Geometrical restrictions of water diffusion in aqueous protein systems. A study using NMR field-gradient techniques

Geometrical restrictions of water diffusion in different aqueous protein systems were studied using two versions of the NMR field gradient technique. The samples were aqueous systems of bovine serum albumin, gelatin and horse myoglobin at concentrations ranging from diluted solutions to almost dry powders being only partly hydrated. Hydrated protein aerogels were produced by the aid of a special preparation procedure and studied in addition. The experiments referred to the, temperature and concentration dependences of the water diffusion coefficient above and below the free-water freezing temperature. The diffusion coefficient within clusters of overlapping hydration shells is reduced by one order of magnitude compared with that of bulk water. Geometrical restrictions manifest themselves (a) by the obstruction effect observed at low protein concentrations, (b) by the topologically two-dimensional diffusion in the network of overlapping hydration shells, (c) by the percolation threshold appearing at about 15%_b.w. water and (d) by the anomalous diffusion behaviour concluded from the protein aerogel study.     

Sulfide Catalysts Supported on Al2O3: VI. Synthesis of Catalysts with the Use of Binuclear Molybdenum(V) Complexes with Sulfur-Containing Ligands

A new method was developed for the preparation of sulfide catalysts supported on aluminum oxide. The surface assembling of a direct precursor of the active component was used in this method. The method consists in the sequential immobilization of binuclear molybdenum complexes with S-containing ligands on the support surface followed by the immobilization of nickel (cobalt) compounds at the surface molybdenum complexes. The complexation and structure of the resulting complexes in solution and the structure of surface complexes were studied by ⁹⁵Mo and ¹⁷O NMR, IR, and EXAFS spectroscopy. The surface assembling of a direct precursor of the active component of sulfide hydrodesulfurization catalysts was demonstrated using IR and EXAFS spectroscopy. The activity of the resulting catalysts in a model reaction of thiophene hydrogenolysis was comparable to the activity of sulfide catalysts of the metal complex origin and was much higher than the activity of commercial catalysts and catalysts prepared by impregnation.     

Synthesis of Cationic Cholesterol Derivatives with Succinyl Spacer Group

Syntheses of N,N,N-trimethyl[2-(3-cholesteryloxy)syccinyloxyethyl]ammonium iodide, N,N-dimethyl-N-2-hydroxyethyl[2-(3-cholesteryloxy)syccinyloxyethyl]ammonium iodide, and N-[(3-cholesteryloxy)syccinyl]piperazine were performed. The compounds synthesized in a liposomal form may be used for delivery of genetical material into cells.     

Synthesis of chiral ferrocenylazines. Negishi cross-coupling or S N H reactions?

Preparation of new hetaryl-containing planar chiral ferrocene by a nucleophilic substitution of hydrogen in azines was performed using a lithium derivative of (S)-ferrocenyl-p-tolylsulfoxide as s nucleophilic reagent     

Cationic amphiphiles of both lipid and nonlipid nature in gene therapy

The synthesis and biological activity of cationic lipids and cationic amphiphiles of different natures are considered. The general factors influencing the transfection efficiency are identified and summarized for various classes of compounds. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 385–400, March. 2000.     

Synthesis of lipid mediators based on 1,2-dialkylglycerol and cholesterol for targeted delivery of oligo- and polynucleotides into hepatocytes

The synthesis of cationic glycolipids containing galactose or lactose residue as hepatocyte-targeted markers is described.     

Visualization and characterization of electroactive defects in the native oxide film on aluminium

Spatial!y localized electrochemical activity at Al/Al2O3 electrodes has been investigated using scanning electrochemical microscopy (SECM) in order to establish the relationship between localized corrosion of Al (and Al alloys) with the defect structure of the native Al2O3 film. Local electron transfer at microscopic defects (2 to 50 microm radius) was visualized in acetonitrile solutions using the nitrobenzene/nitrobenzene radical anion (Eo approximately -1.6 V vs. Ag/Ag+) and tetracyanoquinodimethane/tetracyanoquinodimethane radical anion couples (Eo approximately -0.3 V) as redox mediators for imaging. SECM investigations revealed no significant differences in electrochemical activity at Al/AI203 electrodes in the two mediator solutions, indicating that electrical conduction at the defect sites is weakly dependent on interfacial potential and the electric field across the Al2O3 film. The density of electroactive defects observed by SECM varied by 2 to 3 orders of magnitude between electrodes prepared from the same source of Al (either 99.450% and 99.9995%) suggesting that electrical conduction in the native oxide is very sensitive to surface preparation. Defect densities as low as approximately 3 sites cm(-2) were readily measured by SECM.     

Synthesis of positively charged lipids containing a 1,3-oxathiolane cycle

Positively charged lipids of the 1,3-oxathiolane series were synthesized by interaction of 2-pentadecyl-5-tosyloxymethyl- or -5-iodomethyl-1,3-oxathiolane with 2-(N,N-dimcthyl-amino)ethanol.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2347–2349, September, 1996.     

Synthesis of polycationic lipids based on cholesterol and spermine

The synthesis of cholesterol-based cationic lipids in which the hydrophobic steroidal fragment is linked to a spermine residue as the hydrophilic domain by ester or carbamate linkage is described.