Synthesis,characterization, spectroscopy and thermal analysis of rare earth picrate complexes with <Emphasis Type="Italic">L</Emphasis>-lysine

Summary Rare earth picrate (RE) complexes with L-lysine (Lys) were synthesized and characterized. Elemental analysis (CHN), EDTA titrations and thermogravimetry data suggest a general formula RE(pic)₃·2Lys·2H₂O, where RE=La-Lu (without Pm) and Y, pic=picrate). IR spectra suggest that Lys is coordinated to the central ion through the nitrogen of the α-amino group. Parameters obtained from the absorption spectrum of the Nd compound indicated that the metal-ligand bonds are essentially electrostatic. Emission spectrum and biexponential behavior of the luminescence decay of the Eu compound suggest the existence of polymeric species. Thermogravimetric/derivative thermogravimetric (TG/DTG) and differential scanning calorimetry (DSC) curves of all complexes are very similar, with five events. The final products are the corresponding rare earth oxides and their X-ray diffraction patterns are identical to the calcinated oxides.</o:p>     

A convenient two-step synthesis of 6-methylenesubstituted-4-trichloromethyl-2-methylsulfanyl pyrimidines

This work reports a two-step synthetic strategy to obtain a series of 6-methylenesubstituted-4-trichloromethyl-2-methylsulfanylpyrimidines from the cyclization of 5-bromo-4-methoxy-1,1,1-trichloro-pent-3-en-2-ones with 2-methyl-2-pseudothiourea sulfate, followed by nucleophilic substitution of 6-bromomethyl-4-trichloromethyl-2-methylsulfanylpyrimidine with a series of nucleophiles. Alternative strategies to obtain 6-halomethyl-4-trichloro[fluoro]methyl-2-methylsulfanyl pyrimidines have been addressed.     

Ab initio study of the binding of Trichostatin A (TSA) in the active site of histone deacetylase like protein (HDLP)

Histone deacetylase (HDAC) inhibitors have recently attracted considerable interest because of their therapeutic potential for the treatment of cell proliferative diseases. An X-ray structure of a very potent inhibitor, Trichostatin A (TSA), bound to HDLP (an HDAC analogue isolated from Aquifex aeolicus), is available. From this structure, an active site model (322 atoms), relevant for the binding of TSA and structural analogues, has been derived, and TSA has been minimized in this active site at HF 3-21G* level. The resulting conformation is in excellent accordance with the X-ray structure, and indicates a deprotonation of the hydroxamic acid in TSA by His 131. Also, a water molecule was minimized in the active site. In addition to a similar deprotonation, in accordance with a possible catalytic mechanism of HDAC as proposed by Finnin et al. (M. S. Finnin, J. R. Donigian, A. Cohen, V. M. Richon, R. A. Rifkind and P. A. Marks, Nature, 1999, 401, 188-193), a displacement of the resulting OH- ion in the active site was observed. Based on these results, the difference in energy of binding between TSA and water was calculated. The resulting value is realistic in respect to experimental binding affinities. Furthermore, the mechanism of action of the His 131-Asp 166 charge relay system was investigated. Although the Asp residue in this motif is known to substantially increase the basicity of the His residue, no proton transfer from His 131 to Asp 166 was observed on binding of TSA or water. However, in the empty protonated active site, this proton transfer does occur.     

Liquid chromatography-diode array detection-electrospray ionisation mass spectrometry/nuclear magnetic resonance analyses of the anti-hyperglycemic flavonoid extract of Genista tenera. Structure elucidation of a flavonoid-C-glycoside

The anti-hyperglycemic flavonoid extract obtained from Genista tenera was first studied by liquid chromatography (LC)-diode array detection (DAD) which showed the presence of two major compounds. One of them was identified as genistein-7-O-glucoside. Luteolin-7-O-glucoside was detected as a minor constituent, while luteolin-7,3'-di-O-glucoside and rutin were found in trace amounts. LC-DAD-ESI-MS and NMR were used to confirm the structure of these compounds and allowed the elucidation of the structure of the unknown major compound, which is the flavonoid 5,7,4'-trihydroxyisoflavone-8-C-glucoside.     

The Effects of Beating,Web Forming and Sizing on the Surface Energy of <Emphasis Type="Italic">Eucalyptus globulus</Emphasis> Kraft Fibres Evaluated by Inverse Gas Chromatography

In this work attention has been focused on the effects of papermaking beating, web forming and sizing operations on the physical/chemical surface properties of bleached Eucalyptus globulus kraft fibres. Inverse gas chromatography (IGC) was used to determine the dispersive component of surface tension (γ_s^d) as well as the acidic/basic character (according to the Lewis concept) of the solid surfaces (pulp fibres and pulp handsheets). The results have shown that the main effect of beating is to increase the fibre's Lewis acidic character. Web forming caused a strong decrease in γ_s^d and significant increments in the adhesion works of both acidic and basic probes, lowering the ratio between the two. Nevertheless, the surface of handsheets still exhibited a dominant acidic character. The sizing operation did not change the dispersive component of the surface tension significantly but decreased the difference between the adhesion works of the acidic and basic probes, rendering the handsheet surface less Lewis acidic and more Lewis basic. Thus, although internal sizing is expected to strongly influence liquid spreading at the paper surface and liquid penetration of the fibre's network, it is concluded that beating and web forming lead to important changes in the surface energetic properties of the Eucalyptus globulus kraft fibres.     

Development and validation of a high-performance liquid chromatographic method for the determination of clomazone residues in surface water

A method is described for the determination of clomazone residues in surface water by high-performance liquid chromatography with UV detection. The method involves solid-phase extraction with C18 extraction tubes. Clomazone was separated on a C18 column with a mobile phase of methanol-water (65:35, v/v) at pH 4.0 and a flow-rate of 1.0 ml/min. After optimization of the extraction and separation conditions, the method was validated. The method developed can be used for determination of clomazone in surface water, at the limit of 0.1 mcirog/l set by the European Union drinking water directive, with a 400-fold preconcentration.     

Determination of trace elements in biological materials using tetramethylammonium hydroxide for sample preparation

A method to prepare milk powder, bovine liver and bovine muscle samples for analysis by electrothermal atomic absorption spectrometry (ETAAS) is proposed. Samples are mixed with a small amount of tetramethylammonium hydroxide (TMAH) and a stable and homogeneous slurry is produced in ca. 2 h with heating at 60–70 °C. After such sample preparation and dilution with water, trace elements are determined in certified reference materials. Pyrolysis and atomisation temperatures are optimised for each element, and several modifiers are investigated. External calibration is used for every analyte. Limits of detection (LODs), precision and accuracy are reported for Cd, Pb, Ni, Cr, Cu and Ag and compared with those obtained after conventional acid digestion. The main advantages of the proposed method are the simplicity of sample preparation and the longer lifetime of the graphite tube.     

1H NMR study on the inclusion of bicyclo[3.3.1]nonanes in cyclodextrins

- and -cyclodextrins were found to form 1:1 inclusion complexes with 2,6- and 2,9-substituted bicyclo[3.3.1]nonanes. The binding constants and the structure of the complexes were estimated from titration studies and 2D ROESY experiments.