Journal of Physical Organic Chemistry最新文献

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A Physical Organic Odyssey: From the Ultrafast Dynamics of Carbenes and Nitrenes to Contemporary Chemical Biology and Drug Discovery 物理有机奥德赛:从碳烯和亚烯的超快动力学到当代化学生物学和药物发现
IF 1.9 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-07-27 DOI: 10.1002/poc.70094
Bin Yang, Jin Wang
{"title":"A Physical Organic Odyssey: From the Ultrafast Dynamics of Carbenes and Nitrenes to Contemporary Chemical Biology and Drug Discovery","authors":"Bin Yang,&nbsp;Jin Wang","doi":"10.1002/poc.70094","DOIUrl":"https://doi.org/10.1002/poc.70094","url":null,"abstract":"<p>The field of photoaffinity labeling (PAL) stands as a testament to the enduring power of physical organic chemistry in driving biological discovery. For nearly five decades, Professor Matthew S. Platz has occupied a singular position at the intersection of reactive intermediate chemistry, ultrafast spectroscopy, and chemical biology—transforming our mechanistic understanding of carbenes, nitrenes, oxenium ions, and their excited-state precursors into actionable design principles for molecular probes. This review, dedicated to Professor Platz on the occasion of his 75th birthday, traces the arc of his scientific legacy: from foundational matrix-isolation and laser flash photolysis studies of phenylcarbene and phenylnitrene, through the transformative discovery of the fluorine effect in aryl azide photochemistry, to the rigorous mechanistic revision of widely used nucleotide-based PAL probes. A central section surveys the remarkable breadth of Platz's ultrafast spectroscopic program—encompassing diarylcarbenes, acyl and sulfonyl azides, Wolff rearrangements, oxenium ions, and heteroatom-containing reactive intermediates—establishing the quantitative kinetic framework that underpins rational probe design. We then connect these foundational insights to the contemporary chemoproteomics landscape of 2020–2025: the diazo problem in diazirine labeling, the rational design of PALBOX probes, the emergence of acyl silane photophores, photocatalytic proximity labeling platforms, and quantitative mass spectrometry workflows. Throughout, we argue that the recurring motif of Platz's career—that rigorous kinetic and mechanistic characterization of fleeting intermediates is the prerequisite for rational reagent design—remains as productive and necessary today as when he first turned a laser onto a solution of phenyl azide.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 9","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70094","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148616107","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}
引用次数: 0
Factors Affecting Nitrogen Atom Inversion in the Solid State 影响固态氮原子反转的因素
IF 1.9 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-07-21 DOI: 10.1002/poc.70093
Jesus Daniel Loya, Abigail A. Moravek, Atropa Choi, Ren A. Wiscons
{"title":"Factors Affecting Nitrogen Atom Inversion in the Solid State","authors":"Jesus Daniel Loya,&nbsp;Abigail A. Moravek,&nbsp;Atropa Choi,&nbsp;Ren A. Wiscons","doi":"10.1002/poc.70093","DOIUrl":"https://doi.org/10.1002/poc.70093","url":null,"abstract":"<div>\u0000 \u0000 <p>The advancement of molecular ferroelectric materials for digital information storage requires systems that exhibit predictable polarization switching under ambient conditions. Recently, room-temperature polarization switching was observed from a single crystal of the nitrogen-centered triangulene, azangulene, revealing nitrogen inversion as a promising mechanism by which to achieve ferroelectricity. While an exciting addition to the library of organic molecular ferroelectrics, azangulene is limited by an irreversible single-crystal-to-single-crystal phase transition that kinetically traps the system in a nonpolar and nonferroelectric molecular conformation, necessitating subtle tuning of the conformational energy landscape to preserve room-temperature polarization switching, while eliminating (destabilizing) nonpolar conformers. Two triangulene design principles emerged from computational studies of azangulene derivatives focused on bridging atom selection and aryl functionalization. This work seeks to experimentally validate these computational design principles in the solid state, while identifying additional noteworthy factors that may impact the translatability of computational design principles to experimental solid-state systems. Using two model systems, nitrogen-containing 6/6/6 linear tricycles and bridged triphenylamine derivatives, four factors affecting nitrogen inversion are experimentally explored in the solid state: (i) size mismatch between the central and bridging atoms in triangulenes; (ii) the role of aryl functionalization on the central nitrogen and bridging atom geometries; (iii) (de)coupling between molecular bowl and nitrogen atom inversion; and (iv) the relative magnitude of intra- versus intermolecular factors on solid-state bowl conformation. From this work, we offer actionable strategies to tune nitrogen inversion in azangulene-based ferroelectric materials.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 9","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148533897","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
Molecular Insights Into ESIPT-Controlled Photophysics of Amazonian Xanthones: A DFT/TD-DFT Study for Photoactive Antioxidant Design 亚马逊山酮esipt控制光物理的分子洞察:用于光活性抗氧化剂设计的DFT/TD-DFT研究
IF 1.9 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-07-15 DOI: 10.1002/poc.70092
Murillo H. Queiroz, Roberto Rivelino, Kaline Coutinho, Sylvio Canuto, Rodrigo Gester
{"title":"Molecular Insights Into ESIPT-Controlled Photophysics of Amazonian Xanthones: A DFT/TD-DFT Study for Photoactive Antioxidant Design","authors":"Murillo H. Queiroz,&nbsp;Roberto Rivelino,&nbsp;Kaline Coutinho,&nbsp;Sylvio Canuto,&nbsp;Rodrigo Gester","doi":"10.1002/poc.70092","DOIUrl":"https://doi.org/10.1002/poc.70092","url":null,"abstract":"<div>\u0000 \u0000 <p>Xanthones are a prominent class of natural products with diverse biological activities, often modulated by their photophysical properties. Here, we present a theoretical investigation of the photoemission of five Amazonian xanthones (XAN1–5) in aqueous environment using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT), combined with QTAIM and Voronoi Deformation Density (VDD) analyses. Our results show that all derivatives form stable intramolecular O–H···O hydrogen bonds in the ground state, with interaction energies ranging from −10.3 to −11.8 kcal/mol. Excitation leads to a direct ESIPT transformation only for XAN 2, XAN 3, and XAN 4, whereas XAN 1 and XAN 5 remain stabilized in the enolic form during the first excited-state relaxation. QTAIM topological parameters reveal that while ground-state H-bond strength is relatively similar across the series, VDD identifies a threshold of local charge polarization required for the proton mobility. This indicates that while ground-state H-bonding arrangement and local charge polarization are essential, they are not sufficient to induce ESIPT. Our analysis suggest that this process is governed by the specific electronic redistribution in the lowest excited state, which must enhance the acceptor basicity to trigger proton transfer. These findings provide molecular-level theoretical insights into the photophysics of Amazonian xanthones and offer a guide for the design of new photoactive antioxidant compounds.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 8","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148467290","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
Molecular Crosstalk Between Catecholamine Neurotransmitters and Neurologically Active Ions ( Na + $$ {Na}^{+} $$ , K + $$ {K}^{+} $$ and Cl − $$ {Cl}^{-} $$ ) and Ion-Induced Chemical Reactivity: A DFT Study 儿茶酚胺类神经递质与神经活性离子(Na +)的分子串扰$$ {Na}^{+} $$K + $$ {K}^{+} $$和Cl−$$ {Cl}^{-} $$)和离子诱导的化学反应性:DFT研究
IF 1.9 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-07-01 DOI: 10.1002/poc.70091
Kuppusamy Chandru, Tuhin Pradhan
{"title":"Molecular Crosstalk Between Catecholamine Neurotransmitters and Neurologically Active Ions (\u0000 \u0000 \u0000 \u0000 Na\u0000 +\u0000 \u0000 \u0000 $$ {Na}^{+} $$\u0000 , \u0000 \u0000 \u0000 \u0000 K\u0000 +\u0000 \u0000 \u0000 $$ {K}^{+} $$\u0000 and \u0000 \u0000 \u0000 \u0000 Cl\u0000 −\u0000 \u0000 \u0000 $$ {Cl}^{-} $$\u0000 ) and Ion-Induced Chemical Reactivity: A DFT Study","authors":"Kuppusamy Chandru,&nbsp;Tuhin Pradhan","doi":"10.1002/poc.70091","DOIUrl":"https://doi.org/10.1002/poc.70091","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;p&gt;Theoretical research on the intermolecular interactions (crosstalk) between catecholamine neurotransmitters (CATs) and neurologically active ions (NAIs) such as &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Na&lt;/mi&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Na}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;K&lt;/mi&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {K}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Cl&lt;/mi&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Cl}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; has been performed using the density functional B3LYP method with 6-311++G (d, p)+SDD basis set in aqueous phase. Complexation energy analysis predicts that average interaction energy between CATs and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Na&lt;/mi&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Na}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; ion in aqueous phase is ~−22.9 &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;kcal&lt;/mtext&gt;\u0000 &lt;mo&gt;⋅&lt;/mo&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;mol&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ kcalcdot {mol}^{-1} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, which is ~3 times higher (i.e., stronger) than the reported experimental interaction energy between dopamine and dopamine transporter (−7.4 &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;kcal&lt;/mtext&gt;\u0000 &lt;mo&gt;⋅&lt;/mo&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;mol&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ kcalcdot {mol}^{-1} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;). Interaction with anion (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;Cl&lt;/mi&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {Cl}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;) is weaker than c","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 8","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386263","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
Photochemistry of N-Substituted, N′-Tosyl Diphenyl Sulfondiimines N取代,N′-Tosyl二苯基磺基二亚胺的光化学性质
IF 1.9 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-06-30 DOI: 10.1002/poc.70090
Bashar Aziz, Paul Danyi, John P. Carney, Ryan D. McCulla
{"title":"Photochemistry of N-Substituted, N′-Tosyl Diphenyl Sulfondiimines","authors":"Bashar Aziz,&nbsp;Paul Danyi,&nbsp;John P. Carney,&nbsp;Ryan D. McCulla","doi":"10.1002/poc.70090","DOIUrl":"https://doi.org/10.1002/poc.70090","url":null,"abstract":"<p>Sulfondiimines are an emerging sulfur(VI) functional group with increasing use in synthesis and medicinal chemistry, yet their photochemical behavior has remained largely unexplored. In this work, the photochemistry of a series of six <i>N</i>-substituted, <i>N</i>′-tosyl diphenyl sulfondiimines was analyzed. Upon direct UV irradiation, five derivatives underwent efficient photodenitrenation in a consistent, stepwise order: extrusion of the <i>N</i>-substituent nitrene followed by release of the <i>N</i>-tosyl nitrene from the corresponding sulfilimine. This sequential nitrene release is a rare behavior that has not been observed previously. Quantum yield measurements reveal strong substituent dependence, with aryl substituents exhibiting substantially higher photochemical efficiency (0.22–0.31) than alkyl substituents (~0.1), whereas the NH-substituted compound remained photoinert under our conditions. Product profiles and trapping experiments support the S–N cleavage in sulfondiimines to release the nitrene through a singlet manifold. Photosensitization experiments revealed the triplet manifold is dissociative as well, albeit with a greater number of side reactions. Quantum chemical calculations further supported this mechanism by relating the release order to relative S–N bond strengths and identifying a dissociative excited state along the S–N coordinate.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 8","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70090","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386953","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}
引用次数: 0
An Ultrafast Time Resolved Infrared and Computational Study of the Photochemistry of Ethyl 2-Diazo-3,3,3-Trifluoropropanoate (CF3CN2CO2Et) 2-重氮-3,3,3-三氟丙酸乙酯(CF3CN2CO2Et)的超快时间分辨红外光化学及计算研究
IF 1.9 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-06-19 DOI: 10.1002/poc.70089
Jojo Joseph, Jacek Kubicki, Mrinal Chakraborty, Gotard Burdziński, William H. Coldren, Hoi Ling Luk, Carolyn S. Reid, Matthew S. Platz, Christopher M. Hadad
{"title":"An Ultrafast Time Resolved Infrared and Computational Study of the Photochemistry of Ethyl 2-Diazo-3,3,3-Trifluoropropanoate (CF3CN2CO2Et)","authors":"Jojo Joseph,&nbsp;Jacek Kubicki,&nbsp;Mrinal Chakraborty,&nbsp;Gotard Burdziński,&nbsp;William H. Coldren,&nbsp;Hoi Ling Luk,&nbsp;Carolyn S. Reid,&nbsp;Matthew S. Platz,&nbsp;Christopher M. Hadad","doi":"10.1002/poc.70089","DOIUrl":"https://doi.org/10.1002/poc.70089","url":null,"abstract":"<p>The photochemistry of ethyl 2-diazo-3,3,3-trifluoropropanoate (CF<sub>3</sub>CN<sub>2</sub>CO<sub>2</sub>Et) was studied in solution at ambient temperature with femtosecond (fs) time-resolved infrared (IR) spectroscopy. Experimental results are interpreted with the aid of quantum mechanical calculations. The upper singlet excited state S<sub>n</sub> of CF<sub>3</sub>CN<sub>2</sub>CO<sub>2</sub>Et decays by three processes: internal conversion to the ground state, fragmentation to the singlet carbene, and diazirine formation. The singlet carbene then subsequently decays to triplet carbene or reacts with the solvent. In methanol-D (MeOD), typically a proficient scavenger of singlet carbenes, the carbene-alcohol ylide was produced. The analogous CH<sub>3</sub>CN-ylide of the singlet carbene is produced when the photolysis is performed in acetonitrile, while in CHCl<sub>3</sub>, the C–Cl insertion product was detected.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 8","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70089","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148282499","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}
引用次数: 0
Undergraduate Research in Computational Physical Organic Chemistry: Unleashing the Predictive Power of Nonstationary Points 计算物理有机化学本科研究:释放非平稳点的预测能力
IF 1.8 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-06-05 DOI: 10.1002/poc.70088
Gary W. Breton
{"title":"Undergraduate Research in Computational Physical Organic Chemistry: Unleashing the Predictive Power of Nonstationary Points","authors":"Gary W. Breton","doi":"10.1002/poc.70088","DOIUrl":"https://doi.org/10.1002/poc.70088","url":null,"abstract":"<div>\u0000 \u0000 <p>In many cases, computational geometry optimizations of carbanions containing potential leaving groups are observed to be nonstationary points on the potential energy surface. Instead of optimization leading to an energy minimized stationary point, spontaneous loss of the leaving group may lead to formation of an entirely new compound. Over several years, groups of students taking the Advanced Organic Chemistry course at Berry College have been tasked with investigating instances in which such compound transformations have occurred within the context of a course-based undergraduate research experience (CURE). The spontaneous formation of propellanes, hetero-substituted propellanes, anti-Bredt bridgehead alkenes, and propargyl-substituted cyclooctynes has been studied. The computational results have been compared with known experimental results. Our conclusion is that computational geometry optimizations do an excellent job at reproducing and predicting known experimental results. Such computations are recommended to help experimental chemists select the most promising synthetic targets when many possible options exist.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 7","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148174532","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
Undergraduate Research in Computational Physical Organic Chemistry: Unleashing the Predictive Power of Nonstationary Points 计算物理有机化学本科研究:释放非平稳点的预测能力
IF 1.8 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-06-05 DOI: 10.1002/poc.70088
Gary W. Breton
{"title":"Undergraduate Research in Computational Physical Organic Chemistry: Unleashing the Predictive Power of Nonstationary Points","authors":"Gary W. Breton","doi":"10.1002/poc.70088","DOIUrl":"https://doi.org/10.1002/poc.70088","url":null,"abstract":"<div>\u0000 \u0000 <p>In many cases, computational geometry optimizations of carbanions containing potential leaving groups are observed to be nonstationary points on the potential energy surface. Instead of optimization leading to an energy minimized stationary point, spontaneous loss of the leaving group may lead to formation of an entirely new compound. Over several years, groups of students taking the Advanced Organic Chemistry course at Berry College have been tasked with investigating instances in which such compound transformations have occurred within the context of a course-based undergraduate research experience (CURE). The spontaneous formation of propellanes, hetero-substituted propellanes, anti-Bredt bridgehead alkenes, and propargyl-substituted cyclooctynes has been studied. The computational results have been compared with known experimental results. Our conclusion is that computational geometry optimizations do an excellent job at reproducing and predicting known experimental results. Such computations are recommended to help experimental chemists select the most promising synthetic targets when many possible options exist.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 7","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148174601","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
IF 1.8 4区 化学
{"title":"","authors":"","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 7","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148095838","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
Hydropersulfide Donors: Mechanistic and Kinetic Insights With Biological and Potential Therapeutic Implications 氢过硫化物供体:具有生物学和潜在治疗意义的机械和动力学见解
IF 1.8 4区 化学
Journal of Physical Organic Chemistry Pub Date : 2026-05-28 DOI: 10.1002/poc.70087
Daniel Liu, Jordan Lamar, Andrew Thampoe, Vinayak S. Khodade, John P. Toscano
{"title":"Hydropersulfide Donors: Mechanistic and Kinetic Insights With Biological and Potential Therapeutic Implications","authors":"Daniel Liu,&nbsp;Jordan Lamar,&nbsp;Andrew Thampoe,&nbsp;Vinayak S. Khodade,&nbsp;John P. Toscano","doi":"10.1002/poc.70087","DOIUrl":"https://doi.org/10.1002/poc.70087","url":null,"abstract":"<div>\u0000 \u0000 <p>Hydropersulfides (RSSH) are emerging reactive sulfur species with distinctive chemical properties. Compared with conventional thiols and disulfides, RSSH exhibit enhanced acidity, nucleophilicity, reducing capabilities, and electrophilicity, enabling unique redox and sulfur transfer activity under physiological conditions. Their intrinsic instability and high reactivity have limited direct mechanistic studies. Over the past decade, a range of small-molecule RSSH donors have been developed to probe RSSH chemistry and biology. In this review, we survey different strategies for RSSH generation, including direct-release donors and self-immolative platforms, the latter of which exploit elimination cascades or cyclization-triggered mechanisms to achieve controlled RSSH release. We discuss trigger-specific activation, structure–activity relationships, and factors governing RSSH release kinetics. We also highlight emerging biological applications of RSSH donors, where studies have explored their potential to modulate oxidative and nitrosative stress, maintain cellular redox balance, and mitigate tissue injury in cardiac, hepatic, and neuronal models. These investigations underscore the utility of RSSH donors as chemical biology tools for interrogating redox signaling and as potential pharmacological agents for the treatment of myriad pathologies associated with disrupted redox homeostasis.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 7","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148167000","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
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