying intrinsically selective materials towards gas molecules can dramatically simplify designing selective and sensitive sensors in order to detect these gasses. Researchers have recently explored monolayers with group III–IV elements as encouraging materials for sensing various gasses. Within this piece of research, we undertook first-principles DFT computations for exploring the gas adhesion attributes of a silicon carbide monolayer (SiCML). The adhesion energies, adhesion distances, adhesion nature and strength as well as the charge transports were examined. The changes in workfunction and conductance were also computed to analyze their prospects in electronic- and workfunction-based gas sensor applications. For this purpose, the adhesion of NF₃, H₂S, CO, SO₃ and CO₂ was investigated, and it was found that the SiCML was sensitive to these gasses, especially SO₃ and NF₃ had a chemical adhesion with adsorption energy −0.56 and −0.75 eV, respectively. Also, the workfunction value of SiCML were changed about 18.39 % and 17.94 % after SO₃ and NF₃, respectively. In addition, NF₃ adsorption changed the band gap of SiCML from 2.29 to 0.38 eV. Furthermore, the recovery time for NF₃ at 600 K is about 4.48 s, which showed the sensitive and selective response of NF₃ in the SiCML.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115045"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143161377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactive molecular dynamics simulations on the thermal decomposition of core–shell structured CL-20@Al nanoparticle under external electric field","authors":"Zijian Sun,&nbsp;Weihua Zhu","doi":"10.1016/j.comptc.2024.115059","DOIUrl":"10.1016/j.comptc.2024.115059","url":null,"abstract":"<div><div>The objective of this study is to investigate the thermal decomposition process of CL-20 nanoparticles (NPs) and CL-20@Al NPs with a core–shell structure using reactive force field (ReaxFF) molecular dynamics (MD) method at different electric field strengths. The CL-20@Al NP releases more energy than the unmodified CL-20 NP. The time of the C<img>N bond breaking was affected by the electric field strength. The electric field inhibits the output of both H₂O and CO₂. Meanwhile, it suppresses the production of nitrogen oxides, especially at 0.5 V/Å. The size of aluminized agglomerates increases with the increase of the electric field strength. These findings may provide valuable guidance for the design and development of energetic aluminized explosives.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115059"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effect of nitrogen on the surface hydrogen absorption and diffusion behavior of ZrCo alloy","authors":"Binjing Zhang ,&nbsp;Bosang Luo ,&nbsp;Huaqin Kou ,&nbsp;Ge Sang ,&nbsp;Wenhua Luo","doi":"10.1016/j.comptc.2024.115058","DOIUrl":"10.1016/j.comptc.2024.115058","url":null,"abstract":"<div><div>The susceptibility of ZrCo to air impurities hinders its potential as a candidate for storing deuterium and tritium. The adsorption characteristics of nitrogen on the ZrCo (110) surface were investigated in this study, along with the influence of nitrogen adhesion on the adsorption, dissociation, and diffusion of hydrogen on the surface. The findings suggest that the surface adsorption of N₂ on the alloy is limited by the robustness of the N<img>N bond, posing a formidable challenge for the spontaneous dissociation of N₂. Nitrogen molecules tend to be stably adsorbed on B3 site on the surface, while the presence of N₂ molecules on the surface does not significantly impact on hydrogen adsorption and dissociation at neighboring sites. When a N₂ occupies the B3 site, the migration difficulty of hydrogen atoms on the surface remains relatively unchanged, while the potential barrier for inward diffusion of H from the surface increases. The hydrogen storage performance of ZrCo is ultimately diminished.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115058"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In-Silico scrutinization of (Al, Ga, B, Si, Ge, and P)-doped C60 in sensing EGCG: An application based DFT study","authors":"Praval Pratap Singh ,&nbsp;Chandraniv Dey ,&nbsp;Biswajit Dhal,&nbsp;S. Birupakshya Muduli,&nbsp;Sudip Chakraborty","doi":"10.1016/j.comptc.2024.115001","DOIUrl":"10.1016/j.comptc.2024.115001","url":null,"abstract":"<div><div>Since the invention of the biological sensor, many proposals and techniques have been developed to improve biosensor functionality. Because of its unique physicochemical properties, the recently developed carbon material “fullerene” improves the possibilities for developing highly sensitive biosensors. This study aims to conduct a computational investigations on utilization of fullerene (C₆₀) and the addition of elements as impurities into the same (doped-C₆₀) as sensors for EGCG. The introduction of impurities into nanomaterial structures increases intermolecular interaction. The fullerene structure, doped with Al, Ga, B, Si, Ge, and P, has been studied as an adsorbent. Density Functional Theory (DFT) based methods are used to investigate the interaction between fullerene or doped fullerene and EGCG. The interaction between the optimized doped structures and the optimized EGCG structure was investigated using the hybrid functional B3LYP, and 6-31G(d) basis set. To the best of our knowledge, this is the first such observation related to the intermolecular interaction between EGCG and doped-C₆₀ and its sensitivity. The sensitivity of the doped-C₆₀ towards EGCG were evaluated by the HOMO–LUMO energy gap and Conceptual Density Functional Theory (CDFT). The results depict Al-doped fullerene shows higher interaction/adsorption potential and sensitivity towards EGCG, as compared to the other studied C₆₀ materials. To acquire knowledge about the nature of intermolecular interactions during the adsorption phenomena, we have computed the Quantum Descriptors, Density of States(DOS) plots, Quantum Theory of Atoms in Molecules (QTAIM), and Non-Covalent Interaction (NCI) analysis. By creating high-sensitivity sensors for bioactive molecules like polyphenolic compounds (EGCG) in exploration of variety of dopants can be used in drug delivery, public health, and environmental monitoring. So, this study aims to improve biosensor technology and lays the foundations for future modular and accurate molecular sensor designs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115001"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160641","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}