Synthesis and physicochemical characteristics of polymolybdenum(VI) phenylsiloxanes by means of different methods

Interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane in xylene and under mechanochemical activation conditions has been investigated. The interaction in solution proceeds with splitting of the siloxane bond and formation of polymolybdenum(VI) phenylsiloxane with different silicon/metal ratios. The fractions with the silicon/metal ratio < 2 are characterized with high degree of crystallinity and low solubility, whereas those with the ratio > 2 are amorphous. The interaction of the above reagents under mechanical activation conditions proceeds with the formation of soluble polymers similar to those obtained in a solution with the silicon/molybdenum ratio equal to 2.6. The crystal chemistry parameters of the fraction obtained in solution with the ratio Si/Mo equals to 1:2 have been calculated on the basis of the X-ray diffraction analysis data using the Debye–Shearer equation. It has been demonstrated that the chain cross section found using the Miller–Boyer method coincides with that calculated geometrically on the basis of literature data on bond lengths and angles. It is shown that the interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane takes place in solution more deeply than under the conditions of mechanochemical activation and is accompanied by the process of separation siloxanes connection. This leads to the formation of a fraction with smaller ratio of substances than the initial ratio.     

Towards a Better Prediction of Cell Settling on Nanostructure Arrays—Simple Means to Complicated Ends

Vertical arrays of nanostructures (NSs) are emerging as promising platforms for probing and manipulating live mammalian cells. The broad range of applications requires different types of interfaces, but cell settling on NS arrays is not yet fully controlled and understood. Cells are both seen to deform completely into NS arrays and to stay suspended like tiny fakirs, which have hitherto been explained with differences in NS spacing or density. Here, a better understanding of this phenomenon is provided by using a model that takes into account the extreme membrane deformation needed for a cell to settle into a NS array. It is shown that, in addition to the NS density, cell settling depends strongly on the dimensions of the single NS, and that the settling can be predicted for a given NS array geometry. The predictive power of the model is confirmed by experiments and good agreement with cases from the literature. Furthermore, the influence of cell‐related parameters is evaluated theoretically and a generic method of tuning cell settling through surface coating is demonstrated experimentally. These findings allow a more rational design of NS arrays for the numerous exciting biological applications where the mode of cell settling is crucial.     

Experimental verification of discrete models for combustion of microheterogeneous compositions forming condensed combustion products (Review)

Combustion, Explosion, and Shock Waves - This paper presents an analytical review of modern quasihomogeneous and discrete models of gasless combustion. Particular attention is given to experiments...     

Deliberately Losing Control of C−H Activation Processes in the Design of Small-Molecule-Fragment Arrays Targeting Peroxisomal Metabolism

Combined photochemical arylation, “nuisance effect” (S_NAr) reaction sequences have been employed in the design of small arrays for immediate deployment in medium-throughput X-ray protein–ligand structure determination. Reactions were deliberately allowed to run “out of control” in terms of selectivity; for example the ortho-arylation of 2-phenylpyridine gave five products resulting from mono- and bisarylations combined with S_NAr processes. As a result, a number of crystallographic hits against NUDT7, a key peroxisomal CoA ester hydrolase, have been identified.