RSC AdvancesPub Date : 2025-08-01DOI: 10.1039/D5RA04754D
Mathiyazhagan Sivanantham, Jenis Jacob Stanley, Kesavan Muthu, Sivan Velmathi, Gopal Chandru Senadi and Mohankumar Ramasamy
{"title":"Radical cascade cyclization of amino acid-tethered 1,6-enynones with sulfonyl hydrazides for N-terminal modification: synthesis of functionalized succinimide derivatives†","authors":"Mathiyazhagan Sivanantham, Jenis Jacob Stanley, Kesavan Muthu, Sivan Velmathi, Gopal Chandru Senadi and Mohankumar Ramasamy","doi":"10.1039/D5RA04754D","DOIUrl":"https://doi.org/10.1039/D5RA04754D","url":null,"abstract":"<p >A metal-free strategy for the N-terminal cyclization of amino acids has been developed by synthesizing highly functionalized succinimide derivatives through radical cyclization of amino acid-tethered 1,6-enynones with sulfonyl hydrazide using NIS and H<small><sub>2</sub></small>O<small><sub>2</sub></small> as an oxidant. The notable advantages of this work includes time-efficient, good <em>E</em>/<em>Z</em> ratio, moderate to good yields, and was synthesized on a gram-scale. Furthermore, the synthetic utility of the product <strong>5aa</strong> was performed by (i) Suzuki coupling reaction with iodo-functionality; and (ii) dipeptide formation using glycine methyl ester.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 34","pages":" 27486-27492"},"PeriodicalIF":4.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra04754d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144751139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Celine Nieuwland, Michiel J van Well, Laia Guillaumes, Anna de Vey Mestdagh, Lianne Dekker, Cynthia Nieuweboer, Sílvia Simon, Célia Fonseca Guerra
{"title":"DNA base pairs: the effect of the aromatic ring on the strength of the Watson-Crick hydrogen bonding.","authors":"Celine Nieuwland, Michiel J van Well, Laia Guillaumes, Anna de Vey Mestdagh, Lianne Dekker, Cynthia Nieuweboer, Sílvia Simon, Célia Fonseca Guerra","doi":"10.1039/d5ob00819k","DOIUrl":"https://doi.org/10.1039/d5ob00819k","url":null,"abstract":"<p><p>The aromatic ring in DNA bases affects the Watson-Crick binding strength. Our quantum-chemical analyses, which compare the hydrogen bonding between the DNA bases and unsaturated analogs lacking the aromatic ring, reveal that this arises not from π-resonance assistance but from the electron-withdrawing (purines) or electron-donating (pyrimidines) effect of the heteroatom-containing ring on the frontier atoms. This electron redistribution modulates the electrostatics, steric Pauli repulsion, and σ-orbital interactions upon hydrogen bonding.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144758683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ping Lin, Zezhao Huang, Zeyao Liang, Jiahe Zhang, Li Zhu, Xiaoquan Yao
{"title":"Electrochemical diazenylation of active methylene compounds with aryldiazonium salts: efficient synthesis of β-dicarbonyl benzoylhydrazones.","authors":"Ping Lin, Zezhao Huang, Zeyao Liang, Jiahe Zhang, Li Zhu, Xiaoquan Yao","doi":"10.1039/d5ob01002k","DOIUrl":"https://doi.org/10.1039/d5ob01002k","url":null,"abstract":"<p><p>In this study, an electrochemical synthetic strategy is reported for the diazenylation of various active methylene compounds through their reaction with aryldiazonium salts, leading to the efficient formation of β-dicarbonyl benzoylhydrazones. The reaction efficiency and selectivity are significantly enhanced by the promotion of LiBr, along with the rational selection of electrode materials to effectively suppress the formation of a solid electrolyte interphase (SEI) layer on the electrode surface. The developed methodology exhibits remarkable substrate versatility, accommodating a broad range of substrates including aliphatic, cyclic, and aromatic diketones, as well as malononitrile and malonate derivatives. This work provides a green, cost-effective, and highly efficient approach for the synthesis of valuable benzoylhydrazone derivatives.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144758684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Martin Koall, Eva Pospisilova, Joachim Rewitzer, Thomas Herl, Tatiana V Shishkanova, Frank-Michael Matysik
{"title":"Evaluating possibilities for the determination of novel psychoactive substances in human saliva using capillary electrophoresis with UV detection and mass spectrometry.","authors":"Martin Koall, Eva Pospisilova, Joachim Rewitzer, Thomas Herl, Tatiana V Shishkanova, Frank-Michael Matysik","doi":"10.1039/d5ay00812c","DOIUrl":"https://doi.org/10.1039/d5ay00812c","url":null,"abstract":"<p><p>Novel psychoactive substances are an emerging threat in the field of illegally consumed compounds. The subgroup of synthetic cathinones increased in popularity due to their great variety and the lack of powerful instrumental methods for their efficient monitoring. In the context of detecting drug-related crimes, saliva is a promising sample due to the presence of significant amounts of the respective species and easy and non-invasive accessibility compared to blood or urine samples. Herein, we report two powerful instrumental approaches based on the high separation efficiency and low sample consumption of capillary electrophoresis, combined with commonly used detection principles, namely mass spectrometry and UV detection. Mass spectrometry offers high selectivity and the possibility to identify comigrating analytes but comes with some instrumental challenges and high investment costs, while UV detection provides simple coupling to capillary electrophoresis and cost-efficiency. Moreover, we developed a simple and fast pretreatment protocol for the handling of directly collected human saliva samples for subsequent injection into capillary electrophoretic systems. In this study, we successfully detected butylone and clephedrone, part of the synthetic cathinone family, and 2-aminoindane, which are all listed as psychoactive substances. Furthermore, the methods were characterized in terms of detectability, reproducibility, and limits of detection (6-15 μM). Based on this, an application in the forensic context using CE-UV was simulated for 2-aminoindane and butylone at a concentration of 10 μM (20 μM).</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":2.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144758756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Francisco N Barrera, Aileen Cooney, Niclas Paul Decker, Markus Deserno, Milka Doktorova, Thais A Enoki, Alexander P Fellows, Giacomo Fiorin, Gonen Golani, Daniel Huster, Manpreet Kaur, Ilya Levental, Kandice R Levental, Reinhard Lipowsky, Fabio Lolicato, Erwin London, Joseph H Lorent, Tiemei Lu, Edward Lyman, Jonathan M Machin, Paramita Manna, Shalini Mishra, Luca Monticelli, Walter Nickel, Georg Pabst, John Seddon, Raya Sorkin, Malavika Varma
{"title":"Proteins in asymmetric membranes: general discussion.","authors":"Francisco N Barrera, Aileen Cooney, Niclas Paul Decker, Markus Deserno, Milka Doktorova, Thais A Enoki, Alexander P Fellows, Giacomo Fiorin, Gonen Golani, Daniel Huster, Manpreet Kaur, Ilya Levental, Kandice R Levental, Reinhard Lipowsky, Fabio Lolicato, Erwin London, Joseph H Lorent, Tiemei Lu, Edward Lyman, Jonathan M Machin, Paramita Manna, Shalini Mishra, Luca Monticelli, Walter Nickel, Georg Pabst, John Seddon, Raya Sorkin, Malavika Varma","doi":"10.1039/d5fd90021b","DOIUrl":"https://doi.org/10.1039/d5fd90021b","url":null,"abstract":"","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144758767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
RSC AdvancesPub Date : 2025-08-01DOI: 10.1039/D5RA04076K
Junfeng Chen, Jeff Rao and Adrianus Indrat Aria
{"title":"Combinatorial sputtering of photoluminescent europium titanium oxide thin films†","authors":"Junfeng Chen, Jeff Rao and Adrianus Indrat Aria","doi":"10.1039/D5RA04076K","DOIUrl":"https://doi.org/10.1039/D5RA04076K","url":null,"abstract":"<p >Photoluminescent thin films were fabricated using a combinatorial physical vapour deposition (PVD) sputtering process, enabling rapid variation of europium oxide (Eu<small><sub>2</sub></small>O<small><sub>3</sub></small>) in titanium dioxide (TiO<small><sub>2</sub></small>) with concentrations varying from <em>x</em> = 0–1 in <em>x</em> = Eu/(Eu + Ti). Combinatorial sputtering enables synthesising samples with diverse compositions faster than traditional sol–gel, powder mixing, solvo/hydrothermal, and melt-quench processes. Post-heat treatment at 600 °C produced changes to the phase, structure and optical properties of the thin films. Scanning electron microscopy (SEM) revealed vertically oriented columnar microstructures in samples with concentrations lower than <em>x</em> = 0.5, exhibiting a narrower average columnar width of about 50 nm after annealing at 600 °C. X-ray diffraction (XRD) analysis indicated that TiO<small><sub>2</sub></small> was in the anatase phase while Eu<small><sub>2</sub></small>O<small><sub>3</sub></small> crystallises in a monoclinic structure. The nanocrystalline grain size exhibits noticeable changes after annealing. Fluorescence spectroscopy was used to study the photoluminescence of thin films. The excitation peak at 394 nm (<small><sup>7</sup></small>F<small><sub>0</sub></small> → <small><sup>5</sup></small>L<small><sub>6</sub></small>) measures spectral emissions, with the strongest emission at 613 nm (<small><sup>5</sup></small>D<small><sub>0</sub></small> → <small><sup>7</sup></small>F<small><sub>2</sub></small>).</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 33","pages":" 27415-27428"},"PeriodicalIF":4.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra04076k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144751134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
RSC AdvancesPub Date : 2025-08-01DOI: 10.1039/D5RA03389F
Chunhui Wu, He Zhou, Xiaoling Wu, Huimin Xu, Youshi Zeng, Xinxin Chu and Wei Liu
{"title":"Encapsulation of nanoparticles with Xe adsorption sites into MOFs for enhanced Xe/Kr separation","authors":"Chunhui Wu, He Zhou, Xiaoling Wu, Huimin Xu, Youshi Zeng, Xinxin Chu and Wei Liu","doi":"10.1039/D5RA03389F","DOIUrl":"https://doi.org/10.1039/D5RA03389F","url":null,"abstract":"<p >Xenon (Xe) and krypton (Kr) are important gases with significant industrial and medical applications. Metal–organic frameworks (MOFs) are a promising class of sorbent materials for Xe/Kr separation. To enhance the Xe/Kr separation performance of MOFs, we develop a strategy to encapsulate Pt nanoparticles into MOFs to introduce strong Xe adsorption sites. Xe and Kr adsorption and separation studies show that Pt@UiO-66 exhibits 21% higher Xe uptake capacity and a 7% increase in Xe/Kr selectivity compared to UiO-66 due to the introduced Xe adsorption sites, despite the Brunauer–Emmett–Teller (BET) surface area decreasing. These findings have led to an 88% extension of column breakthrough time during Xe/Kr separation under identical conditions. We further demonstrate that this approach can be extended to other MOFs with potential for Xe/Kr separation.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 34","pages":" 27526-27530"},"PeriodicalIF":4.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra03389f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144751140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
RSC AdvancesPub Date : 2025-08-01DOI: 10.1039/D5RA02649K
Leili Esrafili, Ocean Cheung, Peter Adriaensens, Elien Derveaux, Lawson T. Glasby, Peyman Z. Moghadam and Christophe M. L. Vande Velde
{"title":"Unlocking porosity: structural tuning of urea-based MOFs via reaction parameter control†","authors":"Leili Esrafili, Ocean Cheung, Peter Adriaensens, Elien Derveaux, Lawson T. Glasby, Peyman Z. Moghadam and Christophe M. L. Vande Velde","doi":"10.1039/D5RA02649K","DOIUrl":"https://doi.org/10.1039/D5RA02649K","url":null,"abstract":"<p >In the synthesis of metal–organic frameworks (MOFs), efforts to increase the pore sizes by elongating linkers often result in interpenetration, a challenge that is exacerbated when functional groups are added. Urea groups and their derivatives play an important role in supramolecular chemistry by providing directional hydrogen bonding donor sites and are often considered “privileged groups”. Incorporating these moieties into MOFs allows for their spatial separation, a critical approach to enhancing their functional activity, simultaneously preventing interpenetration, and enlarging the pore size. In this study, we synthesized hydrophilic urea-functionalized MOFs using zinc ions and the ligands 4,4′-(carbonylbis(azanediyl))dibenzoic acid (L1) and 1,3-di(pyridin-4-yl)urea (L2). Different levels of interpenetration and pore size were produced by varying temperature and starting material concentrations. UA-1 and UA-2 displayed 4-fold interpenetration. Notably, UA-3 formed non-interpenetrated 1D hexagonal mesoporous channels with six urea groups around each hexagonal pore, making it the first example of a non-interpenetrated mesoporous urea MOF. This topology differs from existing RCSR representations. We also investigated the host–guest interactions when introducing various organic molecules into UA-3, using a combination of single crystal X-ray diffraction (SCXRD), thermogravimetric analysis (TGA) and solid-state nuclear magnetic resonance (ss-NMR) spectroscopy. SCXRD provided insight into the amount and position of solvent molecules within the channels of the framework.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 34","pages":" 27531-27543"},"PeriodicalIF":4.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra02649k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144751196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Soft MatterPub Date : 2025-08-01DOI: 10.1039/d5sm00338e
Yu Li, Jialin He, Yancong Feng, Guofu Zhou, Yang Zhang, Wei Zhao, Laurens T de Haan
{"title":"Precision engineering of cholesteryl azobenzene dimers: investigating the impact of spacer lengths and terminal groups on photo-responsiveness.","authors":"Yu Li, Jialin He, Yancong Feng, Guofu Zhou, Yang Zhang, Wei Zhao, Laurens T de Haan","doi":"10.1039/d5sm00338e","DOIUrl":"https://doi.org/10.1039/d5sm00338e","url":null,"abstract":"<p><p>The rational molecular engineering of cholesteryl azobenzene dimers provides an effective strategy for designing precisely tunable photo-switchable materials with controllable chiral optical responses. This study systematically explores how spacer length parity and terminal group polarity dictate phase transitions, helical twisting power (HTP) and photoisomerization kinetics of cholesteryl azobenzene dimers, enabling predictive control over their functional performance. A key finding is an odd-even effect of the spacer length, which determines the sign of the helical twisting power change in liquid crystals (LC) upon UV irradiation. Dimers with odd-parity spacers exhibit lower LC compatibility in their <i>cis</i>-conformation, resulting in reduced HTP values. In contrast, even-parity dimers, with their larger molecular aspect ratios, tend to promote the formation of smectic clusters that reversibly assemble and disassemble during photoisomerization, which leads to a higher effective HTP in the <i>cis</i>-conformation. By integrating molecular design with dynamic self-assembly, this study advances the engineering of chiral dopants for cholesteric liquid crystals tailored to adaptive photonic materials and reconfigurable optical systems, underscoring the role of precise molecular modifications in achieving controllable functionality of cholesteryl azobenzene dimers. This is expected to promote the development of photo-responsive LCs with tunable optical properties and practical applications in adaptive photonic technologies.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144758739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
RSC AdvancesPub Date : 2025-08-01DOI: 10.1039/D5RA03301B
Ze Li, Dongfeng Zhang, Hanxun Wang, Haihong Huang, Maosheng Cheng and Hongyi Zhao
{"title":"Mild synthesis of fused polycyclic 1,6-naphthyridin-4-amines and their optical properties","authors":"Ze Li, Dongfeng Zhang, Hanxun Wang, Haihong Huang, Maosheng Cheng and Hongyi Zhao","doi":"10.1039/D5RA03301B","DOIUrl":"https://doi.org/10.1039/D5RA03301B","url":null,"abstract":"<p >A mild and straightforward synthetic route to tri-, tetra-, and pentacyclic 1,6-naphthyridin-4-amines is presented. The protocol involves CF<small><sub>3</sub></small>SO<small><sub>3</sub></small>H- or H<small><sub>2</sub></small>SO<small><sub>4</sub></small>-mediated Friedel–Crafts-type intramolecular cycloaromatisation of 4-(arylamino)nicotinonitriles in which the cyano group acts as a one-carbon synthon. The transformation achieves good to excellent yields and can be performed on a gram scale. Additionally, the exploration of fluorescence properties of these compounds demonstrates their potential application as fluorophores.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 34","pages":" 27551-27557"},"PeriodicalIF":4.6,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra03301b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144758497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}