Crystal structure and conformation of the cyclic dipeptide cyclo-(L-histidyl-L-aspartyl) trihydrate

The crystal structure of cyclo-(L-histidyl-L-aspartyl) trihydrate has been determined by x-ray diffraction techniques, and refined to a final R index of 0.056 for 1601 reflections. The molecule is in a folded conformation, with the imidazole ring facing the diketopiperazine ring. However, since the diketopiperazine ring is essentially planar, the interaction between the two rings is not as intimate as in those cyclic dipeptides in which the diketopiperazine ring is in a boat conformation with the side chain occupying an axial, or flagpole, site. Planarity of the diketopiperazine ring may be dictated by steric interactions between the imidazole ring and the aspartyl side chain. The molecule is a zwitterion, a proton having been transferred from the carboxyl group of the aspartyl side chain to the imidazole ring.

The crystal and molecular structure of the amino terminal tetrapeptide of alamethicin. A novel 310 helical conformation

The molecular structure of N-benzyloxycarbonyl-α-aminoisobutyryl-prolyl-α-aminoisobutyryl-alanyl methyl ester (Z-Aib-Pro-Aib-Ala-OMe), the amino terminal tetrapeptide of alamethicin is reported. The molecule contains two consecutive β-turns with Aib-Pro and Pro-Aib at the corners, forming an incipient 310 helix. This constitutes the first example of an X2-Pro3 β-turn in the crystal structure of a small peptide.

The Electronic Structure of Graphite from Compton Profile Measurements

Compton profile data are used to investigate the ground state wavefunction of graphite. The results of two new $\gamma$-ray measurements are reported and compared with the results of earlier $\gamma$-ray and electron scattering measurements. A tight-binding calculation has been carried out and the results of earlier calculations based on a molecular model and a pseudo-potential wavefunction are considered. The analysis, in terms of the reciprocal form factor, shows that none of the calculations gives an adequate description of the data in the basal plane although the pseudo-potential calculation describes the anisotropy in the plane reasonably well. In the basal plane the zero-crossing theorem appears to be violated and this problem must be resolved before more accurate models can be derived. In the c-axis direction the molecular model and the tight binding calculation give better agreement with the experimental data than does the pseudopotential calculation.

Steroechemistry of the Pyrrolidine rings in the collagen structure

In the collagen triple-helical structure, large side groups occuring at location 3 in the repeating triplet sequences (Gly-Rz-Rz)n are appreciably constrained if a proline residue occurs as Rz in a neighbouring chain. The severity of the steric hindrance depends on the geometry of the prolyl ring. In this paper we propose two different puckerir.gs for the proline ring, the first one being energetically favorable for most types of residue sequences commonly found in collegen while the second is preferable when an amino acid residue with a large side group occurs at location 3 in a neighbouring chain. The puckering of the pyrrolidine ring of hydroxyproline, as proposed earlier, is quite favorable from energy as well as stereochemical considerations.

Fourier transform of the collagen triple-helical structure and its significance

The Fourier transforms of the collagen molecular structure have been calculated taking into consideration various side chain atoms, as well as the presence of bound water molecules. There is no significant change in the calculated intensity distribution on including the side chain atoms of non-imino-acid residues. Taking into account the presence of about two bound water molecules per tripeptide unit, the agreement with the observed x-ray pattern is slightly improved. Fourier transforms have also been calculated for the detailed molecular geometries proposed from other laboratories. It is found that there are no major differences between them, as compared to our structure, either in the positions of peak intensity or in the intensity distribution. Hence it is not possible to judge the relative merits of the various molecular geometries for the collagen triple helix from a comparison of the calculated transforms with the meagre data available from its x-ray fibre pattern. It is also concluded that the collagen molecular structure should be regarded as a somewhat flexible chain structure, capable of adapting itself to the requirements of the different side groups which occur in each local region.

Structural studies of analgesics and their interactions. III. The crystal and molecular structure of amidopyrine

Amidopyrine (1-phenyl-2,3-dimethyl-4-dimethylaminopyrazolone), C13HzvN30, a dimethylamino derivative of antipyrine and an important analgesic and antipyretic agent, crystallizes in the triclinic space group P1 with four molecules in a unit cell of dimensions a= 7.458 (5), b = 10.744 (5), c= 17.486 (15)/~,, e=98.6 (2),/~= 85.6 (3), y= 108-6 (2) . The structure was solved by direct methods and refined to an R value of 0.055 for 3706 photographically observed reflexions. The dimensions of the two crystallographically independent molecules are very nearly the same. The pyrazolone moiety in the molecule has dimensions comparable to those in antipyrine. Unlike antipyrine, the molecular dimensions of amidopyrine in the free state (the present structure) are close to those found in some of its hydrogenbonded complexes. Thus it appears that the presence of the dimethylamino group makes the molecule more resistant to changes in its dimensions resulting from molecular association. An attempt has also been made to correlate the polar nature of the pyrazolone moiety and the hybridization state of the hetero nitrogen atoms in antipyrine, amidopyrine and their complexes.

Second-order statistical structure of geomagnetic field reversals

From the autocorrelation function of geomagnetic polarity intervals, it is shown that the field reversal intervals are not independent but form a process akin to the Markov process, where the random input to the model is itself a moving average process. The input to the moving average model is, however, an independent Gaussian random sequence. All the parameters in this model of the geomagnetic field reversal have been estimated. In physical terms this model implies that the mechanism of reversal possesses a memory.

The structure of turbulent boundary layers along mildly curved surfaces

This paper describes a detailed study of the structure of turbulence in boundary layers along mildly curved convex and concave surfaces. The surface curvature studied corresponds to δ/Rw = ± 0·01, δ being the boundary-layer thickness and Rw the radius of curvature of the wall, taken as positive for convex and negative for concave curvature. Measurements of turbulent energy balance, autocorrelations, auto- and cross-power spectra, amplitude probability distributions and conditional correlations are reported. It is observed that even mild curvature has very strong effects on the various aspects of the turbulent structure. For example, convex curvature suppresses the diffusion of turbulent energy away from the wall, reduces drastically the integral time scales and shifts the spectral distributions of turbulent energy and Reynolds shear stress towards high wavenumbers. Exactly opposite effects, though generally of a smaller magnitude, are produced by concave wall curvature. It is also found that curvature of either sign affects the v fluctuations more strongly than the u fluctuations and that curvature effects are more significant in the outer region of the boundary layer than in the region close to the wall. The data on the conditional correlations are used to study, in detail, the mechanism of turbulent transport in curved boundary layers. (Published Online April 12 2006)

The structure of cyclopropane-1,1-dicarboxamide

Abstract is not available.

Korteweg-de Vries equation for the propagation of fast ion-acoustic waves in multi-dimensions

Abstract is not available.

The structure of phosphacymantrene

Proton NMR spectra of phosphacymantrene (π-phospholyl manganese tricarbonyl) orientated in the nematic phases of liquid crystals have been investigated. The derived H-H and H-P direct dipolar coupling constants have been used to determine the relative proton-proton and proton-phosphorus distances. A comparison of the geometrical data of various 5-membered aromatic heterocycles shows that the relative distances between the protons closest to the heteroatom increase with the van der Waals radius of the heteroatom. The results suggest that NMR spectroscopy of orientated molecules can be used to determine van der Waals radii.

The Crystal and Molecular Structure of 4-Aza-5-oxo-tricyclo[4.4.0.03,8]decane (Aza-twistanone)

Die kristalline Struktur von Aza-twistanon wurde durch eine Röntgenstruktur-analyse untersucht. Die Kristalle gehören zur monoklinen Raumgruppe P21/n mit den Zelldimensionen a = 6,662(6), b = 13,36(2), c = 8,606(9) Å, = 98,97(2)°, V = 757 Å3, Z = 4. Die Struktur wurde mit Direktmethoden gelöst und bis zu R = 0,035 verfeinert (mittlere (c) = 0,003 Å3).Die cis-Amidgruppe ist relativ stark deformiert und hat einen Torsionswinkel C -C -N-C von 14,5(4)° (Deformation aus der Ebene c = 5,0(5)° und N = 13,5(4,0)°). Die gegenüberliegende äthylenbrücke weist einen Torsionswinkel von 25,1(5)° auf. Die entsprechenden Winkel in Twistan betragen je 20°. Das tricyclische Gerüst von Aza-twistanon hat approximative.

X-ray studies of crystalline complexes involving amino acids. II. The crystal structure of L-arginine L-glutamate

Abstract is not available.

Experiments on the fine structure of turbulence

Investigations have been carried out of some aspects of the fine-scale structure of turbulence in grid flows, in boundary layers in a zero pressure gradient and in a boundary layer in a strong favourable pressure gradient leading to relaminarization. Using a narrow-band filter with suitable mid-band frequencies, the properties of the fine-scale structure (appearing as high frequency pulses in the filtered signal) were analysed using the variable discriminator level technique employed earlier by Rao, Narasimha & Badri Narayanan (1971). It was found that, irrespective of the type of flow, the characteristic pulse frequency (say Np) defined by Rao et al. was about 0·6 times the frequency of the zero crossings. It was also found that, over the small range of Reynolds numbers tested, the ratio of the width of the fine-scale regions to the Kolmogorov scale increased linearly with Reynolds number in grid turbulence as well as in flat-plate boundarylayer flow. Nearly lognormal distributions were exhibited by this ratio as well as by the interval between successive zero crossings. The values of Np and of the zero-crossing rate were found to be nearly constant across the boundary layer, except towards its outer edge and very near the wall. In the zero-pressure-gradient boundary-layer flow, very near the wall the high frequency pulses were found to occur mostly when the longitudinal velocity fluctuation u was positive (i.e. above the mean), whereas in the outer part of the boundary layer the pulses more often occurred when u was negative. During acceleration this correlation between the fine-scale motion and the sign of u was less marked.