Communications Chemistry最新文献

{"title":"Through-bond and through-space radiofrequency amplification by stimulated emission of radiation","authors":"Ivan A. Trofimov, Oleg G. Salnikov, Andrey N. Pravdivtsev, Henri de Maissin, Anna P. Yi, Eduard Y. Chekmenev, Jan-Bernd Hövener, Andreas B. Schmidt, Igor V. Koptyug","doi":"10.1038/s42004-024-01313-0","DOIUrl":"10.1038/s42004-024-01313-0","url":null,"abstract":"Radio Amplification by Stimulated Emission of Radiation (RASER) is a phenomenon observed during nuclear magnetic resonance (NMR) experiments with strongly negatively polarized systems. This phenomenon may be utilized for the production of very narrow NMR lines, background-free NMR spectroscopy, and excitation-free sensing of chemical transformations. Recently, novel methods of producing RASER by ParaHydrogen-Induced Polarization (PHIP) were introduced. Here, we show that pairwise addition of parahydrogen to various propargylic compounds induces RASER activity of other protons beyond those chemically introduced in the reaction. In high-field PHIP, negative polarization initiating RASER is transferred via intramolecular cross-relaxation. When parahydrogen is added in Earth’s field followed by adiabatic transfer to a high field, RASER activity of other protons is induced via both J-couplings and cross-relaxation. This through-bond and through-space induction of RASER holds potential for the ongoing development and expansion of RASER applications and can potentially enhance spectral resolution in two-dimensional NMR spectroscopy techniques. Radio Amplification by Stimulated Emission of Radiation (RASER) may produce very narrow NMR lines, background-free NMR spectroscopy, and excitation-free sensing of chemical transformations. Here, the authors show that pairwise addition of parahydrogen to various propargylic compounds induces RASER activity of other protons beyond those chemically introduced in the reaction via through-bond or through-space interactions.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01313-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451310","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":"Women in Chemistry: Q&A with Professor Malika Jeffries-EL","authors":"","doi":"10.1038/s42004-024-01314-z","DOIUrl":"10.1038/s42004-024-01314-z","url":null,"abstract":"Malika Jeffries-EL is the Senior Dean of the Graduate School in Arts and Sciences and Professor of Chemistry and Materials Science at Boston University. Professor Jeffries-EL’s research focuses on the development of organic semiconductors—materials that combine the processing properties of polymers with the electronic properties of semiconductors.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-2"},"PeriodicalIF":5.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01314-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142406205","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 a potent, Kv7.3-selective potassium channel opener from a Polynesian traditional botanical anticonvulsant","authors":"Geoffrey W. Abbott, Rían W. Manville","doi":"10.1038/s42004-024-01318-9","DOIUrl":"10.1038/s42004-024-01318-9","url":null,"abstract":"Plants remain an important source of biologically active small molecules with high therapeutic potential. The voltage-gated potassium (Kv) channel formed by Kv7.2/3 (KCNQ2/3) heteromers is a major target for anticonvulsant drug development. Here, we screened 1444 extracts primarily from plants collected in California and the US Virgin Islands, for their ability to activate Kv7.2/3 but not inhibit Kv1.3, to select against tannic acid being the active component. We validated the 7 strongest hits, identified Thespesia populnea (miro, milo, portia tree) as the most promising, then discovered its primary active metabolite to be gentisic acid (GA). GA highly potently activated Kv7.2/3 (EC50, 2.8 nM). GA is, uniquely to our knowledge, 100% selective for Kv7.3 versus other Kv7 homomers; it requires S5 residue Kv7.3-W265 for Kv7.2/3 activation, and it ameliorates pentylenetetrazole-induced seizures in mice. Structure-activity studies revealed that the FDA-approved vasoprotective drug calcium dobesilate, a GA analog, is a previously unrecognized Kv7.2/3 channel opener. Also an active aspirin metabolite, GA provides a molecular rationale for the use of T. populnea as an anticonvulsant in Polynesian indigenous medicine and presents novel pharmacological prospects for potent, isoform-selective, therapeutic Kv7 channel activation. The voltage-gated potassium (Kv) channel formed by Kv7.2/3 heteromers is a major target for anticonvulsant drug development, however, specificity and potency are key challenges for Kv7.2/3 opener development. Here, the authors report the discovery of gentisic acid as a potent and selective Kv7.3 opener from Thespesia populnea — a plant reportedly used as an anticonvulsant in Polynesian traditional medicine.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-15"},"PeriodicalIF":5.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01318-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142399633","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":"Quasicrystal synthesis by shock compression","authors":"Jinping Hu, Paul D. Asimow, Chi Ma, Paul J. Steinhardt, Luca Bindi","doi":"10.1038/s42004-024-01319-8","DOIUrl":"10.1038/s42004-024-01319-8","url":null,"abstract":"Quasicrystals are of interest because of their unique nonperiodic structures and physical properties. Motivated by naturally occurring icosahedral AlCuFe- and decagonal AlNiFe-phases hosted in a shocked meteorite, different laboratories have undertaken a series of shock recovery experiments to understand their formation mechanism. Shock experiments generate a complex series of processes and conditions, including a near-instantaneous excursion to high pressure and high temperature, large shear stresses, local melting, rapid decompression, fast quenching and post-shock annealing. This highly dynamic scenario offers a very useful but imperfect tool for exploring the stability of novel alloys, such as quasicrystals. So far, all the shock-synthesized quasicrystals differ considerably in composition from any thermodynamically stable or metastable quasicrystals synthesized by metallurgical techniques at low pressure, leaving plenty of questions to be answered about their formation conditions and their nucleation and growth mechanisms occurring during shock experiments. In this Perspective, we summarize the previous studies of shock-synthesized quasicrystals and discuss the advantages and difficulties caused by the experimental complexity. We also propose a few directions for future experiments to better control the shock conditions and understand the properties of quasicrystals. Shock compression is a highly dynamic, useful tool for exploring the stability of novel alloys such as quasicrystals, but their formation conditions and the nucleation-growth mechanisms occurring during shock experiments remain largely elusive. Here, the authors provide a summary of quasicrystal shock-syntheses and discuss the advantages and difficulties caused by the experimental complexity.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01319-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142399634","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":"Plasmonic semi shells derived from simultaneous in situ gold growth and anisotropic acid etching of ZIF-8 for photothermal ablation of metastatic breast tumor","authors":"Kritika Sood, Purvi Mathur, Sulagna Rath, Pranjali Yadav, Navneet Kaur, Priyanka Sharma,  Mimansa, Deepak Singh Chauhan, Sonalika Vaidya, Rohit Srivastava, Abhijit De, Asifkhan Shanavas","doi":"10.1038/s42004-024-01317-w","DOIUrl":"10.1038/s42004-024-01317-w","url":null,"abstract":"Open nanoshells such as nanobowls or nanocups collectively described as ‘semi shells’ have unique plasmonic properties due to their lack of symmetry. So far, their fabrication was based on multistep and laborious methods such as solid state sputter coating or selective deposition/etching using sacrificial templates. In this work, we report a rapid one step colloidal synthetic protocol for PEGylated semi-shell (SS) fabrication by simultaneous facet specific anisotropic chemical etching of rhombic dodecahedral ZIF-8 and heterogenous nucleation & growth of gold. The SS possesses a strong localized surface plasmon resonance in the near-infrared region, which is retained after surface passivation with polyethylene glycol and subsequent cryopreservation for extended shelf-life. Freshly reconstituted PEGylated SS was found to be safe & non-toxic in healthy C57BL/6 mice post intravenous administration. The PEGylated SS displayed significant photothermal efficiency of ~37% with 808 nm laser irradiation. Preclinical assessment of intra-tumoral photothermal efficacy indicated complete remission of primary breast tumor mass with insignificant metastasis to vital organs in 4T1 FL2 tumor bearing CD1 nude mice. Further, PEGylated SS mediated photothermal therapy also yielded morbidity free survivael of 75% for up to 90 days, indicating their potential to significantly improve outcomes in advanced breast tumors. Anisotropic gold-based colloidal nanoparticles such as semi shells have unique optical properties and widespread applications such as in bioimaging, biosensing and therapy, however, the fabrication process of semi shells remains a challenge due to laborious multistep solid state and colloidal procedures. In this study, the authors develop a rapid one-pot colloidal synthetic route for the fabrication of semi shells using ZIF-8 as a sacrificial template, and demonstrate their promise for photothermal therapy.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-13"},"PeriodicalIF":5.9,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11464763/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142388669","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":"Cell stress and phase separation stabilize the monomeric state of pseudoisocyanine chloride employed as a self-assembly crowding sensor","authors":"Roland Pollak, Leon Koch, Benedikt König, Sara S. Ribeiro, Nirnay Samanta, Klaus Huber, Simon Ebbinghaus","doi":"10.1038/s42004-024-01315-y","DOIUrl":"10.1038/s42004-024-01315-y","url":null,"abstract":"Cellular stress and ageing involve an increase in crowding and aggregation of amylogenic proteins. We here investigate if crowding is the intrinsic cause of aggregation and utilise a previously established non-protein aggregation sensor, namely pseudoisocyanine chloride (PIC). PIC shows fibrillization in cells into a highly fluorescent J-aggregated state and is sensitive to crowding. Surprisingly, cell stress conditions stabilise the monomeric rather than the aggregated state of PIC both in the cytoplasm and in stress granules. Regarding the different physiochemical changes of the cytoplasm occurring upon cell stress, involving volume reduction, phase separation and solidification, the intrinsic crowding effect is not the key factor to drive associated self-assembly processes. Cellular stress and ageing involve an increase in crowding and aggregation of amylogenic proteins, but the connection between protein destabilisation and the onset of aggregation is poorly understood. Here, the authors utilize a non-protein aggregation sensor based on pseudoisocyanine chloride to analyse the effect of macromolecular crowding in the cytoplasm on the self-assembly process, and find that the high crowding densities observed in the cytoplasm and stress granules upon stress are not an intrinsic cause for aggregation of amylogenic proteins.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-8"},"PeriodicalIF":5.9,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11458801/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142388668","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":"Switchable protection and exposure of a sensitive squaraine dye within a redox active rotaxane","authors":"Janos Wasternack, Hendrik V. Schröder, J. Felix Witte, Mihkel Ilisson, Henrik Hupatz, Julian F. Hille, Marius Gaedke, Arto M. Valkonen, Sebastian Sobottka, Alexander Krappe, Mario Schubert, Beate Paulus, Kari Rissanen, Biprajit Sarkar, Siegfried Eigler, Ute Resch-Genger, Christoph A. Schalley","doi":"10.1038/s42004-024-01312-1","DOIUrl":"10.1038/s42004-024-01312-1","url":null,"abstract":"In nature, molecular environments in proteins can sterically protect and stabilize reactive species such as organic radicals through non-covalent interactions. Here, we report a near-infrared fluorescent rotaxane in which the stabilization of a chemically labile squaraine fluorophore by the coordination of a tetralactam macrocycle can be controlled chemically and electrochemically. The rotaxane can be switched between two co-conformations in which the wheel either stabilizes or exposes the fluorophore. Coordination by the wheel affects the squaraine’s stability across four redox states and renders the radical anion significantly more stable—by a factor of 6.7—than without protection by a mechanically bonded wheel. Furthermore, the fluorescence properties can be tuned by the redox reactions in a stepwise manner. Mechanically interlocked molecules provide an excellent scaffold to stabilize and selectively expose reactive species in a co-conformational switching process controlled by external stimuli. Incorporating sensitive chromophores into interlocked systems that are mechanically responsive to external stimuli is attractive for tuning of the dye’s optical properties and stability. Here, the authors report the mechanically controlled protection and deprotection of a squaraine dye within a [2]rotaxane, governed by macrocycle shielding/de-shielding upon chloride addition or oxidation.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-11"},"PeriodicalIF":5.9,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11452610/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142375235","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":"Women in Chemistry: Q&A with Dr Shira Joudan","authors":"","doi":"10.1038/s42004-024-01303-2","DOIUrl":"10.1038/s42004-024-01303-2","url":null,"abstract":"Dr Shira Joudan is an Assistant Professor in the Department of Chemistry at the University of Alberta in Edmonton, Canada. Her environmental analytical chemistry research group studies the environmental fate of organic contaminants, including halogenated chemicals like per- and polyfluoroalkyl substances (PFAS).","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-2"},"PeriodicalIF":5.9,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11452680/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142375236","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":"Conditions for enhancement of gas phase chemical reactions inside a dark microwave cavity","authors":"Nimrod Moiseyev","doi":"10.1038/s42004-024-01286-0","DOIUrl":"10.1038/s42004-024-01286-0","url":null,"abstract":"The ability to slow down or enhance chemical reactions, by a seemingly simple setup of reactions inside a cavity made of two parallel mirrors is fascinating. Unfortunately, currently, theory and experiment have not yet fully converged. Since theory and experiment perfectly match for atom/molecular collisions in gas phase the enhancing chemical reactions in gas phase through its coupling to quantized electromagnetic modes in a dark cavity is investigated. Here the conditions and guidelines for selecting the proper type of reactions that can be enhanced by a dark cavity are provided. Showing that the asymmetric reaction rates of O + D2 → [ODD]# → OD + D and H + ArCl → [ArHCl]# → H + Ar + Cl can be enhanced by a dark cavity. On the other hand, an effect of the dark cavity on the symmetric reaction of hydrogen exchange in methane is predicted to be negligible. Notice that the theory is not limited to microwave cavities only. The ability to slow down or enhance chemical reactions inside a cavity made of two parallel mirrors is fascinating but remains somewhat enigmatic. Here, the author presents a theoretical concept aimed at helping experimentalists select chemical reactions whose rates can be enhanced inside a dark microwave cavity.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-10"},"PeriodicalIF":5.9,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01286-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142364715","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":"Machine learning analysis of a large set of homopolymers to predict glass transition temperatures","authors":"Gerardo M. Casanola-Martin, Anas Karuth, Hai Pham-The, Humbert González-Díaz, Dean C. Webster, Bakhtiyor Rasulev","doi":"10.1038/s42004-024-01305-0","DOIUrl":"10.1038/s42004-024-01305-0","url":null,"abstract":"Glass transition temperature of polymers, Tg, is an important thermophysical property, which sometimes can be difficult to measure experimentally. In this regard, data-driven machine learning approaches are important alternatives to assess Tg values, in a high-throughput way. In this study, a large dataset of more than 900 polymers with reported glass transition temperature (Tg) was assembled from various public sources in order to develop a predictive model depicting the structure-property relationships. The collected dataset was curated, explored via cluster analysis, and then split into training and test sets for validation purposes and then polymer structures characterized by molecular descriptors. To find the models, several machine learning techniques, including multiple linear regression (MLR), k-nearest neighbor (k-NN), support vector machine (SVM), random forest (RF), gaussian processes for regression (GPR), and multi-layer perceptron (MLP) were explored. As result, a model with the subset of 15 descriptors accurately predicting the glass transition temperatures was developed. The electronic effect indices were determined to be important properties that positively contribute to the Tg values. The SVM-based model showed the best performance with determination coefficients (R2) of 0.813 and 0.770, for training and test sets, respectively. Also, the SVM model showed the lowest estimation error, RMSE = 0.062. In addition, the developed structure-property model was implemented as a web app to be used as an online computational tool to design and evaluate new homopolymers with desired glass transition profiles. Glass transition temperatures (Tg) of polymers are important thermophysical descriptors, but they can be difficult to determine experimentally. Here, the authors develop a data-driven support vector machine structure-property model to assess Tg values in a high-throughput manner, and implement the model into a web app.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01305-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142364716","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}