Thin Films of Lanthanide Stearates as Modifiers of the Q-Sense Device Sensor for Studying Insulin Adsorption.

This article presents new possibilities of using thin films of lanthanide stearates as sorbent materials. Modification of the Q-sense device resonator with monolayers of lanthanide stearates by the Langmuir-Schaeffer method made it possible to study the process of insulin protein adsorption on the surface of new thin-film sorbents. The resulting films were also characterized by compression isotherms, chemical analysis, scanning electron microscopy, and mass spectrometry. The transition of stearic acid to salt was recorded by IR spectroscopy. Using the LDI MS method, the main component of thin films, lanthanide distearate, was established. The presence of Eu2+ in thin films was revealed. In the case of europium stearate, the maximum value of insulin adsorption was obtained, -1.67·10-10 mole/cm2. The findings suggest the possibility of using thin films of lanthanide stearates as a sorption material for the proteomics determination of the quantitative protein content in complex fluid systems by specific adsorption on modified surfaces and isolation of such proteins from complex mixtures.

Thermodynamic Description of Dilution and Dissolution Processes in the MgCl2-CsCl-H2O Ternary System.

Thermodynamic data on the properties of the water-based electrolyte systems are very valuable for fundamental physical chemistry and for industrial applications. The missing data both on the dilution and dissolution enthalpies for the ternary CsCl-MgCl2-H2O mixed electrolyte system were investigated by means of the calorimetry method. The dilution calorimetry was performed at 298 K for the set of solutions from diluted to concentrated at constant ratio Cs+/Mg2+=1.8. The relative partial molar enthalpies, ideal, total, and excess ones were calculated. By means of the dissolution calorimetry, the standard enthalpies of formation, the enthalpies, and entropies for the double salt formation from simple salts were evaluated. The results obtained indicate that entropy as the major factor affecting the formation of the joint compound, both in the liquid and solid phases. These data can be implemented in thermodynamic databases and allow for accurate thermodynamic calculations for the salts extraction from natural water sources and for its possible application as thermochemical energy storage.

Reactions of 2,4-hexadiyne-1,6-diol with [H2Os3(CO)9(PR3)] clusters. Cyclization of the diyne and reversible exchange of the phosphine ligands between different positions of the "Os3C3" framework.

Reactions between unsaturated [H(2)Os(3)(CO)(9)(PR(3))] clusters (PR(3)= PPh(3), P(4-CF(3)-C(6)H(4))(3), PEt(3)) and 2,4-hexadiyne-1,6-diol have been studied. It was found that the diyne ligand easily reacts with all these complexes to give [HOs(3)(CO)8(PR3)-[mu3, eta1:eta3:eta1)-(CH(3)-C-C=CH-CH=C-O)]] complexes (V, VI and VII, respectively) containing the "Os3C3" pentagonal pyramid cluster framework. This structural pattern is formed through the diyne cyclization, dissociation of a CO ligand and eventual coordination of the cyclized organic moiety to the osmium triangle in the [mu3, eta1:eta3:eta1) manner. In the case of the PEt(3) substituted cluster the second hydride transfer onto the organic fragment occurs to afford the nonhydride [Os(3)(CO)(8)(PR3)[mu3), eta1:eta2:eta1)-(CH(3)-CH-C=CH-CH=C-O)]] cluster, VIII, containing distorted pentagonal pyramid framework with a broken Os-C bond. Heating V, VI of VII and in hexane solutions results in formation of the regioisomers (Va, VIa and VIIa) with the phosphine ligand located at adjacent osmium atoms across the Os-Os bond bridged by the coordinated organic fragment. The most probable mechanism of the isomerization includes reversible phosphine migration between these metal centres. Solid-state structure of V, Va, VI, VIIa and VIII have been established by single crystal X-ray diffraction. A general mechanistic scheme for the diyne ligand cyclization and cluster framework transformations is suggested and discussed.