{"title":"Rhodium-Catalyzed Regioselective Addition of N-Hydroxyl Imides to Internal Alkynes","authors":"Zi Liu, Bernhard Breit","doi":"10.1002/ijch.70014","DOIUrl":"10.1002/ijch.70014","url":null,"abstract":"<p>An intermolecular rhodium-catalyzed regioselective addition of <i>N</i>-hydroxyl imides to internal alkynes leads to branched <i>O</i>-allyl compounds, which can be readily transformed to allylic alcohols and <i>O</i>-allyl hydroxylamines after deprotection. Isotopic labeling experiments suggest a plausible reaction mechanism.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 3","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.70014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147683098","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":"Upcycling Hydrofluorocarbons to Valuable Bis(perfluoroalkyl)carbinols via Nucleophilic Fluoroalkylation","authors":"Hiroto Iwasaki, Masashi Hattori, Norio Shibata","doi":"10.1002/ijch.70015","DOIUrl":"10.1002/ijch.70015","url":null,"abstract":"<p>Hydrofluorocarbon (HFC)-125 (CF<sub>3</sub>CF<sub>2</sub>H) is widely used as a refrigerant; however, its extremely high global warming potential makes it a significant environmental concern. Here, we report a practical strategy to upcycle HFC-125 into valuable bis(perfluoroalkyl)carbinols, a class of fluorinated alcohols with remarkable acidity and lipophilicity. Optimization studies established efficient conditions for the nucleophilic pentafluoroethylation of trifluoromethyl ketones with HFC-125, affording octafluorocarbinols in up to 82% yield. A broad substrate scope, including aryl, heteroaryl, and bioactive ketones, was demonstrated. Extension to other HFCs—including HFC-23, HFC-329p, and 1H-heptadecafluorooctane—further expanded the library of highly fluorinated carbinols. Translation to continuous flow synthesis significantly improved efficiency and scalability, delivering higher yields under milder conditions than batch reactions. This work provides a sustainable route to structurally unique, densely fluorinated motifs while addressing the urgent need for recycling high-global warming potential HFCs.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 3","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147684116","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":"Crystal Facets Reactivity in Metal–Organic Frameworks","authors":"Emilio Borrego-Marin, Jorge A. R. Navarro","doi":"10.1002/ijch.70018","DOIUrl":"10.1002/ijch.70018","url":null,"abstract":"<p>Crystal facets are intrinsically defective, chemically distinct interfaces whose reactivity critically influences the function of crystalline materials. In reticular porous systems, while internal pore chemistry has been extensively engineered, growing evidence shows that chemical transformations in complex environments increasingly occur at external crystal surfaces. In this mini review, it is highlighted how the crystal facets’ reactivity can be dictated by surface functionality, particle size, defect density, or crystal morphology. Precise control of these parameters enables deliberate exposure of crystal facets, leading to enhanced crystal surface accessibility and higher reactivity. Further focus is placed on frameworks based on hemilabile bonds, whose intermediate bond strength enables dynamic yet structurally persistent crystal surfaces. In these materials, surface-confined reactions can initiate self-propagating cascade processes that extend beyond the crystal surface through controlled bond exchange, lattice degradation, and release of reactive species. This behavior transcends classical surface-limited catalysis and establishes crystal facets as active, information-bearing interfaces. Together, these insights position crystal surface reactivity as a key design parameter for developing functional materials capable of programed cascade chemistry in catalytic and biological contexts.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 3","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.70018","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147684305","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}
David Attia, Evgenee Yekymov, Rachel Yerushalmi-Rozen
{"title":"Charge Regulation in Crowded Solutions of a Weak Polyelectrolyte: Steric Interactions","authors":"David Attia, Evgenee Yekymov, Rachel Yerushalmi-Rozen","doi":"10.1002/ijch.70013","DOIUrl":"10.1002/ijch.70013","url":null,"abstract":"<p>Weak polyelectrolytes (WPE) are used to prepare responsive materials in a variety ofapplications. When dissolved in highly crowded environments, of biorelevant media or synthetic complex fluids, that contain substantial concentrations of macromolecules, molecular assemblies, or nanoparticles, WPE exhibit deviations from the acid–base equilibrium observed in single-component solutions. In this mini review, studies of charge regulation (CR) are described in simple yet relevant model systems comprising poly (acrylic acid) (PAA) and high concentrations of non-charged micelles (Pluronic) or nonadsorbing, short chains of poly (vinyl alcohol) (PVA). Titration experiments reveal in the first mixture significant reduction in the degree of ionization of the PAA. In PAA–PVA mixtures, an unexpected increase in the degree of ionization of PAA is observed. Structural characterization of the solutions, via transmission electron microscopy and small-angle X-ray scattering, reveals that the local organization is affected by the interaction between PAA chains and the additives, leading to crowding of the micelles in one case, and crowding of the PAA chains in the other. These systems provide insights into the molecular mechanisms leading to the responsiveness of WPE and the effect of crowding on CR.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 3","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.70013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147684306","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}
Serhiy V. Ryabukhin, Pavel S. Nosik, Dmytro O. Leha, Dmytro M. Volochnyuk
{"title":"Ruppert–Prakash Reagent as a Source of Difluorocarbene: Mechanistic, Synthetic, and Practical Perspectives for Small-Ring Synthesis","authors":"Serhiy V. Ryabukhin, Pavel S. Nosik, Dmytro O. Leha, Dmytro M. Volochnyuk","doi":"10.1002/ijch.70012","DOIUrl":"https://doi.org/10.1002/ijch.70012","url":null,"abstract":"<p>The Ruppert–Prakash reagent (TMSCF<sub>3</sub>) has become one of the most practical and widely used sources of difluorocarbene, enabling the efficient construction of <i>gem</i>-difluorocyclopropane and <i>gem</i>-difluorocyclopropene frameworks. Over the past decade, significant progress has been made in understanding its initiation pathways, reactivity patterns, and the factors that control reaction efficiency and safety. This review summarizes these advances, covering both mechanistic insights and the broad synthetic scope of TMSCF<sub>3</sub>-mediated transformations of alkenes, alkynes, and functionalized complex substrates, mostly leading to three- and four-membered rings. Particular attention is given to strategies that enhance practicality, including “slow addition,” catalytic approaches, and flow chemistry to enable safe handling and scale-up. The emerging structural diversity now accessible through these protocols highlights the growing importance of difluorinated small rings in modern molecular design. Together, these developments establish TMSCF<sub>3</sub> as a cornerstone reagent for difluorocarbene chemistry, pointing toward promising opportunities for future discovery.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 2","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147615201","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}
Renato Veríssimo de Oliveira, Luiz Daniel Alves Rios, Norberto de Kássio Vieira Monteiro
{"title":"The Use of the Legendre Transform in Chemical Thermodynamics: A Powerful Tool","authors":"Renato Veríssimo de Oliveira, Luiz Daniel Alves Rios, Norberto de Kássio Vieira Monteiro","doi":"10.1002/ijch.70010","DOIUrl":"https://doi.org/10.1002/ijch.70010","url":null,"abstract":"<p>This article highlights the importance of the Legendre transform (LT) in thermodynamics, demonstrating its role in replacing nonmeasurable variables, such as entropy, with experimentally accessible coordinates. Despite its essential nature, the LT is rarely covered in Physical Chemistry textbooks, a gap noted in the literature as well. The article clarifies the LT, applies it in detail to Thermodynamics, discusses its connection to the extensiveness of internal energy, and proposes a mnemonic rule for obtaining the differential forms of thermodynamic potentials from the Gibbs equation. It is also shown that the total LT of an extensive function is zero, which leads to Euler's relation and reinforces the relevance of including the topic in teaching materials.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 2","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.70010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147585268","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}
Muhammad Abd El-haq, Awanish Kumar, Yuval Ramot, Abraham Nyska, Abraham J. Domb
{"title":"Biodegradation of Tissue Separation Spacer Implant","authors":"Muhammad Abd El-haq, Awanish Kumar, Yuval Ramot, Abraham Nyska, Abraham J. Domb","doi":"10.1002/ijch.70005","DOIUrl":"https://doi.org/10.1002/ijch.70005","url":null,"abstract":"<p>The biodegradation of inflated spacers made of PLCL 70:30 (poly(L-lactide<i>-</i>co-ε-caprolactone)) is investigated. This spacer is intended to temporarily position the anterior rectal wall away from the prostate during radiotherapy of prostate cancer. When inflated with phosphate buffer solution, this spacer implant creates space in the anterior rectum, thereby reducing radiation-induced damage. The mechanical stability of such inflated biodegradable systems over time is highly compromised, and their stability is uncertain due to continuous hydrolysis of the polymer material and imbalance with the muscular pressure that constantly acts on the inflated implant. Herein, detailed in vitro and in vivo degradation data of the inflated spacer are reported and correlated with its stability under a constant mechanical pressure that impersonates the pressure created by the anterior rectum on the spacers. The mechanical and physicochemical test results have a direct correlation with the degradation profile of the PLCL material. Mechanical testing demonstrates spacer inflation for at least 13 weeks.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 2","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.70005","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147615200","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":"Fluorinated Poly(Aryl Ether) Superacidic Ionomers","authors":"Ying Chang, Chulsung Bae","doi":"10.1002/ijch.70011","DOIUrl":"https://doi.org/10.1002/ijch.70011","url":null,"abstract":"<p>Superacidic ionomers are synthesized via C<span></span>H activation/borylation followed by Suzuki coupling of aromatic rings of fluorinated poly(arylene ether)s. Properties of these superacidic ionomers, such as thermal stability, water uptake, ion exchange capacity (IEC), morphology, and proton conductivity, are systematically investigated. For comparative analysis, a polysulfone ionomer with a similar IEC was examined to elucidate the effect of polymer backbone hydrophobicity on membrane properties. The results demonstrate that polymer backbone hydrophobicity exerts a significant impact on both morphology and performance. Highly fluorinated poly(aryl ether) ionomers exhibit reduced water uptake and enhanced proton conductivity compared to low-fluorine or nonfluorinated polymer analogs. Notably, the TFHFBP-S<sub>1</sub> membrane achieves the highest proton conductivity, comparable to that of Nafion, across the full range of relative humidity at 100 °C.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 2","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146217321","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}
Amir Rudich, Idan Carmon, Daniel Voignac, Shylee Belsey, Ido Simon, Alexander Greenberg, Nardi Caspi, Mona Dvir-Ginzberg, Oded Shoseyov
{"title":"Porous Nanocellulose-Reinforced Polyacrylamide Hybrid Hydrogels for Tissue Engineering","authors":"Amir Rudich, Idan Carmon, Daniel Voignac, Shylee Belsey, Ido Simon, Alexander Greenberg, Nardi Caspi, Mona Dvir-Ginzberg, Oded Shoseyov","doi":"10.1002/ijch.70006","DOIUrl":"https://doi.org/10.1002/ijch.70006","url":null,"abstract":"<p>Hydrogels emerge as promising scaffolds in tissue engineering due to their high water content and tunable mechanical and structural properties. However, balancing biocompatibility with mechanical strength remains a key challenge, especially when introducing porosity, which is crucial for cell population of the scaffold structure, subsequent proliferation and efficient mass transfer of nutrients and waste. Herein, a macroporous hydrogel scaffold composed of polyacrylamide (PAAM) and nanocellulose is presented, in which porosity is introduced via CO<sup>2</sup> generation from sodium bicarbonate decomposition during polymerization. This approach enables tunable pore architecture with minimal compromise to structural integrity, maintaining high resilience under mechanical deformation. Building on prior work demonstrating enhanced mechanical performance and cytocompatibility through nanocellulose reinforcement, this hydrogel system is now explored for cartilage tissue engineering. In vitro studies with human chondrocytes demonstrate enhanced cell adhesion, proliferation, and infiltration in scaffolds with intermediate porosity (≈300 μm), correlating with improved swelling dynamics. The hydrogel's resilience, tunable porosity, and cytocompatibility suggest its strong potential as a customizable scaffold for regenerating load-bearing, extracellular matrix-rich tissues such as cartilage.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 2","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.70006","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146176443","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":"Recent Discovery on Metal-Free Construction of S-Aryl Phosphorothioate Diesters","authors":"Jayshree Nandkumar Solanke, Savita Gat, Rambabu Dandela, Vasudevan Dhayalan","doi":"10.1002/ijch.70008","DOIUrl":"10.1002/ijch.70008","url":null,"abstract":"<p>Recent innovations in metal-free phosphorothioate synthesis have underscored increased utility as a sustainable alternative to metal-catalyzed procedures. Green approaches, such as metal-free coupling reactions and oxidations, radical-induced methods, electrochemical processes, and multicomponent reactions, were reported from 2020 to 2025 for the successful development of S-aryl phosphorothioates and S-heterocyclic phosphorothioates. These methods involve high atom economy, broad functional group tolerance, and mechanistic studies, positioning metal-free phosphorothiolation as an emergent tool of power and sustainability in modern organic synthesis under a green system.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"66 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146155037","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}