Journal of Physical Organic Chemistry最新文献_第6页

Mechanistic Studies on DNA Damage via Independent Generation of Purine Reactive Intermediates 嘌呤反应性中间体独立生成DNA损伤机理研究

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-03-12 DOI: 10.1002/poc.70075

Liwei Zheng, Marc M. Greenberg

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Energetics for Hydrogen Atom Transfer by Ketyl Radicals: Is Thermodynamics on Your Side? 氢键自由基转移氢原子的能量学：热力学站在你这边吗？

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-03-05 DOI: 10.1002/poc.70076

Juan C. Scaiano

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Composite Single-Reference and Explicitly Correlated Multireference Calculations on the Mechanism of Pyrrole Pyrolysis 吡咯热解机理的单参考和显式相关多参考复合计算

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-03-05 DOI: 10.1002/poc.70070

Barry K. Carpenter

{"title":"Composite Single-Reference and Explicitly Correlated Multireference Calculations on the Mechanism of Pyrrole Pyrolysis","authors":"Barry K. Carpenter","doi":"10.1002/poc.70070","DOIUrl":"https://doi.org/10.1002/poc.70070","url":null,"abstract":"The pyrolysis of pyrrole has previously been studied in shock-tube experiments and in jet-stirred reactors. The results have been interpreted with the aid of density functional and ab initio electronic-structure calculations, in combination with kinetic models. The present work has sought to reinvestigate the mechanism and kinetics using more sophisticated electronic structure calculations and a multiwell master equation kinetic model. The intent has been not only to probe the reaction starting with pyrrole at high temperature and pressure but also to use the same mechanistic network to examine the reaction of allyl radical with •CN at low temperature and pressure. The question being addressed is whether the high exothermicity of this radical combination reaction could drive formation of pyrrole in extraterrestrial environments, such as the interstellar medium or in planetary atmospheres. The results reveal that two new intermediates, not considered in previous mechanisms, play important roles in the overall chemistry. Furthermore, two previously proposed mechanistic steps are found not to be viable. The master-equation analysis reveals that only traces of pyrrole would be expected to form from allyl + •CN, despite there being enough excess kinetic energy to overcome all barriers to its formation. An explanation for this conclusion is offered.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70070","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147563765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Noncovalent Interactions Governing Self-Assembly of Oligomeric Phenolic Surfactant Film Models 控制低聚酚类表面活性剂膜模型自组装的非共价相互作用

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-02-26 DOI: 10.1002/poc.70073

Janet H. Gaba, Christine E. DeWolf, Heidi M. Muchall

{"title":"Noncovalent Interactions Governing Self-Assembly of Oligomeric Phenolic Surfactant Film Models","authors":"Janet H. Gaba, Christine E. DeWolf, Heidi M. Muchall","doi":"10.1002/poc.70073","DOIUrl":"10.1002/poc.70073","url":null,"abstract":"Self-assembly of surfactants at interfaces and the structures formed are governed by complex sets of noncovalent interactions. This is exemplified in monolayers of phenolic surfactants, for example, dipalmitoylgalloylglycerol and octadecylgallate, at the air-water interface, that show unusual cohesive properties and a high degree of self-organization. The specific noncovalent interactions responsible for this behaviour are difficult to determine with experimental methods alone, which limits the rational design of phenolic thin film structures. Herein, trimers of gallate surfactant analogues have been investigated by computational methods, using ωB97X-D/6-31+G(d,p)//GFN1-xTB. Analogues varied in their tail length (methyl, ethyl or butyl), the presence of the ester moiety and the presence of hydroxy groups meta to the tail. Two arrangements were studied for each trimer: a cyclic cone arrangement, similar to that observed with phenol, and a stacked 2 + 1 π arrangement. Each trimer was studied in the gas phase and implicit water solvent, using the GBSA model. The 2 + 1 π arrangement is more energetically favourable than the cyclic cone arrangement when ester and/or meta hydroxy groups are introduced, despite its lack of O-H…O interactions between para hydroxy groups. In trihydroxy esters, C-H…O interactions between the ester groups and O-H…O interactions between meta hydroxy groups drive the 2 + 1 π formation. The degree of ring–ring overlap is dictated by the presence of the ester group, highlighting the role of the headgroup-tail linker group. This study lays the groundwork for an understanding of the self-assembly and behaviour of gallate surfactant monolayers at the molecular level.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70073","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147569437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Design of a Fluorescent Probe for Hydrogen Peroxide Detection in Escherichia coli Fermentation Broth Based on ESIPT Mechanism 基于ESIPT机制的大肠杆菌发酵液过氧化氢荧光探针的设计

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-02-26 DOI: 10.1002/poc.70072

Yingmin Hou, Hongbin Zhan, Meng Zhang, Xianzhen Li, Yi Wang

{"title":"Design of a Fluorescent Probe for Hydrogen Peroxide Detection in Escherichia coli Fermentation Broth Based on ESIPT Mechanism","authors":"Yingmin Hou, Hongbin Zhan, Meng Zhang, Xianzhen Li, Yi Wang","doi":"10.1002/poc.70072","DOIUrl":"10.1002/poc.70072","url":null,"abstract":"<div>\u0000 \u0000 In this paper, two novel fluorescent probes, HBTMI-B and HBTOI-B, were designed and synthesized to detect endogenous hydrogen peroxide (H2O2) in the fermentation broth of the bioengineered bacterium Escherichia coli (E. coli DH5α). By fluorescence spectroscopy experiments, the probes showed good sensitivity and selectivity in the reaction, with the fluorescence color shifting from violet to blue-green and an obvious red-shift at 300-μM H2O2 concentration. For the theoretical calculations, the reaction mechanisms of the probe molecules during the reaction with H2O2 were investigated by using density-functional theory (DFT) and time-dependent density-functional theory (TD-DFT). In the S1 state, the reaction barriers of the proton transfer were found to be 1.83 and 3.21 kcal/mol, respectively. Titration experiments further confirmed the high sensitivity of HBTMI-B and HBTOI-B at trace amounts of H2O2, with detection limits of 3.27 × 10−7 M and 3.65 × 10−7 M, respectively. In addition, biocompatibility tests showed that the two probes were non-toxic to E. coli DH5α in a certain concentration range, proving their potential in biological experiments. Ultimately, the experiments validated the effectiveness of these two probes for the detection of endogenous H2O2 in bioengineered fermentation broths, which provides a new tool for the detection of hydrogen peroxide in the field of bioengineering.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147569431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Spectroscopic Characterization and Electrocyclic Ring Opening of Parent 2-Azetine 母体2-Azetine的光谱表征和电环开环

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-02-22 DOI: 10.1002/poc.70071

Adrián Portela-González, Daniel Kühn, André K. Eckhardt

{"title":"Spectroscopic Characterization and Electrocyclic Ring Opening of Parent 2-Azetine","authors":"Adrián Portela-González, Daniel Kühn, André K. Eckhardt","doi":"10.1002/poc.70071","DOIUrl":"https://doi.org/10.1002/poc.70071","url":null,"abstract":"(N-Boc)-protected 2-azetine serves as a suitable precursor for the generation of parent 2-azetine. High-vacuum flash pyrolysis experiments at 200°C induce the deprotection of the (N-Boc)-protected 2-azetine resulting in the release of carbon dioxide and isobutene allowing the trapping of 2-azetine in a solid argon matrix at 3 K and its spectroscopic characterization by infrared spectroscopy. The assignment is supported by isotopic labeling experiments and excellent agreement with anharmonic vibrational frequencies calculated at the B2PLYP-D3/def2-TZVPP level of theory. At elevated pyrolysis temperatures, 2-azetine undergoes selective ring opening to yield 1-azabutadiene, for which both s-trans-(E) and s-trans-(Z) conformers are observed. Computed reaction pathways and free-energy profiles rationalize the temperature-dependent product distribution and the observed torquoselectivity. These results provide fundamental insight into the structure, stability, and reactivity of 2-azetine and establish matrix isolation as a powerful approach for accessing highly strained nitrogen heterocycles.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70071","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147288428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Solution-Phase Photon Upconversion With Sensitizer/4,4′-Substituted 9,10-Diphenylanthracene Mixtures 敏化剂/4,4 ' -取代9,10-二苯基蒽混合物的液相光子上转换

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-02-16 DOI: 10.1002/poc.70066

Toshiko Mizokuro, Emiko Koyama, Shotaro Ito, Yoshihiro Kikkawa

{"title":"Solution-Phase Photon Upconversion With Sensitizer/4,4′-Substituted 9,10-Diphenylanthracene Mixtures","authors":"Toshiko Mizokuro, Emiko Koyama, Shotaro Ito, Yoshihiro Kikkawa","doi":"10.1002/poc.70066","DOIUrl":"https://doi.org/10.1002/poc.70066","url":null,"abstract":"<div>\u0000 \u0000 Triplet–triplet annihilation upconversion (TTA-UC) is a promising strategy for converting low-energy photons into high-energy photons. Among emitter molecules, 9,10-diphenylanthracene (DPA) is widely used owing to its rigid aromatic structure, high fluorescence quantum yield (ΦFL), and favorable triplet energy levels for efficient TTA-UC. However, only a few systematic studies have examined how chemical substitutions at the 4-positions of DPA affect their UC efficiency. Here, we investigate the effect of electron-donating and electron-accepting substituents at the 4-positions of DPA on its fluorescence and TTA-UC properties. DPA derivatives with substituents at the two 4-positions of the phenyl rings were synthesized. The fluorescence properties of solutions of these DPA derivatives and the TTA-UC properties of mixed solutions containing the DPAs and a sensitizer molecule were evaluated under a nitrogen atmosphere. The ΦFL of DCl-DPA was the highest, followed by DCN-DPA. The UC quantum efficiency (ηUC) was estimated, with the highest value obtained for unsubstituted DPA, followed by DCl-DPA and DCN-DPA. Moreover, the saturated UC quantum efficiency (ηUC∞), the quantum yield of triplet–triplet energy transfer, and the quantum yield of TTA (ΦTTA) were also estimated. The results indicate that the ΦTTA value primarily governs the ηUC∞ values. These findings provide insight into the rational design of emitter molecules for optimizing TTA-UC efficiency.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146224449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A New Correlation of 1J(C13,H) and Carbon Atom Orbital s Character Useful for Mapping s Character Frameworks in Molecules and Estimating Bond Angles: Fluorine-Substituent Effects on 1J(C13,H) 1J（C13，H）与碳原子轨道特征的新关联——用于分子中特征框架的绘制和键角的估计：氟取代基对1J（C13，H）的影响

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-01-31 DOI: 10.1002/poc.70067

William R. Carroll, Pablo E. Guzmán, Robert P. Pinnell, John D. Roberts, Stanley L. Manatt

{"title":"A New Correlation of 1J(C13,H) and Carbon Atom Orbital s Character Useful for Mapping s Character Frameworks in Molecules and Estimating Bond Angles: Fluorine-Substituent Effects on 1J(C13,H)","authors":"William R. Carroll, Pablo E. Guzmán, Robert P. Pinnell, John D. Roberts, Stanley L. Manatt","doi":"10.1002/poc.70067","DOIUrl":"https://doi.org/10.1002/poc.70067","url":null,"abstract":"<div>\u0000 \u0000 Previous NMR 1J(C13,H)–s correlations exhibited only marginal degrees of success. Presented here is a new such correlation where it is proposed NMR coupling data is passed by H–C–H and H–H pathways as suggested by the theoretical results of Provasi et al. Used where the current best values of the 1J(C13,H)'s and molecular structure data for the hydrocarbons methane (1), ethane (2), ethene (3), benzene (4), propadiene (5), and ethyne (6). Simple equations for calculation of s character and bond angles are presented. The correlation has been extended to the case of a fluorine substituent. How the s character frameworks of molecules can be mapped out is demonstrated and compared to natural bond orbital (NBO) analysis estimations from density functional theory calculations. The definitions and calculation of the parameters in the master equation, 1J(C13,H) = A s + n B + m C + o D + E + F, are explained in detail.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146140225","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Intramolecular Nonbonding Interactions and Geared Phenyl Twisting in Para-Disubstituted 1,4-Diphenylazines: Electron Correlation Effects on Molecular Conformations and Enantiomerization 对二取代1,4-二苯基嗪分子内非键相互作用和齿轮苯基扭转：电子相关对分子构象和对映异构化的影响

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-01-27 DOI: 10.1002/poc.70069

Kaidi Yang, Harmeet Bhoday, Rainer Glaser

{"title":"Intramolecular Nonbonding Interactions and Geared Phenyl Twisting in Para-Disubstituted 1,4-Diphenylazines: Electron Correlation Effects on Molecular Conformations and Enantiomerization","authors":"Kaidi Yang, Harmeet Bhoday, Rainer Glaser","doi":"10.1002/poc.70069","DOIUrl":"https://doi.org/10.1002/poc.70069","url":null,"abstract":"<div>\u0000 \u0000 The results are reported of potential energy surface (PES) analyses of six symmetrical azines Yp − Ph − RC=N − N=CR − Ph − Yp, namely, the benzaldehyde azines 1H, 2H, and 8H with R = H and the acetophenone azines 1M, 2M, and 8M with R = Me. The Y substituents Cl (1), Br (2), and Me (8) were studied because sets of polymorphs I (C2-symmetry, azine twist τ ≈ 135 ± 10°, disrotatory phenyl twists ϕi ≠ 0°) and II (Ci-symmetry, τ = 180°, conrotatory ϕi ≠ 0°) were crystallized for these three azines. The azine-Me groups in (E,E)-acetophenone azines cause steric strain with the N lone pairs, and this strain is reduced by small rotations about the Az-CH3 bonds and geared phenyl twisting may lead to C2- or Ci-structures. The in-depth exploration of the (τ, ϕ1, ϕ2) conformational space on the MP2(full)/6-311G* PES of 1M shows that the enantiomerization of C2-1M to C2-1M’ involves, first, one Ph twist inversion to a Ci-like structure, the subsequent inversion of the azine twist in, and the, second, Ph twist inversion on the path to C2-1M’. The essential characteristics of this enantiomerization mechanism apply in general to disubstituted acetophenone azine.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146193633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Shedding Light on the Reaction Mechanism of the Catalytic Aza-Wittig Reaction of 2-Methylbenzoxazole: A Bonding Evolution Theory Analysis 2-甲基苯并恶唑催化Aza-Wittig反应机理的键演化理论分析

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2026-01-25 DOI: 10.1002/poc.70065

Joseline Flore Kenmogne Tchidjo, Abel Idrice Adjieufack, Mohamed Chellegui, Vincent Liégeois, Ibrahim Mbouombouo Ndassa, Benoît Champagne

{"title":"Shedding Light on the Reaction Mechanism of the Catalytic Aza-Wittig Reaction of 2-Methylbenzoxazole: A Bonding Evolution Theory Analysis","authors":"Joseline Flore Kenmogne Tchidjo, Abel Idrice Adjieufack, Mohamed Chellegui, Vincent Liégeois, Ibrahim Mbouombouo Ndassa, Benoît Champagne","doi":"10.1002/poc.70065","DOIUrl":"https://doi.org/10.1002/poc.70065","url":null,"abstract":"<div>\u0000 \u0000 Density functional theory (DFT) with the ωB97X-D exchange-correlation functional and the 6-311G(d,p) basis set together with the Bonding Evolution Theory (BET) have been enacted to unravel the mechanism of the catalytic aza-Wittig reaction leading to the formation of 2-methylbenzoxazole 3. The exploitation of the potential energy surface has shown that this reaction takes place following two main Channels, a and b, where favorable Channel a leads to the targeted product and takes place following four steps. A panoply of computational chemistry tools has been employed, leading to comprehensive and consistent results and interpretations: (i) BET analysis has highlighted the successive formation and breaking of chemical bonds leading to the synthesis of 3 and the liberation of a carbon dioxide molecule from the attack of phosphine oxide on the aryl isocyanate; (ii) moreover, BET has revealed that the synthesis of 3 takes place in four steps, with asynchronous transition states; (iii) characterized by large electron density transfers (larger than for the synthesis of the parent 2-methylbenzothiazole, owing to the larger electronegativity of the O vs. S atoms); (iv) the relative energies of the transition state and intermediate isomers have been substantiated by carrying out a NonCovalent Interaction (NCI) analysis, pointing out the role of specific H-bonds and π-π interactions; and (v) the key elements of this NCI analysis have further corroborated the results of the Distortion Interaction/Activation Strain (DIAS) approach.\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 3","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146176523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0