Chemical Science最新文献

{"title":"Valence Activity of SO-Coupled Atomic Core Shells in Solid Compounds of Heavy Elements","authors":"Shiru-ru Wei, Han-Shi Hu, W. H. Eugen Schwarz, Jun Li","doi":"10.1039/d4sc08151j","DOIUrl":"https://doi.org/10.1039/d4sc08151j","url":null,"abstract":"An alert look reveals chemically relevant changes from light to heavy elements of the atomic orbital-energy patterns, relevant for both chemical theory and material applications. We have quantum-chemically investigated the geometric and electronic structures of solid [ThO2] and a series of [UO3] phases at a realistic relativistic level, both with and without spin-orbit (SO) coupling. The observable band gap between the occupied O(2p) bonding valence band and the empty U(5f6d) conduction band is smallest for δ-[UO3], with medium short U-O distances and high Oh symmetry. Both Pauli-repulsion of O(2p) by the strongly SO-split U(6p) core, and additional covalent U(6p)-O(2p) mixing, cause a “pushing up from below” (PFB) and a large SO splitting of the valence band of the light element. PFB has been observed in molecular chemistry, but PFB and PFB-induced SO splitting have so far not been considered in solid-state science. Our finding opens new possibilities for electronic material applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Facile Synthesis of Recyclable Polythioimidocarbonates via Aromatization-driven Alternating Copolymerization of para-Quinone Methide and Isothiocyanates","authors":"Wen-Dao Chu, Si-Yu Dan, Jie Zhan, Bo Chen, Ji Xian, Chun-Mei Wang, Quanzhong Liu, Jincai Wu, Chun-An Fan","doi":"10.1039/d5sc00050e","DOIUrl":"https://doi.org/10.1039/d5sc00050e","url":null,"abstract":"The efficient and controllable alternating copolymerization of para-Quinone Methide (p-QM) is rare and challenging. The aromatization-driven alternating copolymerization of p-QM with isothiocyanates is explored for the first time under mild conditions. In the presence of the key catalyst m-phthalic acid and the initiator TBD, the reaction can efficiently produce completely alternating polythioimidocarbonates with narrow molecular weight distributions and high molar mass (up to 103.6 kg/mol). Experimental studies and DFT calculations suggest that m-phthalic acid plays a synergistic catalytic role. Remarkably, the copolymers can be recycled back into the monomers with excellent yields under vacuum at a temperature of 190 °C in just a few minutes without solvents or catalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of size, charge, and spin state on Hückel and Baird aromaticity in [N]annulenes","authors":"Louis Van Nyvel, Mercedes Alonso, Miquel Solà","doi":"10.1039/d4sc08225g","DOIUrl":"https://doi.org/10.1039/d4sc08225g","url":null,"abstract":"The Hückel and Baird rules provide a framework to understand the aromaticity of monocyclic π-conjugated molecules in their singlet ground state and lowest-lying triplet state, respectively, particularly in the context of [<em>N</em>]annulenes. According to Hückel's rule, a molecule in the ground state is aromatic if it contains 4<em>n</em>+2 π-electrons, while Baird's rule states that a molecule in the lowest-lying triplet state is aromatic if it contains 4<em>n</em> π-electrons, where <em>n</em> = 0, 1, 2, and so on. A previous study (<em>J. Am. Chem. Soc.</em><strong>2021</strong>, <em>143</em>, 2403) examined the changes in the aromaticity of singlet ground-state [<em>N</em>]annulenes as the ring size increased from <em>N</em> = 12 to 66. However, no systematic investigation has yet been conducted for the lowest-lying triplet state of [<em>N</em>]annulenes, or charged [<em>N</em>]annulenes. In this work, we address this gap by performing DFT calculations across several aromaticity descriptors, including structural, electronic, magnetic, and energetic indicators of aromaticity, with a particular focus on aromatic stabilization energies (ASE). Our findings reveal that both neutral and charged [<em>N</em>]annulenes adhere to the Hückel and Baird rules. Nevertheless, for larger ring sizes, these rules diminish in significance, and the distinction between ASEs (and other indices of aromaticity) of [<em>N</em>]annulenes with 4<em>n</em> and 4<em>n</em>+2 π-electrons becomes less and less pronounced.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Access to arynes from arenes via net dehydrogenation: scope, synthetic applications and mechanistic analysis","authors":"Riley A Roberts, Bryan Metze, Nicole Javali, Theresa M. McCormick, David Ross Stuart","doi":"10.1039/d5sc00054h","DOIUrl":"https://doi.org/10.1039/d5sc00054h","url":null,"abstract":"Arynes undergo a wide range of chemical transformations making them versatile reactive intermediates for organic synthesis. Access to arynes has long been dominated by pre-functionalised reagents, e.g., the venerable o-trimethylsilylaryl triflates. However, a move toward developing methods to access arynes that are both mild and efficient has prompted research into aryl “onium” aryne precursors. Here, we leverage aryl “onium” species as in situ or isolated intermediates in a net dehydrogenation of simple arenes as a novel and efficient way to access arynes. We describe a unified strategy in which two different tactics are employed to access diversely substituted arynes from simple arenes. 1) We developed a one-pot method that converts simple arenes into aryl thianthrenium salts and uses them in situ to generate arynes. 2) We developed a two-step process to convert arenes into aryl(Mes)iodonium salts and ultimately trapped arynes to expand the scope of compatible arenes. The net transformations from arenes to trapped arynes are complete with 2-4 hours. Mechanistic analysis through competition experiments, deuterium kinetic isotope effects (DKIE) and Density Functional Theory (DFT) provide key comparisons of the two approaches described in this work and yield a user’s guide for selecting the appropriate “onium” leaving group based on the arene.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multimeric, Multivalent Fusion Carrier Proteins for Site-Selective Glycoconjugate Vaccines Simultaneously Targeting Staphylococcus aureus and Pseudomonas aeruginosa","authors":"Charlotte Sorieul, Bartal Mikladal, Dung-Yeh Wu, Cinzia Giovani, Giusy Adamo, Giacomo Romagnoli, Filippo Carboni, Roberto Adamo, Barbara Brogioni, Immaculada Margarit, Jeroen D Codee, Maria Rosaria Romano","doi":"10.1039/d4sc08622h","DOIUrl":"https://doi.org/10.1039/d4sc08622h","url":null,"abstract":"Staphylococcus aureus and Pseudomonas aeruginosa are major antimicrobial-resistant pathogens that often synergize in polymicrobial infections, such as chronic wound infections. These notorious and increasingly resistant bacteria contribute significantly to reduced antibiotic efficacy. Despite their substantial clinical burden, the urgent need to combat bacterial resistance and extensive research efforts, no vaccines currently exist for either bacterium. Glycoconjugate vaccines, which extend the range of suitable vaccine antigens to bacterial carbohydrates, could play a major role in this emergence. This study introduces a multiepitope vaccine conjugating S. aureus capsular polysaccharide serotype 8 to a chimeric protein fusing Hla and PcrV, two potent cytotoxins from S. aureus and P. aeruginosa, respectively. A conjugation strategy based on selective targeting of a purposefully introduced histidine tag was developed to preserve the structure and antigenicity of epitopes from the two proteins, leveraging their dual role as carrier and antigen. This multivalent, multimeric and multipathogen construct successfully elicited antibodies against all three antigens as well as functional protection. This proof-of-concept highlights the potential for advanced vaccines targeting polymicrobial infections and bacteria with complex pathogenesis calling for multivalent formulations. It also points out the power of site-selective conjugation as tool for vaccine manufacturing.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine Learning-Driven Discovery of Highly Selective Antifungal Peptides Containing Non-Canonical β-Amino Acids","authors":"Douglas H. Chang, Joshua D Richardson, Myung-Ryul Lee, David M. Lynn, Sean P. Palecek, Reid C Van Lehn","doi":"10.1039/d4sc06689h","DOIUrl":"https://doi.org/10.1039/d4sc06689h","url":null,"abstract":"Antimicrobial peptides (AMPs) are promising compounds for the treatment and prevention of multidrug-resistant infections because of their ability to directly disrupt microbial membranes, a mechanism that is less likely to lead to resistance compared to antibiotics. Unfortunately, natural AMPs are prone to proteolytic cleavage in vivo and have relatively low selectivity for microbial versus human cells, motivating the development of synthetic peptidomimetics of AMPs with improved peptide stability, activity, and selectivity. However, a lack of understanding of structure-activity relationships for peptidomimetics constrains development to rational design or experimental predictors, both of which are cost and time prohibitive, especially when the design space of possible sequences scales exponentially with the number of amino acids. To address these challenges, we developed an iterative Gaussian process regression (GPR) approach to explore a large design space of 336,000 synthetic α/β-peptide analogues of a natural AMP, aurein 1.2, based on an initial training set of 147 sequences and their biological activities against microbial pathogens and selectivity for microbes vs. mammalian cells. We show that the quantification of prediction uncertainty provided by GPR can guide the exploration of this design space via iterative experimental measurements to efficiently discover novel sequences with up to a 52-fold increase in antifungal selectivity compared to aurein 1.2. The highest selectivity peptide discovered using this approach features an unconventional substitution of cationic amino acids in the hydrophobic face and would be unlikely to be explored by conventional rational design. Overall, this work demonstrates a generalizable approach that integrates computation and experiment to accurately predict the selectivity of AMPs containing synthetic amino acids, which we employed to discover new α/β-peptides that hold promise as selective antifungal agents to combat the antimicrobial resistance crisis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reversible Redox 19F Magnetic Resonance Imaging Nanoprobes for Monitoring Redox State in Vivo","authors":"Xiaoyao Xiong, Sijia Li, Yumin Li, Suying Xu, Chang Guo, Leyu Wang","doi":"10.1039/d4sc08297d","DOIUrl":"https://doi.org/10.1039/d4sc08297d","url":null,"abstract":"Redox processes are indispensable for physiology, and dysregulated redox balance is critical in various metabolic diseases. The development of imaging diagnosis tools for real-time monitoring of redox state<em> in vivo </em>is of great importance yet highly challenging. Here, we designed the trifluoromethyl (-CF<small>₃</small>) grafted selenide polymer nanoprobes for reversible redox sensing <em>in vivo</em>. Based on the reversible shift of<small>¹⁹</small>F-nuclear magnetic resonance (NMR) peak between oxidation and reduction state of the nanoprobes exposed to different redox species, the <small>¹⁹</small>F-magnetic resonance imaging (MRI) signal ratio of <em>S</em><small>_OX</small>/(<em>S</em><small>_Ox</small>+<em>S</em><small>_Red</small>) was successfully applied to monitor the redox state in a tumor. These nanoprobes demonstrated good biocompatibility and great potential for exploring physiological and pathological redox processes in deep tissues. We envision that this work will enable the rational design of <small>¹⁹</small>F-MRI nanoprobes with excellent redox response for the real-time monitoring of the redox state at lesion location.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modulating the spin–flip rates and emission energies through ligand design in chromium(III) molecular rubies","authors":"Yating Ye, Maxime Poncet, Polina Yaltseva, Pablo Salcedo-Abraira, Antonio Rodríguez-Diéguez, Javier Heredia Martín, Laura Cuevas-Contreras, Carlos M. Cruz, Benjamin Doistau, Claude Piguet, Oliver S. Wenger, Juan Manuel Herrera, Juan-Ramón Jiménez","doi":"10.1039/d4sc08021a","DOIUrl":"https://doi.org/10.1039/d4sc08021a","url":null,"abstract":"Three homoleptic spin–flip (SF) emitters, namely [Cr(Mebipzp)<small>₂</small>]<small>³⁺</small> (<strong>1</strong>), [Cr(IMebipzp)<small>₂</small>]<small>³⁺</small> (<strong>2</strong>) and [Cr(bip*)<small>₂</small>]<small>³⁺</small> (<strong>3</strong>), have been successfully synthesized and characterized. The weak distortion compared to a perfect octahedron imparts favourable structural properties to the three complexes, which display spin–flip (SF) luminescence at approximately 740 nm with quantum yields in the range of 9–11% for <strong>1</strong> and <strong>2</strong> in deaerated acetonitrile solutions at 25 °C. Time-resolved luminescence and transient UV-vis absorption experiments unveiled lifetimes for the lowest-lying <small>²</small>MC (metal-centered) of 1.5 ms for <strong>1</strong> and 350 μs for <strong>2</strong>. The incorporation of iodine atoms onto the ligand scaffold in <strong>2</strong> accelerates the <small>²</small>MC → <small>⁴</small>A<small>₂</small> relaxation process through simultaneous enhancements in the radiative and non-radiative rate constants. In agreement, the experimentally calculated absorption oscillator strength for the <small>²</small>MC ← <small>⁴</small>A<small>₂</small> transition amounts to 9.8 × 10<small>⁻⁷</small> and 2.5 × 10<small>⁻⁶</small> for <strong>1</strong> and <strong>2</strong>, respectively. The 2.5 factor enhancement observed in the iodine derivative indicates a higher spin–flip transition probability, translating into higher values of radiative rate constant (<em>k</em><small>_rad</small>). Interestingly, in compound <strong>3</strong>, the substitution of the distal methyl-pyrazole with indazole rings causes an important bathochromic shift of the SF emission energy to 12 000 cm<small>⁻¹</small> (830 nm). Likely, the extended π-system and the more covalent bond character induced by the indazole decrease the interelectronic repulsion further stabilizing the SF excited states. The recorded excited state lifetime of 111 μs in <strong>3</strong> remains among the longest for a molecular ruby emitting beyond 800 nm. These discoveries signify an underexplored avenue for modifying deactivation pathways and emission energy while retaining high quantum yields and long-lived excited states in molecular rubies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"85 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unusually air-stable copper(I) complexes showing high selectivity for carbon monoxide","authors":"Borna Saeednia, Aria M. Sragow, Yannan Lin, Colton J. Sheehan, Amy S. Metlay, Michael R. Gau, Samantha A. Dye, Sarah P. O'Konski, Thomas E. Mallouk, Ivan J. Dmochowski","doi":"10.1039/d5sc00237k","DOIUrl":"https://doi.org/10.1039/d5sc00237k","url":null,"abstract":"We report two Cu(<small>I</small>)-tren host molecules with unusual air-stability, as revealed by strong preference for axial CO binding over bent O<small>₂</small>. Spectroscopy, electrochemical, and X-ray crystal structure analyses indicate that the phenyl rotators of the capsule select for small axial ligands.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"81 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443958","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrically conductive charge-segregated pseudo-polymorphs comprising highly planar expanded π-electronic cation","authors":"Yohei Haketa, Ryoya Nakajima, Yuto Maruyama, Hiroki Tanaka, Wookjin Choi, Shu Seki, Shunsuke Sato, Hitomi Baba, Yoshiki Ishii, Go Watanabe, Kirill Bulgarevich, Kazuo Takimiya, Kenzo Deguchi, Shinobu Ohki, Kenjiro Hashi, Takashi Nakanishi, Yukihide Ishibashi, Tsuyoshi Asahi, Kazuchika Ohta, Hiromitsu Maeda","doi":"10.1039/d4sc07576e","DOIUrl":"https://doi.org/10.1039/d4sc07576e","url":null,"abstract":"Independently stacked positively and negatively charged π-electronic systems in charge-segregated columnar structures are desired for electronic properties derived from their electron-deficient and -rich assembling states, respectively. An expanded π-electronic cation, benzoporphyrin AuIII complex, was synthesized as the component of ion pairs in combination with counteranions. In contrast to benzoporphyrin, which is known for its insolubility in organic solvents, the ion pairs with bulky anions in this study are soluble in common organic solvents. The ion pairs formed charge-segregated assemblies as two pseudo-polymorphs of single-crystal and less-crystalline (LeC) states based on the stacking of the benzoporphyrin AuIII complex. XRD and solid-state NMR measurements, along with molecular dynamics (MD) simulation, revealed that the LeC states were formed by a less-ordered arrangement of constituting ions induced by bulky counteranions. The electric conductivity properties were observed in the single-crystal and LeC charge-segregated assemblies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"81 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}