Simple polarimetric approach to direct measurement of the near-surface refractive index in graded-index films

In the standard M-line method for the characterization of graded-index film, an analytical curve is fitted to the waveguide mode measurements and extrapolated to provide the refractive index in the zero-depth limit. Here we review our polarimetric approach to a direct near-surface measurement, which complements the M-line method. Also, we present its new and more straightforward version, which is applicable to existing samples and does not require masking before ion exchange.     

Optically monitored dip coating as a contactless viscometry method for liquid films

Real-time interferometric monitoring of the dip coating process is applied to the study of properties of flowing liquids. Nonvolatile Newtonian oils are considered, allowing validity of a simple model after the steady state is reached where film physical thickness depends on time as t(-1/2). Measurement of two distinct mineral oil standards, under several withdrawing speeds, resulted in kinematic viscosities of 1.17+/-0.03 and 9.9+/-0.2 S (1S = 1 cm2/s). Agreement of these results with nominal values from the manufacturer suggests that interferometric monitoring of dip coating may become a valuable method for accurate, contactless viscometry of liquid films. Advantages and present limitations are discussed.     

Electron transfer to sulfides:: Heterogeneous kinetics, CS bond cleavage, and self-protonation

The problem of characterizing the steps associated with the dissociative reduction of sulfides has been addressed. The electrochemical reduction of diphenylmethyl para-methoxyphenyl sulfide in N,N-dimethylformamide, on both glassy carbon and mercury electrodes, was chosen as a test system. The electrode process involves the slow heterogeneous outer-sphere electron transfer to the sulfide, the fast cleavage of the CS bond, the reduction of the ensuing carbon radical, and the self-protonation triggered by the generation of the strong base Ph₂CH⁻. The latter reaction is rather slow, in agreement with the large intrinsic barriers characterizing proton transfers between CH-acids and carbon bases. The dissociative reduction was studied in the presence of an exogenous acid. The results, obtained by convolution analysis, point to a stepwise DET mechanism in which the ET step is accompanied by rather large reorganization energy. Similar results were obtained on both electrode materials. Analysis of the heterogeneous electron transfer and associated CS bond cleavage indicate that the reduction of this and other sulfides lies between the stepwise dissociative electron transfers leading to the formation of stiff π^* radical anions and those going through the intermediacy of loose σ^* radical anions.     

Analogs of squalene and oxidosqualene inhibit oxidosqualene cyclase of <Emphasis Type="Italic">Trypanosoma cruzi</Emphasis> expressed in <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

Recently, a number of inhibitors of the enzyme oxidosqualene cyclase (OSC; EC 5.4.99.7), a key enzyme in sterol biosynthesis, were shown to inhibit in mammalian cells the multiplication of Trypanosoma cruzi, the parasite agent of Chagas’ disease. The gene coding for the OSC of T. cruzi has been cloned and expressed in Saccharomyces cerevisiae. The expression in yeast cells could be a safe and easy model for studying the activity and the selectivity of the potential inhibitors of T. cruzi OSC. Using a homogenate of S. cerevisiae cells expressing T. cruzi OSC, we have tested 19 inhibitors: aza, methylidene, vinyl sulfide, and conjugated vinyl sulfide derivatives of oxidosqualene and squalene, selected as representative of different classes of substrate analog inhibitors of OSC. The IC₅₀ values of inhibition (the compound concentration at which the enzyme is inhibited by 50%) are compared with the values obtained using OSC of pig liver and S. cerevisiae. Many inhibitors of pig liver and S. cerevisiae OSC show comparable IC₅₀ for T. cruzi OSC, but some phenylthiovinyl derivatives are 10–100 times more effective on the T. cruzi enzyme than on the pig or S. cerevisiae enzymes. The expression of proteins of pathogenic organisms in yeast seems very promising for preliminary screening of compounds that have potential therapeutic activity.     

Synthesis and biological activity of new lodoacetamide derivatives on mutants of squalene-hopene cyclase

New iodoacetamide derivatives, containing a dodecyl or a squalenyl moiety, were synthesized. The effect of these new thiol-reacting molecules was studied on two mutants of Alicyclobacillus acidocaldarius squalene-hopene cyclase constructed especially for this purpose. In the quintuple mutant, all five cysteine residues of the enzyme are substituted with serine; in the sextuple mutant, this quintuple substitution is accompanied by the substitution of aspartate D376, located at the enzyme’s active site, with a cysteine. N-Dodecyliodoacetamide had little activity toward either mutant, whereas N-squalenyliodoacetamide showed a stronger effect on the sextuple than on the quintuple mutant, as expected.     

A method for the analysis of Gaussian-like clusters

In this paper we are concerned with the analysis of Gaussian-like point clusters in an n-dimensional space. The method described uses the directed fuzzy graph obtained from the points by linking every point to its neighbors and assigning a measure of the local point density to each node of the graph. Next, the tops of the fuzzy graph are found and a subset of them selected as cluster centers. The rest of the points are then classified based on the selected tops.