HPLC-Electrochemical detection with graphite-poly (tetrafluoroethylene) electrode Determination of the fungicides thiram and disulfiram

The suitability of composite graphite-poly(tetrafluoroethylene) (Teflon) electrodes as amperometric indicator electrodes in HPLC detection is demonstrated. The determination of the fungicides thiram and disulfiram in the presence of ziram has been chosen as an analytical problem. The optimization of working conditions, such as the choice of the organic solvent used in the mobile phase as well as its percentage, the potential applied to the composite electrode, and the time elapsed between mixing the carbamates and the injection, has been accomplished by using the wall-jet flow-cell configuration. The effect of the acetonitrile percentage used in the mobile phase on the retention of thiram, disulfiram, ziram and phenol was evaluated. Resolution up to the baseline can be achieved with 45% acetonitrile. The sensitivity of the determination of thiram and disulfiram in the presence of a constant concentration of ziram is slightly better when using a wall-jet cell; however, the background current is higher, as well as the baseline noise and the time necessary to achieve stabilization of the baseline before the injection. Lower limits of detection for both fungicides, as well as a better repeatability, were obtained when using a thin-layer flow cell configuration. As an application, the determination of thiram in spiked apple samples, at a level of 0.5 mg thiram kg(-1) apple, has been carried out with a mean recovery of 97 +/- 3% for a significance level of 0.05.     

A highly efficient synthetic route to ketones through sequential coupling reactions of grignard reagents with s-phenyl carbonochloridothioate in the presence of nickel or iron catalysts

The sequential coupling reactions of Grignard reagents with $\text{S}$phenyl carbonochloridothioate in the presence of nickel(II) or iron(III) catalysts provides a very mild and straightforward route to symmetrical and unsymmetrical aliphatic and aromatic ketones.     

Synthesis of marrubiin

The synthesis of marrubiin has been achieved starting from the keto lactone (II) which was prepared stereoselectively from the known keto ester (XI).     

The electron-impact induced fragmentation of substituted 4-styrylquinolines

The fragmentation of 4-styrylquinoline (I), 4-(p-nitrostyryl)-quinoline (II), 4-(p-chlorostyryl)-quinoline (III), 4-(p-hydroxystyryl)-quinoline (IV), 4-(p-methoxystyryl)-quinoline (V), 4-(p-dimethylaminostyryl)-quinoline (VI) and 4-(p-cyanostyryl)-quinoline (VII) under electron-impact in the mass spectrometer is reported. The role and the influence of substituents on the fragmentation scheme is discussed. The loss of the substituents from the molecular ion is correlated with LCAOMO quantities.     

Encapsulating bis(beta-ketoiminato) polyethers. Volatile, fluorine-free barium precursors for metal-organic chemical vapor deposition

The synthesis, characterization, and incorporation in volatile metal-organic chemical vapor deposition (MOCVD) precursors of a new class of linked beta-ketoiminate-polyether-beta-ketoiminate ligands is presented. These ligands are designed to encapsulate alkaline-earth cations having low charges and large ionic radii. Barium complexes having the general formula Ba[(RCOCHC(R')N)2(R")] (R = tert-butyl or CF3; R' = tert-butyl, methyl, or CF3; R" = -(CH2CH2O)4CH2CH2- or -(CH2CH2O)5CH2CH2)-) were prepared and characterized by 1H and 13C NMR spectroscopy, elemental analysis, and mass spectrometry. Single-crystal X-ray diffraction analysis of 2,2,5,25,28,28-hexamethyl-9,12,15,18,21-pentaoxa-4,25-diene-6,24- diimino-3,27-pentacosadionatobarium(II) reveals a monomeric, nine-coordinate, tricapped trigonal prismatic coordination geometry. Single-crystal X-ray structural analysis of 1,1,1,24,24,24-hexafluoro-4,21-ditrifluoromethyl-8,11,14,17- tetraoxa-3,21-diene-5,20-diimino-2,23-tetracosadionatobarium(II).2DMSO reveals a monomeric, ten-coordinate, distorted tetracapped trigonal prismatic coordination geometry. Volatility data are presented for these barium complexes, demonstrating viability as MOCVD precursors. In addition, it is demonstrated that thin epitaxial films of BaTiO3 can be grown on (001) MgO by low-pressure MOCVD techniques using one of these barium complexes and Ti(dipivaloylmethanate)2(isopropoxide)2 as precursors.     

AB Initio calculations and vibrational spectra of CH3SC≡CH and CH3SC≡CSCH3

Methylthio- (MTE) and bis-methylthioethyne (BMTE) molecules are calculated by the SCF MO method (geometry optimization, basis set 6–31G*/MP2). The calculated internal rotation barriers of methyl groups are 7.12 kJ/lmole for MTE and 12.86 kJ/mole for BMTE (both groups are simultaneously rotated). The s-gosh-orientation of the thiomethyl fragments corresponds to a stable conformation of BMTE. The estimated values of the s-cis- and s-trans-barriers of mutual rotation of SCH₃ groups about the axis of the C≡C bond are 13.61 and 12.54 kJ/mole, respectively. Conformationally sensitive MOs and vibration frequencies are established. An analysis of the experimental IR absorption and Raman spectra and the calculated vibrational spectrum makes it possible to conclude that in the liquid phase the BMTE molecules also have an s-gosh-conformation. Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 602–609, July–August, 1998.     

Synthesis and Structure of the New Ammonium Indium Phosphate (NH4)In(OH)PO4

A new ammonium indium phosphate (NH₄)In(OH)PO₄ was prepared by hydrothermal reaction in the In₂O₃-NH₄H₂PO₄-NH₃/OH system (T=200°C, autogenous pressure, 7 days). The formula (NH₄)In(OH)PO₄ was determined on the basis of chemical and thermal analysis (TG/DSC), X-ray powder diffraction and IR-spectroscopy. (NH₄)In(OH)PO₄ crystallizes in the tetragonal system with space group P4₃2₁2 (No. 96); a=9.4232(1) Å, c=11.1766(1) Å, V=992.45(2) ų; Z=8. The crystal structure was refined by the Rietveld method (R_w=6.35%, R_p=5.10%). The second-harmonic generation study confirmed that structure of (NH₄)In(OH)PO₄ does not have a center of symmetry. The cis-InO₄(OH)₂ octahedra form helical chains, parallel to the c-axis. The In-O-In bonds are nearly equidistant. The chains are interconnected by phosphate tetrahedra and create tunnels containing the NH₄⁺ ions along the c-axis. (NH₄)In(OH)PO₄ is isostructural with RbIn(OH)PO₄.     

Phthalocyanines and related compounds: XXXVIII. Synthesis of symmetric taurine- and choline-substituted phthalocyanines

Procedures have been developed for the synthesis of a series of metal complexes derived from water-soluble anionic and cationic octa-4,5-carboxyphthalocyanine-taurine and choline conjugates.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1907–1911.Original Russian Text Copyright © 2004 by Mikhalenko, Soloveva, Lukyanets.For communication XXXVII, see [1].This revised version was published online in April 2005 with a corrected cover date.     

Determination of total arsenic in serum and packed cellsof patients with renal insufficiency

In order to investigate the arsenic level in serum and packed cells of patients with renal insufficiency, total arsenic (As) concentrations were determined with hydride generation atomic absorption spectrometry (HGAAS) in serum (S) and packed cells (PC) of 31 non-dialyzed patients. The accuracy of the method was tested by the analysis of arsenic in 3 certified reference materials. Patients showed a three-fold increase of arsenic concentrations in serum and a two-fold increase of arsenic in packed cells compared with controls. Patients (n=10) with higher serum creatinine (>2.0 mg/dL), urea (>0.70 g/L) and urinary protein (mean+/-SD: 1.12+/-0.82 g/L) showed higher arsenic concentrations (5.8+/-3.3 microg/L in serum and 18.0+/-16.7 microg/kg in packed cells) compared with those with lower creatinine (<1.6 mg/dL), urea (<0.6 g/L) and urinary protein (mean+/-SD: 0.27+/-0.82 g/L) (n=16, serum arsenic 1.2+/-1.2 microg/L, packed cells arsenic 2.6+/-1.9 microg/kg). The significant differences (both p < 0.001) in S and PC-arsenic levels of patients in group I and II implies a relationship between the arsenic level and the degree of chronic renal insufficiency.