We achieved 61 % 1H polarization at room temperature and in 0.64 T via Dynamic Nuclear Polarization using photoexcited triplet electrons (Triplet-DNP). Dibenz[a, h]anthracene was introduced as a new host for pentacene-d14, providing a long spin-lattice relaxation time (T1) exceeding 2 h. Single crystals doped with 0.05 mol% pentacene-d14 were grown by the Bridgman method and cut to ∼1 mg for experiments. The 1H polarization buildup and relaxation measurements indicated that paramagnetic relaxation dominates over spin-lattice relaxation. Finally, potential applications of room-temperature hyperpolarization, i.e., nuclear ordering and radiation-tolerant polarized targets, were discussed.
{"title":"1H polarization above 60 % at room temperature by triplet dynamic nuclear polarization","authors":"Kenichiro Tateishi , Shuji Otsuka , Akihiro Yamaji , Shunsuke Kurosawa , Tomohiro Uesaka","doi":"10.1016/j.cplett.2025.142606","DOIUrl":"10.1016/j.cplett.2025.142606","url":null,"abstract":"<div><div>We achieved 61 % <sup>1</sup>H polarization at room temperature and in 0.64 T via Dynamic Nuclear Polarization using photoexcited triplet electrons (Triplet-DNP). Dibenz[<em>a, h</em>]anthracene was introduced as a new host for pentacene-<em>d</em><sub>14</sub>, providing a long spin-lattice relaxation time (<em>T</em><sub>1</sub>) exceeding 2 h. Single crystals doped with 0.05 mol% pentacene-<em>d</em><sub>14</sub> were grown by the Bridgman method and cut to ∼1 mg for experiments. The <sup>1</sup>H polarization buildup and relaxation measurements indicated that paramagnetic relaxation dominates over spin-lattice relaxation. Finally, potential applications of room-temperature hyperpolarization, i.e.<em>,</em> nuclear ordering and radiation-tolerant polarized targets, were discussed.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"885 ","pages":"Article 142606"},"PeriodicalIF":3.1,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838085","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 : 2025-12-11DOI: 10.1016/j.cplett.2025.142600
Hiroki Kobayashi, Kazuki Komatsu, Hiroyuki Kagi
We investigated the densification mechanisms of crystalline purine at room temperature using powder and single-crystal x-ray diffraction under quasi-hydrostatic pressure. The ambient orthorhombic phase exhibits negative linear compressibility until it transforms at 0.7–1.1 GPa into a newly reported high-pressure polymorph. This phase transition can be explained by flipping and translation of hydrogen-bonded molecular arrays. Judging from interatomic distances, intermolecular N–H…N hydrogen bonds in the high-pressure phase are weakened but doubled, leading to an efficient densification.
{"title":"Densification processes of crystalline purine: Negative linear compressibility and pressure-induced phase transition","authors":"Hiroki Kobayashi, Kazuki Komatsu, Hiroyuki Kagi","doi":"10.1016/j.cplett.2025.142600","DOIUrl":"10.1016/j.cplett.2025.142600","url":null,"abstract":"<div><div>We investigated the densification mechanisms of crystalline purine at room temperature using powder and single-crystal x-ray diffraction under quasi-hydrostatic pressure. The ambient orthorhombic phase exhibits negative linear compressibility until it transforms at 0.7–1.1 GPa into a newly reported high-pressure polymorph. This phase transition can be explained by flipping and translation of hydrogen-bonded molecular arrays. Judging from interatomic distances, intermolecular N–H…N hydrogen bonds in the high-pressure phase are weakened but doubled, leading to an efficient densification.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"884 ","pages":"Article 142600"},"PeriodicalIF":3.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797625","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 : 2025-12-10DOI: 10.1016/j.cplett.2025.142592
Dario Campisi , Nadia Balucani , Marzio Rosi
We present a density functional theory characterization of the adiabatic triplet potential energy surfaces for the reactions of atomic oxygen with seven functionalized arenes (aniline, phenol, 1,3-diphenylpropane, diphenyl ether, propylbenzene, formanilide, and benzonitrile) to characterize the competition between ortho and ipso additions. Ortho and ipso additions give rise to O/H or O/R exchange channels, respectively, where R represents the functional groups of the substituted arenes. Our results show that the ortho position is favored in all cases, except for phenol, where ortho competes with ipso. The study provides a useful guide for future experimental investigations.
{"title":"The competition between ortho and ipso attacks in the reactions of O(3P) with functionalized monocyclic aromatic compounds","authors":"Dario Campisi , Nadia Balucani , Marzio Rosi","doi":"10.1016/j.cplett.2025.142592","DOIUrl":"10.1016/j.cplett.2025.142592","url":null,"abstract":"<div><div>We present a density functional theory characterization of the adiabatic triplet potential energy surfaces for the reactions of atomic oxygen with seven functionalized arenes (aniline, phenol, 1,3-diphenylpropane, diphenyl ether, propylbenzene, formanilide, and benzonitrile) to characterize the competition between ortho and ipso additions. Ortho and ipso additions give rise to O/H or O/R exchange channels, respectively, where R represents the functional groups of the substituted arenes. Our results show that the ortho position is favored in all cases, except for phenol, where ortho competes with ipso. The study provides a useful guide for future experimental investigations.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"885 ","pages":"Article 142592"},"PeriodicalIF":3.1,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753916","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 : 2025-12-08DOI: 10.1016/j.cplett.2025.142585
Zhihao Cheng , Jianbang Ge , Biwu Cai , Yang Gao , Shun Cao , Zheng Fang , Fei Zhu , Handong Jiao , Dongbai Sun , Shuqiang Jiao
Magnéli-phase Ti4O7 is widely utilized as an electrode material or conductive support in electrochemical systems due to its outstanding conductivity and stability. However, this material typically exhibits sluggish electrode kinetics during electrochemical tests. Herein, we reveal that a self-passivated oxide layer forms on the Ti4O7 surface, severely impeding the electrode process. A pristine Ti4O7 electrode initially demonstrates significant electrochemical reactivity, which gradually diminishes as the surface becomes passivated via TiO2 formation in both acidic and alkaline solutions. Using a kinetic-thickness model, the TiO2 layer thickness is estimated to be ∼3 nm in alkaline solutions and ∼ 12 nm in acidic solutions.
{"title":"Charge transfer at the Magnéli-phase Ti4O7 surface with a self-passivated oxide layer","authors":"Zhihao Cheng , Jianbang Ge , Biwu Cai , Yang Gao , Shun Cao , Zheng Fang , Fei Zhu , Handong Jiao , Dongbai Sun , Shuqiang Jiao","doi":"10.1016/j.cplett.2025.142585","DOIUrl":"10.1016/j.cplett.2025.142585","url":null,"abstract":"<div><div>Magnéli-phase Ti<sub>4</sub>O<sub>7</sub> is widely utilized as an electrode material or conductive support in electrochemical systems due to its outstanding conductivity and stability. However, this material typically exhibits sluggish electrode kinetics during electrochemical tests. Herein, we reveal that a self-passivated oxide layer forms on the Ti<sub>4</sub>O<sub>7</sub> surface, severely impeding the electrode process. A pristine Ti<sub>4</sub>O<sub>7</sub> electrode initially demonstrates significant electrochemical reactivity, which gradually diminishes as the surface becomes passivated via TiO<sub>2</sub> formation in both acidic and alkaline solutions. Using a kinetic-thickness model, the TiO<sub>2</sub> layer thickness is estimated to be ∼3 nm in alkaline solutions and ∼ 12 nm in acidic solutions.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"884 ","pages":"Article 142585"},"PeriodicalIF":3.1,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748915","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 : 2025-12-07DOI: 10.1016/j.cplett.2025.142596
Arianna Ghelardi , Elisa Carignani , Elionai C. de L. Gomes , Marco Geppi
Solid-state Nuclear Magnetic Resonance (ssNMR) spectroscopy is a powerful tool for the structural and dynamic characterization of polymorphs, whose pharmaceutical properties can differ in terms of solubility, stability, and bioavailability. In this study, we present the first ssNMR characterization of the two polymorphs α and β of leflunomide, a Disease Modifying Anti-Rheumatic Drug. A multinuclear (1H, 19F, 13C, 15N) NMR approach using spectral and relaxation data confirmed distinct structural and dynamic differences between the two polymorphs. In particular, the reorientational motions of the methyl, phenyl, and trifluoromethyl groups are at least two orders of magnitude faster in the β form.
{"title":"Characterization of the structural and dynamic properties of two polymorphs of leflunomide by solid-state NMR","authors":"Arianna Ghelardi , Elisa Carignani , Elionai C. de L. Gomes , Marco Geppi","doi":"10.1016/j.cplett.2025.142596","DOIUrl":"10.1016/j.cplett.2025.142596","url":null,"abstract":"<div><div>Solid-state Nuclear Magnetic Resonance (ssNMR) spectroscopy is a powerful tool for the structural and dynamic characterization of polymorphs, whose pharmaceutical properties can differ in terms of solubility, stability, and bioavailability. In this study, we present the first ssNMR characterization of the two polymorphs α and β of leflunomide, a Disease Modifying Anti-Rheumatic Drug. A multinuclear (<sup>1</sup>H, <sup>19</sup>F, <sup>13</sup>C, <sup>15</sup>N) NMR approach using spectral and relaxation data confirmed distinct structural and dynamic differences between the two polymorphs. In particular, the reorientational motions of the methyl, phenyl, and trifluoromethyl groups are at least two orders of magnitude faster in the β form.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"884 ","pages":"Article 142596"},"PeriodicalIF":3.1,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748914","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 : 2025-12-05DOI: 10.1016/j.cplett.2025.142599
Qamar Abuhassan , Ahmed Aldulaimi , Omayma Salim Waleed , G. PadmaPriya , Subhashree Ray , Y. Sasikumar , Renu Sharma , Saodatkhon Ibragimova , Rafiqjon Kazakov , Zukhra Atamuratova , Aseel Smerat
We employ density functional theory (DFT) calculations to explore CO2 reduction on Fe2N5P/C60 and its heteronuclear variants, CoFeN5P/C60 and NiFeN5P/C60. Fe2N5P/C60 shows a high ΔG*H (>0.61 eV), favoring CO2RR over HER. Phosphorus enhances intermediate stabilization and Fe site activity. NiFeN5P/C60 exhibits superior synergy due to its electronic structure and reduced Fe charge, achieving a low limiting potential (−0.27 V) and overpotential (0.16 V). These results highlight the catalytic promise of Fe2N5P-based DACs and the role of transition metal pairing in optimizing CO2RR performance.
{"title":"Designing dual-atom catalysts for CO2 reduction reactions: Synergistic effects of Ni-Fe in the NiFeN5P/C60","authors":"Qamar Abuhassan , Ahmed Aldulaimi , Omayma Salim Waleed , G. PadmaPriya , Subhashree Ray , Y. Sasikumar , Renu Sharma , Saodatkhon Ibragimova , Rafiqjon Kazakov , Zukhra Atamuratova , Aseel Smerat","doi":"10.1016/j.cplett.2025.142599","DOIUrl":"10.1016/j.cplett.2025.142599","url":null,"abstract":"<div><div>We employ density functional theory (DFT) calculations to explore CO<sub>2</sub> reduction on Fe<sub>2</sub>N<sub>5</sub>P/C<sub>60</sub> and its heteronuclear variants, CoFeN<sub>5</sub>P/C<sub>60</sub> and NiFeN<sub>5</sub>P/C<sub>60</sub>. Fe<sub>2</sub>N<sub>5</sub>P/C<sub>60</sub> shows a high ΔG*H (>0.61 eV), favoring CO<sub>2</sub>RR over HER. Phosphorus enhances intermediate stabilization and Fe site activity. NiFeN<sub>5</sub>P/C<sub>60</sub> exhibits superior synergy due to its electronic structure and reduced Fe charge, achieving a low limiting potential (−0.27 V) and overpotential (0.16 V). These results highlight the catalytic promise of Fe<sub>2</sub>N<sub>5</sub>P-based DACs and the role of transition metal pairing in optimizing CO<sub>2</sub>RR performance.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"884 ","pages":"Article 142599"},"PeriodicalIF":3.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748913","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 : 2025-12-05DOI: 10.1016/j.cplett.2025.142598
Ke Zhao , Peng Xia , Jiamu Cao
Semiconductor heterojunctions are promising for high-performance gas sensors, but atomic-scale mechanisms of their enhanced adsorption and sensing remain to be clarified. This study employs density functional theory (DFT) to investigate NO₂ adsorption on pristine ZnO (100), SnO₂ (110) surfaces, and the ZnO/SnO₂ heterojunction. The heterojunction exhibits synergistic adsorption sites that strengthen NO₂–substrate interactions. Enhanced charge transfer and favorable orbital hybridization drive improved adsorption. The heterojunction shows more remarkable electronic structure modulation and conductivity alteration, amplifying its sensing response. These findings elucidate key mechanisms and provide valuable guidance for advancing high-performance heterojunction-based gas sensors.
{"title":"Atomic-scale mechanisms of enhanced NO2 adsorption and sensing on ZnO/SnO2 heterojunction: A DFT study","authors":"Ke Zhao , Peng Xia , Jiamu Cao","doi":"10.1016/j.cplett.2025.142598","DOIUrl":"10.1016/j.cplett.2025.142598","url":null,"abstract":"<div><div>Semiconductor heterojunctions are promising for high-performance gas sensors, but atomic-scale mechanisms of their enhanced adsorption and sensing remain to be clarified. This study employs density functional theory (DFT) to investigate NO₂ adsorption on pristine ZnO (100), SnO₂ (110) surfaces, and the ZnO/SnO₂ heterojunction. The heterojunction exhibits synergistic adsorption sites that strengthen NO₂–substrate interactions. Enhanced charge transfer and favorable orbital hybridization drive improved adsorption. The heterojunction shows more remarkable electronic structure modulation and conductivity alteration, amplifying its sensing response. These findings elucidate key mechanisms and provide valuable guidance for advancing high-performance heterojunction-based gas sensors.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"884 ","pages":"Article 142598"},"PeriodicalIF":3.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748916","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 : 2025-12-04DOI: 10.1016/j.cplett.2025.142597
Lorran Tesch da Silva, Ana Claudia Monteiro Carvalho, Fernando Sato
In this work, we explore the hydrogen storage capacity of the recently reported Dodecanophene monolayer and its Na- and K-decorated forms through ab initio calculations. Our results showed the stability of the decorated monolayers and the improved adsorption energies over the pristine monolayer, with gravimetric storage densities of 10.59 wt% for the pristine monolayer and 6.34 wt% and 6.93 wt% for Na- and K-decorated monolayers, respectively, meeting DOE’s targets. Thermodynamic analyses further indicate the reversible hydrogen storage under practical storage/release conditions.
{"title":"First-principles investigation of hydrogen storage capacity on Na- and K-decorated Dodecanophene","authors":"Lorran Tesch da Silva, Ana Claudia Monteiro Carvalho, Fernando Sato","doi":"10.1016/j.cplett.2025.142597","DOIUrl":"10.1016/j.cplett.2025.142597","url":null,"abstract":"<div><div>In this work, we explore the hydrogen storage capacity of the recently reported Dodecanophene monolayer and its Na- and K-decorated forms through ab initio calculations. Our results showed the stability of the decorated monolayers and the improved adsorption energies over the pristine monolayer, with gravimetric storage densities of 10.59 wt% for the pristine monolayer and 6.34 wt% and 6.93 wt% for Na- and K-decorated monolayers, respectively, meeting DOE’s targets. Thermodynamic analyses further indicate the reversible hydrogen storage under practical storage/release conditions.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"884 ","pages":"Article 142597"},"PeriodicalIF":3.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748917","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 : 2025-12-04DOI: 10.1016/j.cplett.2025.142593
Ying Gao , Yan-Chun Liu , Yong Wu
We propose a design strategy for Blatter radical derivatives showing SOMO–HOMO inversion (SHI). Starting from a planar Blatter analogue, derivatives (1–6_R) with various substituents (Cz, DPL, PT, PPTA) were investigated using density functional theory. SHI occurs only in selected systems, such as 2–5_PT, where SOMO and HOMO become nearly degenerate. Further tuning shows that only –N(CH3)2 on the PT group induces SHI, yielding pronounced SOMO–HOMO gaps. These findings indicate that PT and –N(CH3)2 can be strategically employed to develop SHI-type Blatter radical derivatives for organic optoelectronics.
{"title":"SOMO-HOMO inversion in Blatter radical derivatives via substituent functionalization","authors":"Ying Gao , Yan-Chun Liu , Yong Wu","doi":"10.1016/j.cplett.2025.142593","DOIUrl":"10.1016/j.cplett.2025.142593","url":null,"abstract":"<div><div>We propose a design strategy for Blatter radical derivatives showing SOMO–HOMO inversion (SHI). Starting from a planar Blatter analogue, derivatives (1–6_R) with various substituents (Cz, DPL, PT, PPTA) were investigated using density functional theory. SHI occurs only in selected systems, such as 2–5_PT, where SOMO and HOMO become nearly degenerate. Further tuning shows that only –N(CH<sub>3</sub>)<sub>2</sub> on the PT group induces SHI, yielding pronounced SOMO–HOMO gaps. These findings indicate that PT and –N(CH<sub>3</sub>)<sub>2</sub> can be strategically employed to develop SHI-type Blatter radical derivatives for organic optoelectronics.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"884 ","pages":"Article 142593"},"PeriodicalIF":3.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692404","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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