Marianna Stampolaki, Abel Cherian Varkey, Evgeny Nimerovsky, Andrei Leonov, Stefan Becker, Loren Andreas
{"title":"Seeing double: the persistent dimer-of-dimers structure of drug resistant influenza A M2.","authors":"Marianna Stampolaki, Abel Cherian Varkey, Evgeny Nimerovsky, Andrei Leonov, Stefan Becker, Loren Andreas","doi":"10.1002/chem.202403129","DOIUrl":"https://doi.org/10.1002/chem.202403129","url":null,"abstract":"<p><p>The currently circulating S31N variant of the M2 proton channel of influenza A is resistant to antiviral drugs. Recently, there has been a growing concern regarding the impact of the lipid environment on the structural features of the S31N variant. The native symmetry of the M2 tetramer remains controversial. Here we show that S31N M2 persists in a dimer-of-dimers structure in different lipid preparations independent of the amount of solvating lipids up to at least 180 lipids per tetramer. NMR spectra clearly detect the characteristic resonances of the dimer-of-dimers of M2 (residues 18-60 or 18-62) reconstituted in lipids. NMR-based distance measurements indicate that two isoleucine residues with upfield shifted alpha carbon resonances, typical of extended conformations, are compatible with a particular side-chain rotameric state and helical backbone geometry. These chemical shifts are therefore compatible with the expected native transmembrane helical fold. Symmetry breaking at the pH sensing H37 residues, detected via peak doubling, is a stable feature of S31N M2 based on the reference strain Udorn/1972(H3N2). By contrast, the spectrum is dramatically altered for Columbia/2014/(H3N2) M2, which differs in sequence in the amphipathic helices. This highlights an allosteric coupling between the amphipathic helices and the pH sensing residues.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403129"},"PeriodicalIF":3.9,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589595","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}
Lei Huang, Chaodong Wang, Zhi Chen, Qianxi Jin, Shengjie Song, Jiadi Zhou, Jianjun Li
{"title":"Photoinduced EDA Complex-Initiated Synthesis of Fluoroalkylated Isoquinolinonediones.","authors":"Lei Huang, Chaodong Wang, Zhi Chen, Qianxi Jin, Shengjie Song, Jiadi Zhou, Jianjun Li","doi":"10.1002/chem.202403286","DOIUrl":"10.1002/chem.202403286","url":null,"abstract":"<p><p>A visible-light-induced radical tandem difluoroalkylation/cyclization to construct CF<sub>2</sub>-containing isoquinolinonedione skeletons with methacryloyl benzamides is developed. Broad substrate scopes are compatible with metal-, oxidant- and photocatalyst-free conditions under room temperature in good-to-excellent yields. Mechanistic analysis revealed that the transformation is initiated by photoinduced electron donor-acceptor (EDA) complexes formation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403286"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581224","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}
Elliott H Denton, Olivera Stepanović, Bill Morandi
{"title":"The Divergent Reactivity of Acid Chlorides Under Transition Metal Catalysis.","authors":"Elliott H Denton, Olivera Stepanović, Bill Morandi","doi":"10.1002/chem.202401852","DOIUrl":"10.1002/chem.202401852","url":null,"abstract":"<p><p>The power and ability of catalysis to build multiple C-C bonds in a single step has had a transformative impact on organic synthesis. While the reactivity of organohalides with metal catalysts is widely appreciated, the related and more intricate reactivity of acid chlorides is less so, despite their use as common reagents in synthesis. Here, we review the transformations of acid chlorides in combination with unsaturated C-C bonds catalyzed by palladium, rhodium, or iridium and provide an outlook for future research opportunities.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202401852"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589610","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}
Ivana Ramírez-Wierzbicki, Luciano Sanchez Merlinsky, German E Pieslinger, Sofía Domínguez, Leonardo D Slep, Luis M Baraldo, Alejandro Cadranel
{"title":"Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models.","authors":"Ivana Ramírez-Wierzbicki, Luciano Sanchez Merlinsky, German E Pieslinger, Sofía Domínguez, Leonardo D Slep, Luis M Baraldo, Alejandro Cadranel","doi":"10.1002/chem.202402700","DOIUrl":"https://doi.org/10.1002/chem.202402700","url":null,"abstract":"<p><p>Visible-light excitation of a family of bimetallic ruthenium polypyridines with the formula [RuII(tpy)(bpy)(𝜇-CN)RuII(py)4L]n+ (RuRuLn+), where L = Cl-, NCS-, DMAP and ACN, was used to prepare photoinduced mixed-valence (PI-MV) MLCT states as models of the photosynthetic reaction center. Ultrafast transient absorption spectroscopy allowed to monitor photoinduced IVCT bands between 6000 and 11000 cm-1. Mulliken spin densities resulting from DFT and (TD)DFT computations revealed the modulation of the charge density distribution depending on the ligand substitution pattern. Results are consistent with PI-MV systems ranging from non-degenerate Class II to degenerate Class III, with electronic couplings between 1000 and 3500 cm-1. These findings guide the control electron localization-delocalization in charge-transfer/charge-separated excited states, like those involved in the photosynthetic reaction center.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202402700"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580910","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":"Sonodynamic Cancer Therapy by Mn(I)-tricarbonyl complexes via Ultrasound-triggered CO release and ROS generation.","authors":"Ashish Kumar Yadav, Virendra Singh, Sagar Acharjee, Sukanta Saha, Samya Banerjee, Arnab Dutta, Biplob Koch, Samya Banerjee","doi":"10.1002/chem.202403454","DOIUrl":"10.1002/chem.202403454","url":null,"abstract":"<p><p>A novel ferrocene conjugated Mn(I)-tricarbonyl complex viz [Mn(Fc-tpy)(CO)3Br] (Mn2) where, Fc-tpy = 4'-ferrocenyl-2,2':6',2''-terpyridine was synthesized and fully characterized along with its non-ferrocene analog [Mn(Ph-tpy)(CO)3 Br] Ph-tpy = 4'-phenyl-2,2':6',2''-terpyridine (Mn1) for ultrasound (US) activated anticancer applications. The X-ray structure of Mn2 confirmed its distorted octahedral geometry. Mn1 and Mn2, for the first time, showed US-triggered release of CO and ROS generation (1O2 and •OH) in an aqueous solution from any Mn(I)-tricarbonyl complexes, indicating its potential for synergetic CO gas therapy and sonodynamic therapy. The above-mentioned in-solution chemistry was successfully translated into in vitro cellular models. These complexes showed unprecedented US-triggered toxicity against T-cell lymphoma and human breast cancer cells (IC50 for Mn2 < 1 μM) while were minimally toxic without US or against normal spleen cells. Mn2 was ca. 12 fold more anticancer active than Mn1, indicating that the ferrocene conjugation augmented the US sensitivity. The apoptotic sonotoxicity of Mn2 was due to US-promoted mitochondrial depolarization via ROS generation and CO release. The apoptosis was triggered by caspase 3 activation. This is the first report of Mn(I)-tricarbonyl-based sonosensitizers for cancer SDT. Overall, this study, for the first time, establishes the effectiveness of 3d metal carbonyls in SDT.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403454"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580877","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}
Panagiota Kalomoiri, Janni S Mortensen, Niels Johan Christensen, Kasper K Sørensen, Hanne Mørck Nielsen, Knud J Jensen, Mikkel B Thygesen
{"title":"Neo-Glycolipid Oximes as Intestinal Permeation Enhancers for Peptide Hormone PYY<sub>3-36</sub>.","authors":"Panagiota Kalomoiri, Janni S Mortensen, Niels Johan Christensen, Kasper K Sørensen, Hanne Mørck Nielsen, Knud J Jensen, Mikkel B Thygesen","doi":"10.1002/chem.202401887","DOIUrl":"10.1002/chem.202401887","url":null,"abstract":"<p><p>Herein, we describe the design and synthesis of 16 neo-glycolipids that are potential permeation enhancers for oral drug delivery of peptide therapeutics. These amphiphilic neo-glycolipids are composed of fatty acids and various carbohydrates (d-glucose, lactose, cellobiose, maltose) via an oxime linker. The ability of the synthesized neo-glycolipids to enhance permeation of fluorescein-labelled dextran (4 kDa) or <sup>3</sup>H-mannitol across intestinal epithelium was investigated in vitro using monolayers of human epithelial Caco-2 cells. Their effects were compared with (pre-)clinically known enhancers as reference compounds; sodium salts of octanoic, decanoic, and dodecanoic acid, and sodium salcaprozate (SNAC). Most neo-glycolipids increased the permeation of the model compounds, proving that neo-glycolipids, which possess vastly different properties from the reference compounds, e. g., in terms of clogD and polar surface area, are effective permeation enhancers. The neo-glycolipid based on decanoic acid and glucose was more potent than related compounds based on disaccharides. Significant differences in solubility and cellular compatibility were found for neo-glyolipids based on different carbohydrates. Finally, neo-glycolipids were evaluated as permeation enhancers for the peptide hormone PYY<sub>3-36</sub>. Glucose- and maltose-derived neo-glycolipids based on decanoic and dodecanoic acid showed promising enhancements in PYY<sub>3-36</sub> permeation in vitro while maintaining good cellular compatibility, relevant for oral delivery of obesity treatments.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202401887"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581222","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}
Qi-Hua Zhao, Yuan-Yuan Guo, Rui-Dong Wang, Xu-Hui Zhao, Hong-Bo Lv, Wei-Ming Wei, Lei Wang, Suo-Shu Zhang, Lin Du
{"title":"Construction and Comparative Research of Two MOFs Proton Conducting Materials Containing Nitro Groups.","authors":"Qi-Hua Zhao, Yuan-Yuan Guo, Rui-Dong Wang, Xu-Hui Zhao, Hong-Bo Lv, Wei-Ming Wei, Lei Wang, Suo-Shu Zhang, Lin Du","doi":"10.1002/chem.202403296","DOIUrl":"https://doi.org/10.1002/chem.202403296","url":null,"abstract":"<p><p>In field of electrochemistry, there has been a growing interest in the potential applications of proton-conducting metal-organic frameworks (MOFs). Therefore, how to design and synthesize MOFs with high proton conductivity is considered crucial. In this study, two examples of nitro-containing Cd-based MOFs, MOF-1 {[Cd3(TIPE)1.5(NO3)5Cl(H2O)2]·17H2O}n and MOF-2 {[Cd(TIPE)0.5(nip)]·10H2O}n (TIPE=1,1,2,2-tetrakis(4-(1H-imidazole-1-yl)phenyl)ethene, H2nip=5-Nitroisophthalic Acid), had been successfully designed and synthesized, and their proton-conducting properties were thoroughly investigated. Notably, both materials displayed peak proton conductivity at 98% RH and 90 °C, exhibiting values of 9.13 × 10-3 and 3.00 × 10-3 S∙cm-1 for MOF-1 and MOF-2, respectively. The plausible proton conduction pathways and mechanisms were elucidated through structural analyses, water vapor adsorption studies, and the determination of activation energy (Ea) values. It was found that the difference in proton conductivity between MOF-1 and MOF-2 was mainly associated with the different water absorption rates of the samples. The uniqueness of this study was that for the first time conducted an in-depth study of the role of nitrate in proton conduction, providing new ideas for designing materials with excellent proton conductivity.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403296"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581210","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}
Anya Mulligan, Greggory Kent, Jiale Zhuang, Arava Zohar, Kaitlin R Albanese, Emily E Morgan, Guang Wu, Anthony K Cheetham, Ram Seshadri
{"title":"Iodide Double Perovskites and the Limits of their Structural Stability.","authors":"Anya Mulligan, Greggory Kent, Jiale Zhuang, Arava Zohar, Kaitlin R Albanese, Emily E Morgan, Guang Wu, Anthony K Cheetham, Ram Seshadri","doi":"10.1002/chem.202404009","DOIUrl":"https://doi.org/10.1002/chem.202404009","url":null,"abstract":"<p><p>While halide double perovskites A2M(I)M(III)X6 have attracted significant attention, examples involving iodides are rare. We examine the limits of the structural stability of iodide double perovskites, presenting the synthesis and single-crystal structures of Cs2NaScI6 and Cs2NaYI6. Bypassing the common expectation that iodides have small band gaps, these compounds display optical gaps of 3.10 eV [M(III) = Sc] and 3.65 eV [M(III) = Y]. Cs2NaScI6 is the only iodide double perovskite to exhibit a cubic crystal structure at room temperature. Density functional theory-based electronic structure calculations help understand the role of competing Cs3M(III)2I9 (3:2:9) phases and provide possible reasons for why iodide double perovskites based around In(III), Sb(III) and Bi(III) cations have proved elusive. We confirm design rules for halide double perovskite based around concepts of the tolerance factor and the radius ratio of the smaller, trivalent ion, but also point to situations such as what is observed for Cs2NaScI6 where a double perovskite can be trapped in a metastable structure.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404009"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589594","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":"Recent Advances in NIR-Switchable Multi-Redox Systems Based on Organic Molecules.","authors":"Takashi Harimoto, Yusuke Ishigaki","doi":"10.1002/chem.202403273","DOIUrl":"https://doi.org/10.1002/chem.202403273","url":null,"abstract":"<p><p>In recent years, near-infrared (NIR) dyes, exhibiting absorption in the NIR region (750-2500 nm), have been applied to various optical applications such as security marking, photovoltaic cells and chemotherapy of deep tissues in vivo. Electrochromic systems capable of switching NIR absorption are attractive from the viewpoint of applications for material and life science, and thus several examples have been reported to date. The development of organic-based materials is needed to reduce the environmental impact and improve biocompatibility, however, the switching of NIR absorption based on redox interconversion is still a challenging issue regarding reversibility and durability during interconversion. To overcome this potential instability, several studies on organic electrochromic systems that allow ON/OFF switching of NIR absorption have been developed in recent years. In this review, we focus on redox-active well-defined small molecules that enable ON/OFF switching of NIR absorption, and present recent studies on their intrinsic electrochemical and spectroscopic properties and/or structural characterization of their charged states. We also address more sophisticated electrochromic systems that can modulate their properties in response to external stimuli such as light, heat, and electric potential.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403273"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581230","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":"Molecular Engineering for High-Performance X-ray Scintillators.","authors":"Min Wang, Guo Qin Xu, Xiaogang Liu","doi":"10.1002/chem.202403772","DOIUrl":"10.1002/chem.202403772","url":null,"abstract":"<p><p>X-ray scintillators, materials that convert high-energy radiation into detectable light in the ultraviolet to visible spectrum, are widely used in industrial and medical applications. Organic and organic-inorganic hybrid systems have emerged as promising alternatives for X-ray detection and imaging due to their mechanical flexibility, lightweight, tunable excited states, and solution processability for large-scale fabrication. However, these systems often suffer from weak X-ray absorption and insufficient exciton utilization, which seriously affects their scintillation performance, limiting their potential for broader application and commercialization. This review highlights recent advances in molecular engineering for developing high-performance X-ray scintillators. It focuses on molecular design principles, such as the heavy atom effect, donor-acceptor/host-guest strategies, hydrogen/halogen bonding, molecular sensitization, and crystal packing, for enhancing scintillation performance. By leveraging these approaches, researchers have made significant strides in improving X-ray scintillation efficiency and advancing the potential of these materials for commercial applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403772"},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581220","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}