Journal of Physical Organic Chemistry最新文献

{"title":"Quantitative Structure–Activity Relationships for Predicting Organic Contaminant Reactivity in Electrochemical Advanced Oxidation Processes: Descriptors, Kinetics, and Machine Learning Frontiers","authors":"Monica Cerro-Lopez,&nbsp;Neyva Daniela Cuatepotzo Vega","doi":"10.1002/poc.70115","DOIUrl":"https://doi.org/10.1002/poc.70115","url":null,"abstract":"<div>\u0000 \u0000 <p>Electrochemical advanced oxidation processes (EAOPs) have become a prominent tool in wastewater remediation of refractory organic pollutants due to their versatility and ability to generate powerful, <i>in situ</i> oxidant species—predominantly hydroxyl radicals (•OH). Concurrently, quantitative structure–activity relationship (QSAR) models have emerged as vital tools for predicting activity in high-priority areas like drug development and toxicity. In this review, we address the application of QSARs in decoding reactivity within electrooxidation processes. We trace their evolution from early origins using the Hammett parameter (<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>σ</mi>\u0000 </mrow>\u0000 <annotation>$$ sigma $$</annotation>\u0000 </semantics></math>) as a molecular descriptor to quantum chemical descriptors—such as <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>E</mi>\u0000 <mtext>HOMO</mtext>\u0000 </msub>\u0000 </mrow>\u0000 <annotation>$$ {E}_{mathrm{HOMO}} $$</annotation>\u0000 </semantics></math>, ionization potentials (IPs), and Fukui functions—and finally to advanced machine learning (ML) approaches like graph neural networks (GNNs) designed to navigate complex real wastewater matrices. Additionally, we highlight the anode as a core mechanistic variable that dictates oxidant selectivity. Finally, we discuss the primary limitations hindering ML adoption in EAOPs—including small training sets, a lack of electrochemical-specific datasets, limited water-matrix transferability, black-box interpretability, and conflicting optimization metrics—and explore emerging strategies to overcome them, such as transfer learning, explainable artificial intelligence (XAI), and physics-informed ML.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149205864","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}

{"title":"Reactions of Isomeric Triplet and Singlet Aryloxenium Cations in the Gas Phase","authors":"Tuong V. Nguyen,&nbsp;Markus Rohdenburg,&nbsp;Jonas Warneke,&nbsp;John J. Nash,&nbsp;Hilkka I. Kenttämaa","doi":"10.1002/poc.70110","DOIUrl":"https://doi.org/10.1002/poc.70110","url":null,"abstract":"<p>Aryloxenium cations are proposed to act as intermediates in many organic reactions. However, the reactivity of only two such cations with a triplet electronic ground state has been reported. One was studied in solution where only reactions with solvents could be explored. Another one was examined in the gas phase by using tandem mass spectrometry where isolation of the cation is possible, making the study of its reactions with reagents other than solvents feasible. In this preliminary study, the 2-amino-4-pyridyloxenium cation was found to exclusively undergo radical reactions, which have not been reported for singlet aryloxenium cations. Herein, the study on the reactivity of the triplet pyridyloxenium cation has been expanded to include experimentation on additional reactions and a more detailed computational examination of the reaction mechanisms. The results are compared to those obtained for the isomeric singlet 3-amino-4-pyridyloxenium and 3-amino-2-pyridyloxenium cations. The triplet cation exhibits radical-like behavior toward most of the studied reagents, with reactions being initiated by (radical) abstraction of atoms, or groups of atoms, or radical addition to C=C bonds. In contrast, the isomeric singlet pyridyloxenium cations are unreactive toward or react very slowly with many of the same reagents. Their reaction efficiencies are substantially lower than those of the previously studied singlet quinolyloxenium cations due to their lower electrophilicity. The mechanisms of the above reactions were explored computationally. Important information was obtained for the relative reactivity and the most reactive sites in different types of aryloxenium cations.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70110","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149205596","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}

{"title":"An Investigations-Based Undergraduate Computational Chemistry Course","authors":"Daniel J. O'Leary","doi":"10.1002/poc.70113","DOIUrl":"https://doi.org/10.1002/poc.70113","url":null,"abstract":"<p>This paper describes an investigations-based undergraduate computational chemistry course taught at Pomona College and enrolled by students within the Claremont Colleges consortium. Class meetings are structured around a series of investigations introducing commonly used computational techniques within the context of examples taken from organic, inorganic, and nuclear magnetic resonance (NMR) spectroscopy. The techniques include conformational searching, relaxed coordinate scans, ground state and transition state optimization, zero-point energy corrections, solvent continuum models, vibrational frequency calculations, intrinsic reaction coordinate (IRC) calculations, electron density surface and molecular orbital and natural bond orbital visualization, atomic charge calculation, nuclear magnetic shielding and spin–spin coupling calculations, isotope effects, and inclusion of effective core potentials for many-electron systems. The investigations focus mainly on primary literature examples, including topics in conformational analysis, the S_N2 reaction, carbocation stability and rearrangement, the E2 reaction, hydroboration, the Diels–Alder reaction, kinetic and equilibrium isotope effects, NMR chemical shifts and coupling constants, and calculations of inorganic and organometallic systems. Investigations are guided by in-class instruction and tutorials, written documentation, and video tutorials. Students compile investigation results for assessment in custom forms containing embedded spreadsheets formatted for calculating energy differences and form fields for inserting graphics and animations of results. An independent and team-designed capstone project further develops student competency with research-grade techniques in areas of chemistry they find interesting.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70113","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149205649","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}

{"title":"Theoretical Insights Into the Molecular Mechanism of Fe Catalysed Sonogashira Cross-Coupling Reaction","authors":"C. Rajalakshmi,&nbsp;Leemol Roy,&nbsp;John B. Kottooran,&nbsp;Shilpa Sarah Mathew,&nbsp;Parvathi Santhoshkumar,&nbsp;Derin Mary Baby,&nbsp;Gopinathan Anilkumar,&nbsp;Vibin Ipe Thomas","doi":"10.1002/poc.70112","DOIUrl":"https://doi.org/10.1002/poc.70112","url":null,"abstract":"<div>\u0000 \u0000 <p>The Sonogashira type cross-coupling reaction constitutes a pivotal method for constructing C(sp<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msup>\u0000 <mrow></mrow>\u0000 <mrow>\u0000 <mn>2</mn>\u0000 </mrow>\u0000 </msup>\u0000 </mrow>\u0000 <annotation>$$ {}^2 $$</annotation>\u0000 </semantics></math>)–C(sp) bonds, enabling the synthesis of structurally diverse aryl alkynes with broad applications in pharmaceuticals and materials science. In the present study, a comprehensive mechanistic investigation of the iron-catalysed Sonogashira-type coupling between phenylacetylene and 4-iodoacetophenone was performed employing density functional theory (DFT) calculations. The catalytic system, comprising FeCl<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mrow></mrow>\u0000 <mrow>\u0000 <mn>3</mn>\u0000 </mrow>\u0000 </msub>\u0000 <mo>·</mo>\u0000 </mrow>\u0000 <annotation>$$ {}_3cdotp $$</annotation>\u0000 </semantics></math>6H<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mrow></mrow>\u0000 <mrow>\u0000 <mn>2</mn>\u0000 </mrow>\u0000 </msub>\u0000 </mrow>\u0000 <annotation>$$ {}_2 $$</annotation>\u0000 </semantics></math>O and 1,10-phenanthroline in aqueous medium under aerobic conditions, was examined in detail. Our results elucidate a mechanistic pathway that proceeds via an initial formation of the pre-catalytic species through an interaction between the metal iron and the ligand phenanthroline, followed by base-assisted activation of the terminal alkyne to form the active catalytic species, culminating in C–C bond formation through a concerted nucleophilic substitution process. This study reveals a feasible redox-neutral mechanistic pathway where the iron centre remains in its +3 oxidation state throughout the reaction cycle and thereby provides valuable insights into the reactivity of the iron-catalysed Sonogashira coupling reaction.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149205648","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}

{"title":"Electrophilicity Descriptors in Urea- and Thiourea-Based Receptors","authors":"Ulises Orozco-Valencia","doi":"10.1002/poc.70116","DOIUrl":"https://doi.org/10.1002/poc.70116","url":null,"abstract":"<div>\u0000 \u0000 <p>A computational analysis employing representative electrophilicity descriptors, mainly derived from Conceptual DFT, together with molecular electrostatic potential (MEP) calculations, is presented for a set of urea- and thiourea-based receptors relevant to anion recognition. This approach focuses on establishing correlations between electrophilicity and anion affinity, an important property in the design of chemosensors. The relationship between electrophilicity and anion affinity was examined for diaryl urea and thiourea derivatives bearing electron-withdrawing substituents using global descriptors derived from parabolic models of <i>E</i>(<i>N</i>), including the electrophilicity index (<i>ω</i>), electroaccepting power (<i>ω</i>⁺), net electrophilicity (Δ<i>ω</i>^±), and electrophilic channel (Δ<i>N</i>_A^<i>ele</i>), as well as Hirshfeld atomic charges within the information-theoretic approach (ITA). Experimental association constants for arylthiourea receptors showed acceptable correlations with the computed descriptors. The results highlight that the electrophilic character of the urea and thiourea subunits, together with the electron-deficient anion-binding region (N<span></span>H) identified through MEP calculations and Hirshfeld atomic charges, are key factors governing anion affinity. Interestingly, the highest Hirshfeld atomic charge among the hydrogen atoms in the N<span></span>H region (<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>q</mi>\u0000 <mi>H</mi>\u0000 </msub>\u0000 </mrow>\u0000 <annotation>$$ {q}_H $$</annotation>\u0000 </semantics></math>) plays an important role in anion affinity, consistent with the deprotonation of several urea and thiourea subunits upon association with anions.</p>\u0000 <p>This simple computational methodology enables the ranking of receptors with common molecular architecture according to their electrophilicity and, consequently, their anion affinity, provided that free access to the N<span></span>H binding region is maintained and conformational flexibility is limited.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149205334","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}

{"title":"A Tale of Two Heterocycles: How Oxygen and Sulfur Shape Divergent Kemp Reactivity","authors":"Ella R. Jennings,&nbsp;Hannah S. Todd,&nbsp;Emilie Perelman,&nbsp;Courtney B. Limehouse,&nbsp;Hunter J. Savage,&nbsp;Marcello Forconi","doi":"10.1002/poc.70114","DOIUrl":"https://doi.org/10.1002/poc.70114","url":null,"abstract":"<p>The Kemp elimination is a well-studied reaction that proceeds through the deprotonation of carbon-3 of benzisoxazoles, coupled with irreversible ring opening by cleavage of the labile O-N bond. The base-catalyzed reaction is concerted, with no detectable intermediate. Due to their compositional and structural similarities, benzisothiazoles are also candidates for Kemp elimination reactions; however, little information was previously available on these compounds. We found that benzisothiazoles also undergo Kemp elimination, and we have characterized the Kemp product. As previously observed with benzisoxazoles, reactions of benzisothiazoles are significantly accelerated by polar, aprotic solvents and by the presence of electron-withdrawing groups (EWG) on the six-membered ring. In mixed water/DMSO systems, we found a strong inverse linear relationship between the logarithm of the second-order rate constant and the mole fraction of water for both benzisoxazoles and benzisothiazoles. Linear free-energy relationship (LFER) analyses reveal opposing solvent-dependent behavior between the two heterocycles: DMSO steepens substituent sensitivity in benzisoxazoles relative to water but dampens it in benzisothiazoles. Extrapolation of the chemically controlled regime suggests that transitioning from water to pure DMSO produces a remarkable ~14-order-of-magnitude increase in the intrinsic chemical reactivity of 5-nitrobenzisoxazole, compared to an ~7-order-of-magnitude acceleration for 5-nitrobenzisothiazole. This divergence highlights fundamental differences in how protic and aprotic media stabilize the localized phenolate versus the soft, polarizable thiophenolate anion.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70114","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146411","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}

{"title":"Mapping the Electronic Topography of Crotofolane Diterpenoids: CDFT Study on Bioactivity, Ambiphilic Collapse, and Steric Quenching","authors":"Emilio Squitieri","doi":"10.1002/poc.70104","DOIUrl":"https://doi.org/10.1002/poc.70104","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;p&gt;The electronic topography of crotofolane diterpenoids &lt;b&gt;M1&lt;/b&gt;–&lt;b&gt;M6&lt;/b&gt; was systematically investigated using conceptual DFT (CDFT) at the B3LYP-D4/def2-TZVP level. By integrating the RIJCOSX-DEF2/J approximation and the CPCM solvation model (water), this study characterizes the reactive profile and its correlation with biological efficacy against human rhinovirus type-2 (HRV-2) and &lt;i&gt;Plasmodium falciparum&lt;/i&gt; Dd2. Global reactivity descriptors reveal that antiplasmodial potency is confined to a specific chemical hardness (&lt;i&gt;η&lt;/i&gt;) window (5.30–5.45 eV). In the bioactive series (&lt;b&gt;M1&lt;/b&gt;–&lt;b&gt;M3&lt;/b&gt;), local analysis identifies a spatially resolved O40–O10 functional axis as the primary pharmacophoric determinant, where the exocyclic O40 acts as the primary nucleophilic site (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;D&lt;/mi&gt;\u0000 &lt;mn&gt;40&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {D}_{40}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; = 1.000) and the lactone O10 as the primary electrophilic locus (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;D&lt;/mi&gt;\u0000 &lt;mn&gt;10&lt;/mn&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {D}_{10}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; = 1.000). Conversely, the inactivity of &lt;b&gt;M4&lt;/b&gt; is driven by an “ambiphilic collapse” at the C14 site, which simultaneously concentrates the absolute primary dominance for both nucleophilic and electrophilic attacks (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;D&lt;/mi&gt;\u0000 &lt;mn&gt;14&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {D}_{14}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; &lt;b&gt;=&lt;/b&gt; &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;D&lt;/mi&gt;\u0000 &lt;mn&gt;14&lt;/mn&gt;\u0000 &lt;mo&gt;+&lt;/mo&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {D}_{14}^{+} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; = 1.000), disrupting the polarized topography required for specific binding. For &lt;b&gt;M5&lt;/b&gt;, angular strain induces an ambiphilic transition at O40 (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;D&lt;/mi&gt;\u0000 &lt;mn&gt;40&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {D}_{40}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; &lt;b&gt;=&lt;/b&gt; &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mro","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145721","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}

{"title":"Primarily Undergraduate-Led Research in Physical Organic Chemistry: A Special Issue","authors":"Zacharias J. Kinney","doi":"10.1002/poc.70109","DOIUrl":"https://doi.org/10.1002/poc.70109","url":null,"abstract":"<p>Primarily undergraduate institutions (PUIs) and emerging research institutions (ERIs) serve a critical purpose for their student populations: quality education in close proximity to home. In the United States, we have witnessed a drastic rise in college-aged individuals—whether for familial or financial reasons—choosing to reside close to their roots for their college education. PUIs and ERIs often feature smaller student-to-faculty ratios and attempt to provide students with a more hands-on personalized college experience. For a student considering an undergraduate degree in STEM, a signature way to stand out among peers is to participate in undergraduate research. For decades PUIs and ERIs have sought to provide valuable research experiences, ultimately setting their students up for success in their academic training.</p><p>Research experience as an undergraduate not only prepares one for graduate studies or entry-level industry roles but also can help a young scientist identify their passion. Physical organic chemistry is essentially a chemistry playground in this regard, where an undergraduate researcher can draw on their course-based knowledge in analytical, computational, inorganic, organic, and physical chemistry to discover new research directions.</p><p>The concept for this special issue was discussed at the Physical Organic Chemistry Gordon Research Conference in 2025, where the volume of research from PUI and ERI faculty was on full display. The initial goal of this collection was to illustrate the wide-ranging nature of the discipline and highlight that physical organic chemistry is a fertile research area for faculty at such institutions. The articles in this special issue speak to this, with traditional research articles on structure–property (and structure–reactivity) relationships and blended experimental/computational approaches to physical organic questions, to integrating course work and research into the curriculum. In total, this special issue is meant to highlight not only the innovative research being undertaken at PUIs and ERIs <i>but also the value of undergraduates working at the forefront of scientific discovery.</i></p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70109","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149084021","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}

{"title":"Photochemistry of Aromatic Azides: Relationship Between Substituents, Intermediates and Reactivity","authors":"Elisa Leyva,&nbsp;Edgar Moctezuma,&nbsp;Silvia E. Loredo-Carrillo,&nbsp;Denisse de Loera,&nbsp;Johana Aguilar,&nbsp;Agobardo Cárdenas-Chaparro","doi":"10.1002/poc.70105","DOIUrl":"https://doi.org/10.1002/poc.70105","url":null,"abstract":"<div>\u0000 \u0000 <p>Aromatic azides are high-energy compounds that decompose easily with light. In recent decades, they have found diverse applications in organic chemistry, biochemistry, materials science and medicinal chemistry. For a better application of these compounds, it is important to understand their basic photochemistry. Aromatic azides photochemical reactions have fascinated researchers for more than a century. Spectroscopists have investigated the intermediates formed using conventional and high-resolution techniques. Theoretical chemists have investigated the intrinsic interplay of several intermediates generated under different experimental conditions. Irradiation of the simplest phenyl azide induces the generation of several intermediates such as triplet nitrene, singlet nitrene, benzazirine, azepine or phenyl nitrenium ion. The placement of different substituents in the aromatic ring modifies the intermediates generated as well as the mechanistic pathways available for a given aryl azide. In this review, the photochemistry of the parent azide and other aromatic azides containing nitro, fluoro or amino substituents will be discussed to determine the relationship between substituents, intermediates and reactivity.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148994474","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}

{"title":"Oleoscopicity and Organic Deliquescence of Hydrophobic Compounds Under a Hydrocarbon Atmosphere","authors":"Steven K. Skaggs,&nbsp;Kevin A. Smith,&nbsp;Margaret J. Ankrom,&nbsp;Paul J. Bracher","doi":"10.1002/poc.70096","DOIUrl":"https://doi.org/10.1002/poc.70096","url":null,"abstract":"<p>This paper examines the acquisition of organic solvent by hydrophobic organic compounds from atmospheres enriched in organic vapor. Hygroscopicity commonly refers to a substance acquiring water vapor from a humid atmosphere, and deliquescence occurs when a solid substance acquires sufficient water vapor to the point that it dissolves into a homogeneous liquid solution. As the terms <i>hygroscopicity</i> and <i>humidity</i> have become so commonly and inexorably linked to water in the scientific literature, we introduce the terms <i>oleoscopicity</i> and <i>oledity</i> to refer to circumstances where a substance acquires organic vapor from the atmosphere. Our initial investigation into trends for oleoscopicity comprised studies of three families of organic compounds under atmospheres of <i>n</i>-hexane as a model solvent. Several of the compounds studied deliquesced by forming homogeneous liquid solutions with hexane acquired from the atmosphere, and deliquescence was observed to require the hexane vapor having exceeded a critical relative oledity. We report how this form of (organic) deliquescence—with hydrophobic compounds acquiring organic solvent—parallels many aspects of standard (aqueous) deliquescence.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":1.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70096","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148994079","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}