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The new variant of known HNCACB and HN(CO)CACB techniques is proposed that employs excitation and evolution of double quantum Calpha-Cbeta coherences. The most important features of the new method are: increased signal dispersion, lack of splittings due to 1J(Calpha-Cbeta) spin-spin couplings, and absence of accidental cancellations of positive and negative signals. The acquisition of both DQ-HN[CACB] and DQ-HN(CO)[CACB] techniques enables sequential assignment of protein backbone, using only Calpha-Cbeta DQ-frequencies. The determination of all Calpha and Cbeta chemical shifts requires, however, a comparison with HN(CO)CA or HNCA spectra. Examples of applications of the DQ-HN[CACB] and DQ-HN(CO)[CACB] experiments are presented, employing the 2D Reduced Dimensionality approach for 13C, 15N-labeled ubiquitin, and the 3D acquisition for 13C, 15N-double labeled Ca2+ -binding bovine S100A1 protein in the apo state (21 kDa) with overall correlation time of 8.1 ns.

Chiral recognition by cyclodextrins is of considerable importance, especially for pharmaceutical industry, in view of the possible side effects of the second enantiometer of chiral drugs. In general, it manifests itself in all NMR parameters (chemical shifts, coupling constants, NOE and ROE effects, and relaxation rates) on one hand. On the other hand, it allows one to determine the thermodynamic parameters characterizing diastereomeric complexes formed by cyclodextrins with enantiomeric guests. After an introduction and a general discussion of NMR manifestations of chiral recognition by cyclodextrin, the existing literature data on this problem will be discussed herein. Chirality 16:90-105, 2004., (Copyright 2004 Wiley-Liss, Inc)

A new, simple procedure is proposed which enables acquisition of two or more chemical shifts encoded in a common dimension simultaneously in quadrature. For n chemical shifts projected in a single dimension, the expected effect is obtained by interleaved acquisition and appropriate combination of 2(n) data sets per increment of respective evolution time. The particular chemical shifts can be calculated from sums and differences of signal frequencies obtained by different combination of the acquired data sets. In comparison to the established reduced dimensionality (RD) techniques, the proposed method enhances resolution due to reduction of the number of signals and requires less evolution time increments owing to narrower spectral width in the RD-domain. We show examples of the application of the new approach to the 2D HNCA and HN(CO)CA techniques with two, and 2D HACANH with three frequencies simultaneously encoded in the t(1) evolution period, for (13)C,(15)N-labeled ubiquitin.

A new general J-HMQC-based technique is presented, which allows an accurate determination of heteronuclear coupling constants. The most important feature of this new approach includes acquisition of the two data sets with and without the additional pi(S)-pulse at the end of coupling evolution period. This enables preservation and separation of the two orthogonal terms of coupling evolution, which are manifested by in- and antiphase cross-peaks, respectively. The coupling magnitudes are evaluated by the nonlinear least-squares fitting of the ratios of integrated signal volumes for both kinds of signals. The effectiveness of the new sequence is demonstrated by determination of the 3J(H3'(i),P(i+1)) couplings in DNA octamer duplex d(GCGTACGC)(2) sample. Additionally, the ability of the new method for the measurement at the natural abundance level of 13C nuclei is presented for the beta-cyclodextrin.

A previously untested essential consequence of the "TICT" (twisted internal charge transfer) interpretation of the nature of the "anomalous" excited state of p-dimethylaminobenzonitrile (1) and related compounds has now been verified: at -90 degreesC, the dual fluorescence of a desymmetrized analogue, 2-(N-methyl-N-isopropylamino)-5-cyanopyridine (2), in methanol (MeOH) is accompanied by syn-anti isomerization around the C-N bond, whereas its ordinary fluorescence in tetrahydrofuran is not.

A new two-dimensional pulse sequence for accurately determining heteronuclear coupling constants is presented. It is derived from HSQC and HECADE techniques with B0 gradient coherence selection. The main feature of the proposed method is spectra with only one component of the IS doublet; i.e., the final result is equivalent to a selective broadband excitation of either Salpha or Sbeta spin states and a preservation of these states during the entire experiment. The effect is obtained by an appropriate combination of in- and antiphase coherences. It is demonstrated that heteronuclear single-bond as well as long-range coupling constants and their relative signs are readily evaluated. The proposed sequence is equally or less sensitive to a variation of heteronuclear one-bond couplings than previously published, closely related sequences. The new method is applied to a peptide sample for determination of 3JN, Hbeta., (Copyright 1999 Academic Press.)

15N and 13C cross-polarization magic-angle spinning nuclear magnetic resonance (CP-MAS NMR) spectra of 5-thiomethyltetrazole have been measured. Two kinds of tetrazole molecules are found in the hydrogen bond chain system depending on the configuration of the S-CH3 group in relation to the ring hydrogen atom. The two-dimensional 15N CP-MAS experiment excludes the possibility of proton tautomeric dynamics in this system.