Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties

The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role.     

Analysis of some medicinal plants in South-western Nigeria using PIXE

Summary Analysis of thirteen medicinal plants of various biological activities commonly used in South-western Nigeria was carried out using PIXE technique. Nine of these plants are anti-cancer while four are antimicrobial. PIXE measurements were carried out using collimated proton beams delivered by the 2. 5 MV AN 2000 Van de Graaff accelerator at the Istituto Nazionale di Fisica Nucleare (INFN), (LNL) Legnaro, (Padova), Italy. The results showed the presence of twenty three different elements in the plants and none of them contains any toxic heavy metals. Only Chenopodium ambrosioides showed detectable levels of selenium which is considered important in cancer prevention.     

Free-radical reactions of diazonium salts with α,β-unsaturated carbonyl compounds. A new synthesis of 1,4-diarylpyrazole derivatives

Free-radical decomposition of diazonium salts catalyzed by titanous or titanous and ferrous salts in the presence of β-substituted α,β-unsaturated carbonyl compounds leads to 1,4-diarylpyrazole derivatives. The reaction occurs via an intermediate azo compound ( 1 ), which can be reduced by the metal salt or can be isolated and hydrogenated to pyrazole derivatives.     

Homolytic reductive alkylation of methylvinyl ketone with ethers by Ti(III) decomposition of t-butyl hydroperoxide

Reductive alkylatin of methylvinylketone has been accomplished by hydrogen abstraction from cyclic ethers with the redox couple: t-butyl hydroperoxide-titanous chloride. A redox radical mechanism is proposed and the selectivity of the hydrogen abstraction by t-butoxy radicals and reduction of α-ketoalkyl radical by titanous ions is discussed.     

Water wafers: structure and melting of a hydrate inclusion compound of a neutral Pt(IV) complex with 1-methylcytosinato ligands

The characterization by X-ray analysis of the trans,trans,trans-[bis(1-methylcytosinate,N4)bis(ammine)bis(hydroxo)platinum(IV)] octahydrate complex (I) reveals an unexpected crystal packing. The neutral complex molecule is hosted by layers, totally built up by water molecules which do not exhibit a direct coordination to metal ions. These corrugated layers are made by puckered eight- and planar four-membered rings of water molecules, held together by hydrogen bonds with an ordered proton arrangement.     

Automated determination of verapamil and norverapamil in human plasma with on-line coupling of dialysis to high-performance liquid chromatography and fluorometric detection

A fully automated method for the simultaneous determination of verapamil and its main metabolite norverapamil in human plasma is described. This method is based on on-line sample preparation using dialysis followed by clean-up and enrichment of the dialysate on a precolumn and subsequent HPLC analysis with fluorometric detection. All sample handling operations were performed automatically by a sample processor equipped with a robotic arm (ASTED system). The plasma samples were dialysed on a cellulose acetate membrane (cut-off: 15 kD) and the dialysate was purified and enriched on a short pre-column filled with cyanopropyl silica. Before starting dialysis, this trace enrichment column (TEC) was first conditioned with the HPLC mobile phase and then with pH 3.0 acetate buffer. 370 μl of plasma sample spiked with the internal standard (gallopamil) were dialysed in the static-pulsed mode. The solution at the donor side was pH 3.0 acetate buffer containing Triton X-100 while the acceptor solution was made of the same acetate buffer. When dialysis was discontinued, the analytes were desorbed from the TEC by the HPLC mobile phase and transferred to the C₁₈ analytical column by means of a switching valve. This mobile phase consisted of a mixture of acetonitrile, pH 3.0 acetate buffer and 2-aminoheptane. The influence of different parameters of the dialysis process on the recovery of verapamil and norverapamil has been studied. The effect of the volume, the aspirating and dispensing flow-rates of the dialysis solution has been investigated. The recoveries of verapamil and norverapamil in plasma were close to 75% and the limits of quantification were 5 ng/ml for both analytes. The method was found to be linear in the concentration range from 5 to 500 ng/ml (r²: 0.9996 for both analytes). The intra-day and inter-day reproducibilities at a concentration of 100 ng/ml were 2.3% and 5.6% for verapamil and 1.7% and 5.1% for norverapamil, respectively.     

Influence of inhibitory compounds and minor sugars on xylitol production by <Emphasis Type="Italic">Debaryomyces hansenii</Emphasis>

To obtain in-depth information on the overall metabolic behavior of the new good xylitol producer Debaryomyces hansenii UFV-170, batch bioconversions were carried out using semisynthetic media with compositions simulating those of typical acidic hemicellulose hydrolysates of sugarcane bagasse. For this purpose, we used media containing glucose (4.3–6.5 g/L), xylose (60.1–92.1 g/L), or arabinose (5.9–9.2 g/L), or binary or ternary mixtures of them in either the presence or absence of typical inhibitors of acidic hydrolysates, such as furfural (1.0–5.0 g/L), hydroxymethylfurfural (0.01–0.30 g/L), acetic acid (0.5–3.0 g/L), and vanillin (0.5–3.0 g/L). D. hansenii exhibited a good tolerance to high sugar concentrations as well as to the presence of inhibiting compounds in the fermentation media. It was able to produce xylitol only from xylose, arabitol from arabinose, and no glucitol from glucose. Arabinose metabolization was incomplete, while ethanol was mainly produced from glucose and, to a lesser less extent, from xylose and arabinose. The results suggest potential application of this strain in xyloseto-xylitol bioconversion from complex xylose media from lignocellulosic materials.     

α-Hydroxyalkylation of heteroaromatic bases by alcohols and hydroxylamine-O-sulphonic acid

The homolytic decomposition of hydroxylamine-O-sulphonic acid in alcoholic solvents was investigated in the presence or absence of protonated heteroaromatic bases and Fe(II) salt. The addition of the α-hydroxyalkyl radicals to the base and their oxidation by Fe(III) salt to the corresponding alkyl cyanide were competitive processes. A redox chain process involving the amino radical cation, NH₃^t., is suggested and the factors affecting the yields of the homolytic substitution are discussed.     

Identification and assay of underivatized urinary acylcarnitines by paper spray tandem mass spectrometry

A new analytical approach, using paper spray tandem mass spectrometry, has been developed for assay of carnitine and acylcarnitines in urine. Paper spray (PS) is a very promising technique, especially in clinical investigations, because of its simplicity, low cost, and rapid sample preparation. A home-made paper spray device was used for assay of urinary acylcarnitines (C2–C18). The performance of solvents with different elution efficiency and paper substrates with different porosity grade and structure were tested by use of spiked synthetic urine. Tandem mass spectrometry in multiple reaction monitoring (MRM) mode was optimized to obtain better specificity and sensitivity. Analyte signals were evaluated for stability and reproducibility. Calibration with [²H₃]propionylcarnitine (C3-d3), [²H₃]octanoylcarnitine (C8-d3), and [²H₃] palmitoylcarnitine (C16-d3) as internal standards was used for quantification. Very good linearity was obtained, with correlation coefficients >0.99 for C0–C12 and C16 acylcarnitines and >0.96 for C14 and C18 acylcarnitines. Accuracy and precision (RSD, %) of the proposed procedure were tested at concentrations of 0.8, 8, and 20 mg L^?1 with very satisfactory results: overall mean accuracy was 98.9 % and overall mean relative standard deviation 1 %. Limits of detection (LOD) between 6 and 208 μg L^?1 for propionylcarnitine and tetradecanoylcarnitine, respectively, can be regarded as very satisfactory. Application of the method to real urine proved that paper spray tandem mass spectrometry is a simple, rapid, and direct tool (no derivatization is required) for assay of carnitine and C2–C12 acylcarnitines in urine.     

Multifunctional Supramolecular Dendrimers with an s‐Triazine Ring as the Central Core: Liquid Crystalline,Fluorescence and Photoconductive Properties

Novel liquid crystal (LC) dendrimers have been synthesised by hydrogen bonding between an s‐triazine as the central core and three peripheral dendrons derived from bis(hydroxymethyl)propionic acid. Symmetric acid dendrons bearing achiral promesogenic units have been synthesised to obtain 3:1 complexes with triazine that exhibit LC properties. Asymmetric dendrons that combine the achiral promesogenic unit and an active moiety derived from coumarin or pyrene structures have been synthesised in order to obtain dendrimers with photophysical and electrochemical properties. The formation of the complexes was confirmed by IR and NMR spectroscopy data. The liquid crystalline properties were investigated by differential scanning calorimetry, polarising optical microscopy and X‐ray diffractometry. All complexes displayed mesogenic properties, which were smectic in the case of symmetric dendrons and their complexes and nematic in the case of asymmetric dendrons and their dendrimers. A supramolecular model for the lamellar mesophase, based mainly on X‐ray diffraction studies, is proposed. The electrochemical behaviour of dendritic complexes was investigated by cyclic voltammetry. The UV/Vis absorption and emission properties of the compounds and the photoconductive properties of the dendrons and dendrimers were also investigated