Diterpenoid Alkaloids of Delphinium buschianum Grossh.

From the aerial parts of Delphinium buschianum Grossh ., collected in Turkey, a new diterpenoid alkaloid 1 , named budelphine, was isolated along with the known diterpenoid alkaloids karakoline ( 2 ), 18‐hydroxy‐14‐O‐methylgadesine ( 3 ), delsoline ( 4 ), lapaconidine ( 5 ), columbianine ( 6 ), 14‐benzoylneoline ( 7 ), and hetisine ( 9 ). The structure of 1 was established on the basis of ¹H‐, ¹³C‐, DEPT, ¹H,¹H‐COSY, NOESY, HSQC, and HMBC NMR studies.     

Alcohol-soluble functional vic-dioxime bearing alcoholhexylsulfanyl moieties: preparation, spectroscopy and electrochemistry

A new alcohol soluble functionalized vic-dioxime, bis-[(1-hydroxyhexyl)-(8,9-hydroxyimino)-7,10-dithiahexacosane (LH₂), and its alcohol-soluble mono and dinuclear complexes (Ni^II, Cu^II, Co^II, Mn^II, Pd^II and UO ₂ ^II ) have been prepared from 6-mercapto-1-hexanol and (E,E)-dichloroglyoxime under high dilution basic conditions. Reactive polyalcohol moieties appended at the periphery of the oxime containing two different heteroatoms (S-, O-), serve as a weak exocyclic binding sites for Pd^II and Ag^I metal ions and also provide solubility for the vic-dioxime complexes in low molecular-weight alcohols. Both mono-nuclear (LH)₂M and homodinuclear (LH)₂(UO₂)₂(OH)₂ and heterotrinuclear (LH)₂MM ₂ ^′ Xn, where M = Co^II M′ = Pd^II, X = Cl⁻, n = 4 and Ag^I X = NO ₃ ⁻ , n = 2) complexes have been obtained with a 1:2, 2:2, 3:2 metal/ligand ratio, respectively. Electronic spectra of the modified vic-dioximes exhibit monitorable changes in UV. All mono and dinuclear-complexes are soluble in common organic solvents. The elemental analysis, ¹H-n.m.r, i.r., u.v–vis, and f.a.b.–m.s data and by cyclic and differential pulse voltammetry measurements are presented.     

Capillary gas chromatographic separation of C10–C12 secondary phenylalkanes on modified cyclodextrin stationary phases

The separation of isomers and enantiomers of branched C₁₀-C₁₂ phenylalkanes by gas chromatography on fused silica capillary columns coated with some modified β- and γ-cyclodextrins was studied. It was shown that the separation of positional isomers of C₁₀-C₁₂ phynylalkanes on modified cyclodextrin capillary columns is not better than that on a column coated with modified polyethylene glycol. Differences were found in the enantioselectivity of modified β- and γ-cyclodextrins for the separation of C₁₀-C₁₂ secondary phenylalkane enantiomers. While alkylderivatives of β-CDs resolve enantiomers of 3-phenylalkanes, alkyl derivatives of γ-CD resolve enantiomers of 2-phenylalkanes. Since shape selectivity factors of modified cyclodextrins have indicated no inclusion of the considered solutes in cyclodextrin cavities, enantioselective interactions most probably occur on the outer sphere of cyclodextrins.     

Electrokinetic properties of sepiolite suspensions in different electrolyte media

The present paper deals with the electrokinetic characterization of sepiolite. A series of systematic zeta potential measurements have been carried out to determine the isoelectric point (iep) and potential-determining ions (pdi), and the effect of mono-, di-, and trivalent electrolytes such as NaCl, KCl, LiCl, NaNO(3), NaCH(3)COO, MgCl(2), CaCl(2), BaCl(2), CoCl(2), CuCl(2), Pb(NO(3))(2), Na(2)CO(3), Na(2)SO(4), AlCl(3), FeCl(3), and Na(3)PO(4) on the zeta potential of sepiolite. Zeta potential has been calculated with the aid of Smoluchowski's equation. Sepiolite yields an isoelectric point at pH 6.6. The zeta potential for the sepiolite has ranged from +23.3 mV at pH approximately 2 to -22.4 mV at pH approximately 8 at 20 +/- 2 degrees C in water. The valency of the ions have proven to have a great influence on the electrokinetic behavior of the suspension. Monovalent cations were found to have a weak effect, while di- and trivalent cations made the zeta potential positive. Charge reversal was observed for divalent cations at 1 x 10(-2) M and for trivalent cations at 3 x 10(-4) M. As a result, it can be said that monovalent cations are indifferent ions when di- and trivalent cations are potential-determining ions.     

Superintegrable cases of four-dimensional dynamical systems

Degenerate tri-Hamiltonian structures of the Shivamoggi and generalized Raychaudhuri equations are exhibited. For certain specific values of the parameters, it is shown that hyperchaotic Lü and Qi systems are superintegrable and admit tri-Hamiltonian structures.     

Rapid determination of 90Sr in urine samples using AnaLig® Sr-01

This paper describes the use of IBC’s AnaLig^® Sr-01 molecular recognition technology product to effectively and selectively pre-concentrate, separate, and recover strontium from urine samples. This method uses two-stage columns separation consisting of two different commercial products Eichrom’s Pre-filter Material and AnaLig^® Sr-01 column from IBC Advanced Technologies. This method does not involve co-precipitation of strontium as phosphates and oxalates from urine samples. The new rapid method separates strontium-90 with high chemical recovery.     

Electro-Oxidative Selective Esterification of Methylarenes and Benzaldehydes

A mild and green electro-oxidative protocol to construct aromatic esters from methylarenes and alcohols is herein reported. Importantly, the reaction is free of metals, chemical oxidants, bases, acids, and operates at room temperature. Moreover, the design of the electrolyte was found critical for the oxidation state and structure of the coupling products, a rarely documented effect. This electro-oxidative coupling process also displays exceptional tolerance of many fragile easily oxidized functional groups such as hydroxy, aldehyde, olefin, alkyne, as well as neighboring benzylic positions. The enantiomeric enrichment of some chiral alcohols is moreover preserved during this electro-oxidative coupling reaction, making it overall a promising synthetic tool.     

Fluorescence Interaction and Determination of Sulfathiazole with Trypsin

The mechanism of interaction of trypsin with the sulfathiazole was studied through using fluorescence quenching and UV-visible absorption spectra at pH 7.4. The Stern-Volmer quenching constants, binding constants, number of binding sites and the corresponding thermodynamic parameters ΔH^o, ΔS^o and ΔG^o were calculated at different temperatures. The effect of common metal ions on the constants was also discussed. The results suggest that sulfathiazole can interact strongly trypsin and that there is the formation of trypsin-sulfathiazole complex and the interaction can be explained on the basis of hydrogen bonds and van der Waals forces. The binding distance (r) between the donor (trypsin) and acceptor (sulfathiazole) was 3.52 nm based on the Förster’s non-radiative energy transfer theory. The detection and quantification limits of sulfathiazole were calculated as 2.52 and 8.40 μM in the presence of trypsin, respectively. The relative standard deviation (RSD) was 4.086 % for determinations (n?=?7) of a sulfathiazole solution with the concentration of 7.54 μM.     

Hydrophobic cryogels for DNA adsorption: Effect of embedding of monosize microbeads into cryogel network on their adsorptive performances

As alternative hydrophobic adsorbent for DNA adsorption, supermacroporous cryogel disks were synthesized via free radical polymerization. In this study, we have prepared two kinds of cryogel disks: (i) poly(2‐hydroxyethyl methacrylate‐N‐methacryloyl‐l ‐tryptophan) [p(HEMA‐MATrp)] cryogel containing specific hydrophobic ligand MATrp; and (ii) monosize p(HEMA‐MATrp) particles synthesized via suspension polymerization embedded into p(HEMA) cryogel structure to obtain p(HEMA‐MATrp)/p(HEMA) composite cryogel disks. These cryogel disks containing hydrophobic functional group were characterized via swelling studies, Fourier transform infrared spectroscopy, elemental analysis, surface area measurements and scanning electron microscopy. DNA adsorption onto both p(HEMA‐MATrp) cryogel and p(HEMA‐MATrp)/p(HEMA) composite cryogels was investigated. Maximum adsorption of DNA on p(HEMA‐MATrp) cryogel was found to be 15 mg/g polymer. Otherwise, p(HEMA‐MATrp)/p(HEMA) composite cryogels significantly increased the DNA adsorption capacity to 38 mg/g polymer. Composite cryogels could be used repeatedly without significant loss on adsorption capacity after 10 repetitive adsorption–desorption cycles. Copyright © 2013 John Wiley & Sons, Ltd.