Kinetic approach to modeling the radical polymerization of styrene in the presence dibenzyl trithiocarbonate

A mathematical model of the kinetics of the radical polymerization of styrene in the presence of dibenzyl trithiocarbonate by the reversible addition-fragmentation chain transfer mechanism with cross-termination of radicals and intermediates and quadratic termination of intermediates is developed. The adequacy of the polymerization mechanism underlying the model and the related mathematical formalism are tested by comparing the calculated and measured values of the average molecular-weight characteristics of resulting polystyrene.     

The influence of a fluoroorganic modifier—stillage residues of alcohol-telomeres—on properties of filled poldienurethanes

The results of an investigation of the influence of stillage residues of polyfluorinated alcoholtelomeres on the properties of polydienurethane compositions and elastomers based on them are presented. It is shown that such modification allows one to raise the sedimentation stability of the compositions and increase the characteristics of physicochemical and dynamic properties of elastomers.     

Synthesis and Properties of Copolymers Having Polyconjugated Blocks in the Macromolecules. III Thermal Behavior of Polyisoprene-Containing Polyazophenylene Fragments in the Main Chains

The thermal and thermooxidative stability of polyisoprene containing polyazophenylene fragments of different composition was investigated. Elevated inhibiting activity of polyazophenylene -methane fragments was found to be caused by the intramolecular synergism due to the combination of the reaction of peroxy radicals with mobile hydrogen atoms of methylene bridge groups and decomposition of hydroperoxides under the influence of polyconjugated blocks.     

Structural Factors and Mechanisms Underlying the Improved Photodynamic Cell Killing with Silicon Phthalocyanine Photosensitizers Directed to Lysosomes Versus Mitochondria

The phthalocyanine photosensitizer Pc 4 has been shown to bind preferentially to mitochondrial and endoplasmic reticulum membranes. Upon photoirradiation of Pc 4-loaded cells, membrane components, especially Bcl-2, are photodamaged and apoptosis, as indicated by activation of caspase-3 and cleavage of poly(ADP-ribose) polymerase, is triggered. A series of analogs of Pc 4 were synthesized, and the results demonstrate that Pcs with the aminopropylsiloxy ligand of Pc 4 or a similar one on one side of the Pc ring and a second large axial ligand on the other side of the ring have unexpected properties, including enhanced cell uptake, greater monomerization resulting in greater intracellular fluorescence and three-fold higher affinity constants for liposomes. The hydroxyl-bearing axial ligands tend to reduce aggregation of the Pc and direct it to lysosomes, resulting in four to six times more killing of cells, as defined by loss of clonogenicity, than with Pc 4. Whereas Pc 4-PDT photodamages Bcl-2 and Bcl-xL, Pc 181-PDT causes much less photodamage to Bcl-2 over the same dose–response range relative to cell killing, with earlier cleavage of Bid and slower caspase-3-dependent apoptosis. Therefore, within this series of photosensitizers, these hydroxyl-bearing axial ligands are less aggregated than is Pc 4, tend to localize to lysosomes and are more effective in overall cell killing than is Pc 4, but induce apoptosis more slowly and by a modified pathway.     

Simple Interpretation of Kinetics of Fast Solid-State Reactions

A simple model of fast solid-state reaction of two substances on the phase boundary is proposed. It is assumed that the reaction is controlled by the formation of new surface. The dependence of a change in the surface on the value of shear deformation is calculated. Thus, the relation between the product yield and shear deformation independently of time is explained.     

Aspect-ratio dependent oscillatory thermocapillary convection in the floating half zone

The dependency of the critical Marangoni number on the geometrical aspect ratio of the floating half zone is essential to predict the onset of oscillatory thermocapillary convection.The experimental studies in the microgravity conditions on floating half zones of several centimeters in diameter have predicted that the critical Marangoni number increases with the increasing aspect ratio,and the terrestrial experimental studies have predicted the contradictory conclusion for floating half zones of several mil...