On the reactivity of benzidinesulfonic acids and their applications in analysis: Reaction of cupric salts with o-benzidinemonosulfonic acid in presence of alkali thiocyanate

In the present work a new method for the detection of coppcr(II) is described. It is based on the reaction of this ion with the alkali salts of o-benzidinemonosulfonic acid, alkali thiocyanate being present. The sensitivity of this test is $\text{1}\text{500,000}$ (l0^-5.7); it ia specific for the Cu⁺² ion and can also be used to distinguish quickly the above-mentioned acid from the benzidine o-o'-disulfonic and benzidine m-m' '-disulfonic acids. It is believed that the mechanism of the reaction can be explained by an oxidation process.     

A closed-shell coupled-cluster treatment of the Breit-Pauli first-order relativistic energy correction

First-order relativistic corrections to the energy of closed-shell molecular systems are calculated, using all terms in the two-component Breit-Pauli Hamiltonian. In particular, we present the first implementation of the two-electron Breit orbit-orbit integrals, thus completing the first-order relativistic corrections within the two-component Pauli approximation. Calculations of these corrections are presented for a series of small and light molecules, at the Hartree-Fock and coupled-cluster levels of theory. Comparisons with four-component Dirac-Coulomb-Breit calculations demonstrate that the full Breit-Pauli energy corrections represent an accurate approximation to a fully relativistic treatment of such systems. The Breit interaction is dominated by the spin-spin interaction, the orbit-orbit interaction contributing only about 10% to the total two-electron relativistic correction in molecules consisting of light atoms. However, the relative importance of the orbit-orbit interaction increases with increasing nuclear charge, contributing more than 20% in H(2)S.     

On solvability of differential equations with the Riesz fractional derivative

We consider the solvability of fractional differential equations involving the Riesz fractional derivative. Our approach basically relies on the reduction of the problem considered to the equivalent nonlinear mixed Volterra and Cauchy-type singular integral equation and on the theory of fractional calculus. By establishing a compactness property of the Riemann–Liouville fractional integral operator on Lebesgue spaces and using the well-known Krasnoselskii's fixed point theorem, an existence of at least one solution is gleaned. An example is finally included to show the applicability of the theory.     

Interactions between octyl-β-D-glucoside and α-amino acids or small peptides

The interactions between octyl--D-glucoside and glycine in water have been investigated by surface tension, viscosity, and density measurements. The results show that the -amino acid causes an unexpected lowering of the critical micellar concentration of octyl--D-glucoside. Such a finding has been interpreted in temss of dipole-dipole interactions between the hydrophilic site of the surfactant and the peptidic cosluttes. From three to seven amino acid molecules have been estimated to be coordinated with each glucoside unity in the micellar state. The research has been extended to glycine oligopeptides and L-lysine. The latter compound has effects similar to those observed with glycine whereas diglycine and triglycine show weaker effects on the micellization process.     

Some existence results for quasilinear elliptic equations in a finite cylinder

We study the existence of solutionsu in the finite cylinderS _a=(?a, a)×ω of the quasilinear elliptic equation $$\sum\limits_{i,j = 1}^n {a_{i,j} (x)\partial _{i,j} u + f(x,u,\nabla u) = 0} $$ with Dirichlet boundary condition on flat parts of σS _a and Neumann condition on the curved parts. In this paper, we focus on the technicality caused by the “corners” ofS _a. We prove the existence of such solutions provided that suitable sub and super solutions are known and under the condition that the coefficientsa _1,i,i#1 vanish on the corners. We also prove a more general result in ?².     

Synthesis of Enantiopure Primary Amines by Stereoselective Ring Opening of Chiral Octahydro-1,3-benzoxazines by Grignard and Organoaluminum Reagents

Chiral 1,3-perhydrobenzoxazines 1, 2, and 9-14, prepared by condensation of 8-(benzylamino)menthol with different aldehydes, react with alkylmagnesium bromides and trimethylaluminum leading to the open amino alcohols 3a-d, 4a-d, and 15-20 in excellent chemical yields and good to excellent diastereomeric excess. The sequential elimination of the menthol appendage by heating with P(2)O(5) and the benzyl group by hydrogenolysis lead to primary amines 7a-d, 8a-d, and 27-30 in excellent chemical yields and ee. The addition of the alkyl group from the Grignard derivatives and the methyl group from the trimethylaluminum occurs from opposite sides of the heterocycle, yielding the final primary amines with the same stereochemistry.     

FeCp]+-induced hexafunctionalization of hexamethylbenzene with dendrons for the direct synthesis of redox-active iron-centered metallodendrimers

Phenol tri- and nonaallyl dendrons (3 and 7, respectively) were functionalized at the focal position to give the new triallyl dendrons 4 and 6 and the nonaallyl dendrons 11 and 13 that contain a iodoalkyl or a bromobenzyl termini. All these dendrons were used for the [FeCp]+-induced hexafunctionalization of hexamethylbenzene in [FeCp(eta6-C6Me6)][PF6] (1) under mild conditions in the presence of KOH. These reactions directly yielded the 18-allyl and 54-allyl dendrimers 9, 10, and 14 with a [FeCp(eta6-arene)]+ unit located at the dendrimer core. Cyclic voltammetry studies were recorded in THF and DMF with these metallodendrimers and compared with those of analogous dendrimers or complexes of smaller size that contain a [FeCp(eta6-arene)]+ unit at the core. The decreased rate of heterogeneous electron transfer when the dendritic size increases first disclosed by Diederich and Gross is confirmed. The variation of the redox potential of the Fe(II/I) redox system with increasing dendritic size is negligible even in a solvent of high dielectric constant such as DMF. This trend is attributed to fact that the involved "redox" orbital is buried on the metal center, well protected by the shell of alkyl chains (electron-reservoir nature), unlike in ferrocene. The chemical irreversibility increases in THF as the dendrimer size increases, due to more facile ligand substitution with THF at the 19-electron level when the chain bulk increases.