Host-guest complexes of carotenoids with beta-glycyrrhizic acid

The structure, stability, and reactivity of the host-guest complexes between a set of carotenoids and the triterpene glycoside, beta-glycyrrhizic acid (GA), were investigated by different physicochemical techniques: high-performance liquid chromatography, optical absorption, and fluorescence spectroscopy. It has been demonstrated recently that the molecular complexes of GA with a number of drugs are characterized by reduced toxicity and increased therapeutic activity of these drugs. In the present work it was found that carotenoids form 1:2 complexes with GA in aqueous solutions as well as in polar organic solvents, methanol, acetonitrile, and dimethylsulfoxide. We assume that the structure of the complex is a cycliclike dimer of GA encapsulating a carotenoid molecule. The stability constants in all solvents are near 10(4) M(-1). In addition, GA forms inclusion complexes with carotenoid radical cations, which results in their stabilization. Complex formation (a) decreases the rate of electron transfer from carotenoids to electron acceptors (Fe3+ or quinone) and (b) considerably increases the lifetime of the carotenoid-quinone charge-transfer complex and the yield of the major product (a carotenoid-quinone adduct). A thermodynamic study shows that hydrophobic interactions are the main driving force of the carotenoid-GA complex formation. These results are important for understanding both the nature of GA complexes and the influence of GA on the therapeutic activity of some drugs. Furthermore, carotenoid-GA complexes could be used for the design of artificial light-harvesting, photoredox, and catalytic systems.     

Microwave-assisted preparations of amidrazones and amidoximes

In an operationally straightforward and efficient method, amidrazones and amidoximes are prepared in yields of 65-87% from imidoylbenzotriazoles by microwave heating for 5-20 min with the appropriate hydrazine or hydroxylamine.     

Complex Formation of Phosphoryl- and Thiophosphorylacylacetonitriles with Different Cations

The enols R 1 R 2 P(E)(CN)C = CR 3 OH (E = O or S) gave in solutions either neutral metal complexes ML x or M(OH) y L x . The anionic ambidentate ligands are coordinated through E and O atoms in solutions, and O, E, and N atoms in in crystals.     

51V magic angle spinning NMR spectroscopy of Keggin anions [PVnW12-nO40](3+n)-: effect of countercation and vanadium substitution on fine structure constants

Vanadium environments in Keggin oxopolytungstates were characterized by (51)V solid-state MAS NMR spectroscopy. (C(4)H(9))(4)N(+)-, K(+)-, Cs(+)-, as well as mixed Na(+)/Cs(+)- salts of the mono-, di-, and trivanadium substituted oxotungstates, [VW(11)O(40)](4-), [V(2)W(10)O(40)](5-), and [V(3)W(9)O(40)](6-), have been prepared as microcrystalline and crystalline solids. Solid-state NMR spectra report on the local environment of the vanadium site in these Keggin ions via their anisotropic quadrupolar and chemical-shielding interactions. These (51)V fine structure constants in the solid state are determined by the number of vanadium atoms present in the oxoanion core. Surprisingly, the quadrupolar anisotropy tensors do not depend to any significant extent on the nature of the countercations. On the other hand, the chemical-shielding anisotropy tensors, as well as the isotropic chemical shifts, display large variations as a function of the cationic environment. This information can be used as a probe of the local cationic environment in the vanadium-substituted Keggin solids.     

Polymorphism of paracetamol

The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG _sub²⁹⁸=60.0 kJ mol⁻¹; ΔH _sub²⁹⁸=117.9±0.7 kJ mol⁻¹; ΔS _sub²⁹⁸=190±2 J mol⁻¹ K⁻¹. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition enthalpy at 298 K, ΔH _tr²⁹⁸(I→II)=2.0±0.4 kJ mol⁻¹, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based on ΔH _tr²⁹⁸ (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification II were also estimated (ΔG _sub²⁹⁸=56.1 kJ mol⁻¹; ΔH _sub²⁹⁸=115.9±0.9 kJ mol⁻¹; ΔS _sub²⁹⁸=200±3 J mol⁻¹ K⁻¹). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported found by classical thermochemical methods.     

General and efficient insertion of carbons carrying benzotriazole

Anions formed from the lithiation of 1-(1-benzotriazolylalkyl)benzotriazoles (1, 6) and 1-(1-methylthioalkyl)benzotriazoles (10 and 10a) with n-BuLi underwent additions to cyclic and acyclic ketones giving intermediates 3a-f, 7b-f, and 11b-d, respectively, in excellent yields. Thermal rearrangements of intermediates 3a,b,d-f and 7b-d,f in the presence of zinc bromide provided one-carbon chain-extended or ring-expanded alpha-benzotriazolyl ketones 4a,b,d-f and 8b-d,f in moderate yields with excellent regioselectivity. By contrast, intermediates 11b-d on treatment with zinc bromide loose a molecule of benzotriazole followed by intramolecular cyclization of the resulting intermediates 12b-d to provide the 2,3- and 1,2,3-substituted indenes 13b-d in good yields.     

Isolation of niobium,tantalum, and titanium complex fluoride salts with alkali metal cations

Fluoride and oxofluoride salts of niobium, tantalum, and titanium were isolated. They precipitated from aqueous solutions and upon washing of organic extracts with aqueous solutions of ammonium, potassium, and sodium salts. The compositions of the isolated compounds were studied. Different compositions were established for the niobium salts that precipitated upon the dissolution of unwashed niobium hydroxide in hydrofluoric acid under the atmospheric pressure, in an autoclave, and upon addition of sodium, potassium, and ammonium salts to purely fluoride solutions of niobium, as well as for the tantalum ammonium and sodium salts isolated from aqueous and organic solutions. The data obtained can be used for the synthesis of niobium, tantalum, and titanium complex fluoride salts with various compositions.     

Genesis of phase composition of supported Al?Fe?O catalysts

XPS, ESR and ESDR methods have been used for studying Al–Fe–O catalysts calcined at 620–1270 K. -Al₂O₃ interaction with impregnating solutions of iron oxalate complexes was shown to lead to the formation of isolated Fe³⁺ ions, and supported phases of solid solutions and associates at 620–820 K.     

Effect of non-covalent interactions in 2,5-di-Me-pyrazine-di-N-oxide - methanol – Carbon nanotube electrocatalytic system

Catalytic oxidation of methanol (MeOH) in the absence of noble metals and noble metal oxides as catalysts, and the use of metal-free materials are inexpensive and attractive process for practical use in electrocatalysis, sensors, and in direct methanol fuel cells. In previous works, it was found that the use of single-walled (SWCNT) or multi-walled (MWCNT) carbon nanotube paper electrodes instead of GC increases the catalytic efficiency of organic compounds oxidation in the presence of aromatic di-N-oxides by several times. In this work, the effect of non-covalent interactions on the catalytic efficiency of MeOH oxidation in the presence of 2,5-di-Me-pyrazine-di-N-oxide (Pyr₁) in 0.1 M Bu₄NClO₄ solution in acetonitrile at SWCNT and MWСNT paper electrodes was studied by the methods of quantum chemical modeling, Raman spectroscopy, and using electrochemical data. New factors determined the features of mechanism of MeOH oxidation on CNT electrodes and lead to an increase in the catalytic efficiency of the electrode process in comparison with the GC electrode were established.     

Capillary chromatography of polyfluorinated carboxylic esters

Retention indices and dI/dT values were obtained for members of six homologous and six pseudohomologous series of polyfluorinated saturated carboxylic esters on capillary columns with OV-101 or XE-60 as stationary phase. There was a nonlinear dependence of retention indices of fluorinated fatty acid esters on carbon chain length of homologs with m, n=1–6. A universal correlation equation was shown to describe the chromatographic behavior of polyfluorinated carboxylic esters.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1740–1745, August, 1991.