Activation temperature, effect crystallinity

Das, K.P. and Surewicz, S.K. 1995. Temperature-induced exposure of hydrophobic surfaces and its effect on the chaperone activity of a-crystallin. FEBSLett. 369 321-325. 

As was found for the polymerization of styrene, CpTiCT/M AO and similar half-sandwich titanocenes are active catalysts for the polymerization of conjugated 1,3 dienes (Table XX) (275). Butadiene, 1,3-pentadiene, 2-methyl-l,3-pentadiene, and 2,3-dimethylbutadiene yield polymers with different cis-1,4, trans-1,4, and 1,2 structures, depending on the polymerization temperature. A change in the stereospecificity as a function of polymerization temperature was observed by Ricci et al. (276). At 20°C, polypen-tadiene with mainly ds-1,4 structures was obtained, whereas at -20°C a crystalline, 1,2- syndiotactic polymer was produced. This temperature effect is attributed to a change in the mode of coordination of the monomer to the metallocene, which is mainly cis-rf at 20°C and trans-rj2 at -20°C. 

Such treatments can raise the activity of Cr/alumina by as much as 10-fold. Presumably, this increase is a result of the increased acidity, and the replacement of hydroxyl ligands by non-coordinating F may possibly also contribute. In Figure 151, the activity of Cr/alumina catalyst is shown as a function of the amount of fluoride impregnated, in which the catalysts were subjected to several different activation temperatures. Fluoride, and other additives as well, is often more effective if it is added after the hydrated starting material AlOOH (boehmite) or Al(OH)3 (bayerite) is first converted into crystalline y- or 11-AI2O3. Thus, the upper graph in... 

GVD Coatings. As in PVD, the stmcture of the deposited material depends on the temperature and supersaturation, roughly as pictured in Figure 8 (12). In the case of CVD, however, the effective supersaturation, ie, the local effective concentration in the gas phase of the materials to be deposited, relative to its equiUbrium concentration, depends not only on concentration, but on temperature. The reaction is thermally activated. Because the effective supersaturation for thermally activated reactions increases with temperature, the opposing tendencies can lead in some cases to a reversal of the sequence of crystalline forms Hsted in Figure 8, as temperature is increased (12). 

Xenon difluoride [4, 5, 7, 8,10] is a white crystalline material obtained through the combination of fluorine and xenon m the presence of light The reagent is commercially available and possesses a relatively long shelf-life when stored cold (freezer) Xenon difluoride is very effective for small-scale fluormation of alkenes and activated nucleophilic substrates. The reactions are usually conducted between 0 °C and room temperature in chloroform or methylene chloride solutions Hydrogen fluoride catalysis is sometimes helpful Xenon difluoride reacts in a manner that usually involves some complexation between the substrate and reagent followed by the formation of radical and radical cation intermediates... 

Finally, we note that all transfers to alcohol-water mixtures or additions of alcohol to crystal mother liquor involve changes in the proton activity of the solution. Care must be taken to ensure that the pH does not change too much, or the crystal may be disrupted. Worse still, the enzymatic activity may be abolished. Control of proton activity in mixed solvents is discussed in Section III,D. If dielectric effects are controlled and pH is properly adjusted, the microenvironment of a crystalline protein will correspond closely to that of aqueous solution at room temperature. Such correspondence is essential for temporal resolution of individual steps in a catalytic reaction. 

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