Raman spectrum of C-deuteratedγ-glycine (NH 3+ CD2COO−)

The Raman spectrum of C-deuterated γ-glycine (NH3+CD2COO-) in the crystal powder form was taken using λ 2536·5 excitation. 26 Raman lines were recorded. Of these, eight lines are attributed to the external oscillations and eighteen Raman lines to the internal oscillations. Proper assignments are given to the observed frequencies.

The C=S stretching frequency and the “-N-C=S bands” in the infrared

A correlation of the infrared spectra of thiocarbonyl derivatives based on the literature data has been carried out. Assignments have also been made in some new systems. Since simple alkyl thioketones are unstable, we have prepared thiofenchone in order to obtain a reference C=S stretching frequency. The C=S stretching frequency in thiofenchone has been found around 1180 cm−1 which is in fair agreement with the value calculated for thioformaldehyde. In the case of the thiocarbonyl derivatives where the C=S group is linked to elements other than nitrogen, the stretching frequency is generally found in the region 1025–1225 cm−1. Strong vibrational coupling is operative in the case of the nitrogen containing thiocarbonyl derivatives and three bands seem to consistently appear in the regions 1395–1570 cm−1, 1260–1420 cm−1, 940–1140 cm−1 due to the mixed vibrations. These bands, which may be tentatively designated as the “-N-C=S I, II and III bands”, could be useful in qualitative analysis.

Evaluation of solute-solvent interactions from solvent blue-shifts of n → π* transitions of C=O, C=S, NO2 and N=N groups: hydrogen bond energies of various donor-acceptor systems

Effects of non-polar, polar and proton-donating solvents on the n → π* transitions of C=O, C=S, NO2 and N=N groups have been investigated. The shifts of the absorption maxima in non-polar and polar solvents have been related to the electrostatic interactions between solute and solvent molecules, by employing the theory of McRAE. In solvents which can donate protons the solvent shifts are mainly determined by solute-solvent hydrogen bonding. Isobestic points have been found in the n → π* bonds of ethylenetrithio-carbonate in heptane-alcohol and heptane-chloroform solvent systems, indicating the existence of equilibria between the hydrogen bonded and the free species of the solute. Among the different proton-donating solvents studied water produces the largest blue-shifts. The blue-shifts in alcohols decrease in the order 2,2,2-trifluoroethanol, methanol, ethanol, isopropanol and t-butanol, the blue-shift in trifluoroethanol being nearly equal to that in water. This trend is exactly opposite to that for the self-association of alcohols. It is suggested that electron-withdrawing groups not merely decrease the extent of self-association of alcohols, but also increase the ability to donate hydrogen bonds. The approximate hydrogen-bond energies for several donor-acceptor systems have been estimated. In a series of aliphatio ketones and nitro compounds studied, the blue-shifts and consequently the hydrogen bond energies decrease with the decrease in the electron-withdrawing power of the alkyl groups. It is felt that electron-withdrawing groups render the chromophores better proton acceptors, and the alcohols better donors. A linear relationship between n → π* transition frequency and the infrared frequency of ethylenetrithiocarbonate has been found. It is concluded that stabilization of the electronic ground states of solute molecules by electrostatic and/or hydrogen-bond interactions determines the solvent shifts.

Vitamin C status of vitamin A-deficient rats

IT was initially suggested that vitamin A-deficiency leads to an interference in the biosynthesis of ascorbic acid, because depletion of vitamin A was found to cause a fall in the tissue-levels of ascorbate and diminished urinary ascorbic acid excretion in animals1-3. Mapson4, however, concluded that lowered ascorbic acid-levels in vitamin A-deficient rats is due to inanition only, because he was able to show that following chloretone treatment vitamin A-deficient and pair-fed vitamin A normal rats excrete comparable amounts of ascorbic acid in their urine and that restriction of food intake reduces the urinary ascorbate even in the chloretone-treated normal rats. Results of our preliminary experiments reported here clearly indicate that the synthesis of ascorbic acid in rats is markedly reduced during vitamin A-deficiency.

Use of Abel integral equations in water wave scattering by two surface-piercing barriers

In this paper the classical problem of water wave scattering by two partially immersed plane vertical barriers submerged in deep water up to the same depth is investigated. This problem has an exact but complicated solution and an approximate solution in the literature of linearised theory of water waves. Using the Havelock expansion for the water wave potential, the problem is reduced here to solving Abel integral equations having exact solutions. Utilising these solutions,two sets of expressions for the reflection and transmission coefficients are obtained in closed forms in terms of computable integrals in contrast to the results given in the literature which,involved six complicated integrals in terms of elliptic functions. The two different expressions for each coefficient produce almost the same numerical results although it has not been possible to prove their equivalence analytically. The reflection coefficient is depicted against the wave number in a number of figures which almost coincide with the figures available in the literature wherein the problem was solved approximately by employing complementary approximations. (C) 2009 Elsevier B.V. All rights reserved.

Potential functions for hydrogen bond interactions - III. Empirical Potential Function for the Peptide N-H...O=C Hydrogen Bond

A careful comparison of the distribution in the (R, θ)-plane of all NH ... O hydrogen bonds with that for bonds between neutral NH and neutral C=O groups indicated that the latter has a larger mean R and a wider range of θ and that the distribution was also broader than for the average case. Therefore, the potential function developed earlier for an average NH ... O hydrogen bond was modified to suit the peptide case. A three-parameter expression of the form {Mathematical expression}, with △ = R - Rmin, was found to be satisfactory. By comparing the theoretically expected distribution in R and θ with observed data (although limited), the best values were found to be p1 = 25, p3 = - 2 and q1 = 1 × 10-3, with Rmin = 2·95 Å and Vmin = - 4·5 kcal/mole. The procedure for obtaining a smooth transition from Vhb to the non-bonded potential Vnb for large R and θ is described, along with a flow chart useful for programming the formulae. Calculated values of ΔH, the enthalpy of formation of the hydrogen bond, using this function are in reasonable agreement with observation. When the atoms involved in the hydrogen bond occur in a five-membered ring as in the sequence[Figure not available: see fulltext.] a different formula for the potential function is needed, which is of the form Vhb = Vmin +p1△2 +q1x2 where x = θ - 50° for θ ≥ 50°, with p1 = 15, q1 = 0·002, Rmin = 2· Å and Vmin = - 2·5 kcal/mole. © 1971 Indian Academy of Sciences.

An optimum criterion for eccentrically loaded R. C. columns

An analysis of eccentrically loaded short reinforced concrete columns using a variable failure strain criterion is presented. The method dispenses with the usual procedure of assuming a fixed value for the ultimate strain in concrete. The analysis is based on the use of a simple, single equation for the complete stress-strain curve of concrete and the adoption of a process of maximisation of moment with respect to extreme fibre concrete compressive strain. Columns of rectangular section and loaded eccentrically along one axis only are considered in this paper. A good agreement is observed between the theoretical and experimental values of some test results.

Confined concrete—Its application in R.C. beams and frames

Stress-strain characteristics of concrete confined in steel binders have been determined. A new factor “confinement index” has been introduced for a quantitative measure of the confinement and using these results a “stress-block” has been developed. Tests have been made on simply supported reinforced concrete beams with spiral binder confinement and analysed on the basis of the proposed stress-block. Tests have also been made oon reinforced concrete portal frames and continuous beams with spiral binder confinement at sections of possible plastic hinge formation. An analysis of these tests indicates that a full redistribution of moments has taken place at ultimate.

Limit analysis of rectangular R.C. slabs on ground

A method is presented for obtaining lower bound on the carrying capacity of reinforced concrete foundation slab-structures subject to non-uniform contact pressure distributions. Functional approach suggested by Vallance for simply supported square slabs subject to uniform pressure distribution has been extended to simply supported rectangular slabs subject to symmetrical non-uniform pressure distributions. Radial solutions, ideally suited for rotationally symmetric problems, are shown to be adoptable for regular polygonal slabs subject to contact pressure paraboloids with constant edge pressures. The functional approach has been shown to be well suited even when the pressure is varying along the edges.

1-[(2-Chloro-8-methylquinolin-3-yl)methyl]pyridin-2(1H)-one

In the title compound, C16H13ClN2O, the quinoline ring system is approximately planar [maximum deviation 0.021 (2) angstrom] and forms a dihedral angle of 85.93 (6)degrees with the pyridone ring. Intermolecular C-H center dot center dot center dot O hydrogen bonding, together with weak C-H center dot center dot center dot pi and pi-pi interactions [centroid-to-centroid distances 3.5533 (9) and 3.7793 (9) angstrom], characterize the crystal structure.

5-(4-Chlorophenyl)-3-(2,4-dimethylthiazol-5-yl)-1,2,4-triazolo[3,4-a]isoquinoline

In the title molecule, C21H15ClN4S, the triazoloisoquinoline ring system is approximately planar, with an r.m.s. deviation of 0.054 (2) angstrom and a maximum deviation of 0.098 (2) angstrom from the mean plane for the triazole ring C atom that is bonded to the thiazole ring. The thiazole and benzene rings are twisted by 66.36 (7) and 56.32 (7)degrees respectively, with respect to the mean plane of the triazoloisoquinoline ring system. In the crystal structure, molecules are linked by intermolecular C-H center dot center dot center dot N interactions along the a axis. The molecular conformation is stabilized by a weak intramolecular pi-pi interaction involving the thiazole and benzene rings, with a centroid-centroid distance of 3.6546 (11) angstrom . In addition, two other intermolecular pi-pi stacking interactions are observed, between the triazole and benzene rings and between the dihydropyridine and benzene rings [centroid-centroid distances = 3.6489 (11) and 3.5967 (10) angstrom, respectively].