Derek P Gates, Tian Zhang, Kurt F Hoffmann, Brian O Patrick
{"title":"Models for the Anionic Polymerization of P=C Bonds: Cyclization of n-BuLi-Initiated MesP=CPh2 and Related Phosphaalkenes with H2C=CPh2.","authors":"Derek P Gates, Tian Zhang, Kurt F Hoffmann, Brian O Patrick","doi":"10.1002/chem.202500389","DOIUrl":"https://doi.org/10.1002/chem.202500389","url":null,"abstract":"<p><p>To model the first propagation step in the anionic polymerization of MesP=CPh2 we studied the addition of Li[MesP(Bu)-CPh2] (and related species) to nonpolymerizable H2C=CPh2. Addition proceeds via the o-CH3 of the P-Mes followed by unprecedented cyclization to C5P-rings with release of Li[CHPh2]. Further investigation of the aforementioned reaction using phosphalkenes, RP=CAr2 (R = Mes, o-Xyl; R' = Ph, 4-FC6H4, 4-MeC6H4, 4-MeOC6H4), resulted in the observation of a relatively long-lived intermediate in two instances (R = Mes, R' = 4-MeC6H4, 4-MeOC6H4). For the latter, the intermediate was identified as n-BuP(CH(4-MeOC6H4)2)[C6(4,6-Me2)H2-(2-CH2CH2CPh2Li) by isolation of the oxidized, H+-quenched product. These observations provide intriguing clues into the complex mechanism of polymerization of P-Mes phosphaalkenes and the chiral cyclophosphane products are of interest as ligands for catalytic applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500389"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143690585","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Youlong Du, Yeping Bian, Daniel Baecker, Gagan Dhawan, Anas Semghouli, Loránd Kiss, Wei Zhang, Alexander E Sorochinsky, Vadim A Soloshonok, Jianlin Han
{"title":"Fluorine in the Pharmaceutical Industry: FDA-Approved Fluorine-Containing Drugs in 2024.","authors":"Youlong Du, Yeping Bian, Daniel Baecker, Gagan Dhawan, Anas Semghouli, Loránd Kiss, Wei Zhang, Alexander E Sorochinsky, Vadim A Soloshonok, Jianlin Han","doi":"10.1002/chem.202500662","DOIUrl":"https://doi.org/10.1002/chem.202500662","url":null,"abstract":"<p><p>Fluorine has become an essential element in the development of modern pharmaceuticals, due to its unique chemical properties which can significantly enhance the biological activity, metabolic stability, and lipophilicity of drug molecules. This review explores recent advancements in the synthesis and application of fluorine-containing drugs approved by the US Food and Drug Administration (FDA) in 2024. These novel drugs demonstrate improved efficacy and safety profiles, addressing a range of therapeutic areas including oncology, infectious diseases, metabolic disorders and genetic disorders that affect the adrenal glands. The incorporation of fluorine atoms into drug candidates has facilitated the development of molecules with optimized pharmacokinetic and pharmacodynamic properties, leading to better patient outcomes. The review further discusses the synthetic methodologies employed, the structural characteristics of these drugs, and their clinical implications, providing insights into the ongoing innovation within the pharmaceutical industry driven by fluorine chemistry.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500662"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ludovic Jean, Aurélie Gernet, Louise-Marie Balivet, Ahmed El Rhaz, Lucas Pagès, Guillaume Laurent, François Maurel
{"title":"Synthesis and Evaluation of the Photochemical Properties of Heterocyclic Hemiindigos.","authors":"Ludovic Jean, Aurélie Gernet, Louise-Marie Balivet, Ahmed El Rhaz, Lucas Pagès, Guillaume Laurent, François Maurel","doi":"10.1002/chem.202500803","DOIUrl":"https://doi.org/10.1002/chem.202500803","url":null,"abstract":"<p><p>This study reports a series of novel heterocyclic hemiindigos (Het-HI) synthesised via the condensation of indoxyl acetate with various heteroaromatic aldehydes. The influence of electron-rich and electron-poor heterocycles on the photochemical and photophysical properties of these compounds have been investigated. Our findings reveal that several Het-HIs exhibit noteworthy photoswitching behaviour, including enhanced absorption at the visible region. Notably, certain derivatives respond efficiently to green and red light, achieving good conversions to the metastable E-isomer and displaying prolonged half-lives of up to 53 days in a polar solvent. The results highlight the potential of these photoswitches for applications in molecular devices and responsive materials.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500803"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143668560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Riho Wakino, Mai Suzuki, Yoshiaki Miyamoto, Masashi Yatomi, Takamichi Matsuno, Atsushi Shimojima
{"title":"Interlayer Modification of Crystalline Layered Silicates with Oligodimethylsiloxane.","authors":"Riho Wakino, Mai Suzuki, Yoshiaki Miyamoto, Masashi Yatomi, Takamichi Matsuno, Atsushi Shimojima","doi":"10.1002/chem.202500262","DOIUrl":"https://doi.org/10.1002/chem.202500262","url":null,"abstract":"<p><p>Crystalline layered silicates are valuable precursors for the synthesis of functional siloxane-based nanomaterials. In this study, vinyl-terminated oligodimethylsiloxane was grafted onto the interlayer surfaces of a crystalline layered silicate, octosilicate. The oligosiloxane modification facilitated the delamination of the layers in hydrophobic organic solvents. Hydrosilylation reactions between the silylated nanosheets and SiH-terminated polydimethylsiloxane (PDMS) resulted in a clear, stretchable elastomer, demonstrating that the nanosheets acted as cross-linkers. Furthermore, the introduction of silanolate groups into the elastomer imparted self-healing properties. These findings expand the potential of crystalline layered silicates as nanobuilding blocks for new materials.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500262"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Organic electrode material based on tris-imidazole ring containing triphenylamine (donor)-anthraquinone (acceptor) for high performance pseudocapacitors.","authors":"Sudhir D Jagadale, Sidhanath Vishwanath Bhosale","doi":"10.1002/chem.202500723","DOIUrl":"https://doi.org/10.1002/chem.202500723","url":null,"abstract":"<p><p>To meet the challenges of the energy sector adaptation of novel electrode materials is urgently needed. Pseudocapacitors are electrochemical energy storage devices and are utilized to fulfill the growing demand of the society. In this connection, donor-acceptor commands are attractive alternatives to inorganic materials die to their optoelectronic properties. Herein, a triphenylamine-anthraquinone based donor-acceptor chromophore was developed in electrode materials. As prepared electrode materials based on TPA-IM-AQ on graphite foil (GF) are employed to fabricate a three-electrode supercapacitor (SC) device in 1M H2SO4 electrolyte. At 0.5 A g-1 current density TPA-IM-AQ electrodes based SC can deliver higher specific capacitance (Csp) of 275.72 F g-1 at 0.5 A g-1 current density and at 5 mV s-1 scan rate with Csp of 233.63 F g-1. Moreover, two-electrode symmetric supercapacitor (SSC) exhibited Csp of 91.63 F g-1 at 0.5 A g-1 with energy density as high as 16.49 Wh kg-1 at a power density of 1079.96 W kg-1. The TPA-IM-AQ/GF based device exhibits good Csp retention with 88.40% after 5000 cycles at 3 A g-1. As-fabricated TPA-Im-AQ/GF electrode demonstrated the advantages of utilizing small organic molecule to achieve wider operational potential window and higher specific capacitance.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500723"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alessandro Marson, Alberto Benozzi, Alessandro Manzardo
{"title":"Looking to the Future: Prospective Life Cycle Assessment of Emerging Technologies.","authors":"Alessandro Marson, Alberto Benozzi, Alessandro Manzardo","doi":"10.1002/chem.202500304","DOIUrl":"https://doi.org/10.1002/chem.202500304","url":null,"abstract":"<p><p>Emerging technologies are expected to contribute to sustainable development, but assessing their future environmental impacts compared to current technologies remains challenging. Prospective Life Cycle Assessment (pLCA) provides a systematic approach to evaluating emerging technologies throughout their life cycle and projecting impacts at future industrial scales. This review aims to identify critical aspects of pLCA methodologies and examine their implementation in recent case studies. Key aspects are highlighted: assessment of initial technology maturity, upscaling methods to model data at higher technology readiness levels, and development of future scenarios to contextualize the scaled-up systems. Specific upscaling techniques such as process simulation, engineering calculations and technology learning curves are discussed. Approaches to generating future scenarios in line with integrated assessment models and common socio-economic pathways are also analyzed. An in-depth literature review covering 2021-2024 publications categorizes 79 articles into literature reviews, methodological papers and pLCA case studies. The identified critical issues serve as a benchmark to assess the completeness and robustness of 20 case studies. Notable contributions, limitations and the need for comprehensive guidelines that integrate scenario development with upscaling methods are highlighted. This review provides valuable insights for researchers conducting pLCA studies of emerging technologies and materials.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500304"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661688","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xin Zheng, Gang Wang, Lijie Liu, Xiaochuan Li, Puhui Xie, Yongchao Fan, Zhanqi Cao, Caoyuan Niu, Dongjie Tian, Lixia Xie
{"title":"Hydrogen Bonding-Induced Multicolor and Thermochromic Emissions of Triphenylamines.","authors":"Xin Zheng, Gang Wang, Lijie Liu, Xiaochuan Li, Puhui Xie, Yongchao Fan, Zhanqi Cao, Caoyuan Niu, Dongjie Tian, Lixia Xie","doi":"10.1002/chem.202500643","DOIUrl":"10.1002/chem.202500643","url":null,"abstract":"<p><p>The fluorescence tuning of stimuli-responsive materials is crucial but challenging. The deep understanding of thermal induced fluorescence change, however, has rarely been conducted. Herein, the thermochromic emission of a triphenylamine (TPA) derivative (1), with one acetyl and two 1-hydroxy-1-methylethyl units on each o-phenyl group around the nitrogen atom, has been investigated. Upon heating, the bright blue-emitting solid 1 turns to a strong green-emitting liquid. Moreover, 1 is green emissive in ethanol but blue emissive with high absolute quantum yields in dimethyl sulfoxide (DMSO). Another TPA derivative (2) is green emitting. X-ray crystallography studies reveal that the strong solid-state fluorescence arises from a rigid pyramidal structure around central nitrogen of 1, due to the OH•••OH, OH•••O = C hydrogen bonding interactions. Comparatively, 2 has a planar configuration of three C─N bonds around central nitrogen atom. This work will provide a new route for constructing multiemission materials using unimolecular platforms.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500643"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tadeu Luiz Gomes Cabral, João Pedro Brussolo da Silva, Claudio Francisco Tormena, Matthias Stein
{"title":"Molecular Recognition and Chiral Discrimination from NMR and Multi-Scale Simulations.","authors":"Tadeu Luiz Gomes Cabral, João Pedro Brussolo da Silva, Claudio Francisco Tormena, Matthias Stein","doi":"10.1002/chem.202404694","DOIUrl":"10.1002/chem.202404694","url":null,"abstract":"<p><p>Chiral molecules are particularly interesting to the pharmaceutical and agrochemical sectors due to their chemical and physical properties. Separation and identification of enantiomers are critical for a broad range of compounds, and discriminating stereoisomers in solution remains a key analytical challenge. Nuclear Magnetic Resonance (NMR) with Matrix-Assisted Diffusion-Ordered Spectroscopy (MAD), in the presence of chiral resolving agents, has emerged as a tool to explore these chiral mixtures. However, insight into the intermolecular interactions that lead to chiral recognition is still limited. Here, we combine experimental MAD studies with computational approaches to investigate the enantioselective discrimination of Mandelic Acid (MA) enantiomers using (R)-BINOL and (S)-BINOL. Molecular dynamics simulations explain the differences in diffusion coefficients for heterochiral complexes. Furthermore, quantum mechanical calculations confirmed enantioselective binding preferences due to differences in Gibbs free energies, highlighting the fundamental interactions and structural criteria that explain the NMR shielding and the diffusion trends. This integrated approach bridges experimental and theoretical studies, offering a comprehensive understanding of chiral recognition mechanisms and elucidating the observed heterochiral preference of BINOL for MA enantiomers. Our findings advance the field of chiral analysis and lay a foundation for future developments for identifying stereoisomers and recognition modes underlying enantioselective binding.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404694"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Slight-Crosslinking: Opening a New Journey for the Intrinsic Elastification of Ferroelectric Polymers.","authors":"Qiuyue Hu, Linping Wang, Liang Pan, Ben-Lin Hu","doi":"10.1002/chem.202500247","DOIUrl":"10.1002/chem.202500247","url":null,"abstract":"<p><p>Elastic electronic materials are essential components in the next generation of wearable devices and soft robots. However, the development of elastic ferroelectric materials has lagged behind that of conductive and semiconductive materials. The successful realization of intrinsically elastic ferroelectrics through slight-crosslinking has opened a new path for making ferroelectric materials elastic. Given the critical need for materials that combine excellent elasticity with robust ferroelectric properties in the field of elastic electronics, we explore various crosslinking techniques and their performance characteristics. We believe that this cutting-edge research direction holds substantial value for both fundamental studies and practical applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500247"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Front Cover: Transitioning to Green Discovery-Based Catalysis (Chem. Eur. J. 17/2025)","authors":"Prof. Dr. Rory Waterman","doi":"10.1002/chem.202581701","DOIUrl":"https://doi.org/10.1002/chem.202581701","url":null,"abstract":"<p><b>Little changes can make a big difference</b>. While little monsters can run amuck, they can make good choices as well. Much like the choices we make in our chemistry, our decisions on how we engage in fundamental catalysis research can not only lead to problem-solving outcomes, but these discoveries can be made in ways that protect people and the planet. More information can be found in the Concept by R. Waterman (DOI: 10.1002/chem.202404602). Artwork by Audrey Mundell.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581701","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}