Revised mechanism of Boyland-Sims oxidation.

New computational insights into the mechanism of the Boyland-Sims oxidation of arylamines with peroxydisulfate (S(2)O(8)(2-)) in an alkaline aqueous solution are presented. The key role of arylnitrenium cations, in the case of primary and secondary arylamines, and arylamine dications and immonium cations, in the case of tertiary arylamines, in the formation of corresponding o-aminoaryl sulfates, as prevalent soluble products, and oligoarylamines, as prevalent insoluble products, is proposed on the basis of the AM1 and RM1 computational study of the Boyland-Sims oxidation of aniline, ring-substituted (2-methylaniline, 3-methylaniline, 4-methylaniline, 2,6-dimethylaniline, anthranilic acid, 4-aminobenzoic acid, sulfanilic acid, sulfanilamide, 4-phenylaniline, 4-bromoaniline, 3-chloroaniline, and 2-nitroaniline) and N-substituted anilines (N-methylaniline, diphenylamine, and N,N-dimethylaniline). Arylnitrenium cations and sulfate anions (SO(4)(2-)) are generated by rate-determining two-electron oxidation of primary and secondary arylamines with S(2)O(8)(2-), while arylamine dications/immonium cations and SO(4)(2-) are initially formed by two-electron oxidation of tertiary arylamines with S(2)O(8)(2-). The subsequent regioselectivity-determining reaction of arylnitrenium cations/arylamine dications/immonium cations and SO(4)(2-), within the solvent cage, is computationally found to lead to the prevalent formation of o-aminoaryl sulfates. The formation of insoluble precipitates during the Boyland-Sims oxidation of arylamines was also computationally studied.

Synthesis and characterization of self-assembled polyaniline nanotubes/silica nanocomposites.

Self-assembled semiconducting, paramagnetic polyaniline nanotubes have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in aqueous medium in the presence of colloidal silica particles of an average diameter approximately 12 nm, without added acid. The electrical conductivity of polyaniline nanotubes/silica nanocomposites is in the range (3.3-4.0)x10(-3) S cm(-1). The presence of paramagnetic polaronic emeraldine salt form of polyaniline and phenazine units in nanocomposites was proved by FTIR, Raman, and EPR spectroscopies. The influence of the initial silica/aniline weight ratio on the morphology of polyaniline/silica nanocomposites was studied by scanning and transmission electron microscopies. Nanocomposites synthesized by using the initial weight ratio silica/aniline

Synthesis and characterization of conducting polyaniline 5-sulfosalicylate nanotubes.

Conducting polyaniline 5-sulfosalicylate nanotubes and nanorods were synthesized by the template-free oxidative polymerization of aniline in aqueous solution of 5-sulfosalicylic acid, using ammonium peroxydisulfate as an oxidant. The effect of the molar ratio of 5-sulfosalicylic acid to aniline on the molecular structure, molecular weight distribution, morphology, and conductivity of polyaniline 5-sulfosalicylate was investigated. The nanotubes, which have a typical outer diameter of 100-250 nm, with an inner diameter of 10-60 nm, and a length extending from 0.4 to 1.5 microm, and the nanorods, with a diameter of 80-110 nm and a length of 0.5-0.7 microm, were observed by scanning and transmission electron microscopies. The presence of branched structures and phenazine units besides the ordinary polyaniline structural features was revealed by infrared and Raman spectroscopies. The stacking of low-molecular-weight substituted phenazines appears to play a major role in the formation of polyaniline nanorods. The precipitation-dissolution of oligoaniline templates as a key element in the formation of polyaniline nanotubes is proposed to explain the crucial influence of the initial pH of the reaction mixture and its decrease during the course of polymerization.