N-H center dot center dot center dot O and C-H center dot center dotcenter dot O interaction mimicry in the 1:1 molecular complexes of 5,5-diethylbarbituric acid with urea and acetamide

The analogy between N-H center dot center dot center dot O and C-H center dot center dot center dot O intermolecular interactions is studied with variable temperature (180-100 K) single crystal X-ray diffraction analysis.5,5-Diethylbarbituric acid (barbital) forms isostructural molecular complexes (co-crystals) with urea (1) and acetamide (2) that respectively contain these analogous interactions.The behaviour of these two interactions as a function of temperature is very similar. This indicates that the C-H center dot center dot center dot O bond in barbital acetamide plays a similar chemical and structural role as does the N-H center dot center dot center dot O bond in barbital urea. The close relationship between these interactions and their comparable nature is further adduced from the formation of a ternary solid solution (3) of barbital, urea and acetamide. The fact that the C-H center dot center dot center dot O interaction in barbital acetamide is weaker than the N-H center dot center dot center dot O interaction in barbital urea is shown by the fact that acetamide is under expressed and urea is over expressed with respect to the quantities of these substances present in solution prior to crystallization of these ternary crystals.

Orientational melting and reorientational motion in a cubane molecular crystal: A molecular simulation study

Detailed molecular simulations are carried out to investigate the effect of temperature on orientational order in cubane molecular crystal. We report a transition from an orientationally ordered to an orientationally disordered plastic crystalline phase in the temperature range 425-450 K. This is similar to the experimentally reported transition at 395 K. The nature of this transition is first order and is associated with a 4.8% increase in unit Cell volume that is comparable to the experimentally reported unit cell volume change of 5.4% (Phys. Rev. Lett. 1997, 78, 4938). An orientational order parameter, eta(T), has been defined in terms of average angle of libration of a molecular 3-fold axis and the orientational melting has been characterized by using eta(T). The orientational melting is associated with an anomaly in specific heat at constant pressure (C-p) and compressibility (kappa). The enthalpy of transition and entropy of transition associated with this orientational melting are 20.8 J mol(-1) and 0.046 J mol(-1) K-1, respectively. The structure of crystalline as well as plastic crystalline phases is characterized by using various radial distribution functions and orientational distribution functions. The coefficient of thermal expansion of the plastic crystalline phase is more than twice that of the crystalline phase.

The oscillation of a spheroid along its axis in a non-Newtonian fluid

The present paper investigates the nature of the fluid flow when a spheroid is suspended in an infinitely extending elastico-viscous fluid defined by the constitutive equations given by Oldroyd or Rivlin and Ericksen, and is made to perform small amplitude oscillations along its axis. The solution of the vector wave equation is expressed in terms of the solution of the corresponding scalar wave equation, without the use of Heine's function or spheroidal wave functions. Two special cases (i) a sphere and (ii) a spheroid of small ellipticity, are studied in detail.

Boxicity and cubicity of asteroidal triple free graphs

The boxicity of a graph G, denoted box(G), is the least integer d such that G is the intersection graph of a family of d-dimensional (axis-parallel) boxes. The cubicity, denoted cub(G), is the least dsuch that G is the intersection graph of a family of d-dimensional unit cubes. An independent set of three vertices is an asteroidal triple if any two are joined by a path avoiding the neighbourhood of the third. A graph is asteroidal triple free (AT-free) if it has no asteroidal triple. The claw number psi(G) is the number of edges in the largest star that is an induced subgraph of G. For an AT-free graph G with chromatic number chi(G) and claw number psi(G), we show that box(G) <= chi(C) and that this bound is sharp. We also show that cub(G) <= box(G)([log(2) psi(G)] + 2) <= chi(G)([log(2) psi(G)] + 2). If G is an AT-free graph having girth at least 5, then box(G) <= 2, and therefore cub(G) <= 2 [log(2) psi(G)] + 4. (c) 2010 Elsevier B.V. All rights reserved.

Physicochemical studies on the gelation of hen's egg yolk: Delipidation of yolk plasma by treatment with phospholipase-C and extraction with solvents

A method for the delipidation of egg yolk plasma using phospholipase-C, n-heptane, and 1-butanol has been described. An aggregating protein fraction and a soluble protein fraction were separated by the action of phospholipase-C. The aggregating protein fraction freed of most of the lipids by treatment with n-heptane and 1-butanol was shown to be the apolipoproteins of yolk plasma, whereas the soluble proteins were identified as the livetins. Carbohydrate and the N-terminal amino acid analysis of these protein fractions are reported. A comparison of these protein fractions with the corresponding fractions obtained by formic acid delipidation of yolk plasma has been made. The gelation of yolk plasma by the action of phospholipase-C has been interpreted as an aggregation of lipoproteins caused by ionic interactions. The role of lecithin in maintaining the structural integrity of lipoproteins has been discussed.

Chain of excitation spot generation by aperture engineering

An optical technique is proposed for obtaining multiple excitation spots. Phase-matched counter propagating extended depth-of-focus fields were superimposed along the optical axis for generating multiple localized excitation spots. Moreover, the filtering effect due to the optical mask increases the lateral resolution. Proposed technique introduces the concept of simultaneous multiplane excitation and improves three-dimensional resolution. (C) 2010 American Institute of Physics.

Site characterization model using least-square support vector machine and relevance vector machine based on corrected SPT data (N-c)

Statistical learning algorithms provide a viable framework for geotechnical engineering modeling. This paper describes two statistical learning algorithms applied for site characterization modeling based on standard penetration test (SPT) data. More than 2700 field SPT values (N) have been collected from 766 boreholes spread over an area of 220 sqkm area in Bangalore. To get N corrected value (N,), N values have been corrected (Ne) for different parameters such as overburden stress, size of borehole, type of sampler, length of connecting rod, etc. In three-dimensional site characterization model, the function N-c=N-c (X, Y, Z), where X, Y and Z are the coordinates of a point corresponding to N, value, is to be approximated in which N, value at any half-space point in Bangalore can be determined. The first algorithm uses least-square support vector machine (LSSVM), which is related to aridge regression type of support vector machine. The second algorithm uses relevance vector machine (RVM), which combines the strengths of kernel-based methods and Bayesian theory to establish the relationships between a set of input vectors and a desired output. The paper also presents the comparative study between the developed LSSVM and RVM model for site characterization. Copyright (C) 2009 John Wiley & Sons,Ltd.

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.