Pub Date : 2026-01-26DOI: 10.1016/j.comptc.2026.115689
Meryem Fıstıkçı , Ferruh Lafzi , Selçuk Eşsiz
A systematic computational study of the intramolecular inverse electron-demand Diels-Alder (IEDDA) reactions of 2-aminopyrazine derivatives and following retro-Diels-Alder (rDA) reactions is disclosed, including an examination of the impact of N, C3 and C6 substituents. The computations are carried out employing DFT and high-level coupled-cluster methods. The IEDDA cycloaddition transition state exhibits the highest activation barrier and is therefore the rate-determining step. N substituents were found to exhibit a remarkable impact on the cycloaddition reactivity of the 2-aminopyrazine without altering, and even more enhancing, the intrinsic cycloaddition regioselectivity. Moreover, the study revealed that the reaction can be predictably modulated by a C3 or C6 substituent and portends extensive synthetic utility for a target pyrrolopyridine scaffolds.
{"title":"Computational determination of pyrrolopyridine formation rates via the intramolecular inverse diels–alder reaction of pyrazine derivatives","authors":"Meryem Fıstıkçı , Ferruh Lafzi , Selçuk Eşsiz","doi":"10.1016/j.comptc.2026.115689","DOIUrl":"10.1016/j.comptc.2026.115689","url":null,"abstract":"<div><div>A systematic computational study of the intramolecular inverse electron-demand Diels-Alder (IEDDA) reactions of 2-aminopyrazine derivatives and following <em>retro</em>-Diels-Alder (<em>r</em>DA) reactions is disclosed, including an examination of the impact of N, C3 and C6 substituents. The computations are carried out employing DFT and high-level coupled-cluster methods. The IEDDA cycloaddition transition state exhibits the highest activation barrier and is therefore the rate-determining step. <em>N</em> substituents were found to exhibit a remarkable impact on the cycloaddition reactivity of the 2-aminopyrazine without altering, and even more enhancing, the intrinsic cycloaddition regioselectivity. Moreover, the study revealed that the reaction can be predictably modulated by a C3 or C6 substituent and portends extensive synthetic utility for a target pyrrolopyridine scaffolds.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115689"},"PeriodicalIF":3.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057319","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 : 2026-01-26DOI: 10.1016/j.comptc.2026.115691
Dongrun Tang , Jiagui Yan , Guanchao Lan , Shangbiao Feng , Yunlu Li , Lizhen Chen , Jianlong Wang
We report a molecular-engineering strategy inspired by macroscopic lantern architectures to design three novel lantern-like cage energetic molecules (L1−L3). The cage scaffold was functionalized with different substituents (-NO₂, -NH₂, -ONO₂) to tune stored chemical energy and stability. The amino group in L2 forms stable intramolecular hydrogen bonds, enhancing thermal stability and reducing impact sensitivity (h₅₀ = 25.94 cm), whereas L3, with nitrate ester groups, shows reduced stability due to uneven charge distribution. Detonation performance analysis indicates that all molecules possess densities above 1.8 g cm−3, with L3 achieving the highest detonation velocity (9329 m s−1) and pressure (41.7 GPa). Among them, L2 achieves an optimal balance between stability and energetic output, while L3 demonstrates the greatest energetic potential. These findings highlight the lantern-type cage as a promising structural motif for developing high-energy, low-sensitivity energetic materials through precise modulation of cage strain and intramolecular noncovalent interactions.
我们报告了一种受宏观灯笼结构启发的分子工程策略，设计了三种新颖的灯笼状笼状能量分子（L1−L3）。笼状支架用不同的取代基（-NO₂，-NH₂，-ONO₂）进行功能化，以调节储存的化学能和稳定性。L2中的氨基形成稳定的分子内氢键，增强热稳定性并降低冲击敏感性（h₅0 = 25.94 cm），而具有硝酸酯基的L3由于电荷分布不均匀而表现出稳定性降低。爆轰性能分析表明，所有分子的密度均在1.8 g cm−3以上，其中L3达到了最高的爆轰速度（9329 m s−1）和压力（41.7 GPa）。其中，L2在稳定性和能量输出之间达到最佳平衡，而L3表现出最大的能量潜力。这些发现强调了灯笼型笼作为一种有前途的结构基序，可以通过精确调节笼应变和分子内非共价相互作用来开发高能量、低灵敏度的含能材料。
{"title":"Lantern-inspired cage frameworks: Translating macroscopic architecture into molecular design of energetic materials","authors":"Dongrun Tang , Jiagui Yan , Guanchao Lan , Shangbiao Feng , Yunlu Li , Lizhen Chen , Jianlong Wang","doi":"10.1016/j.comptc.2026.115691","DOIUrl":"10.1016/j.comptc.2026.115691","url":null,"abstract":"<div><div>We report a molecular-engineering strategy inspired by macroscopic lantern architectures to design three novel lantern-like cage energetic molecules (<strong>L1</strong>−<strong>L3</strong>). The cage scaffold was functionalized with different substituents (-NO₂, -NH₂, -ONO₂) to tune stored chemical energy and stability. The amino group in <strong>L2</strong> forms stable intramolecular hydrogen bonds, enhancing thermal stability and reducing impact sensitivity (<em>h₅₀</em> = 25.94 cm), whereas <strong>L3</strong>, with nitrate ester groups, shows reduced stability due to uneven charge distribution. Detonation performance analysis indicates that all molecules possess densities above 1.8 g cm<sup>−3</sup>, with <strong>L3</strong> achieving the highest detonation velocity (9329 m s<sup>−1</sup>) and pressure (41.7 GPa). Among them, <strong>L2</strong> achieves an optimal balance between stability and energetic output, while <strong>L3</strong> demonstrates the greatest energetic potential. These findings highlight the lantern-type cage as a promising structural motif for developing high-energy, low-sensitivity energetic materials through precise modulation of cage strain and intramolecular noncovalent interactions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115691"},"PeriodicalIF":3.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057320","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 : 2026-01-24DOI: 10.1016/j.comptc.2026.115690
Shuangbao Li , Lingfeng Sheng , Zi'an Wang , Yang Chen , Zhongmin Su
Metallated triplet materials can boost the power conversion efficiency of organic photovoltaics owing to their long-lived and tunable triplet excitons. However, their development is hampered by unclear triplet dynamics and a lack of systematic structure-property relationship studies. To address these challenges, this study presents a series of new Ir(III) complex donors (1–5), engineered by inserting strong electron-withdrawing moieties into the report TBzIr skeleton. DFT and TD-DFT calculations reveal that this design extends π-conjugation, enhances charge separation, and preserves favorable triplet exciton dynamics. Notably, molecules 3–5 show a highly efficient S1 → T5 intersystem crossing pathway. Furthermore, the 4/Y6 system demonstrates optimized molecular torsion that reduces intermolecular Coulomb binding, promoting charge dissociation and transport. With enhanced intersystem crossing and suppressed triplet recombination, molecule 4 emerges as a highly promising donor for triplet-material-based organic photovoltaics (T-OPVs). This work elucidates key structure-property relationships and provides a strategic design framework for developing high-efficiency T-OPV.
{"title":"Iridium(III) complex donors for triplet-material-based organic photovoltaics: a theoretical design strategy for enhanced charge separation","authors":"Shuangbao Li , Lingfeng Sheng , Zi'an Wang , Yang Chen , Zhongmin Su","doi":"10.1016/j.comptc.2026.115690","DOIUrl":"10.1016/j.comptc.2026.115690","url":null,"abstract":"<div><div>Metallated triplet materials can boost the power conversion efficiency of organic photovoltaics owing to their long-lived and tunable triplet excitons. However, their development is hampered by unclear triplet dynamics and a lack of systematic structure-property relationship studies. To address these challenges, this study presents a series of new Ir(III) complex donors (<strong>1</strong>–<strong>5</strong>), engineered by inserting strong electron-withdrawing moieties into the report TBzIr skeleton. DFT and TD-DFT calculations reveal that this design extends π-conjugation, enhances charge separation, and preserves favorable triplet exciton dynamics. Notably, molecules <strong>3–5</strong> show a highly efficient S<sub>1</sub> → T<sub>5</sub> intersystem crossing pathway. Furthermore, the <strong>4</strong>/Y6 system demonstrates optimized molecular torsion that reduces intermolecular Coulomb binding, promoting charge dissociation and transport. With enhanced intersystem crossing and suppressed triplet recombination, molecule <strong>4</strong> emerges as a highly promising donor for triplet-material-based organic photovoltaics (T-OPVs). This work elucidates key structure-property relationships and provides a strategic design framework for developing high-efficiency T-OPV.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115690"},"PeriodicalIF":3.0,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073809","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 : 2026-01-24DOI: 10.1016/j.comptc.2026.115692
Xuhui Wang , Jiahui Qi , Jun Ren , Chaoyang Gao , Yiwei Su
Copper-based core-shell catalyst is a promising way to improve the catalytic activity for methanol dehydrogenation to methyl formate (MF), but the size effect remains unknown. Cu13, Cu38, Cu55 catalysts have been constructed to systematically investigate the reaction mechanism of methyl formate (MF) generation by using density functional theory (DFT) calculations. The results show that the order of catalytic activity is Cu13 > Cu38 > Cu55, confirmed by the results of d-band center and kinetic analysis. Moreover, Cu13 catalyst with optimal performance was subjected to the second-metal (Zn, Ni and Pd) core doping and shell doping, respectively, resulting in the construction of six doping models. This research reveals a normal distribution relationship between the d-band center and free energy barrier for six doped catalysts, and Ni-doped into shell catalysts exhibit excellent catalytic performance, attributing to the closer distance between the d-band center and Fermi level. Additionally, the reaction rate constant is always higher than that on other catalysts at the same temperature, accelerating the reaction process of methanol dehydrogenation to MF. This work provides a theoretical reference for the design and development of copper-based catalysts with a core-shell structure.
{"title":"The effects of size and second metal doping of copper-based core-shell catalysts on methanol dehydrogenation to methyl formate","authors":"Xuhui Wang , Jiahui Qi , Jun Ren , Chaoyang Gao , Yiwei Su","doi":"10.1016/j.comptc.2026.115692","DOIUrl":"10.1016/j.comptc.2026.115692","url":null,"abstract":"<div><div>Copper-based core-shell catalyst is a promising way to improve the catalytic activity for methanol dehydrogenation to methyl formate (MF), but the size effect remains unknown. Cu<sub>13</sub>, Cu<sub>38</sub>, Cu<sub>55</sub> catalysts have been constructed to systematically investigate the reaction mechanism of methyl formate (MF) generation by using density functional theory (DFT) calculations. The results show that the order of catalytic activity is Cu<sub>13</sub> > Cu<sub>38</sub> > Cu<sub>55</sub>, confirmed by the results of d-band center and kinetic analysis. Moreover, Cu<sub>13</sub> catalyst with optimal performance was subjected to the second-metal (Zn, Ni and Pd) core doping and shell doping, respectively, resulting in the construction of six doping models. This research reveals a normal distribution relationship between the d-band center and free energy barrier for six doped catalysts, and Ni-doped into shell catalysts exhibit excellent catalytic performance, attributing to the closer distance between the d-band center and Fermi level. Additionally, the reaction rate constant is always higher than that on other catalysts at the same temperature, accelerating the reaction process of methanol dehydrogenation to MF. This work provides a theoretical reference for the design and development of copper-based catalysts with a core-shell structure.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115692"},"PeriodicalIF":3.0,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073808","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 : 2026-01-22DOI: 10.1016/j.comptc.2026.115684
Yong Wang , Yufeng Yang , Wolong Li , Yongcun Li
All-solid-state zinc-ion batteries (ZIBs) require electrolytes that deliver both high ionic conductivity and high safety; however, the Zn2+ migration mechanisms in composite solid electrolytes remain unclear. In this work, we combine molecular dynamics (MD) simulations with density functional theory (DFT) calculations to study Zn2+ transport in a PEO-Zn(TFSI)2 matrix and in its composites containing SiO2, ZnPS3, and a ZnPS3/MoS2 hybrid filler, with a particular focus on bulk plasticization and interfacial transport pathways. The results show that SiO2 delivers a modest low-temperature gain primarily by reducing crystallinity. ZnPS3 weakens ZnO coordination while forming a Zn-P-dominated interfacial network and a space-charge layer, thereby enhancing diffusion across a broad temperature window. Surface states on ZnPS3(001) induce electron accumulation that electrostatically drives Zn2+ enrichment at the interface. The introduction of MoS2 further enhances the interfacial dipole and geometric connectivity, resulting in a relative increase of approximately 1.5–2.4 times in the MSD slope at medium-to-high temperatures compared to PEO + ZnPS3. MD and DFT calculations demonstrate that the synergistic effect of chemically driven coordination exchange and geometrically guided epitaxial channels substantially enhances zinc ion mobility within the electrolyte.
{"title":"Regulatory mechanism of inorganic fillers on Zn2+ transport in PEO–Zn(TFSI)2 electrolyte within all-solid-state zinc-ion batteries","authors":"Yong Wang , Yufeng Yang , Wolong Li , Yongcun Li","doi":"10.1016/j.comptc.2026.115684","DOIUrl":"10.1016/j.comptc.2026.115684","url":null,"abstract":"<div><div>All-solid-state zinc-ion batteries (ZIBs) require electrolytes that deliver both high ionic conductivity and high safety; however, the Zn<sup>2+</sup> migration mechanisms in composite solid electrolytes remain unclear. In this work, we combine molecular dynamics (MD) simulations with density functional theory (DFT) calculations to study Zn<sup>2+</sup> transport in a PEO-Zn(TFSI)<sub>2</sub> matrix and in its composites containing SiO<sub>2</sub>, ZnPS<sub>3</sub>, and a ZnPS<sub>3</sub>/MoS<sub>2</sub> hybrid filler, with a particular focus on bulk plasticization and interfacial transport pathways. The results show that SiO<sub>2</sub> delivers a modest low-temperature gain primarily by reducing crystallinity. ZnPS<sub>3</sub> weakens Zn<img>O coordination while forming a Zn-P-dominated interfacial network and a space-charge layer, thereby enhancing diffusion across a broad temperature window. Surface states on ZnPS<sub>3</sub>(001) induce electron accumulation that electrostatically drives Zn<sup>2+</sup> enrichment at the interface. The introduction of MoS<sub>2</sub> further enhances the interfacial dipole and geometric connectivity, resulting in a relative increase of approximately 1.5–2.4 times in the MSD slope at medium-to-high temperatures compared to PEO + ZnPS<sub>3</sub>. MD and DFT calculations demonstrate that the synergistic effect of chemically driven coordination exchange and geometrically guided epitaxial channels substantially enhances zinc ion mobility within the electrolyte.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115684"},"PeriodicalIF":3.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076753","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 : 2026-01-20DOI: 10.1016/j.comptc.2026.115683
Vikiho Wotsa, Chinnappan Sivasankar
Density Functional Theory (DFT) studies were carried out to examine the energy profile of Braunschweig's activation and functionalization of dinitrogen (N₂) at a main group element centre. The reaction mechanism involves a sequence of well-defined intermediates, I - IX, which facilitate N₂ activation and ultimately lead to the formation of NH₄Cl through a cascade of reduction and protonation steps using KC₈ and B(OH)₃, respectively. The results indicate that the formation of the pro-ammonia compound NH₄Cl is energetically favorable, with a significantly exergonic Gibbs free energy change (ΔG°) of −368.39 kcal/mol. In contrast, direct formation of NH₃ is thermodynamically unfavourable, showing an endergonic energy change of +142.99 kcal/mol. To further elucidate the nature of the bonding interactions within the key intermediates, an energy decomposition analysis was performed. This analysis reveals that the bonding between the borylene fragment and the dinitrogen ligand exhibits both covalent and ionic character. Notably, the interaction involves σ-donation from the N₂ ligand to the borylene centre, as well as π-backdonation from the borylene to the ligand, highlighting a synergistic bonding mechanism.
{"title":"Theoretical evidence and energetics on the conversion of dinitrogen to ammonium chloride at borylene","authors":"Vikiho Wotsa, Chinnappan Sivasankar","doi":"10.1016/j.comptc.2026.115683","DOIUrl":"10.1016/j.comptc.2026.115683","url":null,"abstract":"<div><div>Density Functional Theory (DFT) studies were carried out to examine the energy profile of Braunschweig's activation and functionalization of dinitrogen (N₂) at a main group element centre. The reaction mechanism involves a sequence of well-defined intermediates<strong>, I - IX</strong>, which facilitate N₂ activation and ultimately lead to the formation of NH₄Cl through a cascade of reduction and protonation steps using KC₈ and B(OH)₃, respectively. The results indicate that the formation of the pro-ammonia compound NH₄Cl is energetically favorable, with a significantly exergonic Gibbs free energy change (ΔG°) of −368.39 kcal/mol. In contrast, direct formation of NH₃ is thermodynamically unfavourable, showing an endergonic energy change of +142.99 kcal/mol. To further elucidate the nature of the bonding interactions within the key intermediates, an energy decomposition analysis was performed. This analysis reveals that the bonding between the borylene fragment and the dinitrogen ligand exhibits both covalent and ionic character. Notably, the interaction involves σ-donation from the N₂ ligand to the borylene centre, as well as π-backdonation from the borylene to the ligand, highlighting a synergistic bonding mechanism.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115683"},"PeriodicalIF":3.0,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076754","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 : 2026-01-19DOI: 10.1016/j.comptc.2026.115679
L. Boughlima , A. Jabar , L. Bahmad , R. Ahl Laamara
First-principles density functional theory calculations are employed to investigate the structural, mechanical, vibrational, electronic, and optical properties of XGaGeH (X = Ca, Sr) hydrides. Both compounds are mechanically and dynamically stable, as confirmed by elastic constants and phonon dispersion relations. SrGaGeH exhibits higher stiffness and lower compressibility than CaGaGeH. Electronic structure calculations reveal semiconducting behavior, with an indirect band gap for CaGaGeH and a direct band gap for SrGaGeH. Density of states analysis indicates significant Ga/Ge-Ca(Sr) p-d hybridization. Optical properties show strong anisotropy, characterized by metallic-like optical response in-plane and semiconducting out-of-plane responses. These results highlight the intrinsic anisotropic nature of XGaGeH hydrides.
采用第一性原理密度泛函理论计算研究了XGaGeH （X = Ca, Sr）氢化物的结构、力学、振动、电子和光学性质。弹性常数和声子色散关系证实了这两种化合物在力学和动力学上都是稳定的。srageh比CaGaGeH具有更高的刚度和更低的压缩性。电子结构计算揭示了半导体行为，CaGaGeH具有间接带隙，srageh具有直接带隙。态密度分析显示明显的Ga/Ge-Ca(Sr) p-d杂化。光学性质具有较强的各向异性，表现为面内类金属光学响应和面外半导体光学响应。这些结果突出了XGaGeH氢化物固有的各向异性。
{"title":"Semiconducting Behavior, Structural Stability, and Optical Response of XGaGeH (X = Ca, Sr) Hydrides: A DFT Study","authors":"L. Boughlima , A. Jabar , L. Bahmad , R. Ahl Laamara","doi":"10.1016/j.comptc.2026.115679","DOIUrl":"10.1016/j.comptc.2026.115679","url":null,"abstract":"<div><div>First-principles density functional theory calculations are employed to investigate the structural, mechanical, vibrational, electronic, and optical properties of XGaGeH (X = Ca, Sr) hydrides. Both compounds are mechanically and dynamically stable, as confirmed by elastic constants and phonon dispersion relations. SrGaGeH exhibits higher stiffness and lower compressibility than CaGaGeH. Electronic structure calculations reveal semiconducting behavior, with an indirect band gap for CaGaGeH and a direct band gap for SrGaGeH. Density of states analysis indicates significant Ga/Ge-Ca(Sr) p-d hybridization. Optical properties show strong anisotropy, characterized by metallic-like optical response in-plane and semiconducting out-of-plane responses. These results highlight the intrinsic anisotropic nature of XGaGeH hydrides.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115679"},"PeriodicalIF":3.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023774","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 : 2026-01-19DOI: 10.1016/j.comptc.2026.115687
DanYang Yu , ZhiHua Zhang , YuanZe Wei , ZiYi He , ShiYu Zhang , JiaNan Wang
First-principles calculations were performed to investigate the electronic structure and lithium-ion diffusion performance of nitrogen doped LiFePO4. The configuration of the Li8Fe8P8O29N3 had the smaller band gap (0.200 eV), which indicated the better electronic conductivity. The introduction of nitrogen would cause electrons to gather around iron ions, thereby attracting lithium ions and accelerating their local diffusion. On the other hand, the results of mean square displacement confirmed that lithium ion could diffuse in one-dimensional path in LiFePO4 along the [010] direction. Doping nitrogen was able to reduce the energy barrier of diffusion to improve the diffusion of lithium ions. The diffusion coefficient and the diffusion rate of lithium ion were 2 orders of magnitude larger than the intrinsic system at most.
{"title":"Electronic and dynamic properties of N-doped LiFePO4 by first-principles calculations","authors":"DanYang Yu , ZhiHua Zhang , YuanZe Wei , ZiYi He , ShiYu Zhang , JiaNan Wang","doi":"10.1016/j.comptc.2026.115687","DOIUrl":"10.1016/j.comptc.2026.115687","url":null,"abstract":"<div><div>First-principles calculations were performed to investigate the electronic structure and lithium-ion diffusion performance of nitrogen doped LiFePO<sub>4</sub>. The configuration of the Li<sub>8</sub>Fe<sub>8</sub>P<sub>8</sub>O<sub>29</sub>N<sub>3</sub> had the smaller band gap (0.200 eV), which indicated the better electronic conductivity. The introduction of nitrogen would cause electrons to gather around iron ions, thereby attracting lithium ions and accelerating their local diffusion. On the other hand, the results of mean square displacement confirmed that lithium ion could diffuse in one-dimensional path in LiFePO<sub>4</sub> along the [010] direction. Doping nitrogen was able to reduce the energy barrier of diffusion to improve the diffusion of lithium ions. The diffusion coefficient and the diffusion rate of lithium ion were 2 orders of magnitude larger than the intrinsic system at most.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115687"},"PeriodicalIF":3.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023772","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 : 2026-01-18DOI: 10.1016/j.comptc.2026.115686
Tien V. Pham, Anh V. Tran, Nghia T. Nguyen
The reaction between o-Toluidine and NH2 radicals has been studied through a detailed potential energy surface analysis at the CCSD(T)//M06-2×/aug-cc-pVTZ level of theory. Both NH2-addition and H-abstraction pathways were examined, and temperature- and pressure-dependent rate coefficients were determined within 300–2000 K and 1–76,000 Torr via TST and RRKM theories. The results show that PR1(o-CH3C6H4NH) and PR3(m-C6H3(CH3)NH2) dominate, with branching ratios of 27–44% and 27–30%, respectively. The overall rate constant at 760 Torr follows k(T) = 9.12 × 10−27 T4.61 exp.(−2.97 ± 0.41 kcal/mol/RT) cm3 molecule−1 s−1. This study provides valuable mechanistic and kinetic insights into the reactivity of amine-substituted aromatic compounds, offering a fundamental basis for understanding radical-induced transformations in atmospheric and combustion chemistry.
{"title":"A theoretical study on mechanism and kinetics of o-toluidine with NH2 radicals","authors":"Tien V. Pham, Anh V. Tran, Nghia T. Nguyen","doi":"10.1016/j.comptc.2026.115686","DOIUrl":"10.1016/j.comptc.2026.115686","url":null,"abstract":"<div><div>The reaction between <em>o</em>-Toluidine and NH<sub>2</sub> radicals has been studied through a detailed potential energy surface analysis at the CCSD(T)//M06-2×/aug-cc-pVTZ level of theory. Both NH<sub>2</sub>-addition and H-abstraction pathways were examined, and temperature- and pressure-dependent rate coefficients were determined within 300–2000 K and 1–76,000 Torr via TST and RRKM theories. The results show that PR<sub>1</sub>(<em>o</em>-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>NH) and PR<sub>3</sub>(<em>m</em>-C<sub>6</sub>H<sub>3</sub>(CH<sub>3</sub>)NH<sub>2</sub>) dominate, with branching ratios of 27–44% and 27–30%, respectively. The overall rate constant at 760 Torr follows <em>k</em>(<em>T</em>) = 9.12 × 10<sup>−27</sup> T<sup>4.61</sup> exp.(−2.97 ± 0.41 kcal/mol/RT) cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>. This study provides valuable mechanistic and kinetic insights into the reactivity of amine-substituted aromatic compounds, offering a fundamental basis for understanding radical-induced transformations in atmospheric and combustion chemistry.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115686"},"PeriodicalIF":3.0,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023775","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 : 2026-01-15DOI: 10.1016/j.comptc.2026.115678
Gang Wang, Ziqian Zhao, Rui-Ning Guo, Zhenyu Qian
The co-aggregation of amyloid-β (Aβ) and α-synuclein (αS) represents a critical pathological link between Alzheimer's and Parkinson's diseases, yet the molecular mechanisms governing their interaction and inhibition remain elusive. Carboxylated graphene quantum dots (GQDs) have emerged as promising nanotherapeutics for amyloid inhibition. In this study, we employed all-atom replica-exchange molecular dynamics (REMD) simulations in explicit water to investigate the co-aggregation of full-length Aβ42 and αS, and to unravel the inhibitory mechanism of GQDs under inflammatory, mildly acidic conditions. Our simulations reveal that in the absence of inhibitors, αS and Aβ form compact heterodimers stabilized by intermolecular three- and four-stranded β-sheets, primarily at the interface between the Aβ N-terminus and the αS preNAC region. Upon the introduction of GQDs, these intermolecular multi-stranded β-sheet motifs, which are often associated with cytotoxic oligomeric species, are substantially reduced. We demonstrate that GQDs induce a conformational expansion of the heterodimer and disrupt the specific inter-peptide hydrogen bond network. Mechanistically, the inhibition is driven by the competitive occupation of N-terminal hotspots. The protonation of histidine residues under acidic conditions amplifies cation-π and salt bridge interactions, allowing GQDs to shield the cationic clusters on Aβ and αS, thereby disrupting the co-aggregation interface. These findings provide atomic-level insights into the design of dual-targeting inhibitors for comorbid neurodegenerative diseases.
淀粉样蛋白-β (a β)和α-突触核蛋白（αS）的共同聚集代表了阿尔茨海默病和帕金森病之间的重要病理联系，但控制它们相互作用和抑制的分子机制尚不清楚。羧化石墨烯量子点（GQDs）已成为抑制淀粉样蛋白的有前途的纳米治疗药物。在这项研究中，我们采用全原子复制交换分子动力学（REMD）模拟，研究了全长Aβ42和αS的共聚集，并揭示了GQDs在炎症、轻度酸性条件下的抑制机制。我们的模拟结果表明，在没有抑制剂的情况下，αS和α β主要在α β n端和αS preNAC区之间的界面上形成紧密的异源二聚体，由分子间的三链和四链β片稳定。在引入GQDs后，这些通常与细胞毒性寡聚物物种相关的分子间多链β-片基序大幅减少。我们证明了GQDs诱导异二聚体的构象扩张，并破坏了特定的肽间氢键网络。机制上，抑制是由竞争性占据n端热点驱动的。组氨酸残基在酸性条件下的质子化放大了阳离子-π和盐桥相互作用，使GQDs屏蔽了Aβ和αS上的阳离子簇，从而破坏了共聚集界面。这些发现为设计用于共病性神经退行性疾病的双靶向抑制剂提供了原子水平的见解。
{"title":"Carboxylated graphene quantum dots inhibit Aβ42 and α-synuclein co-aggregation via competitive N-terminal targeting: An REMD study","authors":"Gang Wang, Ziqian Zhao, Rui-Ning Guo, Zhenyu Qian","doi":"10.1016/j.comptc.2026.115678","DOIUrl":"10.1016/j.comptc.2026.115678","url":null,"abstract":"<div><div>The co-aggregation of amyloid-β (Aβ) and α-synuclein (αS) represents a critical pathological link between Alzheimer's and Parkinson's diseases, yet the molecular mechanisms governing their interaction and inhibition remain elusive. Carboxylated graphene quantum dots (GQDs) have emerged as promising nanotherapeutics for amyloid inhibition. In this study, we employed all-atom replica-exchange molecular dynamics (REMD) simulations in explicit water to investigate the co-aggregation of full-length Aβ<sub>42</sub> and αS, and to unravel the inhibitory mechanism of GQDs under inflammatory, mildly acidic conditions. Our simulations reveal that in the absence of inhibitors, αS and Aβ form compact heterodimers stabilized by intermolecular three- and four-stranded β-sheets, primarily at the interface between the Aβ N-terminus and the αS preNAC region. Upon the introduction of GQDs, these intermolecular multi-stranded β-sheet motifs, which are often associated with cytotoxic oligomeric species, are substantially reduced. We demonstrate that GQDs induce a conformational expansion of the heterodimer and disrupt the specific inter-peptide hydrogen bond network. Mechanistically, the inhibition is driven by the competitive occupation of N-terminal hotspots. The protonation of histidine residues under acidic conditions amplifies cation-π and salt bridge interactions, allowing GQDs to shield the cationic clusters on Aβ and αS, thereby disrupting the co-aggregation interface. These findings provide atomic-level insights into the design of dual-targeting inhibitors for comorbid neurodegenerative diseases.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115678"},"PeriodicalIF":3.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023770","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}
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