Cyclometallated Platinum(II) Complexes for Obtaining Phenyl-Containing Silicone Rubbers via Catalytic Hydrosilylation Reaction

Russian Journal of General Chemistry - C,N-Chelate deprotonated diaminecarbene platinum(II) complexes were studied as polysiloxane system hydrosilylation catalysts. Phenyl-containing silicone...     

Resolution of a nonionic surfactant oligomeric mixture by means of DOSY with inverse micelle assistance

DOSY is a recognized, efficient technique in the analysis of mixtures. It relies on the differences in self-diffusion coefficients, which are determined by the molecular size. Nowadays, efforts are directed towards devising matrices able to interact with the components of the mixture with differential affinity, and therefore capable to interfere with the diffusion processes and to display resolving power towards species of close, or even equal molecular weight, like isomers. Usually, commercial nonionic surfactants are mixtures of oligomeric species, since the head group, which is a short polyoxyehtylene chain, is somewhat polydisperse. The embedment of Igepal CA-520, 5 polyoxyethylene iso-octylphenyl ether, in an inverse microemulsion led to the separation of (1)H signals of the various oligomeric components. This ensued from the differential partitioning between the oil and the surface of the inverse micelles, which depends on the ethyleneoxide number (EON) of the head groups. Thus, it was possible to ascertain that the length distribution of the polyethyleneoxide chains is ingood agreement with the Poisson distribution theoretically predicted for the polymerization of ethylene oxide. The DOSY spectrum contributed to the assignment of the signals and afforded the partition degree, between the two environments, for each individual oligomeric species, providing further insight into nonionic inverse microemulsions, at present widely employed reaction media in the nanotechnological syntheses.     

Effect of Chitosan and Amphiphilic Polymers on the Photosensitizing and Spectral Properties of Rose Bengal

The influence of chitosan (CS) and amphiphilic polymers (AP: pluronic F108 and polyvinylpyrrolidone (PVP)) on the photocatalytic activity of rose bengal (RB) in a model reaction of tryptophan photo-oxidation in phosphate-buffered saline (PBS) was studied. It was shown that in the presence of CS, the effective rate constant k_eff of tryptophan photo-oxidation catalyzed by RB in PBS solution decreases by a factor of two. This is due to the ionic interaction of the RB with the chitosan. Rose bengal in a slightly acidic environment (pH 4.5) passes into a neutral lactone form, which sharply reduces the photosensitizing properties of the dye. It was demonstrated that the introduction of AP into a solution containing RB and CS prevents direct interaction between RB and CS. This is evidenced by the presence of photocatalytic activity of the dye in the RB-AP-CS systems, as well as bathochromic shifts of the main absorption bands of the dye, and an increase in the optical density and luminescence intensity of the RB when AP is introduced into a buffer solution containing RB and chitosan. The presence of RB-CS and RB-AP interaction in aqueous and PBS media is confirmed by the increase in the degree of fluorescence anisotropy (r) of these binary systems. In an aqueous solution, the value of r for the RB-F108-CS system decreases by a factor of 3.5 (compared to the value of r for the RB-CS system), which is associated with the localization of the dye in pluronic micelles. In PBS, the fluorescence anisotropy is practically the same for all systems, which is related to the stability of the dye structure in this medium. The presence of interaction between RB and AP in aqueous solutions was confirmed by the proton NMR method. In addition, the formation of RB-F108 macromolecular complexes, which form associates during solution concentration (in particular, during evaporation), was shown by AFM. Such RB-AP-CS systems may be promising for practical application in the treatment of local foci of infections by aPDT.     

Photosensitizing Activity of Steroid Derivatives of Pyropheophorbide in the Oxidation of Tryptophan in the Aqueous Phase

Russian Journal of Physical Chemistry A - Solubilization with pluronic F-127 gave water-soluble forms of hydrophobic photosensitizers—steroid derivatives of pyropheophorbide a. Solubilization...     

Facile room-temperature assembly of the 1,2,4-oxadiazole core from readily available amidoximes and carboxylic acids

A one-pot ambient-temperature procedure for the synthesis of 3,5-disubstituted-1,2,4-oxadiazoles from amidoximes and carboxylic acids under superbase-promoted conditions is reported.