{"title":"A Base-Mediated Rearrangement of the Benzylic 1,5-Hexadipyridynyl Moiety.","authors":"Wouter A Remmerswaal, Thai-Tony Nguyen, Zijian Han, Fedor Krasovski Slobodian, Ruisheng Xiong, Vadim Kessler, Zhijian Xu, Weiliang Zhu, Mate Erdelyi","doi":"10.1002/cplu.202500252","DOIUrl":"10.1002/cplu.202500252","url":null,"abstract":"<p><p>A previously unrecognized base-mediated rearrangement of a benzylic 1,5-hexadipyridynyl moiety is reported. Upon exposure to base, this structural motif rearranges into a constrained vinyl-pyridine substituted cyclobutene. Computational modeling indicates that the rearrangement takes place following a route involving stepwise deprotonation, shifted reprotonation, and 4π-electrocyclization. The reaction rate and the stereochemical outcome is consistent with the experimental observations. Furthermore, nonbase mediates rearrangements, through well-known Cope-like [3,3]-sigmatropic shifts, are found to be high in energy, and therefore, take a backseat to the base-mediated pathway. This rearrangement may provide a novel reactivity pathway of conjugated systems for synthetic methodology development.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500252"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558620","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}
ChemPlusChemPub Date : 2025-07-02DOI: 10.1002/cplu.202500409
Krishnan Kartha Kalathil, Sudheeshma Satheesan, Anjali K Gopalakrishnan, Deepak D Prabhu
{"title":"Progress in precision synthesis of supramolecular copolymers.","authors":"Krishnan Kartha Kalathil, Sudheeshma Satheesan, Anjali K Gopalakrishnan, Deepak D Prabhu","doi":"10.1002/cplu.202500409","DOIUrl":"https://doi.org/10.1002/cplu.202500409","url":null,"abstract":"<p><p>Supramolecular copolymerization has emerged as a promising tool to organize multiple components in solution. Theoretically, mixing more than one component in solution can lead to different architectures, such as narcissistic, social, blocky, and random. However, controlling the formation of a specific copolymer structure during supramolecular copolymerization remains elusive, owing to the dynamic and reversible nature of non-covalent interactions between the constituent monomers, which facilitate rapid monomer exchange and reorganization in solution. Recent breakthroughs in the synthesis of supramolecular polymers have provided detailed mechanistic insights into supramolecular polymerization, enabling precise control over the size and morphology of the resulting assemblies. Leveraging these mechanistic insights, several attempts have been made to control supramolecular copolymerization. Rational molecular design strategies have been employed to achieve the exclusive synthesis of social and narcissistic copolymers. Conversely, tuning the subtle interplay between homo- and hetero-recognition of structurally matched monomers enabled the selective formation of block copolymers. In this review, we provide an overview of rational design principles and synthetic strategies enabling the precision synthesis of supramolecular copolymers.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500409"},"PeriodicalIF":3.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144551510","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}
ChemPlusChemPub Date : 2025-07-02DOI: 10.1002/cplu.202400694
Simona Klempová, Petra Urbanová, Lucia Mencáková, Katarína Kučíková, Katarína Vizárová
{"title":"The Cross-Infectious Degradation of Plasticized Poly (Vinyl Chloride) and Cellulosic Materials.","authors":"Simona Klempová, Petra Urbanová, Lucia Mencáková, Katarína Kučíková, Katarína Vizárová","doi":"10.1002/cplu.202400694","DOIUrl":"10.1002/cplu.202400694","url":null,"abstract":"<p><p>Plasticized poly (vinyl chloride) (PVC-P), widely used in the 20th century, poses significant risks to numerous artifacts preserved in cultural heritage institutions due to the release of hydrochloric acid (HCl) and plasticizers. While previous studies have examined the impact of PVC-P emissions on cellulose, this study is the first to investigate cross-infectious degradation in systems where PVC-P is in direct contact with cellulosic materials. The interaction between PVC-P and two types of cellulosic materials-pure cellulose paper (Whatman paper) and lignin-containing acidic paper (NOVO paper)-under accelerated aging at 90 °C is examined. In PVC-P, direct contact with the cellulosic material lead to the migration of both the plasticizer and the thermal stabilizer. Dehydrochlorination of PVC-P under these conditions generates enough hydrogen chloride (HCl) to accelerate cellulose depolymerization, followed by a faster decline in surface pH. This study shows that cellulosic materials can destabilize PVC-P while also undergoing degradation as a result of this interaction. In the case of more heterogeneous cellulosic materials, this interaction can lead to uneven degradation of the PVC-P.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202400694"},"PeriodicalIF":2.8,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144537557","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}
ChemPlusChemPub Date : 2025-06-30DOI: 10.1002/cplu.202500311
Diana L Nossa González, Jovanny A Gómez Castaño, Aamer Saeed, Gustavo A Echeverria, Oscar E Piro, Yanina A Lamberti, Mauricio F Erben
{"title":"Structural and Conformational Analysis and Biological Activity of Adamantyl-Based Acyl-Thioureas Bearing Trihalophenyl Substituents.","authors":"Diana L Nossa González, Jovanny A Gómez Castaño, Aamer Saeed, Gustavo A Echeverria, Oscar E Piro, Yanina A Lamberti, Mauricio F Erben","doi":"10.1002/cplu.202500311","DOIUrl":"10.1002/cplu.202500311","url":null,"abstract":"<p><p>A series of six closely related acyl thiourea derivatives featuring adamantyl/noradamantyl groups at the 1-acyl position and 3-trihalophenyl substituents at the thiourea moiety are comprehensively characterized through spectroscopic, computational, and X-ray crystallographic methods. Vibrational spectroscopy (IR and Raman) reveals significant redshifts in the NH and CO stretching bands, confirming the presence of strong intramolecular NH···OC hydrogen bonds. Conformational analysis using molecular mechanics and DFT calculations identifies several conformers, with the most stable adopting an S-shaped geometry where the CO and CS bonds are oppositely oriented-a configuration that was experimentally validated by single-crystal X-ray diffraction. In the solid state, crystal packing is governed by hydrogen-bonding interactions (H···OC and H···SC) facilitated by the acyl-thiourea core. The bulky adamantyl/noradamantyl groups impose steric constraints, whereas the halogenated phenyl rings promote stabilizing π-stacking and halogen interactions. Biological evaluation demonstrates limited antimicrobial activity against Escherichia coli, Pseudomonas aeruginosa, Burkholderia cenocepacia, and Staphylococcus aureus, but moderate cytotoxicity against A549, 16HBE14o-, and HaCaT cell lines (IC<sub>50</sub> = 25-100 μM).</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500311"},"PeriodicalIF":3.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525692","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}
ChemPlusChemPub Date : 2025-06-29DOI: 10.1002/cplu.202500208
Yaron Cohen, Sumesh Sadhujan, Sonal Rajput, Yakov Shitrit, Olga Iliashevsky
{"title":"Deposition of Tin Catalysts from Thiolated Precursor Organic Solutions for CO2 Reduction to Formate: A Potential-Dependent Mechanism Study.","authors":"Yaron Cohen, Sumesh Sadhujan, Sonal Rajput, Yakov Shitrit, Olga Iliashevsky","doi":"10.1002/cplu.202500208","DOIUrl":"https://doi.org/10.1002/cplu.202500208","url":null,"abstract":"<p><p>The production of efficient catalysts is mandatory to attain superior catalytic performance. Once the catalyst deposition mechanism is clear, one can define the optimal physical and chemical conditions of the deposition process, such as electrolyte composition, reduction potential, current operation mode, result chemical composition of the catalyst, its structure and morphology. Here, we investigate the electrodeposition mechanism of tin catalysts in dimethyformamide of a thiolated tin complex under potential control for CO2 reduction to formate. First, a new synthesis route is presented for a tin thiolate precursor, Bis(1,2-ethanedihiolate)Sn(IV). Second, a potential-controlled deposition process of tin from dimethylformamide solutions of this precursor is discussed, with the intention to deposition of tin catalysts on acid-sensitive substrates, such as carbon-composed gas-diffusion-layers. We expose with scan-rate cyclic-voltammetry, scan-rate mass-potential and chronoamperometry measurements irregular current-potential and mass change phenomena along electrodeposition, which reflect a complicated potential-dependent mechanism composed of redox and chemical reactions. Disproportionation and comproportionation reactions of tin are indicated by the holistic picture of the potential and time -dependent mass measurements and complementary structure and morphology analysis and are suggested to have an important role in the deposition mechanism of tin. The complex mechanism is untied and the deposition conditions are defined accordingly.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500208"},"PeriodicalIF":3.0,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525691","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}
ChemPlusChemPub Date : 2025-06-27DOI: 10.1002/cplu.202500287
Evgeniy A Kvetkin, Yelizaveta A Morkhova, Andrey V Sokolov
{"title":"A Mild Recyclable Metal Organic Framework-Based Brominating Agent Br<sub>2</sub>@CAU-10-PDC with HBr Trapping Function.","authors":"Evgeniy A Kvetkin, Yelizaveta A Morkhova, Andrey V Sokolov","doi":"10.1002/cplu.202500287","DOIUrl":"10.1002/cplu.202500287","url":null,"abstract":"<p><p>A wide range of brominating agents and heterogeneous brominating systems indicates a demand in the field of organic compounds bromination. A new mild and recyclable metal-organic framework (MOF)-based brominating agent, Br<sub>2</sub>@CAU-10-PDC (CAU = Christian-Albrechts-University), has been synthesized and successfully applied to the bromination of activated aromatics, such as phenols, amines, and amides. Infrared and Raman spectroscopy as well as powder X-ray diffraction are used to characterize the obtained composite. Rietveld refinement of the composite structure has also been performed; as a result, the positions of bromine species associated with pyridine nitrogen and specific interactions with each other have been determined. The agent synthesis and recycling steps are straightforward. The recyclability of the agent is achieved due to the reversible nature of the linker bonding with Br<sub>2</sub> and HBr. This unique feature makes the composite the first, to knowledge, brominating agent that readily traps HBr without losing its properties. The presented composite can become a valuable addition to the group of mild, reusable, and multifunctional brominating agents.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500287"},"PeriodicalIF":3.0,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504289","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}
ChemPlusChemPub Date : 2025-06-27DOI: 10.1002/cplu.202500228
Rawesh Kumar, Dharmesh M Vadodariya, Norah Alwadai, Abdulaziz A M Abahussain, Maher M Alrashed, Mohammed Al-Yusufi, Salwa B Alreshaidan, Naif Alarifi, Ahmed S Al-Fatesh
{"title":"Hydrogen Rich Syngas Production over Ni Catalysts on Mg-stabilized Zirconia through Partial Oxidation of Methane: The Role of Magnesium as Stabilizer for Support & Active Sites.","authors":"Rawesh Kumar, Dharmesh M Vadodariya, Norah Alwadai, Abdulaziz A M Abahussain, Maher M Alrashed, Mohammed Al-Yusufi, Salwa B Alreshaidan, Naif Alarifi, Ahmed S Al-Fatesh","doi":"10.1002/cplu.202500228","DOIUrl":"https://doi.org/10.1002/cplu.202500228","url":null,"abstract":"<p><p>Catalytic conversion of methane in the presence of O2 into hydrogen-rich syngas is known as partial oxidation of methane (POM). Achieving good H2 yield with H2/CO ~3 by using a low amount of Ni-based active sites at a low reaction temperature (~600 °C) through POM remains challenging. Herein, magnesia-stabilized zirconia (MSZ) is prepared by co-precipitation method by varying the amount of Mg from 8-14 mol%. Ni supported over MSZ catalysts are investigated for POM reaction and characterized by diffraction techniques, spectroscopic techniques, surface area-porosity, temperature-programmed reduction-oxidation, and thermogravimetry. The incorporation of magnesium stabilizes both the support and the active sites. Under the oxidizing environment, the strong interaction of NiO surmounts over moderate interaction. Upon incorporation of 14 mol% Mg into ZrO2 (14MSZ), the catalyst attains stable support and the largest surface area where most of the active sites are formed by \"NiO under strong interaction\". 5 wt % Ni dispersed over 14MSZ acquires the highest H2 yield (37%) and H2/CO ~3 at 600 °C and 85% H2 yield with ~2 H2/CO at 750oC. Over 5Ni/14MSZ catalyst, the high reaction temperature restricts indirect pathway of POM by limiting the CO2 yield and ensures high hydrogen yield through direct pathways of POM.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500228"},"PeriodicalIF":3.0,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144511272","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}
ChemPlusChemPub Date : 2025-06-24DOI: 10.1002/cplu.202500330
Manoj Das, Arghyadeep Bhattacharyya
{"title":"Addressing the Aggregation Phenomenon in a Model Aggregation Induced Enhancement of Emission-Coupled Excited State Intramolecular Proton Transfer Active Probe: Correlating Aggregation States to their Photodynamics.","authors":"Manoj Das, Arghyadeep Bhattacharyya","doi":"10.1002/cplu.202500330","DOIUrl":"10.1002/cplu.202500330","url":null,"abstract":"<p><p>We report a comprehensive study on the spectrodynamic behavior of 4-dimethylamino-2'-hydroxychalcone (DMHC) in crystalline state and in aggregated state in water (pH 7.0) by the aid of steady-state and time-resolved spectroscopy. The studies reveal that the excited-state intramolecular proton transfer (ESIPT) process is slow in the crystalline state (τ<sub>ESIPT</sub> = 3.0 ns) with the emission dominated by ESIPT from 600 nm onwards, with little contribution (550-570 nm) from the local emission with lower lifetime of emission (τ<sub>local-emission</sub> = 140 ps). Spectrodynamic studies in the aqueous solution of DMHC shows the emission lifetime values are both lowered in the aqueous solution with emission from aggregates and the solvated DMHC molecules in aqueous solution (τ<sub>local-emission</sub> = 90 ps and τ<sub>ESIPT </sub>= 35 ps and 1.4 ns). It is concluded that DMHC shows ESIPT emission from the J-aggregated forms, whereas in aqueous solutions, the ESIPT emission in water occurs from the H-aggregates. The current report holds importance owing to the detailed spectroscopic dissection of the aggregation phenomenon of a model aggregation induced enhancement of emission (AIE)-coupled ESIPT active molecule and delineates how the spectroscopic behavior of each aggregated form differs in terms of the nature of the aggregates formed (J- and H-aggregates), which shall aid in the understanding and construction of tailor-made AIE active molecules.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500330"},"PeriodicalIF":3.0,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144473464","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":"Fluorescent Detection of Salicylaldehyde Based on Tb-Based Coordination Polymer.","authors":"Shangzai Wu, Xiaolong Gong, Guojian Ren, Linglong Yi, Qi Zhou, Qinhe Pan","doi":"10.1002/cplu.202500179","DOIUrl":"https://doi.org/10.1002/cplu.202500179","url":null,"abstract":"<p><p>Salicylaldehyde, an essential chemical intermediate, is extensively utilized in pharmaceutical and fragrance industries. However, the excessive usage leads to environmental pollution and poses potential risks to human body. Hence, it is urgent to develop the effective sensor for the detection of salicylaldehyde (SAL). Herein, a new terbium(III)-based coordination polymer (HNU-90-Tb) is constructed by the assembly of 4-carboxytriphenylamine (HL) with Tb<sup>3</sup> <sup>+</sup>. Benefiting from the hydrophobic structure of HL, HNU-90-Tb exhibits remarkable stability in aqueous environments and is capable of maintaining structural integrity in pH range of 2-11. Notably, HNU-90-Tb enables quantitative detection of SAL through fluorescence quenching, achieving a low detection limit of 0.07 ppm and a rapid response time of just 30 s. HNU-90-Tb also shows excellent selectivity toward a variety of aldehyde analogs. The detection mechanism can be attributed to the combined inner filter effect and dynamic quenching mechanism.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500179"},"PeriodicalIF":3.0,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323964","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}
ChemPlusChemPub Date : 2025-06-17DOI: 10.1002/cplu.202500320
Li Song, Yili Dai, Xin Zhou, Yan Tan, Zijie Zhou, Xing Zheng, Fei Zhao, Meifang Yang, Houchao Tao
{"title":"Anthracene-Bridged Detergents for Membrane Protein Studies.","authors":"Li Song, Yili Dai, Xin Zhou, Yan Tan, Zijie Zhou, Xing Zheng, Fei Zhao, Meifang Yang, Houchao Tao","doi":"10.1002/cplu.202500320","DOIUrl":"10.1002/cplu.202500320","url":null,"abstract":"<p><p>Detergents are indispensable for membrane protein (MP) research, yet innovative designs are needed to meet the diverse requirements of MPs. Herein, anthracene-bridged detergents (ABDs) are presented, featuring a curved anthracene-based scaffold with a hydrophobic core and hydrophilic exterior. The modular synthesis of ABDs facilitates a systematic exploration of their structure-property relationships. Evaluation across representative G protein-coupled receptors demonstrates superior or comparable stabilization to conventional detergents. Notably, PP-ABD maintains complete homogeneity of A<sub>2A</sub>AR after heat shock and exhibits strong potential for electron microscopy applications. This study establishes ABDs as versatile and effective tools for MP research, offering valuable insights into the rational design of next-generation detergents.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500320"},"PeriodicalIF":3.0,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144309344","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}