TY - JOUR

T1 - Sequential assignment of NMR spectra of peptides at natural isotopic abundance with zero- And ultra-low-field total correlation spectroscopy (ZULF-TOCSY)

AU - Kiryutin, Alexey S.

AU - Zhukov, Ivan V.

AU - Ferrage, Fabien

AU - Bodenhausen, Geoffrey

AU - Yurkovskaya, Alexandra V.

AU - Ivanov, Konstantin L.

N1 - Funding Information: We thank Olivier Lequin (Sorbonne Université, Paris) for insightful discussions. This work has been supported by the Russian Science Foundation (grant no. 20-62-47038). We thank the French CNRS for funding the PRC project ‘‘Extending the scope of long-lived spin states: field cycling relaxometry and dynamic nuclear polarization’’. Publisher Copyright: © the Owner Societies 2021. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/4/28

Y1 - 2021/4/28

N2 - A novel method dubbed ZULF-TOCSY results from the combination of Zero and Ultra-Low Field (ZULF) with high-field, high-resolution NMR, leading to a generalization of the concept of total correlation spectroscopy (TOCSY). ZULF-TOCSY is a new building block for NMR methods, which has the unique property that the polarization is evenly distributed among all NMR-active nuclei such as1H,13C,15N,31P,etc., provided that they belong to the same coupling network, and provided that their relaxation is not too fast at low fields, as may occur in macromolecules. Here, we show that ZULF-TOCSY correlations can be observed for peptides at natural isotopic abundance, such as the protected hexapeptide Boc-Met-enkephalin. The analysis of ZULF-TOCSY spectra readily allows one to make sequential assignments, thus offering an alternative to established heteronuclear 2D experiments like HMBC. For Boc-Met-enkephalin, we show that ZULF-TOCSY allows one to observe all expected cross-peaks between carbonyl carbons and α-CH protons, while the popular HMBC method provides insufficient information.

AB - A novel method dubbed ZULF-TOCSY results from the combination of Zero and Ultra-Low Field (ZULF) with high-field, high-resolution NMR, leading to a generalization of the concept of total correlation spectroscopy (TOCSY). ZULF-TOCSY is a new building block for NMR methods, which has the unique property that the polarization is evenly distributed among all NMR-active nuclei such as1H,13C,15N,31P,etc., provided that they belong to the same coupling network, and provided that their relaxation is not too fast at low fields, as may occur in macromolecules. Here, we show that ZULF-TOCSY correlations can be observed for peptides at natural isotopic abundance, such as the protected hexapeptide Boc-Met-enkephalin. The analysis of ZULF-TOCSY spectra readily allows one to make sequential assignments, thus offering an alternative to established heteronuclear 2D experiments like HMBC. For Boc-Met-enkephalin, we show that ZULF-TOCSY allows one to observe all expected cross-peaks between carbonyl carbons and α-CH protons, while the popular HMBC method provides insufficient information.

UR - http://www.scopus.com/inward/record.url?scp=85105231310&partnerID=8YFLogxK

U2 - 10.1039/d0cp06337a

DO - 10.1039/d0cp06337a

M3 - Article

C2 - 33861279

AN - SCOPUS:85105231310

VL - 23

SP - 9715

EP - 9720

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 16

ER -