ChemistryEurope最新文献_第5页

Cover Feature: Water Chemistry at the Nanoscale: Clues for Resolving the “Water Paradox” Underlying the Emergence of Life (ChemistryEurope 6/2024) 封面专题：纳米尺度的水化学：解决生命出现背后的 "水悖论 "的线索（欧洲化学展 6/2024）

ChemistryEurope Pub Date : 2024-11-12 DOI: 10.1002/ceur.202480602

Dr. Hye-Eun Lee, Dr. Michael Russell, Prof. Ryuhei Nakamura

引用次数: 0

Developing an On-Resin Synthesis of α-Galactosylceramide-Peptide Conjugate Vaccines 树脂上合成α-半乳糖神经酰胺肽结合疫苗的研究

ChemistryEurope Pub Date : 2024-11-07 DOI: 10.1002/ceur.202400059

Dr. Michael A. Meijlink, Dr. Susanna T. S. Chan, Kathryn J. Farrand, Sarah L. Draper, Dr. Oliva K. Burn, Jasmine M. Seifert-Simpson, Ngarangi C. Mason, Dr. Lisa M. Connor, Prof. Ian F. Hermans, Prof. Gavin F. Painter, Dr. Benjamin J. Compton

{"title":"Developing an On-Resin Synthesis of α-Galactosylceramide-Peptide Conjugate Vaccines","authors":"Dr. Michael A. Meijlink, Dr. Susanna T. S. Chan, Kathryn J. Farrand, Sarah L. Draper, Dr. Oliva K. Burn, Jasmine M. Seifert-Simpson, Ngarangi C. Mason, Dr. Lisa M. Connor, Prof. Ian F. Hermans, Prof. Gavin F. Painter, Dr. Benjamin J. Compton","doi":"10.1002/ceur.202400059","DOIUrl":"https://doi.org/10.1002/ceur.202400059","url":null,"abstract":"The covalent attachment of peptide antigens to the NKT cell agonist, α-galactosylceramide (αGalCer), generates self-adjuvanting vaccines that prevent and/or eliminate disease in animal models of cancer and infectious disease. To date, the manufacture of these glycolipid-peptide (GLP) conjugate vaccines utilises an automated solid-phase process to produce the peptide followed by a manual ‘wet chemistry’ conjugation step. To expedite GLP vaccine manufacture, we sought to develop methodology that enables the attachment of resin-bound peptide antigen to αGalCer via an amide bond thereby avoiding the need to carry out a separate chemoselective conjugation step. To facilitate this approach, novel analogues of αGalCer incorporating an activated ester spaced by an acid-resistant, protease-sensitive linker from either the 6′′-position or the N-acyl lipid were synthesised. Reacting these with resin-bound peptide afforded the conjugate vaccines in good to excellent yields and purity. In vivo testing showed that vaccines incorporating peptide antigen attached via the galactosyl head group induced strong antigen specific CD8+ T cell responses compared to those with antigen attached via the lipid tail and control vaccine manufactured in a stepwise manner.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400059","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143112825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanism of Substrate Activation by Tryptophan Hydroxylase: A Computational Study 色氨酸羟化酶激活底物的机制：一个计算研究

ChemistryEurope Pub Date : 2024-11-07 DOI: 10.1002/ceur.202400067

Dr. Thirakorn Mokkawes, Dr. Sam P. de Visser

{"title":"Mechanism of Substrate Activation by Tryptophan Hydroxylase: A Computational Study","authors":"Dr. Thirakorn Mokkawes, Dr. Sam P. de Visser","doi":"10.1002/ceur.202400067","DOIUrl":"https://doi.org/10.1002/ceur.202400067","url":null,"abstract":"Serotonin is a hormone that is responsible for mood regultion in the brain; however, details on its biosynthetic mechanism remain controversial. Tryptophan hydroxylase catalyzes the first step in the serotonin biosynthesis in the human body, where it regio- and stereoselectively hydroxylates a free tryptophan (Trp) amino acid at the C5-position. In this work, we present a computational study ranging from molecular dynamics (MD) to quantum mechanics (QM) methods, focused on the mechanism of tryptophan hydroxylase. An MD simulation on an enzyme structure with the substrate, co-substrate and dioxygen bound reveals a tightly bound conformation of substrate and co-substrate, while the protein's three-dimensional structure stays virtually intact during the simulation. Subsequently, large active-site cluster models containing more than 200 atoms were created, and oxygen atom transfer reactions were studied. The calculations predict that the co-factor tetrahydrobiopterin binds covalently to the iron center and react with a dioxygen molecule to form an iron(IV)-oxo species and pterin-4a-carbinolamine in a stepwise manner with small energy barriers (<5 kcal mol−1) along an exergonic pathway. However, the rate-determining step, is Trp activation through a C−O activation transition state, followed by a rapid proton relay to produce 5-hydroxy-L-Trp.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400067","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143112824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

(Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals （Ph3P）4C4P4：取代对磷化碳自由基寡聚化的影响

ChemistryEurope Pub Date : 2024-10-30 DOI: 10.1002/ceur.202400061

Dr. Moritz Scharnhölz, Dr. Jose Juan Gamboa Carballo, Dr. Nils Trapp, Dr. Rene Verel, Dr. Peter Coburger, Prof. Dr. Hansjörg Grützmacher

{"title":"(Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals","authors":"Dr. Moritz Scharnhölz, Dr. Jose Juan Gamboa Carballo, Dr. Nils Trapp, Dr. Rene Verel, Dr. Peter Coburger, Prof. Dr. Hansjörg Grützmacher","doi":"10.1002/ceur.202400061","DOIUrl":"https://doi.org/10.1002/ceur.202400061","url":null,"abstract":"Dehalogenation of (PBr)2C2(PPh3)2 with potassium graphite, KC8, leads to Cs-P4C4(PPh3)4, which can be viewed as a PPh3 adduct of a Cs-symmetric P4C4 cage. An isolable intermediate was found and in combination with DFT calculations, the structure of a S4-symmetric P4C4(PPh3)4 cage is proposed for this species. That a 1,3-diphosphete type Ph3P→P2C2←PPh3 heterocycle is a short-lived intermediate in the dehalogenation reaction is indicated by trapping experiments which allowed to isolate and fully characterize the [Fe(CO)4] complexes [Fe(CO)4(κ-P−P2C2{PPh3}2] and [(Fe(CO)4)2(μ2-κ-P−P2C2{PPh3}2]. The conversion of S4-P4C4(PPh3)4 to Cs-P4C4(PPh3)4 prompted a (re)investigation of the isomerization of various P4X4 species (X=S, NH, NMe; CH2), which shows that these proceed on Minimum Energy Reaction Pathways (MERPs) with two transition states embracing one intermediate. In contrast, the isomerization S4-P4C4(PR3)4 to Cs-P4C4(PR3)4 is a one-step process.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400061","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143121282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Luminescence and Single-Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near-Planar Tricoordinate Ytterbium(III) Amide 理想对称化合物的发光和单分子磁特性：近平面三配位镱(III)酰胺实例

ChemistryEurope Pub Date : 2024-10-16 DOI: 10.1002/ceur.202400062

Dr. Nimisha Jain, Dr. Félix Houard, Rémi Marchal, Marie Cordier, Dr. Boris Le Guennic, Dr. Yan Suffren, Dr. Yann Sarazin, Prof. Kevin Bernot

{"title":"Luminescence and Single-Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near-Planar Tricoordinate Ytterbium(III) Amide","authors":"Dr. Nimisha Jain, Dr. Félix Houard, Rémi Marchal, Marie Cordier, Dr. Boris Le Guennic, Dr. Yan Suffren, Dr. Yann Sarazin, Prof. Kevin Bernot","doi":"10.1002/ceur.202400062","DOIUrl":"https://doi.org/10.1002/ceur.202400062","url":null,"abstract":"We are reporting on the use of a low-coordinate YbIII amide with near-ideal planar trigonal [Yb{N(SiMe3)2}3] (1) and on a bipyramidal trigonal derivative [Yb{N(SiMe2H)2}3 ⋅ (thf)2] (2) that constitute quintessential cases to investigate luminescent and magnetic properties otherwise usually blurred on less symmetrical compounds. These compounds represent the first experimental objects that allow for the confirmation of the recent conjecture about best-performing SMM built on the archetypal prolate lanthanide ion. We have performed a combined theoretical, luminescent, and magnetic study on these molecules. For 1, a spectacular split of the 2F7/2 ground state of 1312 cm−1 is measured by low-temperature near-infra-red luminescence as well as the calculated pure wavefunction composition of the low-lying Kramers doublets, making this complex a textbook example of a prolate SMM. These results are corroborated by comparison with 2, that exhibits as expected a 50 % decrease of the ground state splitting compared to 1. Yet, we show that these remarkable features are insufficient to promote SMM behavior, and Orbach relaxation is unlikely to occur even on such an ideal low-coordinate SMM without control of spin-phonon coupling.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"2 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400062","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Water Chemistry at the Nanoscale: Clues for Resolving the “Water Paradox” Underlying the Emergence of Life 纳米尺度的水化学：解决生命出现所依据的 "水悖论 "的线索

ChemistryEurope Pub Date : 2024-10-10 DOI: 10.1002/ceur.202400038

Dr. Hye-Eun Lee, Dr. Michael Russell, Prof. Ryuhei Nakamura

{"title":"Water Chemistry at the Nanoscale: Clues for Resolving the “Water Paradox” Underlying the Emergence of Life","authors":"Dr. Hye-Eun Lee, Dr. Michael Russell, Prof. Ryuhei Nakamura","doi":"10.1002/ceur.202400038","DOIUrl":"https://doi.org/10.1002/ceur.202400038","url":null,"abstract":"Water is the most common, yet highly peculiar, liquid on Earth. Biological systems manipulate the properties of water to perform reactions that are extremely difficult in synthetic chemistry. One such example is polymerization, which is essential for life and requires the removal of water; however, the removal of water adversely affects the redox reactions that harness the free energy to sustain life. This dichotomy in the water chemistry of life is referred to as the “water paradox”, which remains an unsolved puzzle in the origins of life research. In the present concept paper, we propose that the water paradox may be resolved if anomalous water behavior, including the extremely low dielectric constant and modulation of the enthalpy-entropy compensation relationship arising from nanoscale confinement, are considered. The unique properties of confined water allow for polymerization reactions to proceed even in water-rich hydrothermal vent (HV) environments due to the structurally aligned nanopores within HV walls. Studies of how structural changes in water networks in nano-spaces affect catalysis and free energy exchange represent the next frontier in the field of origins of life research and synthetic chemistry.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"2 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Total Synthesis of the Humulene-Derived Sesquiterpenoid (-)-Integrifolian-1,5-dione 葎草素衍生倍半萜类化合物 (-)-Integrifolian-1,5-dione 的全合成

ChemistryEurope Pub Date : 2024-10-10 DOI: 10.1002/ceur.202400064

Anne Zimmer, Prof. Alois Fürstner

引用次数: 0

Steering Photoinduced Electron Transfer in Intramolecular Photocatalysts by Peripheral Ligand Control 通过外围配体控制引导分子内光催化剂中的光诱导电子转移

ChemistryEurope Pub Date : 2024-10-10 DOI: 10.1002/ceur.202300084

Benedikt Bagemihl, Prof. Carolin Müller, Dr. Georgina E. Shillito, Marco Hartkorn, Dr. Alexander K. Mengele, Dr. Stephan Kupfer, Prof. Benjamin Dietzek-Ivanšić, Prof. Sven Rau

{"title":"Steering Photoinduced Electron Transfer in Intramolecular Photocatalysts by Peripheral Ligand Control","authors":"Benedikt Bagemihl, Prof. Carolin Müller, Dr. Georgina E. Shillito, Marco Hartkorn, Dr. Alexander K. Mengele, Dr. Stephan Kupfer, Prof. Benjamin Dietzek-Ivanšić, Prof. Sven Rau","doi":"10.1002/ceur.202300084","DOIUrl":"https://doi.org/10.1002/ceur.202300084","url":null,"abstract":"Bridged photosensitizer-catalyst systems are promising models to study photocatalytic hydrogen evolution. However, the systems in the literature structurally diverse and therefore hard to compare. Many systems show highly complex photophysics including several accepting orbitals for the excited state, as a result catalytic activity is hard to predict. Here we present a bimetallic Ru−Pt photocatalyst bearing peripheral spectator ligands at the ruthenium(II) photocenter as a member of the Ru-tpphz-Pt family. Consequently, it features a single acceptor tpphz ligand and so-called unidirectional electron transfer, i. e., electron transfer without co-occurring transfer to peripheral ligands, from the excited state. Thus – and in contrast to recently used peripheral ligands – the new spectator ligands do not disrupt electron transfer towards the catalytic center. By comparison to known systems, this facilitates unprecedented insight into the importance of electron transfer from the bridge to the catalytic center moving towards more rational design of oligonuclear photocatalysts.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"2 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202300084","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Glucose-based Ionic Liquid Organocatalysts for Asymmetric aza-Diels-Alder Reactions 用于不对称偶氮-狄尔斯-阿尔德反应的葡萄糖基离子液体有机催化剂

ChemistryEurope Pub Date : 2024-10-10 DOI: 10.1002/ceur.202400052

Mirai Komabayashi, Dr. Stefan Jopp

引用次数: 0

Pd-Catalyzed Thiotritylation Cross-Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups Pd 催化溴化芳基和碘化芳基的硫代三苯甲基化交叉偶联以获得硫官能团

ChemistryEurope Pub Date : 2024-10-10 DOI: 10.1002/ceur.202400053

Yue Liu, Dr. Takashi Okazoe, Dr. Tim Gatzenmeier, Prof. Dr. Kyoko Nozaki

{"title":"Pd-Catalyzed Thiotritylation Cross-Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups","authors":"Yue Liu, Dr. Takashi Okazoe, Dr. Tim Gatzenmeier, Prof. Dr. Kyoko Nozaki","doi":"10.1002/ceur.202400053","DOIUrl":"https://doi.org/10.1002/ceur.202400053","url":null,"abstract":"Sulfur-containing functional groups (SFGs) are increasingly important for modern medicinal chemistry and their large structural diversity provides many opportunities for lead optimization. In an effort to simplify the access to the full set of SFGs, we report herein a versatile strategy utilizing (hetero)aryl trityl sulfides (ArSCPh3) as the common precursors. We developed a mild and high yielding Pd-catalyzed thiotritylation cross-coupling methodology to afford ArSCPh3 compounds from (hetero)aryl bromides and iodides. Efficient chemoselective derivatizations provided access to eight different SFGs and sulfur(VI) fluorine exchange (SuFEx) hubs, which open up further downstream derivatizations towards the full set of SFGs. Thereby obtainable sulfur motifs include aryl sulfur pentafluorides (ArSF5), aryl tetrafluoro-λ6-sulfanyl chlorides (ArSF4Cl), aryl sulfonimidoyl fluorides (ArS(O)(NR)F), aryl sulfonyl fluorides (ArSO2F), aryl sulfonic acids (ArSO3H), and aryl sulfinyl fluorides (ArSOF), which are all valuable functional groups in modern drug discovery.","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"2 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400053","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0