Labelling of organotin compounds for fluorimetric detection

A systematic study of the fluorescence of complexes of some flavone derivatives with organotin compounds in hexane and in an aqueous micellar medium on Triton X-100 is reported. Some relationships between fluorescence intensity and the structure of the fluorogenic reagent or that of the organotin compound can be deduced, and the most suitable reagent for each organotin species can be chosen on the basis of sensitivity and selectivity. Results point out that flavone derivatives are appropriate post-column derivatization reagents for organotin compounds in liquid chromatography.     

Synthesis of Densely Functionalised 5‐Halogen‐1,3‐oxazin‐2‐ones by Halogen‐Mediated Regioselective Cyclisation of N‐Cbz‐Protected Propargylic Amines: A Combined Experimental and Theoretical Study

A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I₂, Br₂ and Cl₂ as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed.     

Investigation of the negative thermal expansion mechanism of zeolite chabazite using the pair distribution function method

We have used the pair distribution function (PDF) method to gain insight into the mechanism of contraction of zeolite chabazite. Using this method we followed how the interatomic distances of the local structure changed with temperature. By optimization of the structure by free energy minimization and using the Reverse Monte Carlo technique we were able to find structural models at low and at high temperatures that agreed quantitatively with our experimental PDFs. From these models we conclude that the mechanism of contraction with temperature cannot involve rocking of the tetrahedra as rigid unit modes as there are distortions of the tetrahedra with temperature (indicating internal vibrations) and also that the mechanism of contraction probably involves a mode that translates along the Si-O3-Si-O4-Si linkages inside of the D6R of zeolite chabazite.     

Hydrogen bonding interactions between indole and benzenoid-pi-bases

The NH-pi interactions of indole with benzene, naphthalene, phenanthrene, toluene, m-xylene, and mesitilene, in carbon tetrachloride solutions, have been studied by Fourier transform infrared spectroscopy. The experiments, carried out on the NH stretching band of indole, prove the formation of 1:1 complexes in which the NH bond of indole is engaged. The NH frequency shifts are independent of the number of rings in the base, but they progressively increase as the electron density is enhanced by methylation. The association constants increase with the increase of both, the number of rings and the methyl groups on the base. At higher base concentrations, further shifts on the free NH and associated bands indicate the formation of 1:2 complexes, which suggest hybride NH-pi and van der Waals interactions between one indole ring and two benzene acceptor molecules.     

Application of metabolic engineering to the production of scopolamine

Scopolamine is an alkaloid widely used in medicine for its anticholinergic activity. The aim of this review is to show that metabolic engineering techniques constitute a suitable tool to improve the production of tropane alkaloids, focusing in particular on scopolamine. We present an overview of results obtained by various research groups, including our own, who have studied the overexpression of genes involved in the biosynthesis of scopolamine in different plant species that produce tropane alkaloids. Experiments carried out to improve production in hairy root cultures will also be described, as well as those attempting to biotransform hyoscyamine into scopolamine in roots and transgenic tobacco cells.     

Synthesis and Reactivity of Cationic Triruthenium Clusters Derived from 2‐Methyl‐ and 4‐Methylpyrimidines: From Conventional Cyclometalated Ligands to Novel Types of N‐Heterocyclic Carbenes

The methylation of the uncoordinated nitrogen atom of the cyclometalated triruthenium cluster complexes [Ru₃(μ‐H)(μ‐κ²N¹,C⁶‐2‐Mepyr)(CO)₁₀] ( 1 ; 2‐MepyrH=2‐methylpyrimidine) and [Ru₃(μ‐H)(μ‐κ²N¹,C⁶‐4‐Mepyr)(CO)₁₀] ( 9 ; 4‐MepyrH=4‐methylpyrimidine) gives two similar cationic complexes, [Ru₃(μ‐H)(μ‐κ²N¹,C⁶‐2,3‐Me₂pyr)(CO)₁₀]⁺( 2 ⁺) and [Ru₃(μ‐H)(μ‐κ²N¹,C⁶‐3,4‐Me₂pyr)(CO)₁₀]⁺ ( 9 ⁺), respectively, whose heterocyclic ligands belong to a novel type of N‐heterocyclic carbenes (NHCs) that have the C_carbene atom in 6‐position of a pyrimidine framework. The position of the C‐methyl group in the ligands of complexes 2 ⁺ (on C²) and 9 ⁺ (on C⁴) is of key importance for the outcome of their reactions with K[N(SiMe₃)₂], K‐selectride, and cobaltocene. Although these reagents react with 2 ⁺ to give [Ru₃(μ‐H)(μ‐κ²N¹,C⁶‐2‐CH₂‐3‐Mepyr)(CO)₁₀] ( 3 ; deprotonation of the C²‐Me group), [Ru₃(μ‐H)(μ₃‐κ³N¹,C⁵,C⁶‐4‐H‐2,3‐Me₂pyr)(CO)₉] ( 4 ; hydride addition at C⁴), and [Ru₆(μ‐H)₂{μ₆‐κ⁶N¹,N^1′,C⁵,C^5′,C⁶,C^6′‐4,4′‐bis(2,3‐Me₂pyr)}(CO)₁₈] ( 5 ; reductive dimerization at C⁴), respectively, similar reactions with 9 ⁺ have only allowed the isolation of [Ru₃(μ‐H)(μ₃‐κ²N¹,C⁶‐2‐H‐3,4‐Me₂pyr)(CO)₉] ( 11 ; hydride addition at C²). Compounds 3 and 11 also contain novel six‐membered ring NHC ligands. Theoretical studies have established that the deprotonation of 2 ⁺ and 9 ⁺ (that have ligand‐based LUMOs) are charge‐controlled processes and that both the composition of the LUMOs of these cationic complexes and the steric protection of their ligand ring atoms govern the regioselectivity of their nucleophilic addition and reduction reactions.     

Determination of alumina in sintered aluminium powder by activation with 14-MeV neutrons

Fast neutrons of 14 MeV produced in the IMICAM CISE 150-kV generator by the (d, t) reaction in a tritium-titanium target, were used in the indirect determination of Al(2)O(3). The samples were irradiated for 30 sec and the total (16)N activity was determined, by counting for ten 2-sec periods and graphically integrating. The standards were a known sintered aluminium powder and nylon pieces of identical shape. The method is competitive with the chemical one, because of its quickness, sensitivity and precision.     

Polarography of an acidic degradation product from cephalexin

2-Hydroxy-3-phenyl-6-methylpyrazine is identified as the product obtained by acidic degradation of cephalexin in the presence of formaldehyde. In 5M hydrochloric acid this product gives a well-defined reduction wave with a half-wave potential of -0.45 V vs. SCE. The wave is irreversible and diffusion-controlled. The diffusion current shows a linear relation with the cephalexin concentration and can be used for determination of cephalexin in plasma.     

In vitro cytotoxic evaluation of a novel phosphinyl derivative of boldine

2,9-Dimethoxymethylboldine (2), 2,9-dimethoxymethyl-3-bromoboldine (3) and 2,9-dimethoxymethyl-3-diphenylphosphinylboldine (4) have been synthesized in an effort to find compounds with potential pharmacological applications. The cytotoxic activities of the natural precursor 1 and these three derivatives have been measured as IC?? inhibitory growth. The diphenylphosphinyl derivative 4 showed a significant cytotoxic activity on two breast cancer cell lines, namely MCF-7 and MDA-MB-231, with IC?? values of 55.5 and 62.7 [μM], respectively. These results suggest that the kind of structural modifications introduced to synthesize compound 4 represent a promising way to enhance the cytotoxic activity of boldine derivatives.     

Enzymatic Hydrolysis of Soy Protein Isolates. DSC study

The aim of this work was to analyze the possible use of differential scanning calorimetry (DSC) as a method to study the process of protein modifications during enzymatic hydrolysis. Results of the enzymatic hydrolysis of soy protein showed significant differences in the values of maximum deflection temperature (T _p), heat of reaction (ΔH), and width at half peak height (ΔT _1/2), between DSC curves corresponding to the substrate, or zerotime of hydrolysis, and those of the hydrolysates obtained by the action of cucurbita and pomiferin enzymes. DSC curve changes mentioned were explained by the use of gel-filtration chromatography, denaturing electrophoresis and surface hydrophobicity of the hydrolysis products obtained at 30 min of reaction. This revised version was published online in August 2006 with corrections to the Cover Date.