Communications Chemistry最新文献

{"title":"Women in chemistry: Q&A with Dr Yee Hwee Lim","authors":"","doi":"10.1038/s42004-024-01320-1","DOIUrl":"10.1038/s42004-024-01320-1","url":null,"abstract":"Dr Yee Hwee Lim currently leads a team of more than 25 researchers in the Chemical Biotechnology and Biocatalysis division at the A*STAR Institute of Sustainability for Chemicals, Energy and Environment (A*STAR ISCE2) to develop integrative technologies at the interface between chemistry, biology, informatics, and engineering for sustainable chemical manufacturing.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-1"},"PeriodicalIF":5.9,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01320-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519174","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}

{"title":"Beyond traditional magnetic resonance processing with artificial intelligence","authors":"Amir Jahangiri, Vladislav Orekhov","doi":"10.1038/s42004-024-01325-w","DOIUrl":"10.1038/s42004-024-01325-w","url":null,"abstract":"Smart signal processing approaches using Artificial Intelligence are gaining momentum in NMR applications. In this study, we demonstrate that AI offers new opportunities beyond tasks addressed by traditional techniques. We developed and trained artificial neural networks to solve three problems that until now were deemed “impossible”: quadrature detection using only Echo (or Anti-Echo) modulation from the traditional Echo/Anti-Echo scheme; accessing uncertainty of signal intensity at each point in a spectrum processed by any given method; and defining a reference-free score for quantitative access of NMR spectrum quality. Our findings highlight the potential of AI techniques to revolutionize NMR processing and analysis. Smart signal processing approaches using Artificial Intelligence are gaining momentum in NMR applications. Here, the authors use AI for quadrature detection using only (Anti-)Echo modulation, accessing uncertainties of signal intensities at each point in a spectrum processed by any given method, and to define a reference-free score of NMR spectrum quality.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-8"},"PeriodicalIF":5.9,"publicationDate":"2024-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01325-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142496407","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}

{"title":"Imaging in-operando LiCoO2 nanocrystallites with Bragg coherent X-ray diffraction","authors":"David Serban, Daniel G. Porter, Ahmed H. Mokhtar, Mansoor Nellikkal, Sivaperumal Uthayakumar, Min Zhang, Stephen P. Collins, Alessandro Bombardi, Peng Li, Christoph Rau, Marcus C. Newton","doi":"10.1038/s42004-024-01331-y","DOIUrl":"10.1038/s42004-024-01331-y","url":null,"abstract":"Although the LiCoO2 (LCO) cathode material has been widely used in commercial lithium ion batteries (LIB) and shows high stability, LIB’s improvements have several challenges that still need to be overcome. In this paper, we have studied the in-operando structural properties of LCO within battery cells using Bragg Coherent X-ray Diffraction Imaging to identify ways to optimise the LCO batteries’ cycling. We have successfully reconstructed the X-ray scattering phase variation (a fingerprint of atomic displacement) within a  ≈ (1.6 × 1.4 × 1.3) μm3 LCO nanocrystal across a charge/discharge cycle. Reconstructions indicate strained domains forming, expanding, and fragmenting near the surface of the nanocrystal during charging, with a determined maximum relative lattice displacements of 0.467 Å. While discharging, all domains replicate in reverse the effects observed from the charging states, but with a lower maximum relative lattice displacements of 0.226 Å. These findings show the inefficiency-increasing domain dynamics within LCO lattices during cycling. Although lithium cobalt(III) oxide (LCO) is a widely used and highly stable lithium-ion battery material, several challenges still need to be overcome. Here, the authors use in-operando Bragg Coherent X-ray Diffraction Imaging to visualize the structural properties of LCO in battery cells and identify inefficiency-increasing domain dynamics during cycling.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01331-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142496409","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}

{"title":"Nucleotide-mediated modulation of chemoselective protein functionalization in a liquid-like condensed phase","authors":"Nandha Kumar Ettikkan, Priyanka Priyanka, Rishi Ram Mahato, Subhabrata Maiti","doi":"10.1038/s42004-024-01333-w","DOIUrl":"10.1038/s42004-024-01333-w","url":null,"abstract":"Liquid-like protein condensates are ubiquitous in cellular system and are increasingly recognized for their roles in physiological processes. Condensed phase harbors distinctive chemical microenvironment, markedly different than dilute aqueous phase. Herein, we demonstrate chemoselective modification pattern of nucleophilic canonical amino acid sidechains (namely – cysteine, tyrosine and lysine) of the protein towards 4-chloro-7-nitrobenzofurazan in the dilute and condensed phase. We also delineate how the effect of nucleotides and their in situ enzymatic dissociation temporally modulate the protein condensate’s pH and the protein’s corresponding chemoselective modification. We have shown that the pH of the condensate decreases in the presence of nucleoside triphosphate, whereas it increases in the presence of nucleoside monophosphates or phosphate ion. For instance, we find lysine-specific modification gets inhibited in the presence of adenosine triphosphate (ATP), but significantly enhanced in the presence of monophosphates. This feature enables us to gain temporal control over dynamic change in protein functionalization via enzymatic ATP hydrolysis. Overall, this work substantiates the alteration in pH-responsiveness of Brønsted basicity of a protein’s ε-amine in the condensed phase. Furthermore, this environment sensitivity in chemoselective protein functionalization in condensed phase will be important in adaptable protein engineering to the chemical biology of protein phase separation. Liquid-like protein condensates are ubiquitous in cellular systems and play key roles in physiological processes, with the condensed phase harboring a distinctive chemical microenvironment. Here, the authors systematically investigate how the local chemical environment within protein condensates impacts chemical reactivity, demonstrating nucleotide-mediated modulation of chemoselective protein functionalization.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-10"},"PeriodicalIF":5.9,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01333-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142496410","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}

{"title":"Design of stimuli-responsive transition metal dichalcogenides","authors":"Ramon Torres-Cavanillas, Alicia Forment-Aliaga","doi":"10.1038/s42004-024-01322-z","DOIUrl":"10.1038/s42004-024-01322-z","url":null,"abstract":"Stimuli-responsive systems are an emerging class of materials in fields as diverse as electronics, optoelectronics, cancer detection, drug delivery, or sensing. Especially focusing on nanomaterials, 2D transition metal dichalcogenides have recently attracted the scientific community''s attention due to their remarkable intrinsic stimuli-responsive behaviour upon external stimuli such as pH, light, voltage, or certain pathogens. This significant response can be further enhanced by forming mixed-dimensional heterostructures and by molecular functionalization, capitalizing on chemistry to manipulate and boost their intrinsic stimuli-responsive properties. Furthermore, thanks to the endless possibilities of chemistry, a new class of smart materials based on the combination of stimuli-responsive molecular systems with transition metal dichalcogenides has recently been synthesized. In these materials, the physical properties of the 2D layers are reversibly modified by the switchable molecules, not only enhancing their stimuli-responsive behaviour but also providing memory to the hybrid. Therefore, this review explores the recent breakthroughs in the chemical design of smart transition metal dichalcogenides with built-in responsiveness. Transition metal dichalcogenides not only possess intrinsic stimuli-responsive behaviours upon exposure to external stimuli, but molecular functionalization of these materials and/or combination with other materials to form mixed-dimensional heterostructures enables the manipulation and enhancement of their stimuli-responsive properties. Here, the authors review recent breakthroughs in the chemical design of smart transition metal dichalcogenides with built-in responsiveness.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-14"},"PeriodicalIF":5.9,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01322-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142496408","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}

{"title":"Rapid in situ carbon-13 hyperpolarization and imaging of acetate and pyruvate esters without external polarizer","authors":"Obaid Mohiuddin, Henri de Maissin, Andrey N. Pravdivtsev, Arne Brahms, Marvin Herzog, Leif Schröder, Eduard Y. Chekmenev, Rainer Herges, Jan-Bernd Hövener, Maxim Zaitsev, Dominik von Elverfeldt, Andreas B. Schmidt","doi":"10.1038/s42004-024-01316-x","DOIUrl":"10.1038/s42004-024-01316-x","url":null,"abstract":"Hyperpolarized 13C MRI visualizes real-time metabolic processes in vivo. In this study, we achieved high 13C polarization in situ in the bore of an MRI system for precursor molecules of most widely employed hyperpolarized agents: [1-13C]acetate and [1-13C]pyruvate ethyl esters in their perdeuterated forms, enhancing hyperpolarization lifetimes, hyperpolarized to P13C ≈ 28% at 80 mM concentration and P13C ≈ 19% at 10 mM concentration, respectively. Using vinyl esters as unsaturated Parahydrogen-Induced Polarization via Side-Arm Hydrogenation (PHIP-SAH) precursors and our novel polarization setup, we achieved these hyperpolarization levels by fast side-arm hydrogenation in acetone-d6 at elevated temperatures (up to 90°C) and hydrogenation pressures (up to 32 bar). We optimized the hyperpolarization process, reducing it to under 10 s, and employed advanced pulse sequences to enhance the polarization transfer efficiency. The hyperpolarization system has a small footprint, allowing it to be positioned in the same magnet, where 13C MRI is performed. We exemplified the utility of the design with sub-second in situ 13C MRI of ethyl [1-13C]pyruvate-d6. However, challenges remain in side-arm cleavage and purification in the MRI system to extract highly polarized aqueous agent solutions. Our results showcase efficient and rapid 13C hyperpolarization of these metabolite precursors in an MRI system with minimal additional hardware, promising to enhance future throughput and access to hyperpolarized 13C MRI. Hyperpolarized 13C MRI visualizes real-time metabolic processes in vivo, however, external polarizers are commonly required to produce hyperpolarized metabolites. Here, using a parahydrogen-based approach, the authors achieved up to 30% 13C polarization in situ in an MRI system for precursor molecules [1-13C]acetate and [1-13C]pyruvate ethyl esters in their perdeuterated forms, potentially facilitating future metabolic imaging applications.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11499913/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142496411","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}

{"title":"Ca3[C2O5]2[CO3] is a pyrocarbonate which can be formed at p, T-conditions prevalent in the Earth’s transition zone","authors":"Dominik Spahr, Lkhamsuren Bayarjargal, Maxim Bykov, Lukas Brüning, Pascal L. Jurzick, Yu Wang, Victor Milman, Keith Refson, Mohamed Mezouar, Björn Winkler","doi":"10.1038/s42004-024-01293-1","DOIUrl":"10.1038/s42004-024-01293-1","url":null,"abstract":"Understanding the fate of subducted carbonates is a prerequisite for the elucidation of the Earth’s deep carbon cycle. Here we show that the concomitant presence of Ca[CO3] with CO2 in a subducting slab very likely results in the formation of an anhydrous mixed pyrocarbonate, $${{{{rm{Ca}}}}}_{3}{left[{{{{rm{C}}}}}_{2}{{{{rm{O}}}}}_{5}right]}_{2}left[{{{{rm{CO}}}}}_{3}right]$$ , at moderate pressure ( ≈ 20 GPa) and temperature ( ≈ 1500 K) conditions. We show that at these conditions $${{{{rm{Ca}}}}}_{3}{left[{{{{rm{C}}}}}_{2}{{{{rm{O}}}}}_{5}right]}_{2}left[{{{{rm{CO}}}}}_{3}right]$$ can be obtained by reacting Ca[CO3] with CO2 in a laser-heated diamond anvil cell. The crystal structure was obtained from synchrotron-based single crystal X-ray diffraction data. Density Functional Perturbation Theory calculations in combination with experimental Raman spectroscopy results unambiguously confirmed the structural model. The crystal structure of $${{{{rm{Ca}}}}}_{3}{left[{{{{rm{C}}}}}_{2}{{{{rm{O}}}}}_{5}right]}_{2}left[{{{{rm{CO}}}}}_{3}right]$$ is characterized by the presence of $${left[{{{{rm{CO}}}}}_{3}right]}^{2-}$$ - and $${left[{{{{rm{C}}}}}_{2}{{{{rm{O}}}}}_{5}right]}^{2-}$$ -groups. The results presented here imply that the formation of $${{{{rm{Ca}}}}}_{3}{left[{{{{rm{C}}}}}_{2}{{{{rm{O}}}}}_{5}right]}_{2}left[{{{{rm{CO}}}}}_{3}right]$$ needs to be taken into account when constructing models of the deep carbon cycle of the Earth. Carbonates are transported into the deep Earth by subduction of the oceanic lithosphere, but the stability fields of subducted carbonates as a function of pressure, temperature, and composition remain incompletely described. Here, the authors synthesize the anhydrous, mixed pyrocarbonate Ca3[C2O5]2[CO3] from Ca[CO3] and CO2 in a laser-heated diamond anvil cell at moderate pressure and elucidate its structural features.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-7"},"PeriodicalIF":5.9,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11494096/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459773","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}

{"title":"Design principles, growth laws, and competition of minimal autocatalysts","authors":"Yann Sakref, Olivier Rivoire","doi":"10.1038/s42004-024-01250-y","DOIUrl":"10.1038/s42004-024-01250-y","url":null,"abstract":"The difficulty of designing simple autocatalysts that grow exponentially in the absence of enzymes, external drives or ingenious internal mechanisms severely constrains scenarios for the emergence of evolution by natural selection in chemical and physical systems. Here, we systematically analyze these difficulties in the simplest and most generic autocatalyst: a dimeric molecule that duplicates by templated ligation. We show that despite its simplicity, such an autocatalyst can achieve exponential growth autonomously. We also show, however, that it is possible to design as simple sub-exponential autocatalysts that have an advantage over exponential autocatalysts when competing for a common resource. We reach these conclusions by developing a theoretical framework based on kinetic barrier diagrams. Besides challenging commonly accepted assumptions in the field of the origin of life, our results provide a blueprint for the experimental realization of elementary autocatalysts exhibiting a form of natural selection, whether on a molecular or colloidal scale. Autocatalysis plays an important role in the origin of life and molecular evolution, however, designing simple autocatalysts that grow exponentially remains challenging. Here, the authors computationally design simple autocatalysts-- dimeric molecules that duplicate by templated ligation, --and show that these autocatalysts can achieve exponential growth autonomously.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-10"},"PeriodicalIF":5.9,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11494078/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459774","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}

{"title":"Discovery of Trypanosoma brucei inhibitors enabled by a unified synthesis of diverse sulfonyl fluorides","authors":"Brian S. Mantilla, Jack S. White, William R. T. Mosedale, Andrew Gomm, Adam Nelson, Terry K. Smith, Megan H. Wright","doi":"10.1038/s42004-024-01327-8","DOIUrl":"10.1038/s42004-024-01327-8","url":null,"abstract":"Sets of electrophilic probes are generally prepared using a narrow toolkit of robust reactions, which tends to limit both their structural and functional diversity. A unified synthesis of skeletally-diverse sulfonyl fluorides was developed that relied upon photoredox-catalysed dehydrogenative couplings between hetaryl sulfonyl fluorides and hydrogen donor building blocks. A set of 32 diverse probes was prepared, and then screened against Trypanosoma brucei. Four of the probes were found to have sub-micromolar anti-trypanosomal activity. A chemical proteomic approach, harnessing an alkynylated analogue and broad-spectrum fluorophosphonate tools, provided insights into the observed anti-trypanosomal activity, which likely stems from covalent modification of multiple protein targets. It is envisaged that the unified diversity-oriented approach may enable the discovery of electrophilic probes that have value in the elucidation of biological and biomedical mechanisms. Electrophilic bioactive compounds are useful chemical tools for identifying and modulating protein targets through reaction with nucleophilic amino acid side chain residues. Here, the authors report a modular synthesis of electrophilic sulfonyl fluoride probes, and evaluate their anti-trypanosomal activity using a chemoproteomics approach","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01327-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451337","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}

{"title":"Steviol rebaudiosides bind to four different sites of the human sweet taste receptor (T1R2/T1R3) complex explaining confusing experiments","authors":"Shuang Hao, Brian Guthrie, Soo-Kyung Kim, Sergej Balanda, Jan Kubicek, Babar Murtaza, Naim A. Khan, Pouyan Khakbaz, Judith Su, William A. Goddard III","doi":"10.1038/s42004-024-01324-x","DOIUrl":"10.1038/s42004-024-01324-x","url":null,"abstract":"Sucrose provides both sweetness and energy by binding to both Venus flytrap domains (VFD) of the heterodimeric sweet taste receptor (T1R2/T1R3). In contrast, non-caloric sweeteners such as sucralose and aspartame only bind to one specific domain (VFD2) of T1R2, resulting in high-intensity sweetness. In this study, we investigate the binding mechanism of various steviol glycosides, artificial sweeteners, and a negative allosteric modulator (lactisole) at four distinct binding sites: VFD2, VFD3, transmembrane domain 2 (TMD2), and TMD3 through binding experiments and computational docking studies. Our docking results reveal multiple binding sites for the tested ligands, including the radiolabeled ligands. Our experimental evidence demonstrates that the C20 carboxy terminus of the Gα protein can bind to the intracellular region of either TMD2 or TMD3, altering GPCR affinity to the high-affinity state for steviol glycosides. These findings provide a mechanistic understanding of the structure and function of this heterodimeric sweet taste receptor. Sucrose and other non-caloric sweeteners can bind to different domains of the heterodimeric sweet taste receptor (T1R2/T1R3), resulting in different levels of sweetness. Here, the authors investigate the binding mechanism of various steviol glycosides, artificial sweeteners, and a negative allosteric modulator (lactisole) at four distinct binding sites of T1R2/T1R3 through binding experiments and computational docking studies, revealing multiple binding sites for the tested ligands and structural– function correlations of ligand–receptor interactions.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-17"},"PeriodicalIF":5.9,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01324-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451321","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}