Ternary metal complexes of anionic and neutral pyridoxine (vitamin B6) with 2,2'-bipyridine. Syntheses and x-ray structures of (pyridoxinato)bis(2,2'-bipyridyl)cobalt(III) perchlorate and chloro(2,2'-bipyridyl)(pyridoxine)copper(II) perchlorate hydrate

Ternary metal complexes involving vitamin B6 with formulas [CO",(PN-H)](anCdI [OC)'(bpy)(PN)Cl]C10(.bpHy 0 = 2,2'-bipyridine, PN = neutral pyridoxine, PN-H = anionic pyridoxine) have been prepared for the first time and characterized by means of magnetic and spectroscopic measurements. The crystal structures of the compounds have also been determined. [CO(PN-H)](CcryIsOta,l)lize s in the space group P2,/c with a = 18.900 (3) A, b = 8.764 (1) A, c = 20.041 (2) A,p = 116.05 (l)', and Z = 4 and [Cu(bpy)(PN)C1]C104-H20in the space group Pi with a = 12.136 (5) A, b = 13.283 (4) A,c = 7.195 (2) A, a = 96.91 (Z)', 0 = 91.25 (3)', y = 71.63 (3)', and Z = 2. The structures were solved by the heavy-atom method and refined by least-squares techniques to R values of 0.080 and 0.042 for 3401 and 2094 independent reflections, respectively. Both structures consist of monomeric units. The geometry around Co(II1) is octahedral and around Cu(I1) is distorted square pyramidal. In [CO(PN-H)]t(wCo IoxOy~ge)n~s ,fro m phenolic and 4-(hydroxymethyl) groups of PN-H and two nitrogens from each of two bpy's form the coordination sphere. In [Cu(bpy)(PN)C1]C104.H20o ne PN and one bpy, with the same donor sites, act as bidentate chelates in the basal plane, with a chloride ion occupying the apical position. In both structures PN and PN-H exist in the tautomeric form wherein pyridine N is protonated and phenolic 0 is deprotonated. However, a novel feature of the cobalt compound is that PN-H is anionic due to the deprotonation of the 4-(hydroxymethyl) group. The packing in both structures is governed by hydrogen bonds, and in the copper compound partial stacking of bpy's at a distance of -3.55 also adds to the stability of the system. Infrared, NMR, and ligand field spectroscopic results and magnetic measurements are interpreted in light of the structures.

Structures of isopropylidene nucleoside derivatives - implications for ribose ring flexibility under external cyclic constraints

Crystal structures of six isopropylidene nucleoside derivatives are described. The results show that, under external cyclic constraints, the ribose assumes a variety of unusual conformations. In those compounds which possess a base-to-sugar cyclization through the C(4′) atom, the furanose pucker is predominantly C(4′)-endo, O(4′)-exo. The possible relevance of the sulphur geometry in two of the compounds to certain structural aspects of the action of the enzyme thymidylate synthetase is also pointed out.

Polarized ethylenes: structures of (1,3-dimethyl-2-imidazolidinylidene)malononitrile and (1,3-dimethyl-2-perhydropyrimidinylidene)malononitrile

Crystal structures of the title compounds, (I) and (II), have been determined by three-dimensional diffraction methods. Crystals of CsHIoN 4 (I) are monoclinic, space group P21/a with Z = 4, Mr= 162, a = 7.965 (1), b = 16.232 (2), c = 7.343 (1) A, fl = 113.54 (1) °, V = 890.7 A 3, D,n = 1.218, D x = 1.208 gcm -3, g(Cu Ka, 2 = 1.5418/~) = 6.47 em -1, F(000) = 344. The crystals of C9H12N4 (II) are orthorhombic, space group P21en, with Z = 4, Mr = 176, a = 7.983 (3), b = 8.075 (2), c = 14.652 (3) ./k, V = 944.43/~3, Dm= 1.219, D x = 1.237 g cm -3, #(Mo Ka, ). = 0.7107 ,/k) = 0.868 cm -1, F(000) = 376. Both structures were solved by direct methods and refined to R = 5.8% for (I) and 5.3 % for (II). The C-C double-bond distances are 1.407 (3) in (I) and 1.429 (6)/~ in (II), appreciably longer than normal. The steric and push-pull effects result in rotation about the C=C bond, the rotation angles being 20.2 (3) in (I) and 31.5 (6) o in (II).

Self-assembly of three new coordination complexes: Formation of 2-D square grid, 1-D chain and tape structures

Three distinct coordination complexes, viz., [Co(imi)(2)(tmb)(2)] (1) [where imi = imidazole], {[Ni(tmb)(2)(H2O)(3)]center dot 2H(2)O}(n) (2) and [Cu-2(mu-tmb)(4)(CH3OH)(2)] (3), have been synthesized hydrothermally by the reactions of metal acetates,2,4,6-trimethylbenzoic acid (Htmb) and with or without appropriate amine. The Ni analogue of 1 and the Co analogue of 2 have also been synthesized. X-ray single-crystal diffraction suggests that complex 1 represents discrete mononuclear species and complex 2 represents a 1D chain coordination polymer in which the Ni(H) ions are connected by the bridging water molecules. Complex 3 represents a neutral dinuclear complex. In 1, the central metal ions are associated by the carboxylate moiety and imidazole ligands, whereas the central metal atom is coordinated to the carboxylate moiety and the respective solvent molecules in 2 and 3. In 3, the four 2,4,6-trimethylbenzoate moieties act as a bridge connecting two copper (11) ions and the 0 atoms of methanol coord geometry, with the methanol molecule at the apical position. In all the three structures the central metal atom sits on a crystallographic inversion centre. In all the cases, the coordination entities are further organized via hydrogen bonding interactions to generate multifarious supramolecular networks. Complexes 1, 2 and 3 have also been characterized by spectroscopic (UV/Vis and IR) and thermal analysis (TGA). In addition, the complexes were found to exhibit antimicrobial activity. The magnetic susceptibility measurements, measured from 8 to 300 K, revealed antiferromagnetic interactions between the Co(II) ions in compound 1 and the Ni(II) ions in la, respectively.

A new method for generation of quasi-periodic structures withn fold axes: Application to five and seven folds

A new geometrical method for generating aperiodic lattices forn-fold non-crystallographic axes is described. The method is based on the self-similarity principle. It makes use of the principles of gnomons to divide the basic triangle of a regular polygon of 2n sides to appropriate isosceles triangles and to generate a minimum set of rhombi required to fill that polygon. The method is applicable to anyn-fold noncrystallographic axis. It is first shown how these regular polygons can be obtained and how these can be used to generate aperiodic structures. In particular, the application of this method to the cases of five-fold and seven-fold axes is discussed. The present method indicates that the recursion rule used by others earlier is a restricted one and that several aperiodic lattices with five fold symmetry could be generated. It is also shown how a limited array of approximately square cells with large dimensions could be detected in a quasi lattice and these are compared with the unit cell dimensions of MnAl6 suggested by Pauling. In addition, the recursion rule for sub-dividing the three basic rhombi of seven-fold structure was obtained and the aperiodic lattice thus generated is also shown.

Some studies on free vibration of composite laminates

Free vibration analysis is carried out to study the vibration characteristics of composite laminates using the modified shear deformation, layered, composite plate theory and employing the Rayleigh-Ritz energy approach. The analysis is presented in a unified form so as to incorporate all different combinations of laminate boundary conditions and with full coverage with regard to the various design parameters of a laminated plate. A parametric study is made using a beam characteristic function as the admissible function for the numerical calculations. The numerical results presented here are for an example case of fully clamped boundary conditions and are compared with previously published results. The effect of parameters, such as the aspect ratio of plates, ply-angle, number of layers and also the thickness ratios of plies in laminates on the frequencies of the laminate, is systematically studied. It is found that for anti-symmetric angle-ply or cross-ply laminates unique numerical values of the thickness ratios exist which improve the vibration characteristics of such laminates. Numerical values of the non-dimensional frequencies and nodal patterns, using the thickness ratio distribution of the plies, are then obtained for clamped laminates, fabricated out of various commonly used composite materials, and are presented in the form of the design curves.

A laminated anisotropic curved beam and shell stiffening finite element

The details of development of the stiffness matrix of a laminated anisotropic curved beam finite element are reported. It is a 16 dof element which makes use of 1-D first order Hermite interpolation polynomials for expressing it's assumed displacement state. The performance of the element is evaluated considering various examples for which analytical or other solutions are available.

Phased-Mission Analysis for Evaluating the Effectiveness of Aerospace Computing-Systems

Effectiveness evaluation of aerospace fault-tolerant computing systems used in a phased-mission environment is rather tricky and difficult because of the interaction of its several degraded performance levels with the multiple objectives of the mission and the use environment. Part I uses an approach based on multiobjective phased-mission analysis to evaluate the effectiveness of a distributed avionics architecture used in a transport aircraft. Part II views the computing system as a multistate s-coherent structure. Lower bounds on the probabilities of accomplishing various levels of performance are evaluated.

Ecological restoration of forests in Fennoscandia : Defining reference stand structures and immediate effects of restoration.

The first aim of this thesis was to explore the structural characteristics of near-natural forests and to quantify how human utilization has changed them. For this, we examined the stand characteristics in Norway spruce Picea abies (L.) Karst-dominated old-growth stands in northwestern Russia and in old Scots pine Pinus sylvestris L.-dominated stands in three regions from southern Finland to northwestern Russia. In the second study, we also compared stands with different degrees of human impact, from near-natural stands and stands selectively cut in the past to managed stands. Secondly, we used an experimental approach to study the short-term effects of different restorative treatments on forest structure and regeneration in managed Picea abies stands in southern Finland. Restorative treatments consisted of a partial cut combined with three levels of coarse woody debris retention, and a fire/no-fire treatment. In addition, we examined burned and unburned reference stands without cutting treatments. Results from near-natural Picea abies forests emphasize the dynamic character of old-growth forests, the variety of late-successional forest structures, and the fact that extended time periods are needed to attain certain late-successional stages with specific structural and habitat attributes, such as large-diameter deciduous trees and a variety of deadwood. The results from old Pinus sylvestris-dominated forests showed that human impact in the form of forest utilization and fire exclusion has strongly modified and reduced the structural complexity of stands. Consequently, small protected forest fragments in Finland may not serve as valid natural reference areas for forest restoration. However, results from the restoration experiment showed that early-successional natural stand characteristics can be restored to structurally impoverished managed Picea abies stands, despite a significant portion of wood volume being harvested. A variety of restoration methods is needed, due to differences in the condition of the forest when restoration is initiated and the variety of successional stages of forest structures after anthropogenic and natural disturbances. Keywords: dead wood, disturbance dynamic, fire, near-natural stand, rehabilitation, succession

Deflection analysis of hybrid laminated composite plates

In this paper an attempt is made to obtain deflections of hybrid, laminated, rectangular and skew composite plates. Analysis is performed by employing the Galerkin technique. Numerical results have been obtained for two types of layups employing Kevlar/epoxy and Boron/epoxy laminae. It is observed that for a given aspect ratio the rigidity of the skew plate increases with an increase in the skew angle. Further, for a specified deflection, the hybrid laminates turn out to be lighter.

Finite element analysis of bimodulus composite stiffened thin shells of revolution

This paper is a sequel to the work published by the first and third authors[l] on stiffened laminated shells of revolution made of unimodular materials (materials having identical properties in tension and compression). A finite element analysis of laminated bimodulus composite thin shells of revolution, reinforced by laminated bimodulus composite stiffeners is reported herein. A 48 dot doubly curved quadrilateral laminated anisotropic shell of revolution finite element and it's two compatible 16 dof stiffener finite elements namely: (i) a laminated anisotropic parallel circle stiffener element (PCSE) and (ii) a laminated anisotropic meridional stiffener element (MSE) have been used iteratively. The constitutive relationship of each layer is assumed to depend on whether the fiberdirection strain is tensile or compressive. The true state of strain or stress is realized when the locations of the neutral surfaces in the shell and the stiffeners remain unaltered (to a specified accuracy) between two successive iterations. The solutions for static loading of a stiffened plate, a stiffened cylindrical shell. and a stiffened spherical shell, all made of bimodulus composite materials, have been presented.

Crystal and molecular structures of alkali- and alkaline-earth-metal complexes of N,N-dimethylformamide

Structures of lithium, sodium, magnesium, and calcium complexes of NJ-dimethylformamide (DMF) have been investigated by X-ray crystallography. Complexes with the formulas LiCl.DMF.1/2H20, NaC104.2DMF, CaC12.2DMF.2H20, and Mg(C104)2.6DMF crystallized in space groups P2]/c, P2/c, Pi, and Ella, respectively, with the following cell dimensions: Li complex, a = 13.022 (7) A, b = 5.978 (4) A, c = 17.028 (10) A, = 105.48 (4)O, Z = 8; Na complex, a = 9.297 (4)A, b = 10.203 (3) A, c = 13.510 (6) A, /3 = 110.08 (4)O, Z = 4; Ca complex, a = 6.293 (4) A, b = 6.944 (2) A, c = 8.853(5) A, a = 110.15 (3)O, /3 = 105.60 (6)", y = 95.34 (5)", Z = 1; Mg complex, a = 20.686 (11) A, b = 10.962 (18) A,c = 14.885 (9) A, /3 = 91.45 (5)O, Z = 4. Lithium is tetrahedrally coordinated while the other three cations are octahedrally coordinated; the observed metal-oxygen distances are within the ranges generally found in oxygen donor complexes of these metals. The lithium and sodium complexes are polymeric, with the amide and the anion forming bridging groups between neighboring cations. The carbonyl distances become longer in the complexes accompanied by a proportionate decrease in the length of the central C-N bond of the amide; the N-C bond of the dimethylamino group also shows some changes in the complexes. The cations do not deviate significantly from the lone-pair direction of the amide carbonyl and remain in the amide plane. Infrared spectra of the complexes reflect the observed changes in the amide bond distances.

On the Fourier refinement of protein structures

The situation normally encountered in the high-resolution refinement of protein structures is one in which the inaccurate positions of P out of a total of N atoms are known whereas those of the remaining atoms are unknown. Fourier maps with coefficients (FN -- F'P) × exp (i[alpha]'P) and (mFN -- nF'P) exp (i[alpha]'P), where FN is the observed structure factor and F'P and [alpha]'P are the magnitude and the phase angle of the calculated structure factor corresponding to the inaccurate atomic positions, are often used to correct the positions of the P atoms and to determine those of the Q unknown atoms. A general theoretical approach is presented to elucidate the effect of errors in the positions of the known atoms on the corrected positions of the known atoms and the positions of the unknown atoms derived from such maps. The theory also leads to the optimal choice of parameters used in the different syntheses. When the errors in the positions of the input atoms are systematic, their effects are not taken care of automatically by the syntheses.

Infrared spectra of some oxides of K2NiF4 and related structures

The i.r. spectra of some Ln2BO4 and LnSrBO4 compounds (Ln = La, Pr, Nd, Sm or Gd;B = Fe, Al, Co or Cu) with K2NiF4 or related structures have been studied in the range 800-300 cm−1. The BO6 octahedra in compounds with K2NiF4 structure are elongated. The assignment of the bands in terms of internal modes of sheets of bridged BO6 octahedra or square-planar BO4 sheets has been considered. The observed spectra are correlated with those of solid solutions of these oxides and of LnBO3 perovskites. Unusually high stretching frequencies found in some of the oxides are discussed in terms of the short B---O bonds in the basal plane and the Ln---O bonds along the c axis.