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Hyperpolarisiertes Wasser kann NMR-Signale schnell austauschender Protonen des intrinsisch unstrukturierten Proteins Osteopontin (OPN), welches eine Rolle bei Metastasenbildung spielt, bei annahernd physiologischem pH-Wert und Temperatur verstarken. Der Transfer der Magnetisierung des hyperpolarisierten Wassers beschrankt sich auf losungsmittelexponierte Aminosauren und verstarkt deshalb nur selektiv bestimmte Signale in (1H,15N-)Korrelationsspektren. Die Bindung des Polysaccharids Heparin induziert die Entfaltung vorgeformter Strukturelemente von OPN.

The lifetimes T-LLS of long-lived states or T-LLC of long-lived coherences can be used for the accurate determination of dissociation constants of weak protein ligand complexes. The remarkable contrast between signals derived from LLS or LLC in free and bound ligands can be exploited to search for weak binders with large dissociation constants K-D > 1 mM that are important for fragment-based drug discovery but may escape detection by other screening techniques. Alternatively, the high sensitivity of the proposed method can be exploited to work with large ligand-to-protein ratios, with an evident advantage of reduced consumption of precious proteins. The detection of F-19-F-19 long-lived states in suitably designed fluorinated spy molecules allows one to perform competition binding experiments with high sensitivity while avoiding signal overlap that tends to hamper the interpretation of proton spectra of mixtures.

In gas phase, collisions that affect the rotational angular momentum lead to the return of the magnetization to its equilibrium (relaxation) in Nuclear Magnetic Resonance (NMR). To the best of our knowledge, the longitudinal relaxation rates R1 = 1/T1 of protons in H2O and HDO have never been measured in gas phase. We report R1 in gas phase in a field of 18.8 T, i.e., at a proton Larmor frequency ν0 = 800 MHz, at temperatures between 353 and 373 K and pressures between 9 and 101 kPa. By assuming that spin rotation is the dominant relaxation mechanism, we estimated the effective cross-section σJ for the transfer of angular momentum due to H2O-H2O and HDO-D2O collisions. Our results allow one to test theoretical predictions of the intermolecular potential of water in gas phase.

The authors want to thank Dr. Jean-Nicolas Dumez for helpful discussions; Sven Sieber, Michael Schenkel, Rolf Hensel, Jacco van Beek, Ion Prisucaru, and Armin Purea for contributions to the system design and implementation; and Frank Engelke, Pietro Lendi, Klemens Kessler, Daniel Eckert, Daniel Guy Baumann, Dirk Wilhelm, Roberto Seydoux, Uwe Wagner, Cengiz Cetrefli, Tonio Gianotti, and Jorg Hinderer for contributions to the system specification. Some of the work in this article employed the SpinDynamica code for Mathematica, programmed by Malcolm H. Levitt, with contributions from Jyrki Rantaharju, Andreas Brinkmann, and Soumya Singha Roy, available at www.SpinDynamica.soton.ac.uk.; International audience; We present novel means to hyperpolarize deuterium nuclei in 13CD2 groups at cryogenic temperatures. The method is based on cross-polarization from 1H to 13C and does not require any radio-frequency fields applied to the deuterium nuclei. After rapid dissolution, a new class of long-lived spin states can be detected indirectly by 13C NMR in solution. These long-lived states result from a sextet-triplet imbalance (STI) that involves the two equivalent deuterons with spin I = 1. An STI has similar properties as a triplet-singlet imbalance that can occur in systems with two equivalent I = 12/ spins. Although the lifetimes T STI are shorter than T 1(Cz), they can exceed the life-time T 1(Dz) of deuterium Zeeman magnetization by a factor of more than 20.