Phase and extraction equilibria in the water-ammonium chloride-Sintamid-5 system

The solubility isotherm of the H₂O-NH₄Cl-Sintamid-5 ternary system at 298 K was constructed on the basis of refractometer measurements. It was found that the region of two-phase liquid equilibrium existed over a wide pH range at inorganic acid concentrations from 10 to 2 mol/l. The distribution of some metal ions between the phases was studied. Conditions for quantitative extraction of thallium(III) and gallium were determined.     

Arc plasma jet cleaning of the silicon surface before CoSi2/Si contact formation

Cleaning of the silicon surface before Co film deposition is a key procedure in the synthesis of silicide (CoSi₂) and, hence, in the production of the metal-semiconductor contact. This study deals with a new method of surface cleaning using arc plasma jet treatment (APJT) at atmospheric pressure. The results show that cleaning of the Si surface using APJT (Ar/CCIF₃) improves the Schottky barrier contact parameters in comparison with conventional wet HF final cleaning and additional cleaning using in situ Ar-ion-beam sputter etching. Moreover, substantially longer time of wafer exposure to air between final cleaning and metal deposition is acceptable. Auger electron spectroscopy shows that APJT removes oxygen from the Si surface.     

Interaction of EHF radiation with biomolecular systems

Data on the absorption of EHF electromagnetic energy by aqueous solutions are summarized. Experimental tests for positive (hydrophilic and hydrophobic) and negative (hydrophilic) hydration are formulated. The applicability of the proposed approach to the study of the hydration of high-molecular-weight systems, including aqueous solutions of proteins, is demonstrated. A model is proposed that explains the interaction of EHF radiation with real biological systems, including under conditions of EHF therapy. The experimental data on the absorption of EHF radiation by aqueous solutions of organic and inorganic electrolytes and nonelectrolytes as well as globular proteins are used to construct a model that explains certain details of EHF therapy. The fraction of mobile water molecules in the skin is considered the primary molecular target for EHF radiation; they are capable of transporting the EHF energy to primary physiological targets of the protein type.Institute of Radio Engineering and Electronics, Russian Academy of Sciences. Institute of Organic Chemistry, Russian Academy of Sciences. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 37, No. 1, pp. 42–55, January, 1994.     

Molecular details of ovalbumin-pectin complexes at the air/water interface: a spectroscopic study

To stabilize air-water interfaces, as in foams, the adsorption of surface-active components is a prerequisite. An approach to controlling the surface activity of proteins is noncovalent complex formation with a polyelectrolyte in the bulk phase. The molecular properties of egg white ovalbumin in a complex with pectin in the bulk solution and at air/water interfaces were studied using drop tensiometry (ADT) and time-resolved fluorescence anisotropy techniques. The complex formation of ovalbumin with pectin in the bulk resulted in the formation of a compact structure with a different spatial arrangement depending on the protein/pectin ratio. Complex formation did not provide an altered protein structure, whereas the conformational stability was slightly increased in the complex. In excess pectin, an overall condensed complex structure is formed, whereas at limited pectin concentrations the structure of the complex is more "segmental". The characteristics of these structures did not depend on pH in the 7.0 to 4.5 regime. Interaction with pectin in the bulk solution resulted in a significantly slower adsorption of the protein to the air/water interface. The limited mobility of the protein at the interface was found for both ovalbumin and ovalbumin-pectin complexes. From both the rotational dynamics and total fluorescence properties of the protein in the absence and presence of pectin, it was suggested that the complex does not dissociate at the interface. Ovalbumin in the complex retains its initial "aqueous" microenvironment at the interface, whereas in the absence of pectin the microenvironment of the protein changed to a more nonpolar one. This work illustrates a more general property of polyelectrolytes, namely, the ability to retain a protein in its microenvironment. Insight into this property provides a new tool for better control of the surface activity of complex biopolymer systems.     

Fluorescent system based on bacterial expression of hybrid KcsA channels designed for Kv1.3 ligand screening and study

Human voltage-gated potassium channel Kv1.3 is an important pharmacological target for the treatment of autoimmune and metabolic diseases. Increasing clinical demands stipulate an active search for efficient and selective Kv1.3 blockers. Here we present a new, reliable, and easy-to-use analytical system designed to seek for and study Kv1.3 ligands that bind to the extracellular vestibule of the K⁺-conducting pore. It is based on Escherichia coli spheroplasts with the hybrid protein KcsA-Kv1.3 embedded into the membrane, fluorescently labeled Kv1.3 blocker agitoxin-2, and confocal laser scanning microscopy as a detection method. This system is a powerful alternative to radioligand and patch–clamp techniques. It enables one to search for Kv1.3 ligands both among individual compounds and in complex mixtures, as well as to characterize their affinity to Kv1.3 channel using the “mix and read” mode. To demonstrate the potential of the system, we performed characterization of several known Kv1.3 ligands, tested nine spider venoms for the presence of Kv1.3 ligands, and conducted guided purification of a channel blocker from scorpion venom.

Mesomorphic and dielectric properties of the p-n-hexyloxybenzoic acid-p-n-heptyloxybenzoic acid liquid crystal system

Thep-n-hexyloxybenzoic acid (I)-p-n-heptyloxybenzoic acid (II) system was investigated by thermal and X-ray phase analyses and dielcometry. Solid solutions of three types were found in the low-temperature region of the system, namely, solid solution based on I (up to 15 mol % II); solid solution based on a compound with the equimolar ratio of the components (γ); and solid solution based on II (>15 mol % II). The range of the two-phase equilibrium (N + I) was 2°–4°; a continuous nematic solution (N) formed in the system. The temperature and composition dependences of dielectric anisotropy Δ? were characterized. The γ compound showed negative dielectric anisotropy, Δ? = ?1.4, which was constant over the whole temperature range of the nematic phase.     

Stereoselective Synthesis of γ-(Acyloxy)carboxylic Acids and γ-Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ-Hydroxycarboxylate Homologues

Scalable protocols of straightforward synthesis of enantiomeric γ-(acyloxy)carboxylic acids and γ-lactones are presented. The key step is lipase-catalyzed stereoselective acylation of γ-hydroxycarboxylic acid sodium salt in organic solvent followed by acidification of the product, extraction and acidic relactonization of the unreacted enantiomer. The mixture of γ-(acyloxy)carboxylic acid and γ-lactone is separated either by extraction with solution of sodium bicarbonate or by distillation. A switch of enantioinduction of Candida antarctica lipase B along homologous nucleophiles from R configuration of γ-hydroxyhexanoic acid salt to S configuration of the C7 and longer-chain homologues has been disclosed. Both enantiomers of γ-(acyloxy)pentanoic acids; γ-(acetyloxy)octanoic and -nonanoic acids with S configuration; [(1S,5R)-5-(chloroacetyloxy)cyclopent-2-en-1-yl]acetic acid and enantiomeric γ-lactones derived from them were prepared with e. r. >98.5/1.5. The rates of acylation of C5 to C9 homologous salts differ by three orders of magnitude but remain applicable for preparative synthesis by variation of the enzyme loading and reaction time.     

Optical spectroscopy of europium 3,5-dinitrosalicylates—Intense red luminophores

It was found, that alkali metal-europium dinitrosalicylates of composition M₃Eu(3,5-NO₂-Sal)₃·nH₂O (M = Li, Na, K, Cs) are intense red luminophores with wide excitation band. Using methods of optical spectroscopy we studied the influence of nitrogroups and alkali metal counterions on Eu³⁺ luminescence efficiency and on processes of excitation energy transfer to Eu³⁺ ion in compounds synthesized. The Eu³⁺ luminescence and Eu³⁺ luminescence excitation spectra, as well as vibrational IR and Raman spectra were investigated. Details of the structure of compounds were discussed. The network of hydrogen bonds in lanthanide dinitrosalicylates is weakening at introduction of large alkali metal ions in compounds and at the increase of the temperature. As a consequence, the long-wavelength shift of the intraligand charge transfer (ILCT) band in Eu³⁺ excitation spectra arises at inclusion of Cs⁺ cations instead of Li⁺ in the crystal lattice of europium dinitrosalicylates and at heating of these compounds. To obtain the energy of the lowest excited triplet state the phosphorescence spectra of alkali metal-gadolinium compounds M₃Gd(3,5-NO₂-Sal)₃·nH₂O, of alkali metal dinitrosalicylate and salicylate salts were measured with time delay. Change of the energies of ligand electronic states and ligand–metal charge transfer state (LM CTS) can give a two-three orders of magnitude enhancement of the Eu³⁺ luminescence efficiency in dinitrosalicylates in comparison with salicylates and ten-fold enhancement at the substitution of Li⁺ and Na⁺ for Cs⁺ in dinitrosalicylates.