[{"isi":1,"tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"intvolume":"       147","has_accepted_license":"1","date_published":"2025-08-01T00:00:00Z","ddc":["540"],"OA_type":"hybrid","corr_author":"1","author":[{"last_name":"Tatman","first_name":"Benjamin","id":"71cda2f3-e604-11ee-a1df-da10587eda3f","full_name":"Tatman, Benjamin"},{"first_name":"Vidhyalakshmi","last_name":"Sridharan","full_name":"Sridharan, Vidhyalakshmi"},{"first_name":"Motilal","last_name":"Uttarkabat","full_name":"Uttarkabat, Motilal"},{"full_name":"Jaroniec, Christopher P.","first_name":"Christopher P.","last_name":"Jaroniec"},{"last_name":"Ernst","first_name":"Matthias","full_name":"Ernst, Matthias"},{"last_name":"Rovo","first_name":"Petra","orcid":"0000-0001-8729-7326","id":"c316e53f-b965-11eb-b128-bb26acc59c00","full_name":"Rovo, Petra"},{"last_name":"Schanda","first_name":"Paul","id":"7B541462-FAF6-11E9-A490-E8DFE5697425","full_name":"Schanda, Paul","orcid":"0000-0002-9350-7606"}],"day":"01","PlanS_conform":"1","year":"2025","file":[{"file_id":"20337","file_name":"2025_JACS_Tatman.pdf","success":1,"access_level":"open_access","checksum":"b350d56ddddefea96cebd62c277c0ff5","relation":"main_file","date_created":"2025-09-10T07:53:10Z","file_size":5235353,"date_updated":"2025-09-10T07:53:10Z","content_type":"application/pdf","creator":"dernst"}],"status":"public","pmid":1,"publication_status":"published","publisher":"American Chemical Society","article_type":"original","date_updated":"2026-06-10T08:33:41Z","acknowledged_ssus":[{"_id":"NMR"},{"_id":"LifeSc"}],"page":"29315-29326","external_id":{"isi":["001542746200001"],"pmid":["40748291"]},"article_processing_charge":"Yes (via OA deal)","file_date_updated":"2025-09-10T07:53:10Z","abstract":[{"lang":"eng","text":"Microsecond-to-millisecond motions are instrumental for many biomolecular functions, including enzymatic activity and ligand binding. Bloch-McConnell Relaxation Dispersion (BMRD) Nuclear Magnetic Resonance (NMR) spectroscopy is a key technique for studying these dynamic processes. While BMRD experiments are routinely used to probe protein motions in solution, the experiment is more demanding in the solid state, where dipolar couplings complicate the spin dynamics. It is believed that high deuteration levels are required and sufficient to obtain accurate and quantitative data. Here we show that even under fast magic-angle spinning and high levels of deuteration artifactual “bumps” in 15N R1ρ BMRD profiles are common. The origin of these artifacts is identified as a second-order three-spin Mixed Rotational and Rotary Resonance (MIRROR) recoupling condition. These artifacts are found to be a significant confounding factor for the accurate quantification of microsecond protein dynamics using BMRD in the solid state. We show that the application of low-power continuous wave (CW) decoupling simultaneously with the 15N spin-lock leads to the suppression of these conditions and enables quantitative measurements of microsecond exchange in the solid state. Remarkably, the application of decoupling allows the measurement of accurate BMRD even in fully protonated proteins at 100 kHz MAS, thus extending the scope of μs dynamics measurements in MAS NMR."}],"publication":"Journal of the American Chemical Society","volume":147,"title":"Bumps on the road: The way to clean relaxation dispersion magic-angle spinning NMR","issue":"32","language":[{"iso":"eng"}],"quality_controlled":"1","OA_place":"publisher","department":[{"_id":"PaSc"},{"_id":"NMR"}],"oa":1,"oa_version":"Published Version","date_created":"2025-09-10T05:37:19Z","doi":"10.1021/jacs.5c09057","publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"_id":"20321","related_material":{"record":[{"id":"19696","status":"public","relation":"used_in_publication"}]},"acknowledgement":"The authors thank Alexey Krushelnitsky for useful discussions. C.P.J. thanks NSF (MCB-2303862) and NIH (R35GM156238 and S10OD012303) for funding. This research was supported by the Scientific Service Units (SSU) of Institute of Science and Technology Austria (ISTA) through resources provided by the Nuclear Magnetic Resonance and the Lab Support Facilities.","scopus_import":"1","citation":{"ista":"Tatman B, Sridharan V, Uttarkabat M, Jaroniec CP, Ernst M, Rovo P, Schanda P. 2025. Bumps on the road: The way to clean relaxation dispersion magic-angle spinning NMR. Journal of the American Chemical Society. 147(32), 29315–29326.","apa":"Tatman, B., Sridharan, V., Uttarkabat, M., Jaroniec, C. P., Ernst, M., Rovo, P., &#38; Schanda, P. (2025). Bumps on the road: The way to clean relaxation dispersion magic-angle spinning NMR. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.5c09057\">https://doi.org/10.1021/jacs.5c09057</a>","short":"B. Tatman, V. Sridharan, M. Uttarkabat, C.P. Jaroniec, M. Ernst, P. Rovo, P. Schanda, Journal of the American Chemical Society 147 (2025) 29315–29326.","mla":"Tatman, Benjamin, et al. “Bumps on the Road: The Way to Clean Relaxation Dispersion Magic-Angle Spinning NMR.” <i>Journal of the American Chemical Society</i>, vol. 147, no. 32, American Chemical Society, 2025, pp. 29315–26, doi:<a href=\"https://doi.org/10.1021/jacs.5c09057\">10.1021/jacs.5c09057</a>.","ieee":"B. Tatman <i>et al.</i>, “Bumps on the road: The way to clean relaxation dispersion magic-angle spinning NMR,” <i>Journal of the American Chemical Society</i>, vol. 147, no. 32. American Chemical Society, pp. 29315–29326, 2025.","ama":"Tatman B, Sridharan V, Uttarkabat M, et al. Bumps on the road: The way to clean relaxation dispersion magic-angle spinning NMR. <i>Journal of the American Chemical Society</i>. 2025;147(32):29315-29326. doi:<a href=\"https://doi.org/10.1021/jacs.5c09057\">10.1021/jacs.5c09057</a>","chicago":"Tatman, Benjamin, Vidhyalakshmi Sridharan, Motilal Uttarkabat, Christopher P. Jaroniec, Matthias Ernst, Petra Rovo, and Paul Schanda. “Bumps on the Road: The Way to Clean Relaxation Dispersion Magic-Angle Spinning NMR.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2025. <a href=\"https://doi.org/10.1021/jacs.5c09057\">https://doi.org/10.1021/jacs.5c09057</a>."},"month":"08","user_id":"317138e5-6ab7-11ef-aa6d-ffef3953e345","type":"journal_article"},{"day":"11","year":"2024","file":[{"file_name":"2024_BioMacromolecules_Wu.pdf","file_id":"18180","success":1,"relation":"main_file","date_created":"2024-10-07T08:33:35Z","checksum":"9552b6d52f1e8a350764849a535fc13e","access_level":"open_access","creator":"dernst","file_size":6597227,"date_updated":"2024-10-07T08:33:35Z","content_type":"application/pdf"}],"publication_status":"published","pmid":1,"status":"public","publisher":"American Chemical Society","article_type":"original","date_updated":"2025-09-08T09:52:18Z","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"isi":1,"intvolume":"        25","has_accepted_license":"1","date_published":"2024-03-11T00:00:00Z","ddc":["540"],"corr_author":"1","author":[{"last_name":"Wu","first_name":"Dongqing","full_name":"Wu, Dongqing"},{"full_name":"Koscic, Anamaria","last_name":"Koscic","first_name":"Anamaria"},{"last_name":"Schneider","first_name":"Sonja","full_name":"Schneider, Sonja"},{"last_name":"Dubini","first_name":"Romeo C. A.","full_name":"Dubini, Romeo C. A."},{"full_name":"Rodriguez Camargo, Diana C.","last_name":"Rodriguez Camargo","first_name":"Diana C."},{"full_name":"Schneider, Sabine","first_name":"Sabine","last_name":"Schneider"},{"first_name":"Petra","last_name":"Rovo","full_name":"Rovo, Petra","id":"c316e53f-b965-11eb-b128-bb26acc59c00","orcid":"0000-0001-8729-7326"}],"language":[{"iso":"eng"}],"quality_controlled":"1","issue":"3","department":[{"_id":"NMR"}],"oa":1,"oa_version":"Published Version","_id":"18168","publication_identifier":{"eissn":["1526-4602"],"issn":["1525-7797"]},"doi":"10.1021/acs.biomac.3c01239","date_created":"2024-10-02T10:09:53Z","acknowledgement":"We thank Dr. Pavel Kielkowski for performing the MS/MS measurement and providing feedback on the manuscript. We are grateful to Rodrigo Ledesma Amaro for introducing the Golden Gate Assembly technique in our lab. We acknowledge the support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)─SFB 1309-325871075, the Center for NanoScience (CeNS), the Fonds der Chemischen Industrie, and Universitätsgesellschaft München.","citation":{"ista":"Wu D, Koscic A, Schneider S, Dubini RCA, Rodriguez Camargo DC, Schneider S, Rovo P. 2024. Unveiling the dynamic self-assembly of a recombinant dragline-silk-mimicking protein. Biomacromolecules. 25(3), 1759–1774.","apa":"Wu, D., Koscic, A., Schneider, S., Dubini, R. C. A., Rodriguez Camargo, D. C., Schneider, S., &#38; Rovo, P. (2024). Unveiling the dynamic self-assembly of a recombinant dragline-silk-mimicking protein. <i>Biomacromolecules</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acs.biomac.3c01239\">https://doi.org/10.1021/acs.biomac.3c01239</a>","mla":"Wu, Dongqing, et al. “Unveiling the Dynamic Self-Assembly of a Recombinant Dragline-Silk-Mimicking Protein.” <i>Biomacromolecules</i>, vol. 25, no. 3, American Chemical Society, 2024, pp. 1759–74, doi:<a href=\"https://doi.org/10.1021/acs.biomac.3c01239\">10.1021/acs.biomac.3c01239</a>.","ieee":"D. Wu <i>et al.</i>, “Unveiling the dynamic self-assembly of a recombinant dragline-silk-mimicking protein,” <i>Biomacromolecules</i>, vol. 25, no. 3. American Chemical Society, pp. 1759–1774, 2024.","short":"D. Wu, A. Koscic, S. Schneider, R.C.A. Dubini, D.C. Rodriguez Camargo, S. Schneider, P. Rovo, Biomacromolecules 25 (2024) 1759–1774.","chicago":"Wu, Dongqing, Anamaria Koscic, Sonja Schneider, Romeo C. A. Dubini, Diana C. Rodriguez Camargo, Sabine Schneider, and Petra Rovo. “Unveiling the Dynamic Self-Assembly of a Recombinant Dragline-Silk-Mimicking Protein.” <i>Biomacromolecules</i>. American Chemical Society, 2024. <a href=\"https://doi.org/10.1021/acs.biomac.3c01239\">https://doi.org/10.1021/acs.biomac.3c01239</a>.","ama":"Wu D, Koscic A, Schneider S, et al. Unveiling the dynamic self-assembly of a recombinant dragline-silk-mimicking protein. <i>Biomacromolecules</i>. 2024;25(3):1759-1774. doi:<a href=\"https://doi.org/10.1021/acs.biomac.3c01239\">10.1021/acs.biomac.3c01239</a>"},"scopus_import":"1","type":"journal_article","user_id":"317138e5-6ab7-11ef-aa6d-ffef3953e345","month":"03","external_id":{"pmid":["38343096"],"isi":["001166501000001"]},"article_processing_charge":"Yes (via OA deal)","page":"1759-1774","file_date_updated":"2024-10-07T08:33:35Z","volume":25,"abstract":[{"text":"Despite the considerable interest in the recombinant production of synthetic spider silk fibers that possess mechanical properties similar to those of native spider silks, such as the cost-effectiveness, tunability, and scalability realization, is still lacking. To address this long-standing challenge, we have constructed an artificial spider silk gene using Golden Gate assembly for the recombinant bacterial production of dragline-mimicking silk, incorporating all the essential components: the N-terminal domain, a 33-residue-long major-ampullate-spidroin-inspired segment repeated 16 times, and the C-terminal domain (N16C). This designed silk-like protein was successfully expressed in Escherichia coli, purified, and cast into films from formic acid. We produced uniformly 13C–15N-labeled N16C films and employed solid-state magic-angle spinning nuclear magnetic resonance (NMR) for characterization. Thus, we could demonstrate that our bioengineered silk-like protein self-assembles into a film where, when hydrated, the solvent-exposed layer of the rigid, β-nanocrystalline polyalanine core undergoes a transition to an α-helical structure, gaining mobility to the extent that it fully dissolves in water and transforms into a highly dynamic random coil. This hydration-induced behavior induces chain dynamics in the glycine-rich amorphous soft segments on the microsecond time scale, contributing to the elasticity of the solid material. Our findings not only reveal the presence of structurally and dynamically distinct segments within the film’s superstructure but also highlight the complexity of the self-organization responsible for the exceptional mechanical properties observed in proteins that mimic dragline silk.","lang":"eng"}],"publication":"Biomacromolecules","title":"Unveiling the dynamic self-assembly of a recombinant dragline-silk-mimicking protein"},{"intvolume":"         5","tmp":{"name":"Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)","short":"CC BY-NC-ND (4.0)","image":"/images/cc_by_nc_nd.png","legal_code_url":"https://creativecommons.org/licenses/by-nc-nd/4.0/legalcode"},"has_accepted_license":"1","date_published":"2023-01-01T00:00:00Z","ddc":["530"],"author":[{"full_name":"Dass, Avinash Vicholous","first_name":"Avinash Vicholous","last_name":"Dass"},{"full_name":"Wunnava, Sreekar","last_name":"Wunnava","first_name":"Sreekar"},{"full_name":"Langlais, Juliette","last_name":"Langlais","first_name":"Juliette"},{"first_name":"Beatriz","last_name":"von der Esch","full_name":"von der Esch, Beatriz"},{"first_name":"Maik","last_name":"Krusche","full_name":"Krusche, Maik"},{"full_name":"Ufer, Lennard","last_name":"Ufer","first_name":"Lennard"},{"last_name":"Chrisam","first_name":"Nico","full_name":"Chrisam, Nico"},{"first_name":"Romeo C. A.","last_name":"Dubini","full_name":"Dubini, Romeo C. A."},{"first_name":"Florian","last_name":"Gartner","full_name":"Gartner, Florian"},{"full_name":"Angerpointner, Severin","last_name":"Angerpointner","first_name":"Severin"},{"last_name":"Dirscherl","first_name":"Christina F.","full_name":"Dirscherl, Christina F."},{"orcid":"0000-0001-8729-7326","id":"c316e53f-b965-11eb-b128-bb26acc59c00","full_name":"Rovo, Petra","last_name":"Rovo","first_name":"Petra"},{"full_name":"Mast, Christof B.","first_name":"Christof B.","last_name":"Mast"},{"first_name":"Judit E.","last_name":"Šponer","full_name":"Šponer, Judit E."},{"full_name":"Ochsenfeld, Christian","first_name":"Christian","last_name":"Ochsenfeld"},{"full_name":"Frey, Erwin","first_name":"Erwin","last_name":"Frey"},{"full_name":"Braun, Dieter","first_name":"Dieter","last_name":"Braun"}],"year":"2023","day":"01","file":[{"success":1,"file_name":"2023_ChemSystemsChem_Dass.pdf","file_id":"17355","creator":"dernst","date_updated":"2024-07-31T11:20:58Z","content_type":"application/pdf","file_size":860679,"date_created":"2024-07-31T11:20:58Z","relation":"main_file","checksum":"b1e78c60e371f87bdf43970f17d1cb0b","access_level":"open_access"}],"publication_status":"published","status":"public","date_updated":"2025-07-10T11:51:15Z","article_type":"original","publisher":"Wiley","article_processing_charge":"Yes (via OA deal)","volume":5,"publication":"ChemSystemsChem","abstract":[{"lang":"eng","text":"For the emergence of life, the abiotic synthesis of RNA from its monomers is a central step. We found that in alkaline, drying conditions in bulk and at heated air‐water interfaces, 2′,3′‐cyclic nucleotides oligomerised without additional catalyst, forming up to 10‐mers within a day. The oligomerisation proceeded at a pH range of 7–12, at temperatures between 40–80 °C and was marginally enhanced by K<jats:sup>+</jats:sup> ions. Among the canonical ribonucleotides, cGMP oligomerised most efficiently. Quantification was performed using HPLC coupled to ESI‐TOF by fitting the isotope distribution to the mass spectra. Our study suggests a oligomerisation mechanism where cGMP aids the incorporation of the relatively unreactive nucleotides C, A and U. The 2′,3′‐cyclic ribonucleotides are byproducts of prebiotic phosphorylation, nucleotide syntheses and RNA hydrolysis, indicating direct recycling pathways. The simple reaction condition offers a plausible entry point for RNA to the evolution of life on early Earth."}],"file_date_updated":"2024-07-31T11:20:58Z","title":"RNA oligomerisation without added catalyst from 2′,3′‐cyclic nucleotides by drying at air-water interfaces","article_number":"e202200026","language":[{"iso":"eng"}],"quality_controlled":"1","issue":"1","oa_version":"Published Version","oa":1,"department":[{"_id":"NMR"}],"acknowledgement":"We would like to thank Ulrich Gerland, Tobias Göppel, Joachim Rosenberger and Bernhard Altaner for their helpful remarks and discussions; Thomas Matreux, Alexandra Kühnlein, Noël Yeh Martin and Maximilian Weingart for comments on the manuscript. The authors thank J. Kussmann (LMU Munich) for providing a development version of the FermiONs++ program package. Financial support was provided by the European Research Council (ERC Evotrap, grant no. 787356, the Simons Foundation (grant no. 327125), the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – Project-ID 364653263 – TRR 235 (CRC 235), the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy – EXC-2094 – 390783311, and the Center for NanoScience. Open Access funding enabled and organized by Projekt DEAL.","_id":"17078","publication_identifier":{"issn":["2570-4206"]},"date_created":"2024-05-29T06:13:48Z","doi":"10.1002/syst.202200026","type":"journal_article","month":"01","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","citation":{"apa":"Dass, A. V., Wunnava, S., Langlais, J., von der Esch, B., Krusche, M., Ufer, L., … Braun, D. (2023). RNA oligomerisation without added catalyst from 2′,3′‐cyclic nucleotides by drying at air-water interfaces. <i>ChemSystemsChem</i>. Wiley. <a href=\"https://doi.org/10.1002/syst.202200026\">https://doi.org/10.1002/syst.202200026</a>","ista":"Dass AV, Wunnava S, Langlais J, von der Esch B, Krusche M, Ufer L, Chrisam N, Dubini RCA, Gartner F, Angerpointner S, Dirscherl CF, Rovo P, Mast CB, Šponer JE, Ochsenfeld C, Frey E, Braun D. 2023. RNA oligomerisation without added catalyst from 2′,3′‐cyclic nucleotides by drying at air-water interfaces. ChemSystemsChem. 5(1), e202200026.","ama":"Dass AV, Wunnava S, Langlais J, et al. RNA oligomerisation without added catalyst from 2′,3′‐cyclic nucleotides by drying at air-water interfaces. <i>ChemSystemsChem</i>. 2023;5(1). doi:<a href=\"https://doi.org/10.1002/syst.202200026\">10.1002/syst.202200026</a>","chicago":"Dass, Avinash Vicholous, Sreekar Wunnava, Juliette Langlais, Beatriz von der Esch, Maik Krusche, Lennard Ufer, Nico Chrisam, et al. “RNA Oligomerisation without Added Catalyst from 2′,3′‐cyclic Nucleotides by Drying at Air-Water Interfaces.” <i>ChemSystemsChem</i>. Wiley, 2023. <a href=\"https://doi.org/10.1002/syst.202200026\">https://doi.org/10.1002/syst.202200026</a>.","short":"A.V. Dass, S. Wunnava, J. Langlais, B. von der Esch, M. Krusche, L. Ufer, N. Chrisam, R.C.A. Dubini, F. Gartner, S. Angerpointner, C.F. Dirscherl, P. Rovo, C.B. Mast, J.E. Šponer, C. Ochsenfeld, E. Frey, D. Braun, ChemSystemsChem 5 (2023).","mla":"Dass, Avinash Vicholous, et al. “RNA Oligomerisation without Added Catalyst from 2′,3′‐cyclic Nucleotides by Drying at Air-Water Interfaces.” <i>ChemSystemsChem</i>, vol. 5, no. 1, e202200026, Wiley, 2023, doi:<a href=\"https://doi.org/10.1002/syst.202200026\">10.1002/syst.202200026</a>.","ieee":"A. V. Dass <i>et al.</i>, “RNA oligomerisation without added catalyst from 2′,3′‐cyclic nucleotides by drying at air-water interfaces,” <i>ChemSystemsChem</i>, vol. 5, no. 1. Wiley, 2023."},"scopus_import":"1"},{"has_accepted_license":"1","keyword":["General Chemistry","Catalysis"],"intvolume":"        61","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"isi":1,"author":[{"full_name":"Xu, Felix","last_name":"Xu","first_name":"Felix"},{"full_name":"Crisp, Antony","last_name":"Crisp","first_name":"Antony"},{"last_name":"Schinkel","first_name":"Thea","full_name":"Schinkel, Thea"},{"full_name":"Dubini, Romeo C. A.","first_name":"Romeo C. A.","last_name":"Dubini"},{"last_name":"Hübner","first_name":"Sarah","full_name":"Hübner, Sarah"},{"first_name":"Sidney","last_name":"Becker","full_name":"Becker, Sidney"},{"full_name":"Schelter, Florian","last_name":"Schelter","first_name":"Florian"},{"first_name":"Petra","last_name":"Rovo","full_name":"Rovo, Petra","id":"c316e53f-b965-11eb-b128-bb26acc59c00","orcid":"0000-0001-8729-7326"},{"last_name":"Carell","first_name":"Thomas","full_name":"Carell, Thomas"}],"date_published":"2022-11-07T00:00:00Z","ddc":["540"],"file":[{"creator":"dernst","date_updated":"2023-01-27T10:28:45Z","content_type":"application/pdf","file_size":1076715,"date_created":"2023-01-27T10:28:45Z","checksum":"4e8152454d12025d13f6e6e9ca06b5d0","relation":"main_file","access_level":"open_access","success":1,"file_name":"2022_AngewandteChemieInternat_Xu.pdf","file_id":"12422"}],"year":"2022","day":"07","date_updated":"2025-06-11T13:40:23Z","article_type":"original","publisher":"Wiley","publication_status":"published","pmid":1,"status":"public","external_id":{"isi":["000866428500001"],"pmid":["36063071"]},"article_processing_charge":"No","title":"Isoxazole nucleosides as building blocks for a plausible proto‐RNA","article_number":"e202211945","volume":61,"publication":"Angewandte Chemie International Edition","abstract":[{"lang":"eng","text":"The question of how RNA, as the principal carrier of genetic information evolved is fundamentally important for our understanding of the origin of life. The RNA molecule is far too complex to have formed in one evolutionary step, suggesting that ancestral proto-RNAs (first ancestor of RNA) may have existed, which evolved over time into the RNA of today. Here we show that isoxazole nucleosides, which are quickly formed from hydroxylamine, cyanoacetylene, urea and ribose, are plausible precursors for RNA. The isoxazole nucleoside can rearrange within an RNA-strand to give cytidine, which leads to an increase of pairing stability. If the proto-RNA contains a canonical seed-nucleoside with defined stereochemistry, the seed-nucleoside can control the configuration of the anomeric center that forms during the in-RNA transformation. The results demonstrate that RNA could have emerged from evolutionarily primitive precursor isoxazole ribosides after strand formation."}],"file_date_updated":"2023-01-27T10:28:45Z","oa":1,"oa_version":"Published Version","department":[{"_id":"NMR"}],"language":[{"iso":"eng"}],"quality_controlled":"1","issue":"45","type":"journal_article","month":"11","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","citation":{"apa":"Xu, F., Crisp, A., Schinkel, T., Dubini, R. C. A., Hübner, S., Becker, S., … Carell, T. (2022). Isoxazole nucleosides as building blocks for a plausible proto‐RNA. <i>Angewandte Chemie International Edition</i>. Wiley. <a href=\"https://doi.org/10.1002/anie.202211945\">https://doi.org/10.1002/anie.202211945</a>","ista":"Xu F, Crisp A, Schinkel T, Dubini RCA, Hübner S, Becker S, Schelter F, Rovo P, Carell T. 2022. Isoxazole nucleosides as building blocks for a plausible proto‐RNA. Angewandte Chemie International Edition. 61(45), e202211945.","chicago":"Xu, Felix, Antony Crisp, Thea Schinkel, Romeo C. A. Dubini, Sarah Hübner, Sidney Becker, Florian Schelter, Petra Rovo, and Thomas Carell. “Isoxazole Nucleosides as Building Blocks for a Plausible Proto‐RNA.” <i>Angewandte Chemie International Edition</i>. Wiley, 2022. <a href=\"https://doi.org/10.1002/anie.202211945\">https://doi.org/10.1002/anie.202211945</a>.","ama":"Xu F, Crisp A, Schinkel T, et al. Isoxazole nucleosides as building blocks for a plausible proto‐RNA. <i>Angewandte Chemie International Edition</i>. 2022;61(45). doi:<a href=\"https://doi.org/10.1002/anie.202211945\">10.1002/anie.202211945</a>","mla":"Xu, Felix, et al. “Isoxazole Nucleosides as Building Blocks for a Plausible Proto‐RNA.” <i>Angewandte Chemie International Edition</i>, vol. 61, no. 45, e202211945, Wiley, 2022, doi:<a href=\"https://doi.org/10.1002/anie.202211945\">10.1002/anie.202211945</a>.","ieee":"F. Xu <i>et al.</i>, “Isoxazole nucleosides as building blocks for a plausible proto‐RNA,” <i>Angewandte Chemie International Edition</i>, vol. 61, no. 45. Wiley, 2022.","short":"F. Xu, A. Crisp, T. Schinkel, R.C.A. Dubini, S. Hübner, S. Becker, F. Schelter, P. Rovo, T. Carell, Angewandte Chemie International Edition 61 (2022)."},"scopus_import":"1","acknowledgement":"We thank Stefan Wiedemann for the synthesis of reference compounds and Pia Heinrichs for assistance in the NMR measurements of the oligonucleotides. We also thank Dr. Luis Escobar and Jonas Feldmann for valued discussions. This work was supported by the German Research Foundation (DFG) for financial support via CRC1309 (Project ID 325871075, A04), CRC1361 (Project ID 893547839, P02) and CRC1032 (Project ID 201269156, A5). This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program under grant agreement No 741912 (EpiR). We are grateful for additional funding from the Volkswagen Foundation (EvoRib). Open Access funding enabled and organized by Projekt DEAL.","publication_identifier":{"eissn":["1521-3773"],"issn":["1433-7851"]},"_id":"12228","doi":"10.1002/anie.202211945","date_created":"2023-01-16T09:49:05Z"},{"language":[{"iso":"eng"}],"quality_controlled":"1","issue":"3","department":[{"_id":"NMR"}],"oa_version":"Published Version","oa":1,"_id":"10758","publication_identifier":{"eissn":["2694-2445"]},"related_material":{"link":[{"relation":"earlier_version","url":"https://www.biorxiv.org/content/10.1101/2021.12.14.472563"}]},"date_created":"2022-02-16T11:18:21Z","doi":"10.1021/acsphyschemau.1c00050","acknowledgement":"We thank Markus Müller for valued discussions and Felix Xu for assistance in the measurement of UV/vis melting profiles. This work was supported in part by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – SFB 1309-325871075, EU-ITN LightDyNAmics (ID: 765266), the ERC-AG EpiR (ID: 741912), the Center for NanoScience, the Excellence Clusters CIPSM, and the Fonds der Chemischen Industrie. Open access funding provided by Institute of Science and Technology Austria (ISTA).\r\n\r\n","citation":{"ieee":"R. C. A. Dubini, E. Korytiaková, T. Schinkel, P. Heinrichs, T. Carell, and P. Rovo, “1H NMR chemical exchange techniques reveal local and global effects of oxidized cytosine derivatives,” <i>ACS Physical Chemistry Au</i>, vol. 2, no. 3. American Chemical Society, pp. 237–246, 2022.","mla":"Dubini, Romeo C. A., et al. “1H NMR Chemical Exchange Techniques Reveal Local and Global Effects of Oxidized Cytosine Derivatives.” <i>ACS Physical Chemistry Au</i>, vol. 2, no. 3, American Chemical Society, 2022, pp. 237–46, doi:<a href=\"https://doi.org/10.1021/acsphyschemau.1c00050\">10.1021/acsphyschemau.1c00050</a>.","short":"R.C.A. Dubini, E. Korytiaková, T. Schinkel, P. Heinrichs, T. Carell, P. Rovo, ACS Physical Chemistry Au 2 (2022) 237–246.","chicago":"Dubini, Romeo C. A., Eva Korytiaková, Thea Schinkel, Pia Heinrichs, Thomas Carell, and Petra Rovo. “1H NMR Chemical Exchange Techniques Reveal Local and Global Effects of Oxidized Cytosine Derivatives.” <i>ACS Physical Chemistry Au</i>. American Chemical Society, 2022. <a href=\"https://doi.org/10.1021/acsphyschemau.1c00050\">https://doi.org/10.1021/acsphyschemau.1c00050</a>.","ama":"Dubini RCA, Korytiaková E, Schinkel T, Heinrichs P, Carell T, Rovo P. 1H NMR chemical exchange techniques reveal local and global effects of oxidized cytosine derivatives. <i>ACS Physical Chemistry Au</i>. 2022;2(3):237-246. doi:<a href=\"https://doi.org/10.1021/acsphyschemau.1c00050\">10.1021/acsphyschemau.1c00050</a>","ista":"Dubini RCA, Korytiaková E, Schinkel T, Heinrichs P, Carell T, Rovo P. 2022. 1H NMR chemical exchange techniques reveal local and global effects of oxidized cytosine derivatives. ACS Physical Chemistry Au. 2(3), 237–246.","apa":"Dubini, R. C. A., Korytiaková, E., Schinkel, T., Heinrichs, P., Carell, T., &#38; Rovo, P. (2022). 1H NMR chemical exchange techniques reveal local and global effects of oxidized cytosine derivatives. <i>ACS Physical Chemistry Au</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsphyschemau.1c00050\">https://doi.org/10.1021/acsphyschemau.1c00050</a>"},"scopus_import":"1","type":"journal_article","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","month":"02","project":[{"name":"IST Austria Open Access Fund","_id":"B67AFEDC-15C9-11EA-A837-991A96BB2854"}],"article_processing_charge":"Yes (via OA deal)","external_id":{"pmid":["35637781"]},"page":"237-246","file_date_updated":"2022-07-29T07:53:20Z","volume":2,"abstract":[{"text":"5-Carboxycytosine (5caC) is a rare epigenetic modification found in nucleic acids of all domains of life. Despite its sparse genomic abundance, 5caC is presumed to play essential regulatory roles in transcription, maintenance and base-excision processes in DNA. In this work, we utilize nuclear magnetic resonance (NMR) spectroscopy to address the effects of 5caC incorporation into canonical DNA strands at multiple pH and temperature conditions. Our results demonstrate that 5caC has a pH-dependent global destabilizing and a base-pair mobility enhancing local impact on dsDNA, albeit without any detectable influence on the ground-state B-DNA structure. Measurement of hybridization thermodynamics and kinetics of 5caC-bearing DNA duplexes highlighted how acidic environment (pH 5.8 and 4.7) destabilizes the double-stranded structure by ∼10–20 kJ mol–1 at 37 °C when compared to the same sample at neutral pH. Protonation of 5caC results in a lower activation energy for the dissociation process and a higher barrier for annealing. Studies on conformational exchange on the microsecond time scale regime revealed a sharply localized base-pair motion involving exclusively the modified site and its immediate surroundings. By direct comparison with canonical and 5-formylcytosine (5fC)-edited strands, we were able to address the impact of the two most oxidized naturally occurring cytosine derivatives in the genome. These insights on 5caC’s subtle sensitivity to acidic pH contribute to the long-standing questions of its capacity as a substrate in base excision repair processes and its purpose as an independent, stable epigenetic mark.","lang":"eng"}],"publication":"ACS Physical Chemistry Au","title":"1H NMR chemical exchange techniques reveal local and global effects of oxidized cytosine derivatives","day":"11","year":"2022","file":[{"success":1,"file_id":"11692","file_name":"2022_ACSPhysChemAU_Dubini.pdf","file_size":2351220,"date_updated":"2022-07-29T07:53:20Z","content_type":"application/pdf","creator":"dernst","access_level":"open_access","relation":"main_file","checksum":"5ce3f907848f5c7caf77f1adfe5826c6","date_created":"2022-07-29T07:53:20Z"}],"publication_status":"published","pmid":1,"status":"public","publisher":"American Chemical Society","article_type":"original","date_updated":"2025-04-15T06:53:09Z","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"intvolume":"         2","has_accepted_license":"1","date_published":"2022-02-11T00:00:00Z","ddc":["540"],"corr_author":"1","author":[{"first_name":"Romeo C. A.","last_name":"Dubini","full_name":"Dubini, Romeo C. A."},{"full_name":"Korytiaková, Eva","first_name":"Eva","last_name":"Korytiaková"},{"full_name":"Schinkel, Thea","first_name":"Thea","last_name":"Schinkel"},{"last_name":"Heinrichs","first_name":"Pia","full_name":"Heinrichs, Pia"},{"full_name":"Carell, Thomas","first_name":"Thomas","last_name":"Carell"},{"id":"c316e53f-b965-11eb-b128-bb26acc59c00","full_name":"Rovo, Petra","orcid":"0000-0001-8729-7326","last_name":"Rovo","first_name":"Petra"}]}]