Micellar effect on the electron transfer reaction of chromium(V) ion with organic sulfides

The rate of electron transfer from organic sulfides to [Cr^V(ehba)₂]⁻ (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO₄⁻, HSO₅⁻ and HCO₄⁻ oxidation of organic sulfides.     

Photochemical degradation of hyaluronic acid by singlet oxygen

Changes of the rheological properties of hyaluronic acid (sodium-magnesium salt) solutions after exposure to UV radiation indicate a vigorous decrease in their viscosity, but its still strong shear rate dependence. Whereas the presence of the singlet oxygen sensitizer (anthracene-1-sulphonic acid) brings about a loss of shear dependence; the studied solutions show newtonian behavior.     

Tunneling conductance of a Bi2Sr2CaCu2O8-SnO2 junction along the c-axis

fine structure was observed in the conductance curve of a tunneling junction composed of a single crystalline Bi2212 and an evaporated SnO₂ film. It is similar to those of Bi2212-GaAs mechanical junctions and there is a certain correspondence between the structure and the phonon density of states. Thus the previous conclusion that the structure is due to phonons has been complemented by this work. The energy gap 2 was 57 meV at 13 K and T _c was 78 K. 2(0)/k _B T _c is then 8.3. (T) showed the BCS-like temperature dependence.     

Darstellung,Ramanspektren und Kristallstrukturen von V2O3(SO4)2, K[VO(SO4)2] und NH4[VO(SO4)2]

Preparation, Raman Spectra, and Crystal Structures of V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] The oxo-sulfato-vanadates(V) V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] have been prepared as crystals suitable for X-ray structure determination. In all structures sulfate acts as an unidentate ligand only toward a single vanadium atom. The structure of V₂O₃(SO₄)₂ consists of a threedimensional network of pairs of cornershared VO₆ octahedra with one terminal oxygen atom each, and SO₄ tetrahedra. All oxygen atoms of the sulfate ions are coordinated. NH₄[VO(SO₄)₂] and K[VO(SO₄)₂] are isostructural. VO₆ octahedra with one terminal oxygen atom and pairs of sulfate tetrahedra form infinite chains by corner sharing. The chains are weakly interlinked to layers. The sulfate ions are distorted towards planar SO₃ molecules and single oxygen atoms attached to vanadium. This structural detail gives an explanation for the mechanism of the reversible reaction K[VO(SO₄)₂] ? K[VO₂(SO₄)] + SO₃ at 400°C. Raman spectra of the compounds have been recorded and interpreted with respect to their structures. Crystal data: V₂O₃(SO₄)₂, monoclinic, space group P2₁/a, a = 947.2(4), b = 891.3(3), c? 989.1(4) pm, β = 104.56(3)°, Z = 4, 878 unique data, R(R_w) = 0.039(0,033); K[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(2), b = 869.6(9), c = 1 627(1)pm, Z = 4, 642 unique data, R(R_w) = 0,11(0,10); NH₄[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(1), b = 870.0(2), c = 1 676.7(4)pm, Z = 4, 768 unique data, R(R_w) = 0.088(0.083).     

Photochemistry of β, γ-unsaturated ketones-V: The direct irradiation of some γ-phenyl β, γ-enones

The photochemistry of some members of the two series of γ-phenyl substituted acyclic β, γ-unsaturated ketones 1 and 2 upon direct irradiation with γ 310nm has been investigated, viz 1c–1h and 2b+2c.The alkyl substituted (E)-5-phenyl-4-penten-2-ones 1c–1h yield the corresponding 1,3-acyl shift products and (Z)-isomers, and 1g and 1h in addition two decarbonylated products. 2b only yields the (Z)-isomer and some benzaldehyde, but 2c yields the 1,3-acyl shift product, the ODPM product, three hydrocarbons formed by disproportionation of the allyl radical, and some benzaldehyde. The β-phenyl β, γ-UK 3a proved to be photostable. The 1,3-acyl shift products of 1c–1h result mainly from the singlet excited state in a cage radical process. The exclusive formation of the (E)-configuration of the 1,3-acyl shift product is explained in terms of conformational preference of the intermediate allyl radical. It is proposed that the formation of the (Z)-isomer proceeds from ¹T(π -π^*) which is populated according to

. Evidence is presented which supports the proposed mechanism.The β,γ-UK 2b containing a benzoyl moiety leads to a higher degree of (E)-(Z) isomerization than the corresponding 1d which has an acetyl moiety.The triplet energies of (E)- and (Z)-1h are 56 and ca 70 kcal/mol respectively.     

Phosphan-, Phosphit- und Phosphido-Komplexe des Vanadiums(V)

Phosphane, Phosphite, Phosphido, Complexes of Vanadium(V) Complex formation of tert-butylimidovanadium(V)trichloride ( 1 ) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds ^tC₄H₉N?VCp(NH^tC₄H₉)[P(SiMe₃)₂] and ^tC₄H₉N?VCp(NⁱProp₂)(PR₂) (R?SiMe₃, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV complex [(μ-PF₂)₂V₂Cl₂)(N^tC₄H₉)₂]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [^tC₄H₉N?VCl₂ · PPh₃]⁺PF₆^? has been isolated. 1 reacts with an excess of diisopropylamine forming ^tC₄H₉N?V(NⁱProp₂)Cl₂ ( 16 ); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds ^tC₄H₉N?VCp(NⁱProp₂)Cl ( 3 ) and ^tC₄H₉N?V(NⁱProp₂)X₂ (X?CH₂CMe₃, O^tC₄H₉, CH₃COO) has been prepared. All compounds obtained are characterized by ¹H, ⁵¹V, ³¹P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom.     

Kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium

The kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium has been carried out. The reaction is first order with respect to vanadium(V) and the substrate and is acid catalysed.Hammett acidity function (H ₀) andBunnett hypothesis have been applied. The formation of free radicals during the course of the reaction has been indicated. A probable reaction mechanism is proposed.

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Die Kinetik der Oxidation von Ethyldigol mit Vanadium(V) in wäßrigem saurem Medium

Zusammenfassung Es wurde die Kinetik der Oxidation von Ethyldigol mittels Vanadium(V) in wäßriger saurer Lösung untersucht. Die Reaktion ist erster Ordnung bezüglich Vanadium(V) und Substrat und ist säurekatalysiert. Es wurden dieHammett-Aciditätsfunktion (H ₀) und dieBunnett-Hypothese angewandt. Die Bildung von freien Radikalen während der Reaktion konnte bestätigt werden. Es wird ein Reaktionsmechanismus vorgeschlagen.

     

RP-HPLC study of redox equilibria in vanadium-PAR binary and ternary systems: Direct determination of vanadium in steel

The reversed-phase high-performance liquid Chromatographic (RP-HPLC) behaviour of the binary chelates of V(V) and V(IV) with 4-(2-pyridylazo) resorcinol (PAR) and ternary chelates of vanadium with PAR and auxiliary ligands: hydrogen peroxide, hydroxylamine, tartrate and citrate were studied using a C₁₈ column. The complex double-peak chromatograms of V(IV)/V(V)-PAR systems were studied and the origin of each peak was proved. Vanadium in ternary systems with PAR and hydrogen peroxide was found exclusively in V(V)-H₂O₂-PAR complex (single peak on the chromatogram) despite its initial oxidation state. The double role of hydroxylamine (complex agent and reductor) in vanadium systems with PAR was confirmed: in the V(V) system three species were identified (V(V)-PAR, V(V)-NH₂OH-PAR and V(IV)-PAR), but in the V(IV) system only two: V(IV)-PAR and V(V)-NH₂OH-PAR. Citrate and tartrate giving single peak were found as auxiliary ligands in ternary V(V) systems of analytical importance. Due to its masking potential towards iron (III) ions, citrate was chosen as the most suitable third component of a ternary vanadium system with PAR, to form the basis of an RP-HPLC method for direct determination of V in steel.     

Trinuclear Schiff base complexes with uranium(V) and copper(II) or zinc(II) ions

Treatment of the uranium(IV) complexes [{ML¹(py)}₂U^IV] (M = Cu, Zn; L¹ = N,N′-bis(3-hydroxysalicylidene)-1,3-propanediamine) with silver nitrate in pyridine led to the formation of the corresponding cationic uranium(V) species which were found to be thermally unstable and were converted back into the parent U^IV complexes; no electron transfer was observed in solution between the U^IV and U^V compounds. In the crystals of [{ML¹(py)}₂U^IV][{ML¹(py)}₂U^V][NO₃], the neutral U^IV and cationic U^V species are clearly identified by the distinct U–O distances. Similar reaction of [{ZnL²(py)}₂U^IV] [L² = N,N′-bis(3-hydroxysalicylidene)-1,4-butanediamine] with AgNO₃ gave crystals of [{ZnL²(py)}U^V{ZnL²(py)₂}][NO₃] but the copper counterpart was not isolated. Crystals of [{ZnL¹(py)}₂U^V][OTf] · THF (OTf = OSO₂CF₃) were obtained fortuitously from the reaction of [Zn(H₂L¹)] and U(OTf)₃.     

Determination of chikusetsusaponin V and chikusetsusaponin IV in rat plasma by liquid chromatography–mass spectrometry and its application to a preliminary pharmacokinetic study

A sensitive liquid chromatography–electrospray ionization–mass spectrometry method has been developed and validated for determination of two major bioactive saponins in rat plasma after oral administration of saponins extracted from Rhizoma Panacis Japonici, including chikusetsusaponin V and chikusetsusaponin IV for the first time. Akebia saponin D was used as the internal standard (IS). Plasma samples were prepared by protein precipitation with methanol. A Phenomenex C₁₈ column (150 × 4.6 mm, 4 µm) was used as the analytical column with a mobile phase of acetonitrile and 0.05% aqueous formic acid. Mass spectrometric detection was achieved by single quadrupole mass spectrometer equipped with an electrospray ionization interface operating in negative ionization mode. Calibration curves showed good linearity over the concentration range of 5–500 ng/mL for the two analytes in rat plasma. The lower limit of quantification was 5 ng/mL. The intra‐ and inter‐batch precisions were within 10.3% and accuracy ranged from ?3.9 to 5.4%. The method was validated and successfully applied to the preliminary pharmacokinetic study of chikusetsusaponin V and chikusetsusaponin IV in rat plasma after oral administration of saponins extracted from Rhizoma Panacis Japonici. Copyright © 2013 John Wiley & Sons, Ltd.