Creation or destruction of sourceless abelian gauge strings in a Robertson-Walker universe

Following Morris’s [5] consideration of a sourceless abelian gauge string in a Robertson-Walker universe with flat space sections we have generalized the treatment to the case of arbitrary spatial curvature. We find that creation or destruction of the gauge string is not possible if the spatial curvature is nonzero.     

A competent pot and atom-efficient synthesis of Betti bases over nanocrystalline MgO involving a modified Mannich type reaction

A simple, efficient, and eco-friendly method for the synthesis of 1-(α-aminoalkyl) naphthols, the Betti bases, has been carried out over a basic nanocrystalline MgO catalyst in aqueous condition. The method has been applied for the synthesis of a range of compounds with variable functionalities in excellent yield and selectivity.     

Recent advances in the chemistry of lignans

The recent literature on the chemistry of simple lignans has been comprehensively reviewed.     

Axially symmetric electrovac solutions

Two classes of electrovac solutions are obtained in oblate spheroidal coordinates, which are the electromagnetic analogs of Zipoy's monopole and dipole solutions. The asymptotic behavior of the solutions is studied to gain some insight into the nature of the source of the gravitational and electromagnetic fields. A similar stationary solution of the pure gravitational field is found to belong to Papapetrou's class.     

The inhibition of factor inhibiting hypoxia-inducible factor (FIH) by beta-oxocarboxylic acids

Cyclic beta-oxocarboxylic acids inhibit factor inhibiting hypoxia-inducible factor via ligation to the active site iron.     

Total synthesis of the originally proposed and revised structures of palmerolide A and isomers thereof

Palmerolide A is a recently disclosed marine natural product possessing striking biological properties, including potent and selective activity against the melanoma cancer cell line UACC-62. The total syntheses of five palmerolide A stereoisomers, including the originally proposed (1) and the revised [ent-(19-epi-20-epi-1)] structures, have been accomplished. The highly convergent and flexible strategy developed for these syntheses involved the construction of key building blocks 2, 19-epi-2, 20-epi-2, ent-2, 3, ent-3, 4, and ent-4, and their assembly and elaboration to the target compounds. For the union of the building blocks, the Stille coupling reaction, Yamaguchi esterification, Horner-Wadsworth-Emmons olefination, and ring-closing metathesis reaction were employed, the latter being crucial for the stereoselective formation of the macrocycle of the palmerolide structure. The Horner-Wadsworth-Emmons olefination and the Yamaguchi lactonization were also investigated and found successful as a means to construct the palmerolide macrocycle. The syntheses were completed by attachment of the enamide moiety through a copper-catalyzed coupling process.     

Examination of nonendocytotic bulk transport of nanoparticles across phospholipid membranes

Nonendocytotic transport is believed to play a role in the transmigration of particles less than 100 nm within biological systems. Determining the fundamental mechanism of this transport across cell membranes is essential if nanotechnology is to be utilized in general medical practice and may lead to methods of treating the deleterious internalization of ambient, possibly pollutant, nanoparticles. In order to gain a broader understanding of nonendocytotic transmembrane transport, it becomes essential to devise a method which allows the isolation of fundamental modes of transport such as passive Brownian diffusion through a membrane, as opposed to effusion-like transport of particles through transmembrane channels. The passive Brownian diffusion contribution was investigated using gold nanoparticles and mimetic biomembranes. Specifically, gold nanoparticle dispersions consisting of 7, 10, and 15 nm diameter particles were captured in giant unilamelar vesicles composed of phosphatidylcholine, phosphatidic acid, and cholesterol. Nonendocytotic transmembrane transport was modeled as the time derivative of the appearance of nanoparticles in the phosphate buffer outside the vesicles at 37 degrees C. The results show the transport rate to be zero; hence, a simple diffusive process of transmembrane transport is not supported.     

Kinetics and mechanism of the oxidation of substituted benzaldehydes by hexamethylenetetramine‐bromine

The oxidation of thirty‐six monosubstituted benzaldehydes by hexa‐methylenetetramine‐bromine (HABR), in aqueous acetic acid solution, leads to the formation of the corresponding benzoic acids. The reaction is first order with respect to HABR. Michaelis‐Menten–type kinetics were observed with respect to aldehyde. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of hexamethylenetetramine on the reaction rate. The oxidation of [²H]benzaldehyde (PhCDO) indicated the presence of a substantial kinetic isotope effect. The effect of solvent composition indicated that the reaction rate increases with an increase in the polarity of the solvent. The rates of oxidation of meta‐ and para‐substituted benzaldehydes showed excellent correlations in terms of Charton's triparametric LDR equation, whereas the oxidation of ortho‐substituted benzaldehydes correlated well with tetraparametric LDRS equation. The oxidation of para‐substituted benzaldehydes is more susceptible to the delocalization effect but the oxidation of ortho‐ and meta‐substituted compounds displayed a greater dependence on the field effect. The positive value of γ suggests the presence of an electron‐deficient reaction center in the rate‐determining step. The reaction is subjected to steric acceleration when ortho‐substituents are present. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 615–622, 2000     

Kinetics and mechanism of the oxidation of lower oxyacids of phosphorus by hexamethylenetetramine bromine

The oxidation of lower oxyacids of phosphorus by hexamethylenetetramine bromine (HABR) in glacial acetic acid resulted in the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibited 2:1 stoichiometry. The reaction is first order with respect to HABR. Michaelis–Menten‐type kinetics were observed with respect to the acids. The formation constant of the phenylphosphinic acid–HABR complex also has been determined spectrophotometrically. The thermodynamic parameters for the complex formation and the activation parameters for their decomposition were calculated. The reaction showed the presence of a substantial kinetic isotope effect. It is proposed that the HABR itself is the reactive oxidizing species. It has been shown that the pentacoordinated tautomer of the phosphorus oxyacid is the reactive reductant. A suitable mechanism has been proposed. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 165–170, 2000     

Kinetics and mechanism of the oxidation of diols by pyridinium bromochromate

The kinetics of oxidation of four vicinal diols, four nonvicinal diols, and one of their monoethers by pyridinium bromochromate (PBC) have been studied in dimethyl sulfoxide. The main product of oxidation is the corresponding hydroxyaldehyde. The reaction is first-order with respect to each the diol and PBC. The reaction is acid-catalyzed and the acid dependence has the form: k_obs=a+b[H⁺]. The oxidation of [1,1,2,2-²H₄]ethanediol exhibited a primary kinetic isotope effect (k_H/k _D=6.70 at 298 K). The reaction has been studied in 19 organic solvents including dimethyl sulfoxide and the solvent effect has been analyzed using multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 285–290, 1998.