Photostimulated reactions of vinyl phosphate esters with triorganostannides. evidence for an SRN1 vinylic mechanism

Ketones are converted into vinyl diethyl phosphate esters (VinDEP), which under photostimulation reacted with sodium trimethylstannide (1) or sodium triphenylstannide (2) in liquid ammonia affording vinylstannanes via a vinylic S(RN)1 mechanism. Thus, (1-phenylvinyl)DEP (3), (3,4-dihydro-1-naphthyl)DEP (7), (3,4-dihydro-2-naphthyl)DEP (9), (E)-(1,2-diphenylvinyl)DEP (12), (E/Z)-(1-methyl-2-phenylvinyl)DEP (14) and (E)-(1-phenyl-2-methylvinyl)DEP (16) react with 1 and 2, under photostimulation, leading to the corresponding substitution products in good to excellent yields (45-89%). On the other hand, there is no reaction between (1-cyclohexenyl)DEP (5) or (1-benzylvinyl)DEP (18) with either 1 or 2, under similar conditions. These reactions appear to be strongly dependent on structural features of the vinyl phosphate since only conjugated vinyl phosphates afforded substitution products. These substitution reactions are completely regioselective and stereoconvergent. It seems to be the first example of a vinylic S(RN)1 process involving organotin anions as nucleophiles.     

The enthalpimetric determination of the michaelis constant of the α-chymotrypsin-catalysed hydrolysis of n-acetyl-l-tyrosine ethyl ester based on the integrated michaelis—menten equation

An enthalpimetric method is discussed for the determination of the Michaelis constant (K_m )for the α-chymotrypsin-catalysed hydrolysis of N-acetyl-L-tyrosine ethyl ester (ATEE). The integrated form of the Michaelis—Menten equation is used to achieve a graphical determination of K_m in a single experiment (s_r = 7.6%). The inhibitory effect of ethanol is briefly described.     

Synthesis of substituted furo[3,2-e][1,2,4]triazolo[4,3-c]pyrimidines and furo[3,2-e]tetrazolo[1,5-c]pyrimidines

A series of substituted furo[3,2-e][1,2,4]triazolo[4,3-c]pyrimidines and furo[3,2-e]tetrazolo[1,5-c]pyrimidines were obtained from reactions of substituted 2-dimemylamino-4-hydrazmofuro[2,3-d]pyrimidines with orthoesters or sodium nitrite in acetic acid, respectively.     

PHASE BEHAVIOUR OF PHOSPHINOPOLYACRYLATE SCALES INHIBITOR

The influence of the Ca⁺⁺ and inhibitor concentrations, pH, and temperature on the phase behaviour and precipitation yield of a phosphinopolyacrylate scale inhibitor, PPAA, has been studied. The results are interpreted in terms of the chemical processes governing PPAA-Ca⁺⁺ complexation, and evidence for the role of inhibitor molecular weight in determining the degree of precipitation is produced. Comparative adsorption and precipitation squeezes, carried out in sandpacks, demonstrate that significant enhancement of the treatment lifetime can be achieved when conditions giving extensive inhibitor precipitation are used. The sandpack experiments and dissolution studies on the precipitated inhibitor both suggest strongly that kinetic phenomena influence the return level of inhibitor in the field. Together these studies point the way to approaches for optimising inhibitor precipitation squeeze treatments in order to control scale deposition in petroleum reservoirs.     

Working group report: Heavy-ion physics and quark-gluon plasma

This is the report of Heavy Ion Physics and Quark-Gluon Plasma at WHEPP-09 which was part of Working Group-4. Discussion and work on some aspects of quark-gluon plasma believed to have created in heavy-ion collisions and in early Universe are reported.     

Does amino acid sequence determine the properties of Aβ dimer?

The effect of random reshuffling of amino acids on the properties of dimers formed by Aβ peptides is studied using replica exchange molecular dynamics and united atom implicit solvent model. We show that thermodynamics of dimer assembly and the dimer globule-like state are not affected by sequence permutation. Furthermore, sequence reshuffling does not change the distributions of non-local interactions and, to a large extent, amino acids in the dimer volume. To rationalize these results, we demonstrate that Gaussian statistics applies surprisingly well to the end-to-end distances of the peptides in the dimer implying that non-bonded interactions between distant along the chain amino acids are effectively screened. This observation suggests that peptides in the dimer behave as ideal chains in polymer melt, in which amino acids lose their "identity" and therefore the memory of sequence position. As a result large-scale properties of the dimer become universal or sequence independent. Comparison of our simulations with the prior theoretical studies and their implications for experiments are discussed.     

Measurement of a sign-changing two-gap superconducting phase in electron-doped Ba(Fe(1-x)Co(x))2As2 single crystals using scanning tunneling spectroscopy

Scanning tunneling spectroscopic studies of Ba(Fe(1-x)Co(x))(2)As(2) (x=0.06, 0.12) single crystals reveal direct evidence for predominantly two-gap superconductivity. These gaps decrease with increasing temperature and vanish above the superconducting transition T(c). The two-gap nature and the slightly doping- and energy-dependent quasiparticle scattering interferences near the wave vectors (±π, 0) and (0, ±π) are consistent with sign-changing s-wave superconductivity. The excess zero-bias conductance and the large gap-to-T(c) ratios suggest dominant unitary impurity scattering.     

Gravity Probe B: final results of a space experiment to test general relativity

Gravity Probe B, launched 20 April 2004, is a space experiment testing two fundamental predictions of Einstein's theory of general relativity (GR), the geodetic and frame-dragging effects, by means of cryogenic gyroscopes in Earth orbit. Data collection started 28 August 2004 and ended 14 August 2005. Analysis of the data from all four gyroscopes results in a geodetic drift rate of -6601.8±18.3 mas/yr and a frame-dragging drift rate of -37.2±7.2 mas/yr, to be compared with the GR predictions of -6606.1 mas/yr and -39.2 mas/yr, respectively ("mas" is milliarcsecond; 1 mas=4.848×10(-9) rad).     

Investigation of sampling-probe distorted temperature fields with X-ray fluorescence spectroscopy

Flame-sampling experiments, especially in conjunction with laminar low-pressure premixed flames, are routinely used in combustion chemistry studies to unravel the identities and quantities of key intermediates and their pathways. In many instances, however, an unambiguous interpretation of the experimental and modeling results is hampered by the uncertainties about the probe-induced, perturbed temperature profile. To overcome this limitation, two-dimensional perturbations of the temperature field caused by sampling probes with different geometries have been investigated using synchrotron-based X-ray fluorescence spectroscopy. In these experiments, which were performed at the 7-BM beamline of the Advanced Photon Source (APS) at the Argonne National Laboratory, a continuous beam of hard X-rays at 15?keV was used to excite krypton atoms that were added in a concentration of 5?vol.-% to the unburnt gas mixture and the resulting krypton fluorescence at 12.65?keV was subsequently collected. The highly spatially resolved signal was converted into the local flame temperature to obtain temperature fields at various burner-probe separations as functions of the distance to the burner surface and the radial distance from the centerline. Multiple measurements were performed with different probe geometries and because of the observed impact on the temperature profiles the results clearly revealed the need to specify the sampling probe design to enable quantitative and meaningful comparisons of modeling results with flame-sampled mole fraction data.     

Possible competing order-induced Fermi arcs in cuprate superconductors

We investigate the scenario of competing order (CO) induced Fermi arcs and pseudogap in cuprate superconductors. For hole-type cuprates, both phenomena as functions of temperature and doping level can be accounted for if the CO vanishes at $T^1$ above the superconducting transition $T_c$ and the CO wave-vector Q is parallel to the antinodal direction. In contrast, the absence of these phenomena and the non-monotonic $d$-wave gap in electron-type cuprates may be attributed to $T^1<T_c$ and a CO wave-vector Q parallel to the nodal direction.