An eels study of water, methanol, formaldehyde and formic acid adsorbed on clean and oxygen-covered zinc(0001) surfaces

Water adsorbs molecularly on a clean Zn(0001) surface; on a surface covered with atomic oxygen, however, hydroxyl species is produced due to proton abstraction by the surface oxygen atoms. Methanol, molecularly adsorbed on a clean surface at 80 K, transforms to methoxy species above 110 K. On an atomic oxygen-covered surface, adsorbed methanol gives rise to methoxy species and water, the latter arising from proton abstraction. HCHO adsorbs molecularly at 80 K on both clean as well as oxygen-covered surfaces and polymerizes at higher temperatures. Formic acid does not adsorb on a clean Zn surface, but on an oxygen-covered surface gives rise to formate and hydroxyl species.

Split-Freedom And Mvd-Intersection - A New Characterization Of Multivalued Dependencies Having Conflict-Free Covers

Sets of multivalued dependencies (MVDs) having conflict-free covers are important to the theory and design of relational databases [2,12,15,16]. Their desirable properties motivate the problem of testing a set M of MVDs for the existence of a confiict-free cover. In [8] Goodman and Tay have proposed an approach based on the possible equivalence of M to a single (acyclic) join dependency (JD). We remark that their characterization does not lend an insight into the nature of such sets of MVDs. Here, we use notions that are intrinsic to MVDs to develop a new characterization. Our approach proceeds in two stages. In the first stage, we use the notion of “split-free” sets of MVDs and obtain a characterization of sets M of MVDs having split-free covers. In the second, we use the notion of “intersection” of MVDs to arrive at a necessary and sufficient condition for a split-free set of MVDs to be conflict-free. Based on our characterizations, we also give polynomial-time algorithms for testing whether M has split-free and conflict-free covers. The highlight of our approach is the clear insight it provides into the nature of sets of MVDs having conflict-free covers. Less emphasis is given in this paper to the actual efficiency of the algorthms. Finally, as a bonus, we derive a desirable property of split-free sets of MVDs,thereby showing that they are interesting in their own right.

A Radical Cyclization Route To +/-Andirolactone, A Spiro-Gamma-Butyrolactone

Synthesis of Andirolactone (Image ), starting from 4-methyl cyclohex-3-en-1-one (Image ), via the radical cyclisation of the bromoacetal (Image ), is described.

Multiple-quantum artifacts in single-quantum two-dimensional correlated NMR spectra of strongly coupled spins

Artifacts in the form of cross peaks have been observed along two- and three-quantum diagonals in single-quantum two-dimensional correlated (COSY) spectra of several peptides and oligonucleotides. These have been identified as due to the presence of a non-equilibrium state of kind I (a state describable by populations which differ from equilibrium) of strongly coupled spins carried over from one experiment to the next in the COSY algorithm.

Enzyme-catalysed non-oxidative decarboxylation of aromatic acids: I.Purification and spectroscopic properties of 2,3 dihydroxybenzoic acid decarboxylase from Image Image

In order to understand the molecular mechanism of non-oxidative decarboxylation of aromatic acids observed in microbial systems, 2,3 dihydroxybenzoic acid (DHBA) decarboxylase from Image Image was purified to homogeneity by affinity chromatography. The enzyme (Mr 120 kDa) had four identical subunits (28 kDa each) and was specific for DHBA. It had a pH optimum of 5.2 and Km was 0.34mM. The decarboxylation did not require any cofactors, nor did the enzyme had any pyruvoyl group at the active site. The carboxyl group and hydroxyl group in the Image -position were required for activity. The preliminary spectroscopic properties of the enzyme are also reported.

Hydrothermal phase equilibria in Ln2O3-H2O-CO2 systems : I. The lighter lanthanides

Phase diagrams for Nd2O3-H2O-CO2 and Gd2O3-H2O-CO2 systems at 1500 atm are given along with the results of selected runs in La, Sm and Eu systems. The stable phases in systems of La and Nd, are Ln(OH)CO3-B, Ln2O2CO3-II and LnOOH, in addition to the Ln(OH)3 phase at extremely low partial pressures of CO2 in the system. The systems become more and more complex with decreasing ionic radi and the number of stable carbonate phases increases. Ln2(CO3)3 · 3H2O orthorhombic (tengerate-like phase) is stable from Sm to Gd in addition to the other phases. The Gd(OH)CO3-A (ancylite-like phase) is hydrothermally stable at XCO2 greater-or-equal, slanted 0.5 while its hexagonal polymorph, Gd(OH)CO3-B is stable at low partial pressures of CO2 in the system.

Evolution of three-dimensional character across the Lan+1NinO3n+1 homologous series with increase in n1

Electrical and magnetic properties of La3Ni2O7 and La4Ni3O10 have been investigated in comparison with those of La2NiO4, LaNiO3, and LaSrNiO4. The results suggest an increasing 3-dimensional character across the homologous series Lan+1NinO3n+1 with increase in n. Accordingly, the electrical resistivity decreases in the order La3Ni2O7, La4Ni3O10, and LaNiO3 and this trend is suggested to be related to the percolation threshold. Magnetic properties of these oxides also show some interesting trends across the series.

Non-linear resonance in strings under narrow band random excitation, part I: Planar response and stability

Non-linear planar response of a string to planar narrow band random excitation is investigated in this paper. A response equation for the mean square deflection σ2 is obtained under a single mode approximation by using the equivalent linearization technique. It is shown that the response is triple valued, as in the case of harmonic excitation, if the centre frequency of excitation Ω lies in a certain specified range. The triple valued response occurs only if the excitation bandwidth β is smaller than a critical value βcrit which is a monotonically increasing function of the intensity of excitation. An approximate method of investigating the almost sure asymptotic stability of the solution is presented and regions of instability in the Ω-σ2 plane have been charted. It is shown that planar response can become unstable either due to an unbounded growth of the in-plane component of motion or due to a spontaneous appearance of an out-of-plane component.

Satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds

An attempt has been made at synthesis and in resolving some of the uncertainties related to the assignments of charge-transfer satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds. New satellites are reported in the ligand core-hole spectra as well as in the metal core-level spectra of oxides of second- and third-row transition metals including rare earths. Satellites in the ligand levels and the metal levels tend to be mutually exclusive, a behaviour that can be understood on the basis of metal-ligand overlap. Systematics in the intensities and energy separations of satellites in the first-row transition-metal compounds have been examined in order to gain an insight into the nature of these satellites. A simple model involving the sudden approximation has been employed to explain the observed systematics in intensities of satellites appearing next to metal and ligand core levels on the basis of metal-ligand overlap.

Flexure of composite plates

A new higher order shear deformation theory of laminated composite plates is developed. The basic displacement variables in this theory are two partial normal displacements and two in-plane displacement parameters. The governing equations are presented in the form of four simultaneous partial differential equations. The shear deformation theories of Bhimareddy and Stevens, and of Reddy are special cases of this formulation. In their models, transverse shear strains will become zero at points in the plate where displacements are constrained to be zero such as those on fixed edges. This limitation has been overcome in the present formulation.

Isolation and characterization of a methionine adduct of DOPA o-quinone

The o-quinone of DOPA, an important intermediate implicated in many biological processes, has been found to react with methionine. The product has been isolated and studied, and tentative structure has been assigned.

Aircraft pursuit-evasion problems with variable speeds

Aircraft pursuit-evasion encounters in a plane with variable speeds are analysed as a differential game. An engagement-dependent coordinate system confers open-loop optimality on the game. Each aircraft's optimal motion can be represented by extremel trajectory maps which are independent of role, adversary and capture radius. These maps are used in two different ways to construct the feedback solution. Some examples are given to illustrate these features. The paper draws on earlier results and surveys several existing papers on the subject.

Macromechanical behaviour of composite laminates

An improved higher order transverse shear deformation theory is employed to arrive at modified constitutive relations which can be used in the flexural, buckling and vibration analysis of laminated plates and shells. The strain energy for such systems is then expressed in terms of the displacements and the rotations for ready reference and use. Numerical values of vibration frequencies are obtained using this formulation employing Ritz's method of analysis. The results are compared with those available in the literature to validate the analysis presented.

Analysis of EXAFS data of multiphasic heterogeneous catalysts

Cu K-edge EXAFS spectra of Cu-Ni/Al2O3 and Cu-ZnO catalysts, both of which contain more than one Cu species, have been analysed making use of an additive relation for the EXAFS function. The analysis, which also makes use of residual spectra for identifying the species, shows good agreement between experimental and calculated spectra.

Biosynthesis of cytoplasmic subunits of cytochrome C oxidase in rat liver

The biosynthesis of the cytoplasmic subunits of cytochrome oxidase from rat liver has been studied in vitro by translating liver poly (A)-containing RNA in the wheat germ cell-free system and immunoprecipitating the products with anti-cytochrome oxidase antibody. Analysis of the labelled immunoprecipitate on SDS-gels does not reveal the presence of a polyprotein precursor. On the other hand discrete products which are either slightly bigger or closely similar to the mature subunits present in purified cytochrome oxidase have been detected.