---
OA_place: publisher
OA_type: hybrid
PlanS_conform: '1'
_id: '20321'
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.
acknowledged_ssus:
- _id: NMR
- _id: LifeSc
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.
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Benjamin
full_name: Tatman, Benjamin
id: 71cda2f3-e604-11ee-a1df-da10587eda3f
last_name: Tatman
- first_name: Vidhyalakshmi
full_name: Sridharan, Vidhyalakshmi
last_name: Sridharan
- first_name: Motilal
full_name: Uttarkabat, Motilal
last_name: Uttarkabat
- first_name: Christopher P.
full_name: Jaroniec, Christopher P.
last_name: Jaroniec
- first_name: Matthias
full_name: Ernst, Matthias
last_name: Ernst
- first_name: Petra
full_name: Rovo, Petra
id: c316e53f-b965-11eb-b128-bb26acc59c00
last_name: Rovo
orcid: 0000-0001-8729-7326
- first_name: Paul
full_name: Schanda, Paul
id: 7B541462-FAF6-11E9-A490-E8DFE5697425
last_name: Schanda
orcid: 0000-0002-9350-7606
citation:
ama: 'Tatman B, Sridharan V, Uttarkabat M, et al. Bumps on the road: The way to
clean relaxation dispersion magic-angle spinning NMR. Journal of the American
Chemical Society. 2025;147(32):29315-29326. doi:10.1021/jacs.5c09057'
apa: 'Tatman, B., Sridharan, V., Uttarkabat, M., Jaroniec, C. P., 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. American
Chemical Society. https://doi.org/10.1021/jacs.5c09057'
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.” Journal of
the American Chemical Society. American Chemical Society, 2025. https://doi.org/10.1021/jacs.5c09057.'
ieee: 'B. Tatman et al., “Bumps on the road: The way to clean relaxation
dispersion magic-angle spinning NMR,” Journal of the American Chemical Society,
vol. 147, no. 32. American Chemical Society, pp. 29315–29326, 2025.'
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.'
mla: 'Tatman, Benjamin, et al. “Bumps on the Road: The Way to Clean Relaxation Dispersion
Magic-Angle Spinning NMR.” Journal of the American Chemical Society, vol.
147, no. 32, American Chemical Society, 2025, pp. 29315–26, doi:10.1021/jacs.5c09057.'
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.
corr_author: '1'
date_created: 2025-09-10T05:37:19Z
date_published: 2025-08-01T00:00:00Z
date_updated: 2026-06-10T08:33:41Z
day: '01'
ddc:
- '540'
department:
- _id: PaSc
- _id: NMR
doi: 10.1021/jacs.5c09057
external_id:
isi:
- '001542746200001'
pmid:
- '40748291'
file:
- access_level: open_access
checksum: b350d56ddddefea96cebd62c277c0ff5
content_type: application/pdf
creator: dernst
date_created: 2025-09-10T07:53:10Z
date_updated: 2025-09-10T07:53:10Z
file_id: '20337'
file_name: 2025_JACS_Tatman.pdf
file_size: 5235353
relation: main_file
success: 1
file_date_updated: 2025-09-10T07:53:10Z
has_accepted_license: '1'
intvolume: ' 147'
isi: 1
issue: '32'
language:
- iso: eng
month: '08'
oa: 1
oa_version: Published Version
page: 29315-29326
pmid: 1
publication: Journal of the American Chemical Society
publication_identifier:
eissn:
- 1520-5126
issn:
- 0002-7863
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
related_material:
record:
- id: '19696'
relation: used_in_publication
status: public
scopus_import: '1'
status: public
title: 'Bumps on the road: The way to clean relaxation dispersion magic-angle spinning
NMR'
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 317138e5-6ab7-11ef-aa6d-ffef3953e345
volume: 147
year: '2025'
...
---
_id: '18168'
abstract:
- lang: eng
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.'
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.
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Dongqing
full_name: Wu, Dongqing
last_name: Wu
- first_name: Anamaria
full_name: Koscic, Anamaria
last_name: Koscic
- first_name: Sonja
full_name: Schneider, Sonja
last_name: Schneider
- first_name: Romeo C. A.
full_name: Dubini, Romeo C. A.
last_name: Dubini
- first_name: Diana C.
full_name: Rodriguez Camargo, Diana C.
last_name: Rodriguez Camargo
- first_name: Sabine
full_name: Schneider, Sabine
last_name: Schneider
- first_name: Petra
full_name: Rovo, Petra
id: c316e53f-b965-11eb-b128-bb26acc59c00
last_name: Rovo
orcid: 0000-0001-8729-7326
citation:
ama: Wu D, Koscic A, Schneider S, et al. Unveiling the dynamic self-assembly of
a recombinant dragline-silk-mimicking protein. Biomacromolecules. 2024;25(3):1759-1774.
doi:10.1021/acs.biomac.3c01239
apa: Wu, D., Koscic, A., Schneider, S., Dubini, R. C. A., Rodriguez Camargo, D.
C., Schneider, S., & Rovo, P. (2024). Unveiling the dynamic self-assembly
of a recombinant dragline-silk-mimicking protein. Biomacromolecules. American
Chemical Society. https://doi.org/10.1021/acs.biomac.3c01239
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.” Biomacromolecules.
American Chemical Society, 2024. https://doi.org/10.1021/acs.biomac.3c01239.
ieee: D. Wu et al., “Unveiling the dynamic self-assembly of a recombinant
dragline-silk-mimicking protein,” Biomacromolecules, vol. 25, no. 3. American
Chemical Society, pp. 1759–1774, 2024.
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.
mla: Wu, Dongqing, et al. “Unveiling the Dynamic Self-Assembly of a Recombinant
Dragline-Silk-Mimicking Protein.” Biomacromolecules, vol. 25, no. 3, American
Chemical Society, 2024, pp. 1759–74, doi:10.1021/acs.biomac.3c01239.
short: D. Wu, A. Koscic, S. Schneider, R.C.A. Dubini, D.C. Rodriguez Camargo, S.
Schneider, P. Rovo, Biomacromolecules 25 (2024) 1759–1774.
corr_author: '1'
date_created: 2024-10-02T10:09:53Z
date_published: 2024-03-11T00:00:00Z
date_updated: 2025-09-08T09:52:18Z
day: '11'
ddc:
- '540'
department:
- _id: NMR
doi: 10.1021/acs.biomac.3c01239
external_id:
isi:
- '001166501000001'
pmid:
- '38343096'
file:
- access_level: open_access
checksum: 9552b6d52f1e8a350764849a535fc13e
content_type: application/pdf
creator: dernst
date_created: 2024-10-07T08:33:35Z
date_updated: 2024-10-07T08:33:35Z
file_id: '18180'
file_name: 2024_BioMacromolecules_Wu.pdf
file_size: 6597227
relation: main_file
success: 1
file_date_updated: 2024-10-07T08:33:35Z
has_accepted_license: '1'
intvolume: ' 25'
isi: 1
issue: '3'
language:
- iso: eng
month: '03'
oa: 1
oa_version: Published Version
page: 1759-1774
pmid: 1
publication: Biomacromolecules
publication_identifier:
eissn:
- 1526-4602
issn:
- 1525-7797
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Unveiling the dynamic self-assembly of a recombinant dragline-silk-mimicking
protein
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 317138e5-6ab7-11ef-aa6d-ffef3953e345
volume: 25
year: '2024'
...
---
_id: '17078'
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+ 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.
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.
article_number: e202200026
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Avinash Vicholous
full_name: Dass, Avinash Vicholous
last_name: Dass
- first_name: Sreekar
full_name: Wunnava, Sreekar
last_name: Wunnava
- first_name: Juliette
full_name: Langlais, Juliette
last_name: Langlais
- first_name: Beatriz
full_name: von der Esch, Beatriz
last_name: von der Esch
- first_name: Maik
full_name: Krusche, Maik
last_name: Krusche
- first_name: Lennard
full_name: Ufer, Lennard
last_name: Ufer
- first_name: Nico
full_name: Chrisam, Nico
last_name: Chrisam
- first_name: Romeo C. A.
full_name: Dubini, Romeo C. A.
last_name: Dubini
- first_name: Florian
full_name: Gartner, Florian
last_name: Gartner
- first_name: Severin
full_name: Angerpointner, Severin
last_name: Angerpointner
- first_name: Christina F.
full_name: Dirscherl, Christina F.
last_name: Dirscherl
- first_name: Petra
full_name: Rovo, Petra
id: c316e53f-b965-11eb-b128-bb26acc59c00
last_name: Rovo
orcid: 0000-0001-8729-7326
- first_name: Christof B.
full_name: Mast, Christof B.
last_name: Mast
- first_name: Judit E.
full_name: Šponer, Judit E.
last_name: Šponer
- first_name: Christian
full_name: Ochsenfeld, Christian
last_name: Ochsenfeld
- first_name: Erwin
full_name: Frey, Erwin
last_name: Frey
- first_name: Dieter
full_name: Braun, Dieter
last_name: Braun
citation:
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. ChemSystemsChem.
2023;5(1). doi:10.1002/syst.202200026
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. ChemSystemsChem. Wiley.
https://doi.org/10.1002/syst.202200026
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.”
ChemSystemsChem. Wiley, 2023. https://doi.org/10.1002/syst.202200026.
ieee: A. V. Dass et al., “RNA oligomerisation without added catalyst from
2′,3′‐cyclic nucleotides by drying at air-water interfaces,” ChemSystemsChem,
vol. 5, no. 1. Wiley, 2023.
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.
mla: Dass, Avinash Vicholous, et al. “RNA Oligomerisation without Added Catalyst
from 2′,3′‐cyclic Nucleotides by Drying at Air-Water Interfaces.” ChemSystemsChem,
vol. 5, no. 1, e202200026, Wiley, 2023, doi:10.1002/syst.202200026.
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).
date_created: 2024-05-29T06:13:48Z
date_published: 2023-01-01T00:00:00Z
date_updated: 2025-07-10T11:51:15Z
day: '01'
ddc:
- '530'
department:
- _id: NMR
doi: 10.1002/syst.202200026
file:
- access_level: open_access
checksum: b1e78c60e371f87bdf43970f17d1cb0b
content_type: application/pdf
creator: dernst
date_created: 2024-07-31T11:20:58Z
date_updated: 2024-07-31T11:20:58Z
file_id: '17355'
file_name: 2023_ChemSystemsChem_Dass.pdf
file_size: 860679
relation: main_file
success: 1
file_date_updated: 2024-07-31T11:20:58Z
has_accepted_license: '1'
intvolume: ' 5'
issue: '1'
language:
- iso: eng
month: '01'
oa: 1
oa_version: Published Version
publication: ChemSystemsChem
publication_identifier:
issn:
- 2570-4206
publication_status: published
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: RNA oligomerisation without added catalyst from 2′,3′‐cyclic nucleotides by
drying at air-water interfaces
tmp:
image: /images/cc_by_nc_nd.png
legal_code_url: https://creativecommons.org/licenses/by-nc-nd/4.0/legalcode
name: Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
(CC BY-NC-ND 4.0)
short: CC BY-NC-ND (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 5
year: '2023'
...
---
_id: '10758'
abstract:
- lang: eng
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.
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"
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Romeo C. A.
full_name: Dubini, Romeo C. A.
last_name: Dubini
- first_name: Eva
full_name: Korytiaková, Eva
last_name: Korytiaková
- first_name: Thea
full_name: Schinkel, Thea
last_name: Schinkel
- first_name: Pia
full_name: Heinrichs, Pia
last_name: Heinrichs
- first_name: Thomas
full_name: Carell, Thomas
last_name: Carell
- first_name: Petra
full_name: Rovo, Petra
id: c316e53f-b965-11eb-b128-bb26acc59c00
last_name: Rovo
orcid: 0000-0001-8729-7326
citation:
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. ACS Physical Chemistry Au. 2022;2(3):237-246. doi:10.1021/acsphyschemau.1c00050
apa: Dubini, R. C. A., 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. American
Chemical Society. https://doi.org/10.1021/acsphyschemau.1c00050
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.” ACS Physical Chemistry Au.
American Chemical Society, 2022. https://doi.org/10.1021/acsphyschemau.1c00050.
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,” ACS Physical Chemistry Au, vol. 2, no.
3. American Chemical Society, pp. 237–246, 2022.
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.
mla: Dubini, Romeo C. A., et al. “1H NMR Chemical Exchange Techniques Reveal Local
and Global Effects of Oxidized Cytosine Derivatives.” ACS Physical Chemistry
Au, vol. 2, no. 3, American Chemical Society, 2022, pp. 237–46, doi:10.1021/acsphyschemau.1c00050.
short: R.C.A. Dubini, E. Korytiaková, T. Schinkel, P. Heinrichs, T. Carell, P. Rovo,
ACS Physical Chemistry Au 2 (2022) 237–246.
corr_author: '1'
date_created: 2022-02-16T11:18:21Z
date_published: 2022-02-11T00:00:00Z
date_updated: 2025-04-15T06:53:09Z
day: '11'
ddc:
- '540'
department:
- _id: NMR
doi: 10.1021/acsphyschemau.1c00050
external_id:
pmid:
- '35637781'
file:
- access_level: open_access
checksum: 5ce3f907848f5c7caf77f1adfe5826c6
content_type: application/pdf
creator: dernst
date_created: 2022-07-29T07:53:20Z
date_updated: 2022-07-29T07:53:20Z
file_id: '11692'
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name: IST Austria Open Access Fund
publication: ACS Physical Chemistry Au
publication_identifier:
eissn:
- 2694-2445
publication_status: published
publisher: American Chemical Society
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link:
- relation: earlier_version
url: https://www.biorxiv.org/content/10.1101/2021.12.14.472563
scopus_import: '1'
status: public
title: 1H NMR chemical exchange techniques reveal local and global effects of oxidized
cytosine derivatives
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 2
year: '2022'
...
---
_id: '12228'
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.
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.
article_number: e202211945
article_processing_charge: No
article_type: original
author:
- first_name: Felix
full_name: Xu, Felix
last_name: Xu
- first_name: Antony
full_name: Crisp, Antony
last_name: Crisp
- first_name: Thea
full_name: Schinkel, Thea
last_name: Schinkel
- first_name: Romeo C. A.
full_name: Dubini, Romeo C. A.
last_name: Dubini
- first_name: Sarah
full_name: Hübner, Sarah
last_name: Hübner
- first_name: Sidney
full_name: Becker, Sidney
last_name: Becker
- first_name: Florian
full_name: Schelter, Florian
last_name: Schelter
- first_name: Petra
full_name: Rovo, Petra
id: c316e53f-b965-11eb-b128-bb26acc59c00
last_name: Rovo
orcid: 0000-0001-8729-7326
- first_name: Thomas
full_name: Carell, Thomas
last_name: Carell
citation:
ama: Xu F, Crisp A, Schinkel T, et al. Isoxazole nucleosides as building blocks
for a plausible proto‐RNA. Angewandte Chemie International Edition. 2022;61(45).
doi:10.1002/anie.202211945
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. Angewandte Chemie International Edition. Wiley. https://doi.org/10.1002/anie.202211945
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.” Angewandte Chemie International
Edition. Wiley, 2022. https://doi.org/10.1002/anie.202211945.
ieee: F. Xu et al., “Isoxazole nucleosides as building blocks for a plausible
proto‐RNA,” Angewandte Chemie International Edition, vol. 61, no. 45. Wiley,
2022.
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.
mla: Xu, Felix, et al. “Isoxazole Nucleosides as Building Blocks for a Plausible
Proto‐RNA.” Angewandte Chemie International Edition, vol. 61, no. 45, e202211945,
Wiley, 2022, doi:10.1002/anie.202211945.
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).
date_created: 2023-01-16T09:49:05Z
date_published: 2022-11-07T00:00:00Z
date_updated: 2025-06-11T13:40:23Z
day: '07'
ddc:
- '540'
department:
- _id: NMR
doi: 10.1002/anie.202211945
external_id:
isi:
- '000866428500001'
pmid:
- '36063071'
file:
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checksum: 4e8152454d12025d13f6e6e9ca06b5d0
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creator: dernst
date_created: 2023-01-27T10:28:45Z
date_updated: 2023-01-27T10:28:45Z
file_id: '12422'
file_name: 2022_AngewandteChemieInternat_Xu.pdf
file_size: 1076715
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success: 1
file_date_updated: 2023-01-27T10:28:45Z
has_accepted_license: '1'
intvolume: ' 61'
isi: 1
issue: '45'
keyword:
- General Chemistry
- Catalysis
language:
- iso: eng
month: '11'
oa: 1
oa_version: Published Version
pmid: 1
publication: Angewandte Chemie International Edition
publication_identifier:
eissn:
- 1521-3773
issn:
- 1433-7851
publication_status: published
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: Isoxazole nucleosides as building blocks for a plausible proto‐RNA
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 61
year: '2022'
...