Diffusion layer titration of dipyrone in pharmaceuticals at a dual-band electrochemical cell

This paper describes the use of a thin-layered dual-band electrochemical cell operating at flow conditions to determine dipyrone (sodium salt of 1-phenil-2,3-dimethyl-4-methylaminomethanesulfonate-5-pyrazolone) by reaction with electrogenerated iodine. The electrolytic cell consisted of two closely spaced gold electrodes, the upper stream electrode serving as the generator electrode and the downstream electrode working as the collector electrode. A linear dynamic range from 2 to 15 μmol l⁻¹ dipyrone was obtained by using a sample volume of 100 μl, with a detection limit of 1.1 μmol l⁻¹. Standard deviation (S.D.) of 3.4% for 20 repetitive injections of a 40 μmol l⁻¹ dipyrone solution and sampling frequency of 90 h⁻¹ were achieved. The results obtained with the thin-layered dual-band electrochemical cell for dipyrone determination in three different pharmaceutical samples compared well with those found by iodimetry with coulometrically generated iodine.     

Multivariate optimisation of the experimental conditions for determination of three methylxanthines by reversed-phase high-performance liquid chromatography

Caffeine (1,3,7-trimethylxanthine), theobromine (3,7-dimethylxanthine) and theophylline (1,3-dimethylxanthine) are the most important naturally occurring methylxanthines. Caffeine is a constituent of coffee and other beverage and included in many medicines. Theobromine and theophylline are formed as metabolites of caffeine in humans, and are also present in tea, cocoa and chocolate products.

In order to improve the chromatographic resolution (R_s) with a good analysis time, experimental designs were applied for multivariate optimisation of the experimental conditions of an isocratic reversed-phase high-performance liquid chromatographic (RP-HPLC) method used for the simultaneous determination of caffeine, theobromine and theophylline. The optimisation process was carried out in two steps using full three-level factorial designs. The factors optimised were: flow rate and mobile phase composition. Optimal conditions for the separation of the three methylxanthines were obtained using a mixture of water/ethanol/acetic acid (75:24:1%, v/v/v) as mobile phase and a flow rate of 1.0 mL min⁻¹. The RP-HPLC/UV method was validated in terms of limit of detection (LOD), limit of quantitation (LOQ), linearity, recovery and the precision, calculated as relative standard deviation (R.S.D.). In these conditions, the LOD was 0.10 μg L⁻¹ for caffeine, 0.07 μg L⁻¹ for theobromine and 0.06 μg L⁻¹ for theophylline. The proposed method is fast, requires no extraction step or derivatization and was suitable for quantification of these methylxanthines in coffee, tea and human urine samples.     

Elucidating interactions of ionic liquids with polymer films using confocal Raman spectroscopy

We report on the molecular interactions between room-temperature ionic liquids (RTILs) and Nafion and PDMS membranes, proving that in contact with these polymers RTILs behave like electrolytes rather than solvents.     

Fractionation of metals and metalloids by chemical bonding from particles accumulated by electrostatic precipitation in an Argentine thermal power plant

A study was undertaken to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in fly ashes collected in the electrostatic precipitator of a thermal power plant in San Nicolás (Argentina). Five samples were collected during one week of operation. For the fractionation, the scheme applied consisted in extracting the elements in four fractions namely (i) soluble and exchangeable elements; (ii) carbonates, oxides and reducible elements; (iii) bound to sulfidic metals; and (iv) residual elements. Metals and metalloids at μg g^− 1 level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). For validation, a standard reference material (SRM 1633 coal fly ash) from NIST was subjected to the same chemical sequential extraction procedure that the samples. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the major minerals present in the matrix. Total analyte concentration (in μg g^− 1) varied from 10.6 for Pb to 17,622 for Al. Minimum and maximum concentrations (in μg g^− 1) found in individual samples in the four fractions were: Al, 92.7–9668; As, < 0.3–143; Cr, 2.0–10.4; Cu, < 0.2–35.6; Fe, < 0.3–4992; Mn, < 0.1–128; Ni, < 0.3–139; Pb, < 0.5–9.1; Ti, < 0.3–2243; V, 17.0–112.9; and Zn, < 0.1–68.2. The leachability of the 11 elements under study proved to be different. Low percentages of Al (1%), V (7%) and Cr (8%) were detected in the most bioavailable fraction. Arsenic was found to be most abundant in the non-silicate phase, represented by the second and third fractions, while Cr, Fe, Ni, Pb and Zn were mostly associated to the residual fraction.     

Multiple bonds between main group elements and transition metals, 155. (Hexamethylphosphoramide) methyl(oxo) bis(η-peroxo)rhenium(VII), the first example of an anhydrous rhenium peroxo complex: crystal structure and catalytic properties

Methyl(oxo)bis(η²-peroxo)rhenium(VII)1, the active species of the system CH₃ReO₃/H₂O₂ in the catalytic oxidation of different organic and organometallic compounds, is stabilized by a water molecule attached to the rhenium center. This water molecule can be removed and substituted by hexamethylphosphoramide (HMPA) to yield (hexamethylphosphoramide)methyl(oxo)bis(η²-peroxo rhenium(VII) (3). The synthesis, crystal structure (X-ray difraction study), and catalytic properties of which compound are reported. Crystal data are as follows: monoclinic, space group P2₁/n, A = 900.76(7) pm, B = 1229.80(11) pm, C = 1318.57(11) pm, β = 90.251(7)°, R_w = 0.034 for 1878 reflections. The catalytic properties of compound 3 in the oxidation of olefins with H₂O₂ are similar to those of 1.     

The relationship between the structures of Cu(II) complexes and their chemical transformations

The paper presents the results of a study of M ₂ ^I M ^II(SO₄)₂ compounds withM ^I= K, Rb, Cs or Tl, andM ^II=Cu or Ni, in the interval from room temperature to the melting temperature. All the compounds studied show endo- or exothermic excursions in their DTA curves, corresponding to phase transitions connected with colour changes of the compounds. For M ₂ ^I Cu(SO₄)₂, whereM ^I is K or Tl, several modifications could be prepared at laboratory temperature, probably distortion isomers. No modifications of this type could be prepared, however, for M ₂ ^I Ni(SO₄)₂ compounds.

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Zusammenfassung Die Ergebnisse einer Untersuchung von M ₂ ^I M ^II(SO₄)₂-Verbindungen Cs, Tl;M ^II=Cu, Ni) im Temperaturbereich von Raum- bis Schmelztemperatur werden beschrieben. Alle untersuchten Verbindungen zeigen in ihren DTA-Kurven mit Farbänderungen einhergehende, durch Phasenumwandlungen bedingte endo- und exotherme Peaks. Bei Laboratoriumstemperatur konnten verschiedene Modifikationen von M ₂ ^I Cu(SO₄)₂ (mitM ^I gleich K oder Tl) hergestellt werden, wobei es sich wahrscheinlich um Distorsionsisomere handelt. Keine Modifikationen dieses Typs konnten jedoch für M ₂ ^I Ni(SO₄)₂ erhalten werden.

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M ₂ ^I M ^II(SO₄)₂, ¹-, Rb, Cs Tl, aM ¹¹-Cu Ni, . - -, , . M ₂ ^I Cu(SO₄)₂, ¹- l, , , , . , M _i ² Ni(SO₄)₂ .

     

Synthesis of new 6-substituted purinyl-5′-nor-1′-homocarbanucleosides based on indanol

A series of new 6-substituted purinyl-5′-nor-1′-homocarbanucleosides based on indanol were synthesized from (±)-cis-3-hydroxymethyl-1-indanol, an appropriately functionalized derivative of which was reacted with 6-chloropurine in the presence of NaH and 18-crown-6 ether to prepare a key intermediate that gave access to the target molecules, purinylcarbanucleosides in which position 6 is occupied by a chloro, hydroxy, methoxy, amino or substituted phenyl group.     

Synthesis and characterization of three novel perfluoro-oligothiophenes ranging in length from the trimer to the pentamer

In this Article, we report on the synthesis and full characterization of three perfluorinated oligothiophenes, ranging in length from the trimer to the pentamer (PF-nT, with n = 3, 4, or 5). The differential pulse voltammetry (DPV) analysis of the compounds showed that they can be both oxidized and reduced (i.e., they display a dual or amphoteric electrochemical behavior), with the reduction peaks positively shifted relative to those of the corresponding unsubstituted oligothiophenes. The electrochemically determined energy gaps are in agreement with those measured from the UV-vis-NIR absorption spectra in solution. The conjugational properties have been investigated by means of FT-Raman spectroscopy, both as pure solids and as dilute solutes in CH(2)Cl(2), revealing that: (i) pi-conjugation does not still reach saturation with chain length for the longest oligomer, and (ii) conformational distortions from a nearly coplanar arrangement of the successive thiophene units upon solution are not too large. DFT and TDDFT quantum chemical calculations have been performed, at the B3LYP/6-31G level, to assess information about the optimized molecular structure, equilibrium atomic charges distribution, energies and topologies of the frontier molecular orbitals (MO) around the gap, vibrational normal modes associated with the most outstanding Raman scatterings, and vertical one-electron excitations that give rise to the main optical absorptions.     

31P{1H}-n.m.r. as a tool for identification of ruthenium isomers containing PPh3 or 1,4-bis(diphenylphosphino)butane ligands. X-ray structures of the cis-{RuCl2(PPh3)2 [4,4′-(-X)2-2,2′-bipy]} complexes [X=-H, -Me, -SMe and (-Cl, -Me)]

A series of cis-{RuCl₂(PPh₃)₂[4,4-(X)₂-2,2-bipy]} [cis-chlorines; X=-H, -Me, -SMe, and (-Cl,-Me)] complexes have had their structures determined by single crystal X-ray diffraction. The geometry of these complexes, also determined in CH₂Cl₂ solution by ³¹P{¹H}-n.m.r. spectroscopy, showed that the chemical shifts for the phosphorus atoms are slightly dependent on the pKa of the 4,4-(-X)₂-2,2-bipy ligands.     

IR-Spektren der Caesium-bis-sulfato-metallate(III)

Compounds of the type CsLn(SO₄)₂, (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were prepared at 300°C. IR spectra were recorded in the range 4,000-250cm^–1 and tentatively assigned. The number of observed bands exceeds the predicted number by site symmetry selection rules. Streching bands show bathochromic shifts whereas the deformations exibit hypsochromic shifts on going to heavier lanthanides. At the same time there is an increased splitting of these bands in the same direction. All these facts indicate an increased coupling in the layer structure which is in accordance with the lanthanide contraction.

N. Bukovec, P. Bukovec undJ. iftar, Vest. Slov. Kem. Drus.26, 103 (1979).