Understanding Overhauser Dynamic Nuclear Polarisation through NMR relaxometry

Abstract

Overhauser dynamic nuclear polarisation (DNP) represents a potentially outstanding tool to increase the sensitivity of solution and solid state NMR experiments, as well as of magnetic resonance imaging. DNP signal enhancements are strongly linked to the spin relaxation properties of the system under investigation, which must contain a paramagnetic molecule used as DNP polariser. In turn, nuclear spin relaxation can be monitored through NMR relaxometry, which reports on the field dependence of the nuclear relaxation rates, opening a route to understand the physical processes at the origin of the Overhauser DNP in solution. The contributions of dipole–dipole and Fermi-contact interactions to paramagnetic relaxation are here described and shown to be responsible to both the relaxometry profiles and the DNP enhancements, so that the experimental access to the former can allow for predictions of the latter.

GRAPHICAL ABSTRACT

KEYWORDS:

• Dipolar relaxation
• contact relaxation
• coupling factor
• solution DNP
• NMR sensitivity

Disclosure statement

No potential conflict of interest was reported by the authors.

ORCID

Giacomo Parigi http://orcid.org/0000-0002-1989-4644

Enrico Ravera http://orcid.org/0000-0001-7708-9208

Claudio Luchinat http://orcid.org/0000-0003-2271-8921

Additional information

Funding

This work was supported by European Cooperation in Science and Technology [Grant Number CA15209 (EURELAX)]; Ministero dell’Istruzione, dell’Università e della Ricerca [Grant Number PRIN 2012SK7ASN]; Fondazione Cassa di Risparmio di Firenze; Instruct-ERIC Core Centre CERM, Italy.