New Carbonyl Compounds in the High-Boiling Fraction of Lavender Oil. 2nd Communication

In addition to the sesquiterpenoid compounds reported in [1] the in-depth analysis of lavender oil also led to the identification of new constituents with caryophyllane ( 1 – 6 ), cedrane ( 7 and 8 ) and other skeletons ( 9 – 21 ). Spectroscopic properties as well as partial syntheses of these compounds are discussed.     

Oxygen equilibrium pressure above V2O5−x and thermodynamic properties of this oxide system

Measurements of oxygen equilibrium pressure above the V₂O_5?x oxide system have been performed within the temperature range 575 to 615°C. The results have been used to determine the standard enthalpy and entropy in the reaction V₆O₁₃ + O₂ = 3 V₂O₅. The thermodynamic properties of the V₂O_5?x system (at x < 1) cited in the literature have been discussed for all the equilibria postulated.     

pH gradient high-performance liquid chromatography: theory and applications

pH gradient high-performance liquid chromatography (HPLC) is a method of reversed-phase high-performance liquid chromatography suitable for ionogenic substances. It consists in programmed increase during the chromatographic process of the eluting strength of eluent with respect to the analytes separated. On the analogy of the conventional organic modifier gradient reversed-phase HPLC, in the pH gradient approach the eluting strength of the mobile phase increases due to its changing pH: increasing in case of acids or decreasing in case of bases. At the same time the content of organic modifier remains constant. A theory of the pH gradient HPLC has been elaborated. The resulting mathematical model is easily manageable. Its ability to predict changes in retention and separation of analytes following the changes in chromatographic conditions is demonstrated. The pH gradient method is uniquely suitable to determine pKa values of analytes. An equation is presented allowing to calculate pKa values basing on appropriate retention data. The effects on pKa are discussed of the concentration of methanol in the mobile phase. The RP HPLC-derived pKa data correlate to the reference pKa values (w(w)pKa) but are not identical. That may be explained by the effects on the chromatographically determined pKa of the specific interactions of analytes with stationary phases. The proposed pH gradient RP HPLC procedure offers a fast and convenient means to get comparable acidity parameters for larger series of compounds, like drug candidates, also when the analytes are available only in minute amounts and/or as complex mixtures.     

Toward efficient Zn(II)-based artificial nucleases

A series of cis-cis-triaminocyclohexane Zn(II) complex-anthraquinone intercalator conjugates, designed in such a way to allow their easy synthesis and modification, have been investigated as hydrolytic cleaving agents for plasmid DNA. The ligand structure comprises a triaminocyclohexane platform linked by means of alkyl spacers of different length (from C(4) to C(8)) to the anthraquinone group which may intercalate the DNA. At a concentration of 5 microM, the complex of the derivative with a C(8) alkyl spacer induces the hydrolytic stand scission of supercoiled DNA with a rate of 4.6 x 10(-6) s(-1) at pH 7 and 37 degrees C. The conjugation of the metal complex with the anthraquinone group leads to a 15-fold increase of the cleavage efficiency when compared with the anthraquinone lacking Zn-triaminocyclohexane complex. The straightforward synthetic procedure employed, allowing a systematic change of the spacer length, made possible to gain more insight on the role of the intercalating group in determining the reactivity of the systems. Comparison of the reactivity of the different complexes shows a remarkable increase of the DNA cleaving efficiency with the length of the spacer. In the case of too-short spacers, the advantages due to the increased DNA affinity are canceled due to the incorrect positioning of the reactive group, thus leading to cleavage inhibition.     

Parabolic focal conics in self-assembled solid films of cellulose nanocrystals

Suspensions of cellulose nanocrystals form colloidal chiral nematic phases. The liquid crystalline order in these suspensions can be captured in solid films by slow evaporation of the liquid. Studies of the microstructure of such chiral nematic solid films revealed parabolic focal conic (PFC) defects, a symmetric form of focal conic defects in which the line defects form a pair of perpendicular, antiparallel, and confocal parabolas. The cellulose films with PFC defects were characterized by polarized-light and atomic force microscopy. The film surface showed a regular array of large and small elevations resulting from the displacement of the structural layers. Film fracture lines showed a series of layered half-cones. The microstructure of the films was modeled by computer. The model revealed that many structural layers terminate at the film surface.     

Adsorption-penetration studies of glucose oxidase into phospholipid monolayers at the 1,2-dichloroethane/water interface.

The interaction between glucose oxidase (GOx) and phospholipid monolayers is studied at the 1,2-dichloroethane/water interface by electrochemical impedance spectroscopy. Electrochemical experiments show that the presence of GOx induces changes in the capacitance curves at both negative and positive potentials, which are successfully explained by a theoretical model based on the solution of the Poisson-Boltzmann equation. These changes are ascribed to a reduced partition coefficient of GOx and an increase of the permittivity of the lipid hydrocarbon domain. Our results show that the presence of lipid molecules enhances the adsorption of GOx molecules at the liquid/liquid interface. At low lipid concentrations, the adsorption of GOx is probably the first step preceding its penetration into the lipid monolayer. The experimental results indicate that GOx penetrates better and forms more stable monolayers for lipids with longer hydrophobic tails. At high GOx concentrations, the formation of multilayers is observed. The phenomenon described here is strongly dependent on 1) the GOx and lipid concentrations, 2) the nature of the lipid, and 3) the potential drop across the interface.     

Ferromagnetism in a dinuclear nickel(II) complex containing triethylenetetramine and tricyanomethanide

Triethylenetetramine (L(4)) was used as a tetradentate blocking ligand that, after complexation with Ni(II), leaves two sites ready for ligation with tricyanomethanide. The formed binuclear complex [L(4)Ni(NCC(CN)CN)(2)NiL(4)](ClO(4))(2) exhibits a ferromagnetic coupling with J/hc = +0.15 cm(-1) and g(Ni) = 2.126; below 16 K, a ferromagnetic ordering is evidenced by ac magnetic susceptibility (both in-phase and out-of-phase), magnetization, field-cooled magnetization, and zero-field-cooled magnetization measurements.     

Spectral properties of selected UV-blocking and UV-transmitting covering materials with application for production of high-value crops in high tunnels

The spectral properties of selected UV-blocking and UV-transmitting covering materials were characterized by means of a UV-VIS spectroradiometer or a UV-VIS spectrometer to provide researchers and growers with guidelines for selecting suitable materials for use in studying the effects of ambient solar UV radiation on the production of tomatoes and other high-value crops in high tunnels. A survey was made of a wide range of plastic covering materials to identify commercially available products that had the desired characteristics of transmitting high levels of photosynthetically active radiation and of being stable under ambient solar UV radiation. The study was focused on evaluating films that either blocked or transmitted UV wavelengths below 380 nm to determine comparative growth, yield and market quality and to provide a tool for integrated pest management. Based on this survey, two contrasting covering materials of similar thickness (0.152 mm) and durability (4-year polyethylene), one a UV-blocking film and the other a UV-transmitting film, were selected and used to cover two high tunnels at Beltsville, MD. Spectroradiometric measurements were made to determine comparative spectral irradiance in these two high tunnels covered with these materials and under ambient solar UV radiation. Comparative measurements were also made of selected glass and plastic materials that have been used in UV exclusion studies.