X-ray diffraction and solid-state NMR studies of a germanium binuclear complex

A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2] x 4 H2O (where pmida(4-) = N-(phosphonomethyl)iminodiacetate and C4H12N2(2+) = piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2- complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H-X(13C,31P) heteronuclear correlation (HETCOR) and 1H-1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee-Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic-organic hybrids. We assigned the NMR resonances with the help of C...H and P...H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry).     

Absolute rate calculations: atom and proton transfers in hydrogen-bonded systems.

We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature.     

Thin-Layer Chromatography with an Isolated Support and Forced Flow of the Mobile Phase

JPC – Journal of Planar Chromatography – Modern TLC -     

Multiplex polymerase chain reaction analysis of Glu-1 high-molecular-mass glutenin genes from wheat by capillary electrophoresis with laser-induced fluorescence detection

The unique bread-making properties of wheat are closely correlated with composition and quantity of high-molecular-mass (HMW) glutenin subunits encoded by the Glu-1 genes. We report the development of a multiplex polymerase chain reaction (PCR) method to identify bread wheat genotypes carrying HMW glutenin allele composition of Glu-1 complex loci (Glu-A1, Glu-B1 and Glu-D1) by capillary electrophoresis(CE) with laser-induced fluorescence (LIF) detection. Two triplex primer sets of HMW glutenin subunit genes were examined. An automated and rapid CE-LIF technique is helpful in the multiplex PCR optimization process. Two fluorescent intercalating dyes (EnhanCE, and YO-PRO-1) are compared for detection of DNA fragments. Amplified DNA fragments of HMW glutenin Glu-1 genes were well separated both by agarose slab-gel electrophoresis and CE, and revealed minor differences between the sequences of 1Ax2*, 1Axnull, 1Bx6, 1Bx7, 1Bx17 and 1Dx5 genes. Moreover, CE technique requires samples of smaller volumes in comparison to slab-gel electrophoresis, and data can be obtained in less than 20 min. There was a very high concordance in the assessment of the molecular size of PCR-generated DNA markers. Fast and accurate identification of molecular markers of Glu-1 genes by CE-LIF can be an efficient alternative to standard procedure separation for early selection of useful wheat genotypes with good bread-making quality.     

Stereoselective Rh-catalyzed hydrogenation of cyclobutyl chiral enamides: double stereodifferentiation vs catalyst-controlled diastereoselection

The hydrogenation reactions of several cyclobutyl enamides derived from (-)-alpha-pinene or (-)-verbenone have been investigated by using different catalysts. The chiralities of both the substrate and the catalyst as well as the Z/E stereochemistry of the double bond have been considered, and the observed diastereoselectivity has been rationalized. For enamides with the double bond separated from the cyclobutane by a methylene, the Wilkinson catalyst did not induce any diastereoselection, but excellent diastereoselectivity was observed when using Et-DuPHOS-Rh and ChiraPHOS-Rh. The configuration of the new stereogenic center was catalyst-dependent and can be rationalized according to the Halpern mechanism. For (Z)-enamides with the double bond directly linked to the cyclobutane ring, the chirality of the substrate governed the diastereoselection and the Halpern mechanism seemed not to be operative in the hydrogenation with ChiraPHOS, with the configuration of the new stereogenic center being determined by steric effects. On the contrary, the chirality of the catalyst was the factor determining the stereochemistry of the major products with alkyl-DuPHOS-Rh. Z/E stereochemistry influenced the stereodifferentiation, and a different behavior for each Z or E stereoisomer was found. For both (Z)- and (E)-enamides, some instances of match/mismatch between the chirality of the substrate and that of the catalyst were observed. As a result of all of these studies, a series of new cyclobutyl alpha-amino acids has been synthesized. These products are interesting to incorporate into conformationally constrained peptides.     

Radionuclides in a sediment trap and bottom sediment samples from the eastern Turkish coast of the Black Sea

Summary Radionuclide (¹³⁷Cs, ²³⁸U, ²³²Th and ⁴⁰K) concentrations were determined in a sediment trap and bottom sediment samples collected from a station at the eastern Turkish coast of the Black Sea. The specific activity of the ¹³⁷Cs radionuclide in the settling particles ranged from 0.04±0.01 to 0.10±0.02 Bq^. g^-1dry weight. The calculated flux rate of the ¹³⁷Cs was between 0.37 and 2.59 Bq^. m^-2. d^-1in the sampling periods of 2002 and 2003. The ¹³⁷Cs concentration in the bottom sediment profile were between 0.039±0.013-9.083±0.017 Bq^. g^-1dry weight in the same station. The vertical profile of the radionuclides suggests that they have little mobility during the 17 years after the Chernobyl accident.     

Nickel determination in osteoblast-like cell culture medium by adsorptive cathodic stripping voltammetry with a mercury microelectrode

The purpose of this study is to investigate the influence of nickel, which is an alloying element in commonly used metallic biomaterials, on the biomaterials mineralization process. An electrochemical method was developed to quantify this metal ion in osteoblast-like cell culture medium (OST) by performing adsorptive cathodic stripping voltammetry (CSV) with dimethylglyoxime (DMG) at a mercury film microelectrode (MFM). The optimized analytical conditions and the square-wave CSV parameters for the analysis are: DMG concentration: 5.00 × 10⁻⁴ mol L⁻¹; ammonium chloride buffer: 0.10 mol L⁻¹ (pH 9.2); frequency: 50 Hz, amplitude 20 mV; step: 2 mV; adsorption time: 10 s, deposition potential: −0.70 V and reduction potential: −1.20 V. The limit of detection was 7.70 × 10⁻⁹ mol L⁻¹ for an adsorption time of 10 s. The results achieved by CSV using the MFM were compared to those obtained by atomic absorption spectrometry (AAS) to ensure the reliability of the electrochemical method. The mineralization process was evaluated by biochemical and histochemical assays.     

Determination of ambroxol in an automated multi-pumping pulsed flow system.

A new flow methodology exploiting the multi-pumping approach was developed for the spectrophotometric determination of ambroxol hydrochloride in pharmaceutical preparations. The flow manifold was implemented by using, exclusively, multiple solenoid-actuated micro-pumps, which acted simultaneously as sample insertion, solutions propelling and reagents commutation units. Linear calibration plots were obtained over an ambroxol concentration ranging from 10 to 200 mg l(-1) (r.s.d. < 0.5%, n = 15) and a sampling rate of about 60 samples per hour (flow rate = 1.92 ml min(-1), sample volume = 80 microl).     

Solid-phase extraction-liquid chromatography-fluorimetry for organotin speciation in natural waters

Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT) species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C₁₈ enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole process have been determined. The method has been applied to the determination of organotin species in spiked natural water samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low ng L⁻¹ level (1–3 ng Sn L⁻¹ for DPhT, DBT, and PhT and 40 ng Sn L⁻¹ for TBT when 250 mL spiked sea water is processed.)