M. Ramanadham

Structure determination of Ls-threonine by neutron diffraction

The structure of the aminoacid, Ls-threonine [NH3+ CH(CHOHCH3)COO−], space groupP212121,a=13.630(5),b=7.753(1),c=5.162(2) Å,z=4, has been determined from neutron diffraction data using direct methods. The intensities of 1148 neutron Bragg reflections were measured from a single crystal. The structural parameters were refined by the method of least squares using anisotropic temperature factors. The finalR(F2) is 0.068. The structure was also refined from the x-ray data of Shoemakeret al (1950J. Am. Chem. Soc.72 2328); there is good agreement between the two sets of heavy atom parameters. The parameters of hydrogen atoms are of course more precisely determined in our neutron study. The molecular conformation and the hydrogen bonding scheme are discussed. Weighted average values of bond distances and angles from 14 aminoacid structures with ionized carboxylic groups studied by neutron diffraction at Brookheven and Trombay are also presented.

Structural changes during the unfolding of Bovine serum albumin in the presence of urea: A small-angle neutron scattering study

The native form of serum albumin is the most important soluble protein in the body plasma. In order to investigate the structural changes of Bovine serum albumin (BSA) during its unfolding in the presence of urea, a small-angle neutron scattering (SANS) study was performed. The scattering curves of dilute solutions of BSA with different concentrations of urea in D2O at pH 7.2 ± 0.2 were measured at room temperature. The scattering profile was fitted to a prolate ellipsoidal shape (a, b, b) of the protein witha = 52.2 Å andb = 24.2 Å. The change in the dimensions of the protein as it unfolds was found to be anisotropic. The radius of gyration of the compact form of the protein in solution decreased as the urea concentration was increased.

Hydrogen bonding in oxalic acid and its complexes: A database study of neutron structures

The basic result of carboxylic group that the oxygen atom of the -OH never seems to be a hydrogen bond acceptor is violated in the cases, namely urea oxalic acid and bis urea oxalic acid complexes, where the hydroxyl oxygen atom is an acceptor of a weak N—H… O hydrogen bond. The parameters of this hydrogen bond, respectively in these structures are: hydrogen acceptor distance 2.110 Å and 2.127 Å and the bending angle at hydrogen, 165.6° and 165.8°. The bond strength around the hydroxyl oxygen is close to 1.91 valence units, indicating that it has hardly any strength left to form hydrogen bonds. These two structures being highly planar, force the formation of this hydrogen bond. As oxalic acid is the common moiety, the structures of the two polymorphs, α-oxalic acid and β-oxalic acid, also were looked into in terms of hydrogen bonding and packing.

Zinc (tris) thiourea sulphate (ZTS): A single crystal neutron diffraction study

The crystal structure of ZTS has been determined by neutron diffraction with a finalR-value of 0.026. Using the structural parameters, the contributions from the structural groups to the linear optical susceptibility and linear electro-optic coefficients have been evaluated. Results showed a significant contribution from the hydrogen bonds in the structure.

Low-temperature neutron diffraction study of La0.95Nd0.05CrO3

We have synthesized polycrystalline La0.95Nd0.05CrO3 sample by doping the La-site of LaCrO3 with Nd and its magnetic properties have been studied using DC magnetization and neutron diffraction techniques. DC magnetization study shows a paramagnetic to a weak ferromagnetic-like transition at ∼295 K followed by signatures of a spin reorientation phenomenon at 233 and 166 K and, finally a transition to an antiferromagnetic-like phase at ∼21 K. Low-temperature neutron diffraction measurements confirm a weak ferrimagnetic ordering of Cr3+ moments at all temperatures below 295 K.

Phase transition in triglycine family of hydrogen bonded ferroelectrics: An interpretation based on structural studies

Using the crystal structure, a comprehensive interpretation of the origin of ferroelectricity in the hydrogen bonded triglycine family of crystals is given. Our detailed analysis showed that the instability of nitrogen double well potential plays a driving role in the mechanism of the ferroelectric transitions in these crystals.

Structural stability of orthorhombic and rhombohedral La0.75Nd0.25CrO3: a high-temperature neutron diffraction study

A high-temperature neutron diffraction study of La0.75Nd0.25CrO3 compound has been carried out in the temperature range 300?1400?K. The sample has been studied for its structural stability of the two observed crystallographic phases at elevated temperatures. It was found to contain orthorhombic and rhombohedral phases with weight percentages 85% and 15%, respectively, at ambient temperature. It was observed that the two phases coexist even up to 1400?K; however, the fraction of the rhombohedral phase increases with increasing temperature at the expense of the orthorhombic phase. At 1400?K, the weight fractions of the orthorhombic and rhombohedral phases are about 11% and 89%, respectively. This study reveals a negative thermal expansion along the b-axis for the orthorhombic phase and along the c-axis for the rhombohedral phase from 950?K up to 1200?K, where a rapid transformation of one phase to the other occurs. Below 950?K as well as above 1200?K, both the phases show a normal positive thermal expansion. The La?La and Cr?Cr bond distances show an abrupt drop from 950?K up to 1200?K and a sharp rise after that, which corroborates the negative thermal expansion of the cell volume and b-axis of the orthorhombic phase. The Cr?Cr distance in the rhombohedral phase shows a reduction in magnitude in the temperature range 950?1200?K, explaining the negative thermal expansion of the c-axis of this phase. The coefficients of volume thermal expansion and linear thermal expansion have been determined for both the phases. The significance of the present study has been discussed for practical applications of the studied compound in solid oxide fuel cells.

NEUTRON DIFFRACTION STUDIES ON La2-xDyxCa2xBa2Cu4+2xOz SUPERCONDUCTORS

Structural studies on Dy-substituted La-2125 type superconductors have been carried out by neutron diffraction experiments at room temperature using a monochromatic neutron beam of wavelength (λ) = 1.249 Å. A series of samples with La2-xDyxCa2xBa2Cu4+2xOz stoichiometric composition, forx = 0.1–0.5, have been studied for their structural properties. A tetragonal Y-123 unit cell was taken as the starting model for the Rietveld analysis. All the samples fit into the starting model, with no structural transition taking place with increasing dopant concentration. The results of Rietveld analysis and structural properties will be discussed in detail.

Crystallization and preliminary X-ray diffraction analysis of human seminal plasma protein PSP94.

The human seminal plasma protein PSP94 is a small protein of 94 residues that contains ten cysteines. Since its discovery about 25 years ago, several potential biological functions have been reported for this protein. Many PSP94 homologues have also been identified since then from various species, but no crystal structure has been determined to date. PSP94 has been purified from human seminal plasma and crystallized. These crystals diffracted to approximately 2.3 A resolution and belonged to space group P4(1)2(1)2, with unit-cell parameters a = 107.9, b = 107.9, c = 92.1 A. There are four molecules in the asymmetric unit. Structure solution by the heavy-atom method is currently in progress.