Jakob B Wolf, Martin Zühlke, Dominik Weh, Marlene C S Dal Colle, Christian Thoben, Toralf Beitz, Klaus Bienert, Dario Cambié, Eric T Sletten, Martina Delbianco, Stefan Zimmermann, Peter H Seeberger
{"title":"Rapid Stereochemical Analysis of Glycosylations in Flow by Ion Mobility Spectrometry.","authors":"Jakob B Wolf, Martin Zühlke, Dominik Weh, Marlene C S Dal Colle, Christian Thoben, Toralf Beitz, Klaus Bienert, Dario Cambié, Eric T Sletten, Martina Delbianco, Stefan Zimmermann, Peter H Seeberger","doi":"10.1002/chem.202500311","DOIUrl":"10.1002/chem.202500311","url":null,"abstract":"<p><p>Glycans are biologically important molecules that are difficult to synthesize and analyze due to their structural diversity and conformational flexibility. Stereoselective glycosylation reactions are key to achieving high-yielding glycan syntheses. The stereochemical outcome of glycosylations is significantly influenced by factors such as the choice of activator and leaving group systems, solvent type, temperature, concentration, and stoichiometry. We introduce a flow chemistry approach to efficiently screen glycosylation conditions, using minimal material and time to enable a rapid design-make-test-analyze cycle with precise parameter control for reaction optimization. Ion mobility spectrometry provides rapid separation and analysis of crude glycosylation reaction mixtures that requires less method development than liquid chromatography thus making it a valuable tool for optimizing glycosylation reactions.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500311"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661698","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":"Cover Feature: Tetrabutylammonium Chlorite as an Efficient Oxidant for Controlled Oxidation of Sulfides to Sulfoxides (Chem. Eur. J. 17/2025)","authors":"Yuki Itabashi, Shuto Ogata, Yusuke Shimada, Minato Kondo, Nagatoshi Nishiwaki, Tsuyoshi Inoue, Haruyasu Asahara, Kei Ohkubo","doi":"10.1002/chem.202581702","DOIUrl":"https://doi.org/10.1002/chem.202581702","url":null,"abstract":"<p><b>The Cover Features</b> illustrates the selective oxidation of diphenyl sulfide to diphenyl sulfoxide by using tetrabutylammonium chlorite. The background features Arima Onsen, one of oldest hot springs in Japan, renowned for its mineral-rich “golden water”, which contains sulfur. This setting symbolizes our Osaka-based research and the sulfur chemistry underlying this transformation. More information can be found in the Research Article by H. Asahara, K. Ohkubo and co-workers (DOI: 10.1002/chem.202404279).\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.202581702","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688958","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}
Gurusamy Sivakumar, Akkarakkaran Thayyil Muhammed Munthasir, Prof. Dr. Pakkirisamy Thilagar, Prof. Dr. Srinivasan Natarajan
{"title":"Cover Feature: Towards White Light Emission Through Metal-to-Metal Charge Transfer (MMCT) Effect in Bi3+ Activated Ca2YTi2-mZrmGa3O12 (0≤m≤2) Garnets (Chem. Eur. J. 17/2025)","authors":"Gurusamy Sivakumar, Akkarakkaran Thayyil Muhammed Munthasir, Prof. Dr. Pakkirisamy Thilagar, Prof. Dr. Srinivasan Natarajan","doi":"10.1002/chem.202581703","DOIUrl":"https://doi.org/10.1002/chem.202581703","url":null,"abstract":"<p><b>The emission behaviour</b> of Bi<sup>3+</sup> was explored in two different hosts, Ca<sub>2</sub>YTi<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub> (<b>CYT:Bi</b>) and Ca<sub>2</sub>YZr<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub>: Bi<sup>3+</sup> (<b>CYTZ:Bi</b>). A broad emission in the yellow–orange region in the former with a maximum at 552 nm was attributed to Bi<sup>3+</sup>–Ti<sup>4+</sup> MMCT transitions. In the latter, the Bi<sup>3+</sup> ions were found to emit in the violet region (<i>λ</i><sub>em</sub>=395 nm) due to the <sup>3</sup>P<sub>0,1</sub>→<sup>1</sup>S<sub>0</sub> transition. After suitable modification, the compounds <b>CYT:Bi</b> and <b>CYTZ:Bi</b> emit white light. More information can be found in the Research Article by P. Thilagar, S. Natarajan and co-workers (DOI: 10.1002/chem.202404016).\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.202581703","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688959","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}
Dylan J Abrams, Mathew R Johnson, Caitlin R Lacker, Tehshik P Yoon, Joseph R Martinelli, Shannon S Stahl
{"title":"Mediated Electrochemical Oxidation of Nucleosides to Their 5'-Carboxylic Acid Derivatives.","authors":"Dylan J Abrams, Mathew R Johnson, Caitlin R Lacker, Tehshik P Yoon, Joseph R Martinelli, Shannon S Stahl","doi":"10.1002/chem.202500713","DOIUrl":"https://doi.org/10.1002/chem.202500713","url":null,"abstract":"<p><p>Nucleoside 5'-carboxylic acids are important synthetic targets, but most existing methods to access these compounds use (super)stoichiometric chemical oxidants to oxidize the primary alcohol. The present study introduces an aminoxyl-mediated electrochemical method for oxidation of nucleosides and ribosugars to afford their 5'-carboxylic acid derivatives. The optimized conditions employ 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl (ACT) as the aminoxyl mediator in a water/acetonitrile solvent mixture with tetraethylammonium bicarbonate or monohydrogen phosphate as a base within an undivided electrolysis cell. The reaction tolerates diverse functionality at the nucleobase and sugar positions and is showcased in the oxidation of 10 different substrates, including a 10 g-scale oxidation of 2'-O-methylcytidine.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500713"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143668555","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}
Simon Sengupta, Maximillian Broek, Phil Köhler, Matthias Westerhausen
{"title":"Synthesis of Heteroleptic Amidinato Calcium Halides via the In-Situ Grignard Addition Method (iGAM) Complementing the Metalation of Amidines.","authors":"Simon Sengupta, Maximillian Broek, Phil Köhler, Matthias Westerhausen","doi":"10.1002/chem.202500210","DOIUrl":"10.1002/chem.202500210","url":null,"abstract":"<p><p>The in-situ Grignard addition method adds intermediately prepared organo alkaline-earth metal halides onto a suitable substrate. Here, freshly rasped calcium and the carbodiimide R'─N═C═N─R' (R' = SiMe<sub>3</sub>, iPr) are suspended in THF at room temperature and then an organyl halide R─X (X = Br, I) is added. Within several hours, intermediately formed R─Ca─X adds onto the carbodiimide yielding the corresponding thf adducts of the amidinato calcium halide {(R'N)<sub>2</sub>C─R}CaX. Suitable organyl halides besides aryl iodide are methyl and ethyl halide whereas bulkier isopropyl and tert-butyl iodides give very low yields.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500210"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661702","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}
Nidal Saleh, Valerio Zullo, Estefanía Sucre-Rosales, Lorenzo Arrico, Francesco Zinna, Gennaro Pescitelli, Céline Besnard, Eric Vauthey, Jérôme Lacour
{"title":"Tethered Enantiopure Boramidines for Advanced Chiroptical Studies.","authors":"Nidal Saleh, Valerio Zullo, Estefanía Sucre-Rosales, Lorenzo Arrico, Francesco Zinna, Gennaro Pescitelli, Céline Besnard, Eric Vauthey, Jérôme Lacour","doi":"10.1002/chem.202500490","DOIUrl":"10.1002/chem.202500490","url":null,"abstract":"<p><p>Boramidines are promising chromophores capable of circularly polarized luminescence (CPL). The synthesis, characterization, and photophysical analysis of novel BINOL- and H8-BINOL-tethered boramidines 1 and 2 are reported, leveraging the chiral perturbation strategy for CPL material design. These enantiopure compounds, prepared in a concise three-step synthesis, exhibit high fluorescence quantum yields ϕ (up to 95% in N₂-saturated solutions) and luminescence dissymmetry factors (|g<sub>lum</sub>| ∼ 10<sup>-</sup> <sup>3</sup>). Transient absorption spectroscopy and quantum-chemical calculations provide insight into their singlet-triplet spin-orbit coupling and intersystem crossing mechanisms.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500490"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143655635","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":"Chiral Porous Organic Polymers (CPOPs): Design, Synthesis and Applications in Asymmetric Catalysis.","authors":"Keshaba Nanda Parida, Chetna Yadav, Swati Jindal, Parag Tamuly, Yashwant D Vankar, Jarugu Narasimha Moorthy","doi":"10.1002/chem.202404525","DOIUrl":"https://doi.org/10.1002/chem.202404525","url":null,"abstract":"<p><p>Since the recognition of the area of asymmetric synthesis in 2000, there has been a tremendous focus on the development of heterogeneous catalysts for asymmetric synthesis. Porous organic polymers (POPs) have emerged in recent years as inextricable materials of high physicochemical and hydrolytic stabilities, permitting infinite possibilities to modulate and tune reactivity, engineer porosity, regulate spatial environments and pore attributes, and manoeuver material transport. With a diligent design of building blocks and the exploitation of organic reactions judiciously, the synthesis of POPs with BET surface areas of the order of a few thousand cm3/g has been demonstrated. The incorporation of reactive functional groups and chiral centres into the porous matrices of polymers offers opportunities to conduct asymmetric synthesis. Very high enantioselectivities of the order of 99% ee have been exemplified in the reactions mediated by chiral POPs (CPOPs). The design-driven tunability of POPs allows the development of catalytic materials for targeted applications in a tailor-made fashion. This review, while placing the development of chiral materials for asymmetric synthesis in the right perspective, delves into different design principles to pave the way for continued research on futuristic CPOP materials by a creative design, limited by one's imagination, for heretofore unprecedented results.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404525"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661684","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}
Zhenqiang Xia, Dasharath Kondhare, Sushma Deshmukh, Somnath Chandankar, Peter Leonard
{"title":"Bioorthogonal Functionalization in the Minor Groove of DNA: Inverse-Electron Demand Diels Alder Reactions with Cyclopropenyl and Heptenoyl Protected 2-Amino-2'-deoxyadenosine as Target Site.","authors":"Zhenqiang Xia, Dasharath Kondhare, Sushma Deshmukh, Somnath Chandankar, Peter Leonard","doi":"10.1002/chem.202500529","DOIUrl":"https://doi.org/10.1002/chem.202500529","url":null,"abstract":"<p><p>Bioorthogonal functionalization in the minor groove of DNA with protected 2-amino-2'-deoxyadenosine (2-amino-dA, 1) as target site is described. Cyclopropene and heptene as part of 2-aminoacyl protecting groups served as dienophiles in inverse-electron demand Diels-Alder (iEDDA) reactions with 3,6-dipyridyl-1,2,4,5-tetrazine as diene. For the purpose, bis-protection of 1 with cyclopropenyl and heptenoyl groups was conducted. Selective removal of the 6-amino protecting groups gave mono-protected 1. 2-Amino-dA pyridazine conjugates were accessed by iEDDA cycloaddition with tetrazine. Second order rate constants disclosed faster reaction kinetics for cyclopropenyl than for heptenoyl 2-amino-dA. To access protected oligonucleotides, phosphoramidites prepared from bis-protected 2-amino-dA were used in standard solid-phase synthesis. 2-Amino protecting groups were retained using mild deprotection conditions. Hybridization experiments disclosed increased duplex stability when protected 2-amino-dA-dT pairs replaced 1-dT pairs. Mismatch discrimination of cyclopropenyl and heptenoyl 2-amino-dA was superior to 2-amino-dA. iEDDA reactions on protected oligonucleotides furnished oligonucleotide pyridazine conjugates. In base pairs with dT, 2-amino-dA pyridazine conjugates connected by a short rigid cyclopropenyl ring led to reduced thermal stability, whereas pyridazine conjugates attached by a long flexible linker retained duplex stability. The findings of this investigation pave the way for functionalization and labelling in the minor groove of DNA using copper free iEDDA cycloaddition.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500529"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661682","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}
Mengtian Lu, Tianye Zhang, Yue Yang, Xin Lin, Jin Huang, Yuan Sun, Tiedong Sun
{"title":"MXene Loaded with Cu(2-x)Se Nanozyme for Nanocatalytic Tumor Therapy.","authors":"Mengtian Lu, Tianye Zhang, Yue Yang, Xin Lin, Jin Huang, Yuan Sun, Tiedong Sun","doi":"10.1002/chem.202500574","DOIUrl":"https://doi.org/10.1002/chem.202500574","url":null,"abstract":"<p><p>Traditional tumor treatments have certain limitations which have serious negative effects, such as the difficulty in cutting out tumors, the damage to normal tissues, and complications. Ordinary nanozymes generally have low catalytic activity and require higher doses for treatment, which can increase the toxicity and side effects. Here, we designed a Cu(2-x)Se-loaded on MXene, which can catalyze the conversion of the overexpressed hydrogen peroxide into O2 and -OH in cancer cells by Cu(2-x)Se with the catalase (CAT)-like activity and peroxidase (POD) activity, which can effectively alleviate the tumor microenvironment (TEM) hypoxia, as well as degrading the overexpressed glutathione (GSH) and killing the tumor cells to a large extent. At the same time, we used Nanozyme-Carrier Interface Modulation (NCIM): by regulating the interface interaction between nanozymesand carrier materials , the catalytic activity of nanozymes and the photothermal performance of the support were optimized. This regulation can be achieved by adjusting the mass ratio of nanozymes to carriers, surface modification, etc. to improve the performance of the composites. Dual enzyme-active nanozymes loaded with MXene provide a way to synergies catalytic and photothermal therapies, which are considered to be promising materials for future development in the field of nanocomposites for disease treatment.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500574"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661697","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}
Maren Neubrand, Jessica Stubbe, Richard Rudolf, Robert R M Walter, Maite Nößler, Biprajit Sarkar
{"title":"Activation and Fixation of Atmospheric CO<sub>2</sub> through a 1,2,3-Triazole-Based Mesoionic Carbene-Borane Adduct.","authors":"Maren Neubrand, Jessica Stubbe, Richard Rudolf, Robert R M Walter, Maite Nößler, Biprajit Sarkar","doi":"10.1002/chem.202403942","DOIUrl":"10.1002/chem.202403942","url":null,"abstract":"<p><p>Capturing atmospheric CO<sub>2</sub> and converting it to valuable chemicals are important goals in contemporary science. We present here a simple, transition metal-free triazolylidene-borane adduct that can capture atmospheric CO<sub>2</sub> and convert it to formate. Several key intermediates were isolated and characterized by a combination of multinuclear NMR spectroscopy, IR spectroscopy and single crystal X-ray diffraction. A first closed cycle for the conversion of CO<sub>2</sub> to formic acid by using the aforementioned triazolylidene-borane compound is presented as well.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403942"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143655715","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}