X-ray and ultraviolet photoelectron spectroscopy studies of the interaction of carbon monoxide with oxygen adsorbed on silver covered with potassium, caesium or barium

X-ray and He(II) ultraviolet photoelectron spectroscopy studies of the interaction of CO with oxygen on potassium-, caesium- and barium-covered Ag surfaces have shown the formation of carbonate at 300 K. While on a caesium-covered surface only carbonate formation takes place, on the potassium- and barium-covered surfaces molecularly chemisorbed CO is also formed. The variation of the surface concentrations of carbon and oxygen with temperature has been examined and a reaction sequence for the interaction of CO with adsorbed oxygen on potassium-, caesium- and barium-covered Ag surfaces is suggested.

On exact solutions of the unsteady navierstokes equationsâ the vortex with instantaneous curvilinear axis

The unsteady pseudo plane motions have been investigated in which each point of the parallel planes is subjected to non-torsional oscillations in their own plane and at any given instant the streamlines are concentric circles. Exact solutions are obtained and the form of the curve , the locus of the centers of these concentric circles, is discussed. The existence of three infinite sets of exact solutions, for the flow in the geometry of an orthogonal rheometer in which the above non-torsional oscillations are superposed on the disks, is established. Three cases arise according to whether is greater than, equal to or less than , where is angular velocity of the basic rotation and is the frequency of the superposed oscillations. For a symmetric solution of the flow these solutions reduce to a single unique solution. The nature of the curve is illustrated graphically by considering an example of the flow between coaxial rotating disks.

The effect of some catalysts on the curing of oxiranes with p-phenylenediamine

The effect of some alcohols, acetylacetonates of transition metals, and manganese stearate and naphthenate on the curing reaction of a diglycidyl ether of ether of bisphenol-A with p-phenylenediamine is studied. Maximum catalytic activity is shown by the manganese compounds and triethanolamine.

New constraints on the pion EM form factor using Pi `(-Q(2))

We study the constraints arising on the expansion parameters c and d of the pion electromagnetic form factor from the inclusion of pure spacelike data and the phase of timelike data along with one spacelike datum, using as input the first derivative of the QCD polarization amplitude Pi'(-Q(2)). These constraints when combined with other analyses, provide a valuable check on a determination of c due to Guo et al. and on our previous work where pionic contribution to the (g - 2) of the muon was used as the input. This work further illustrates the power of analyticity techniques in form factor analysis.

On the Arrangement of Cliques in Chordal Graphs with respect to the Cuts

A cut (A, B) (where B = V - A) in a graph G = (V, E) is called internal if and only if there exists a vertex x in A that is not adjacent to any vertex in B and there exists a vertex y is an element of B such that it is not adjacent to any vertex in A. In this paper, we present a theorem regarding the arrangement of cliques in a chordal graph with respect to its internal cuts. Our main result is that given any internal cut (A, B) in a chordal graph G, there exists a clique with kappa(G) + vertices (where kappa(G) is the vertex connectivity of G) such that it is (approximately) bisected by the cut (A, B). In fact we give a stronger result: For any internal cut (A, B) of a chordal graph, and for each i, 0 <= i <= kappa(G) + 1 such that vertical bar K-i vertical bar = kappa(G) + 1, vertical bar A boolean AND K-i vertical bar = i and vertical bar B boolean AND K-i vertical bar = kappa(G) + 1 - i. An immediate corollary of the above result is that the number of edges in any internal cut (of a chordal graph) should be Omega(k(2)), where kappa(G) = k. Prompted by this observation, we investigate the size of internal cuts in terms of the vertex connectivity of the chordal graphs. As a corollary, we show that in chordal graphs, if the edge connectivity is strictly less than the minimum degree, then the size of the mincut is at least kappa(G)(kappa(G)+1)/2 where kappa(G) denotes the vertex connectivity. In contrast, in a general graph the size of the mincut can be equal to kappa(G). This result is tight.

Circular dichroism and nuclear magnetic resonance studies on the complexation of valinomycin with calcium

Complexation of valinomycin (VM) with the divalent cation Ca2+ in a lipophilic solvent, acetonitrile (CH3-CN), has been studied by using circular dichroism and proton and carbon- 13 nuclear magnetic resonance (‘H NMR and I3C NMR). From analyses of the spectral data, it is concluded that VM forms a 2:l (peptideion-peptide) sandwich complex with Ca2+, at low concentration of VM. At moderate conocentrations of the salt, in addition to the sandwich complex, an equimolar (1:l) complex different from those observed for potassium and sodium is also observed. At very large concentrations of the calcium salt, the data suggested a complex with a conformation similar to that of the free VM in polar solvents. Possible conformations for the sandwich and the equimolar VM-calcium complexes are proposed.

On the origin of the inflectional instability of a laminar separation bubble

This is an experimental and theoretical Study of a laminar separation bubble and the associated linear stability mechanisms. Experiments were performed over a flat plate kept in a wind tunnel, with an imposed pressure gradient typical of an aerofoil that would involve a laminar separation bubble. The separation bubble was characterized by measurement of surface-pressure distribution and streamwise velocity using hot-wire anemometry. Single component hot-wire anemometry was also used for a detailed study of the transition dynamics. It was foundthat the so-called dead-air region in the front portion of the bubble corresponded to a region of small disturbance amplitudes, with the amplitude reaching a maximum value close to the reattachment point. An exponential growth rate of the disturbance was seen in the region upstream of the mean maximum height of the bubble, and this was indicative of a linear instability mechanism at work. An infinitesimal disturbance was impulsively introduced into the boundary layer upstream of separation location, and the wave packet was tracked (in an ensemble-averaged sense) while it was getting advected downstream. The disturbance was found to be convective in nature. Linear stability analyses (both the Orr-Sommerfeld and Rayleigh calculations) were performed for mean velocity profiles, starting from an attached adverse-pressure-gradient boundary layer all the way up to the front portion of the separation-bubble region (i.e. up to the end of the dead-air region in which linear evolution of the disturbance could be expected). The conclusion from the present work is that the primary instability mechanism in a separation bubble is inflectional in nature, and its origin can be traced back to upstream of the separation location. In other words, the inviscid inflectional instability of the separated shear layer should be logically seen as an extension of the instability of the upstream attached adverse-pressure-gradient boundary layer. This modifies the traditional view that pegs the origin of the instability in a separation bubble to the detached shear layer Outside the bubble, with its associated Kelvin-Helmholtz mechanism. We contendthat only when the separated shear layer has moved considerably away from the wall (and this happens near the maximum-height location of the mean bubble), a description by the Kelvin-Helmholtz instability paradigm, with its associated scaling principles, Could become relevant. We also propose a new scaling for the most amplified frequency for a wall-bounded shear layer in terms of the inflection-point height and the vorticity thickness and show it to be universal.

Mass transfer effects on the generalised vortex flow over a stationary surface with or without magnetic field

The effect of injection and suction on the generalised vortex flow of a steady laminar incompressible fluid over a stationary infinite disc with or without magnetic field under boundary-layer approximations has been studied. The coupled nonlinear ordinary differential equations governing the self-similar flow have been numerically solved using the finite-difference scheme. The results indicate that the injection produces a deeper inflow layer and de-stabilises the motion while suction or magnetic field suppresses the inflow layer and produces stability. The effect of decreasingn, the parameter characterising the nature of vortex flow, is similar to that of increasing the injection rate.

Studies on the effects of in vitro methyiation on aminoacylation of transfer RNA

In vitro methyiation of Escherichia coli transfer ribonucleic acid by cell free extracts of Mycobacterium smegmatis leads exclusively to the formation of 1-methyl adenine [Vani, B. R., Ramakrishnan, T., Taya, Y., Noguchi, S., Yamaiuzumi, Z. and Nishimura, S.(1978) J. Bact., 137,1085]. We have studied the effect of this modification on aminoacylation of Escherichia coli tRNA by mycobacterial enzymes. Aminoacylation with total algal protein hydrolysate as well as several individual aminoacids like methionine, valine, tyrosine, aspartic acid and lysine were monitored. In all the cases methyiation had a positive effect on the extent of aminoacylation by mycobacterial enzymes. Decreased aminoacylation in vitro was observed when hypomethylated transfer RNA from ethionine treated cells was used as the substrate for aminoacylation.

On the propagation of a multi-dimensional shock of arbitrary strength

In this paper the kinematics of a curved shock of arbitrary strength has been discussed using the theory of generalised functions. This is the extension of Moslov’s work where he has considered isentropic flow even across the shock. The condition for a nontrivial jump in the flow variables gives the shock manifold equation (sme). An equation for the rate of change of shock strength along the shock rays (defined as the characteristics of the sme) has been obtained. This exact result is then compared with the approximate result of shock dynamics derived by Whitham. The comparison shows that the approximate equations of shock dynamics deviate considerably from the exact equations derived here. In the last section we have derived the conservation form of our shock dynamic equations. These conservation forms would be very useful in numerical computations as it would allow us to derive difference schemes for which it would not be necessary to fit the shock-shock explicitly.

A hypothesis on the role of hydroxyproline in stabilizing collagen structure

The possibility of hydroxyproline residues stabilizing the collagen triple-helical structure by the formation of additional hydrogen bonds through their γ-hydroxyl group has been studied from structural considerations. It is not possible for this hydroxyl group to form a direct hydrogen bond with a suitable group in a neighbouring chain of the triple-helical protofibril. However, in the modified one-bonded structure, which is stabilized by additional hydrogen bonds being formed through water molecules as intermediaries (put forward in 1968 by Ramachandran, G. N. and Chandrasekharan, R.), it is found that the γ-hydroxyl group of hydroxyproline can form a good hydrogen bond with the water oxygen as acceptor, the hydrogen bond length being 2.82 Å. It is proposed that, in addition to stabilizing the collagen triple-helical structure due to the stereochemical properties of the pyrrolidine ring, hydroxyproline gives added stability by the formation of an extra hydrogen bond. Experimental studies on the determination of shrinkage and denaturation temperatures of native collagen and its synthetic analogues, as a function of their hydroxyproline content, are being undertaken to test this hypothesis.

A study on the reaction of silicon tetrahalides with phosphorus pentoxide and of alkali metal fluorosilicates with phosphorus pentoxide and sulphur trioxide

Silicon tetrahalides, SiX4 (X=F, Cl, Br) and the fluorosilicates of sodium and potassium react with phosphorus pentoxide above 300°C. The tetrahalides give rise to the corresponding phosphoryl halides and silica, while the fluorosilicates form the corresponding metal fluorophosphates and silicon tetrafluoride. The reaction of the fluorosilicates of sodium and potassium with sulphur trioxide occurs at room temperature to give rise to the corresponding metal fluorosulphates and silicon tetrafluoride.

Influence of Lithium Fluoride on the Burning Rate of AP-Polyester Propellant

THE addition of catalysts normally serves the purpose of imparting a desired burning rate change in a composite propellant. These may either retard or enhance the burning rate. Some often quoted catalysts are oxides, chromites and chromates of metals. A lot of work has been done on rinding the effect of the addition of some of these catalysts on the burning rate; however, none seems to have appeared on the influence of lithium fluoride (LiF). Only qualitative reduction in the burning rate of composite propellants with the addition of LiF was reported by Williams et al.1 Dickinson and Jackson2 reported a slight decrease in the specific impulse of composite propellant with the addition of LiF; however, they made no mention of the effect of its addition on the burning rate. We have studied the effect of the addition of varying amounts of LiF on the burning rate of Ammonium Perchlorate (AP)-Polyester propellant.

Mode of action of antitumour antibiotics: Spectrophotometric studies on the interaction of chromomycin A3 with DNA and chromatin of normal and neoplastic tissue

The binding of chromomycin A3, an antitumour antibiotic, to various DNA and chromatin isolated from mouse and rat liver, mouse fibrosarcoma and Yoshida ascites sarcoma cells was studied spectrophotometrically at 29°C in 10−2 M Tris-HCl buffer, pH 8.0, containing small amounts of MgCl2 (4.5 · 10−5−25 · 10−5 M). An isobestic point at 415 nm was observed when chromomycin A3 was gradually titrated with Image and its spectrum shifted towards higher wavelength. The rates and extent of these spectral changes were found to be dependent on the concentration of Mg2+. The change in absorbance at 440 nm was used to calculate apparent binding constant (Ka p M−1) and sites per nucleotide (n) from Scatchard plots for various DNA and chromatins. As expected, values of n for chromatin (0.06–0.10) were found to be lower than that found for corresponding DNA (0.10–0.15). Apparently no such correlation exists between binding constants (Ka p M−1 · 10−4) of DNA (6.4–11.2) and of chromatin (3.1–8.3), but Ka p M−1 of chromatin isolated from mouse fibrosarcoma and Yoshida ascites sarcoma are 1.5–3 times higher than that found for mouse and rat liver chromatin. These differences may be taken to indicate structural difference in nucleoprotein complexes caused by neoplasia. The relevance of this finding to tumour suppressive action of chromomycin A3 is discussed.

On the Specificity of Carbohydrate-Lectin Recognition The Interaction of a Lectin from Ricinus communis Beans with Simple Saccharides and Concanavalin A

A galactose-specific protein (RC1) isolated from Ricinus communis beans was found to give a precipitin reaction with concanavalin A. Its carbohydrate content amounted to 8–9% of the total protein and was found to be rich in mannose. The interaction of RC1 with galactose and lactose was measured in 0.05 M phosphate buffer containing 0.2 M NaCl (pH 6.8) by the method of conventional equilibrium dialysis. From the analysis of the binding data according to Scatchard method the association constant (Ka) at 5°C was calculated as 3.8 mM−1 and 1.2 mM−1 for lactose and galactose, respectively. In both cases the number of binding sites per molecule of RC1 with molecular weight of 120000 was found to be 2. From the temperature-dependent Ka values for the binding of lactose, the values of –5.7 kcal/mol and –4.3 cal × mol−1× K−1 were calculated for ΔH and ΔS, respectively. The addition of concanavalin A to RC1 or vice versa led to the formation of the insoluble complex RC1· ConA4 containing one molecule of RC1 and one molecule of tetrameric concanavalin A (ConA4) which could be dissociated upon addition of concanavalin A-specific sugars. The complex formation results in a time-dependent appearance of turbidity in the time range from 10s to 10 min. From the measurement of the time-dependent appearance and disappearance of the turbidity the formation (kf) and dissociation (kd) rate constants were calculated as 3 mM−1× s−1 and 0.07 ks−1 respectively. The ratio kf/kd (43μM −1), that corresponds to the association constant of complex RC1· ConA4, is higher than that of mannoside · ConA4 and thereby suggests that protein-protein interaction contributes significantly in stabilising glycoprotein · lectin complexes. The relevance of this finding to the understanding of the chemical specificities that are involved in a model cell-lectin interaction is discussed.