Methods for sequential resonance assignment in solid, uniformly 13C, 15N labelled peptides: quantification and application to antamanide.

The application of adiabatic polarization-transfer experiments to resonance assignment in solid, uniformly 13C-15N-labelled polypeptides is demonstrated for the cyclic decapeptide antamanide. A homonuclear correlation experiment employing the DREAM sequence for adiabatic dipolar transfer yields a complete assignment of the C(alpha) and aliphatic side-chain 13C resonances to amino acid types. The same information can be obtained from a TOBSY experiment using the recently introduced P9(12)1 TOBSY sequence, which employs the J couplings as a transfer mechanism. A comparison of the two methods is presented. Except for some aromatic phenylalanine resonances, a complete sequence-specific assignment of the 13C and 15N resonances in antamanide is achieved by a series of selective or broadband adiabatic triple-resonance experiments. Heteronuclear transfer by adiabatic-passage Hartmann-Hahn cross polarization is combined with adiabatic homonuclear transfer by the DREAM and rotational-resonance tickling sequences into two- and three-dimensional experiments. The performance of these experiments is evaluated quantitatively.

Iterative lineshape analysis of quadrupolar echo spectra of a damped CD(3) quantum rotor: preliminary evidence of a novel mechanism of stochastic spin exchange.

It is demonstrated that the wealth of information about damped quantum rotation of CD(3) groups, contained in quadrupolar echo spectra, can be fully explored in a broad temperature range using a method of iterative analysis of the spectral lineshapes. The recently reported lineshape equation which, apart from the quantum tunneling and the dissipative Alexander--Binsch terms, contains an additional dissipative term having no classical analog is shown to be capable of describing even subtle details of the spectra of a crystal of acetylsalicylic acid--CD(3) oriented specifically in the magnetic field. Preliminary evidence of the occurrence of this novel dissipative mechanism in the system studied is reported. The results obtained seem to suggest that there is no "classical limit" in the dissipative behavior of this system.

Dynamic Hydrogen Disorder in Solid Tropolone. A Single-Crystal NMR Study of the Hydroxyl Deuterons

The orientation and temperature dependences of the deuterium NMR spectrum and spin-lattice relaxation time of the hydroxyl deuterons in single crystals of tropolone-d 1 are reported. The results are interpreted in terms of a dynamic hydrogen disorder model in which the hydrogen nuclei move in an asymmetric double well potential. According to this model, the hydrogen-bonded dimer structure as determined by X-ray diffraction constitutes a majority species in the tropolone crystal, comprising more than 98% of the molecules at room temperature. However, there also exists a tautomeric minority species formed by a concerted back and forth shifting of the hydroxyl hydrogens (deuterons) along the hydrogen bonds to the nearby carbonyl oxygens. This process results in a modulation of the electric field gradient tensor at the site of the deuterons, thus providing an efficient relaxation mechanism. The concentration of the minority species is too low and its lifetime is too short to make its direct observation possible. Still, structural information about this species and kinetic and thermodynamic parameters of the hydrogen shift process can be derived by fitting the measured T 1 values to the above model.

Spin-lattice relaxation in ammonium compounds with a complex molecular dynamics.

Expressions are derived for the initial relaxation rate 1/T1 of protons and deuterons of nontunnelling NH4 and ND4 groups reorienting about various symmetry axes in solids. The reorientation rates are modified by a trigonal, tetragonal or monoclinic distortion of the predominantly cubic hindering potential. When the rates differ sufficiently from each other, two T1 minima are observed with a characteristic ratio. Experiments were performed in NH4VO3, (NH4)2S2O8, (NH4)2PtCl4, and their deuterated modifications, which all exhibit two T1 minima. In NH4VO3 and ND4VO3 the relaxation and spectral data agree rather well with the model of trigonal distortion. Also (NH4)2S2O8 has a preferred threefold axis but there, the large tunnel splitting of protons has to be taken into account before an agreement is reached. All the purely reorientational models fail with (NH4)2PtCl4, where, instead, the ammonium groups are proposed to be ordered into domains at low temperatures. The groups inside the domains and boundary regions give rise to the high- and low-temperature T1 minima, respectively. The boundaries are also believed to give rise to the narrow component in the deuteron spectrum at low temperatures. Evidence for a proton tunnelling frequency of 32 MHz is found in (NH4)2PtCl4.