Magic angle spinning29Si and27Al NMR study of mordenite dealumination

Magic angle spinning²⁹Si NMR presents a rapid qualitative method of assessing the degree of dealumination of sodium mordenite modified by acid leaching and heat treatment. A quantitative determination of the²⁹Si coordination sphere is hampered by the overlap of chemical shift ranges for Si?O?Al and Si?O?H species. MAS²⁷Al NMR indicates the presence of octahedrally coordinated Al in interstitial sites in all treated samples. On treating mordenite samples at high temperatures (～700°C) much of the Al becomes invisible to the NMR experiment because of its location in sites of low symmetry and large quadrupole coupling constant.     

Derivative spectrophotometric resolution of mixtures of the food colourants Tartrazine, Amaranth and Curcumin in a micellar medium

A study of the absorption spectra of the food colourants Tartrazine (E-102), Amaranth (E-123) and Curcumin (E-100) in various organic solvents and pH media, have been carried out. In addition, the spectral behaviour in aqueous micellar systems of anionic, cationic and non-ionic surfactants, as well as beta-cyclodextrin, was investigated. Analytical methods are proposed for the determination of the three dyes in mixtures without any prior separation step, by the application of the derivative technique to the normal absorption spectra, based on the use of cetyltrimethylammonium bromide (CTAB) in 0.1 M NaOH, over the concentration range 2-50 mug ml(-1). The methods are applied for determining the three dyes in commercial food products.     

Development and validation of a capillary electrophoresis method for the determination of phenothiazines in human urine in the low nanogram per milliliter concentration range using field-amplified sample injection

A capillary zone electrophoresis (CZE) method with ultraviolet-visible detection has been established and validated for the determination of five phenothiazines: thiazinamium methylsulfate, promazine hydrochloride, chlorpromazine hydrochloride, thioridazine hydrochloride, and promethazine hydrochloride in human urine. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 150 mM tris(hydroxymethyl)aminomethane and 25% acetonitrile at pH 8.2, with temperature and voltage of 25 degrees C and 20 kV, respectively. Naphazoline hydrochloride was used as an internal standard. Field-amplified sample injection (FASI) has been applied to improve the sensitivity of the detection. Considering the influence of parameters affecting the on-line preconcentration (nature of preinjection plug, sample solvent composition, injection times, and injection voltage) and due to the significant interactions among them, in this paper we propose for the first time the application of a multivariate approach to carry out the study. The optimized conditions were as follows: preinjection plug of water for 7 s at 50 mbar, electrokinetic injection for 40 s at 6.2 kV, and 32 microm of H3PO4 in the sample solvent. Also, a solid-phase extraction (SPE) procedure is developed to obtain low detection limits and an adequate selectivity for urine samples. The combination of SPE and FASI-CZE-UV allows adequate linearities and recoveries, low detection limits (from 2 to 5 ng/mL), and satisfactory precisions (3.0-7.2% for an intermediate RSD %).     

CuSO<Subscript>4</Subscript> as a Mild,Green, and Efficient Catalyst for the One-pot Conversion of <Emphasis Type="Italic">THP</Emphasis> Ethers to Acetates

Summary. An efficient direct conversion of THP ethers into the corresponding acetates was achieved with acetic anhydride in the presence of CuSO₄ · 5H₂O as an available and green catalyst in high yields.     

Stereospecific synthesis of 1,2-cis glycosides by vinyl-mediated IAD

[reaction: see text] Stereospecific 1,2-cis glycosylation of 2-O-vinyl thioglycosides, synthesized from the corresponding alcohols by Ir-catalyzed transvinylation with vinyl acetate, is achieved by iodine-mediated tethering of a range of primary and secondary carbohydrate acceptors, followed by intramolecular aglycon delivery (IAD). The use of such an intramolecular glycosylation strategy furnishes the desired alpha-gluco and beta-manno disaccharides in an entirely stereoselective manner.     

Enaminones in heterocyclic synthesis: Synthesis and chemical reactivity of 3‐anilino‐1‐substituted‐2‐propene‐1‐ one

The 3‐anilinoenones 3a,b were prepared from the corresponding 3‐dimemyl‐aminopropenones. The reactivity of 3a,b towards a variety of carbon and nitrogen nucleophiles as well as naphthoquinones is reported.     

Ability of porous graphitic carbon to support electroosmotic flow in capillary electrochromatography

The existence of a cathodic EOF (electroosmotic flow) in the case of a porous graphitic carbon (PGC) partially packed column has been demonstrated. Then, the ability of PGC to afford electroosmosis has been brought to the fore with a fully PGC packed column. Experimental data have shown that PGC particles are negatively charged and their electrophoretic mobility has been evaluated. In order to investigate the conditions of existence of EOF different mobile phases have been tested. An EOF occurs when the conductivity of the PGC packed column is larger than the conductivity of an empty fused-silica capillary operating in the same conditions i.e. when the PGC participates in the electric conduction. Since the local electric fields in the two segments of the column are different, an evaluation of the electroosmotic mobility is not possible and the effect of the operational parameters such as the composition of the mobile phase (acetonitrile ratio and total ionic strength) has been studied in term of electroosmotic velocity V(eo).     

New many fold 1,2,3‐selenadiazole aromatic derivatives

The many fold aromatic ketones 2a‐d are versatile compounds for the synthesis of the many fold 1,2,3‐selenadiazole aromatic derivatives 5a‐d . The preparation starts with the reaction between the many fold bromomethylene benzene derivatives 1a‐d and 4‐hydroxyacetophenone, which are transformed through the reaction with semicarbazide hydrochloride or ethylhydrazine carboxylate into the corresponding semicarbazones derivatives 3a‐d or hydrazones 4a‐d . The reaction with selenium dioxide leads to regiospecific ring closure of semicarbazones or hydrazones to give the many fold 1,2,3‐selenadiazole aromatic derivatives in high yield.     

Optimization of a GFAAS method for determination of total inorganic arsenic in drinking water

The new 10 μg l⁻¹ arsenic standard in drinking water has been a spur to the search for reliable routine analytical methods with a limit of detection at the μg l⁻¹ level. These methods also need to be easy to handle due to the routine analyses that are required in drinking water monitoring. Graphite furnace atomic absorption spectrometry (GFAAS) meets these requirements, but the limit of detection is generally too high except for methods using a pre-concentration or separation step. The use of a high-intensity boosted discharge hollow-cathode lamp decreases the baseline noise level and therefore allows a lower limit of detection. The temperature program, chemical matrix modifier and thermal stabilizer additives were optimized for total inorganic arsenic determination with GFAAS, without preliminary treatment. The optimal furnace program was validated with a proprietary software. The limit of detection was 0.26 μg As l⁻¹ for a sample volume of 16 μl corresponding to 4.2 pg As. This attractive technique is rapid as 20 samples can be analysed per hour. This method was validated with arsenic reference solutions. Its applicability was verified with artificial and natural groundwaters. Recoveries from 91 to 105% with relative standard deviation <5% can be easily achieved. The effect of interfering anions and cations commonly found in groundwater was studied. Only phosphates and silicates (respectively at 4 and 20 mg l⁻¹) lead to significant interferences in the determination of total inorganic arsenic at 4 μg l⁻¹.