Theoretical Study on the Isomerization Mechanism of Enol Ester from 2-Acyl-1, 3-cyclohexanediones

The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.     

THE 'OPSIN SHIFT' IN BACTERIORHODOPSIN: STUDIES WITH ARTIFICIAL BACTERIORHODOPSINS

Abstract— The difference (in cm⁻¹) in absorption maxima between the protonated Schiff base of retinals and the pigment derived therefrom has been defined as the opsin shift. It represents the influence of the opsin binding site on the chromophore. The analysis of the opsin shifts of a series of dihydrobacteriorhodopsins has led to the external point-charge model, which in addition to a counter anion near the Schiff base ammonium, carries another negative charge in the vicinity of the β-ionone ring. This is in striking contrast to the external point-charge model proposed earlier for the bovine visual pigment. The absorption maxima of rhodopsins formed from bromo- and phenyl retinals support the two models. A retinal carrying a photoaffinity label has yielded a nonbleachable bacteriorhodopsin.     

Synthesis of polysilanes bearing pendant carbosilyl groups and Si-NMR probe on the tacticity using side chain silicon atoms

New functional polysilanes [R₂R¹Si(CH₂)₂SiH]_n (R=Me, R¹=H (1); R=R¹=Et (2); R=Me, R¹=Ph (3)) bearing carbosilyl side chains have been synthesized by catalytic dehydropolymerization of precursor carbosilanes R₂R¹SiCH₂CH₂SiH₃ using Cp₂TiCl₂–BuLi as a catalyst. These polymers are characterized by ¹H, ¹³C, ²⁹Si, {¹H–²⁹Si} HSQC NMR spectroscopy, GPC and TGA. Attempts to delineate the tacticity from the analysis of deconvoluted ²⁹Si{¹H}-NMR signals associated with the side chain silicon atoms reveal that the triad concentration ratio follows a Bernoullian statistical model for polymers 1 and 2 only.     

Conformational studies of basic poly (α-amino acid)s in reversed micelles

The conformation of various basic poly (-amino acid)s was investigated by CD measurements in aqueous solutions containing bis (2-ethylhexyl)sodium sulfosuccinate (AOT) as well as in the AOT reversed micelles. The addition of AOT into an aqueous solution of poly(L-lysine) induces the conformational transition from coil to ordered structure, followed by aggregation. On the other hand, poly(L-lysine) assumes-structure in the reversed micelles at low w_ovalue (w_o=[H₂O]/[AOT]). Similarly to poly(L-lysine), poly(L-ornithine) takes an ordered structure in the aqueous solution containing AOT and-structure in the reversed micelles. In this case, however, these ordered structures are not so stable, compared with that of poly(L-lysine). Poly(L-arginine) undergoes the conformational transition from coil to helix by addition of AOT into the aqueous solution. Further addition of AOT allows transformation into-structure. Copoly(L-lysyl-L-leucine) with 63% leucine residue was shown to take a stable helical conformation even in pure water. In the reversed micelles, however, this ordered structure is significantly changed probably because the hydrophobic interaction among the leucyl residues is lowered in the reversed micelles.     

Kinetics and mechanism of the oxidation of thiosulphate by hexachloroplatinate(IV)

Summary Rate constants for the oxidation of thiosulphate by hexachloroplatinate(IV) have been measured. The kinetics of the oxidation of thiosulphate follow a second-order rate law, first order with respect to thiosulphate and first order with respect to platinum(IV). The influence of pH is small. The rates are found to depend on the nature and concentration of the cations and follow the order: Cs⁺>Rb⁺>K⁺>Na⁺>Li⁺. The activation parameters calculated from the temperature studies are: H=42.9 k J mol^–1 and S=–102 JK^–1 mol^–1. A mechanism of the reaction in terms of intermediate formation of free radicals followed by the formation of tetrathionate is postulated to explain the kinetic behaviour.     

Net information measures for modified Yukawa and Hulthén potentials

The dimensional analyses of the position and momentum variances‐based quantum mechanical Heisenberg uncertainty measure, as well as the entropic information measures given by the Shannon information entropy sum and the product of Fisher information measures are carried out for two widely used nonrelativistic isotropic exponential‐cosine screened Coulomb potentials generated by multiplying the superpositions of (i) Yukawa‐like, ?Z(e^?μr/r), and (ii) Hulthén‐like, ?Zμ(1/(e^μr ? 1)), potentials by cos(bμr) followed by addition of the term a/r², where a and b ≥ 0, μ are the screening parameters and Z, in case of atoms, denotes the nuclear charge. Under the spherical symmetry, all the information measures considered are shown to be independent of the scaling of the set [μ, Z] at a fixed value of μ/Z, a, and b and the other parameters defining the superpositions of the potentials. Numerical results are presented, which support the validity of the scaling properties. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Relative reactivities of glycerophosphates towards permanganate in perchloric acid medium

Summary The reactivities of - and -glycerophosphates towards MnO ₄ ^– in HClO₄ medium have been examined. The reactions between glycerophosphates and MnO ₄ ^– are first order with respect to [glycerophosphate], [MnO ₄ ^– ] and [H⁺]. There is no evidence for cleavage of the C–O–P bond rather than the terminal –CH₂OH group being oxidized to the respective phosphoglyceraldehyde.     

Further study of theE/f 1 (1420) meson in central production

We have studied the reactions \(({{\pi ^ + } \mathord{\left/ {\vphantom {{\pi ^ + } p}} \right. \kern-0em} p})p \to ({{\pi ^ + } \mathord{\left/ {\vphantom {{\pi ^ + } p}} \right. \kern-0em} p})(K\bar K\pi )p\) where the \(K\bar K\pi \) system is centrally produced, at 85 GeV/c and 300 GeV/c using the CERN Omega spectrometer. A spin-parity analysis of theK _S ⁰ K ^± π ^? system shows the presence of a strongJ ^PC=1⁺⁺ signal which we identify as theE/f ₁ (1420) meson. We also find evidence for the decayE/f ₁(1420)→K _S ⁰ K _S ⁰ π ⁰ which determines theC-parity of this state to be positive. Alternative explanations of the data have been tested and ruled out. Hence we obtain the quantum numbers of theE/f ₁ (1420) to beI ^G(J^PC)=0⁺(1⁺).