Calcium-43 NMR studies of polymorphic transition of calcite to aragonite.

Phase transformation between calcite and aragonite is an important issue in biomineralization. To shed more light on the mechanism of this process at the molecular level, we employ solid-state (43)Ca NMR to study the phase transformation from calcite to aragonite as regulated by magnesium ions, with (43)Ca enrichment at a level of 6%. Using the gas diffusion approach, the phase of Mg-calcite is formed initially and the system subsequently transforms to aragonite as the reaction time proceeds. Our (43)Ca solid-state NMR data support the dissolution-recrystallization mechanism for the calcite to aragonite transition. We find that the (43)Ca NMR parameters of Mg-calcite are very similar to those of pure calcite. Under the high-resolution condition provided by magic-angle spinning at 4 kHz, we can monitor the variation of the (43)Ca NMR parameters of the aragonite signals for the samples obtained at different reaction times. Our data suggest that in the presence of a significant amount of Mg(2+) ions, aragonite is the most stable polymorph of calcium carbonate. The initial precipitated crystallites of aragonite have spine-like morphology, for which the (43)Ca spin-lattice relaxation data indicate that the ions in the lattice have considerable motional dynamics. As the crystallinity of aragonite improves further, the (43)Ca T(1) parameter of the aragonite phase changes considerably and becomes very similar to that obtained for pure aragonite. For the first time, the difference in crystal morphologies and crystallinity of the aragonite phase has been traced down to the subtle difference in the motional dynamics at the molecular level.

Steric zipper formed by hydrophobic peptide fragment of Syrian hamster prion protein.

Steric zippers, where the residues of two neighboring ß-sheet layers are tightly interdigitated, have been proposed as fundamental structural units of amyloid fibrils by Eisenberg and co-workers. The steric zipper formed by polypeptides containing the palindromic sequence AGAAAAGA has a distinctive feature that the distance between two interdigitated ß-sheet layers is comparable to the interstrand distance of the individual ß-sheet. This structural motif is of great interest in the study of prion disease because the AGAAAAGA sequence is highly conserved in prion proteins of different species. In this work, the amyloid fibrils formed by the polypeptides of PrP(113-127), viz. Ac-AGAAAAGAVVGGLGG-NH(2), are taken as the model compound to investigate the biophysical principles governing the steric zipper formation. The target fibrils adopt the structural motif of class 7 steric zipper, which is formed by stacking of antiparallel ß-sheet layers with residue 117 + k forming backbone hydrogen bonds to residue 120 - k. Implication of our results in the infectivity of scrapie prion is briefly discussed.

Internal symmetry of basic elements in symmetry-based recoupling sequences under magic-angle spinning.

In solid-state NMR, many powerful pulse sequences under the condition of magic-angle spinning can be analyzed on the basis of the C- and R-sequences developed by Levitt and co-workers. It has been speculated for some years that the basic elements commonly used in symmetry-based recoupling pulse sequences have certain kind of internal symmetries. We show by a detailed analysis that a set of internal selection rules does exist for many basic elements. These internal selection rules may allow a more versatile design of CN(n)(ν) or RN(n)(ν) sequences when n is an integer or half-integer multiple of N. As an illustration, we have derived the symmetry arguments to rationalize the observation that the C-REDOR pulse sequence can suppress homonuclear dipole-dipole interaction, leading to the design of new windowed basic elements usable for heteronuclear dipolar recoupling with active suppression of homonuclear dipole-dipole interaction. Numerical simulations and experiments measured for [U-(13)C,(15)N]-L-alanine have been used to validate our approach. On a more general note, the symmetry rules discussed in this work can also be applied for the design of supercycles.

Compensated DRAMA sequence for homonuclear dipolar recoupling under magic-angle spinning.

The DRAMA sequence has been considered as the milestone in the development of homonuclear dipolar recoupling. Although it has a high efficiency for double-quantum excitation in spin 1/2 systems, it is seldom used today for real applications because of its susceptibility to the deteriorating effects of chemical shift anisotropy and resonance offsets. We show in this work that the practicability of DRAMA can be greatly enhanced by incorporating four pi pulses with XY-4 phases into the basic DRAMA cycles. Average Hamiltonian theory is used to evaluate the performance of the resulting pulse sequence with respect to the compensation of chemical shift anisotropy. Numerical simulations and experimental measurements on hydroxyapatite indeed show that the performance of DRAMA-XY4 is very satisfying for 31P DQ excitation, provided that the resonance offset is within the range of [-4, 4]kHz.