Spherical tensor analysis of nuclear magnetic resonance signals

In a nuclear magnetic-resonance (NMR) experiment, the spin density operator may be regarded as a superposition of irreducible spherical tensor operators. Each of these spin operators evolves during the NMR experiment and may give rise to an NMR signal at a later time. The NMR signal at the end of a pulse sequence may, therefore, be regarded as a superposition of spherical components, each derived from a different spherical tensor operator. We describe an experimental method, called spherical tensor analysis (STA), which allows the complete resolution of the NMR signal into its individual spherical components. The method is demonstrated on a powder of a (13)C-labeled amino acid, exposed to a pulse sequence generating a double-quantum effective Hamiltonian. The propagation of spin order through the space of spherical tensor operators is revealed by the STA procedure, both in static and rotating solids. Possible applications of STA to the NMR of liquids, liquid crystals, and solids are discussed.     

Automated multiresidue analysis of pesticides in olive oil by on-line reversed-phase liquid chromatography-gas chromatography using the through oven transfer adsorption-desorption interface

A multiresidue, automated and rapid method for the determination of pesticide residues in olive oil is presented. The method employs the through oven transfer adsorption-desorption interface for the on-line coupling of reversed-phase liquid chromatography and gas chromatography. In this fully automated system, olive oil is directly injected with no sample pre-treatment step other than filtration. Methanol-water is used as eluent in the liquid chromatography pre-separation step. The selected liquid chromatography fraction containing the pesticides is automatically transferred to the gas chromatography. The liquid chromatography column flow during elution is different from the flow during the transfer. Using a flame ionisation detector, pesticide detection limits varied from 0.1 to 0.3 mg/l.     

Effect of Photosensitizer Delivery System and Irradiation Parameters on the Efficiency of Photodynamic Therapy of B16 Pigmented Melanoma in Mice

Abstract— Previous studies (Biolo et al., Photochem. Photobiol. 59, 362-365, 1994) showed that liposome-delivered Si(IV)-na-phthalocyanine (SiNc) photosensitizes B16 pigmented melanoma subcutaneously transplanted in C57 mice to the action of 776 nm light. However, the efficacy of the phototreatment was limited by a lack of selectivity of tumor targeting by SiNc as well as by incomplete necrosis of the neoplastic mass. The present investigations show that the use of a different delivery system (Cremophor emulsion vs liposomes of dipalmitoylphosphatidylcholine) causes no significant increase in the selectivity of tumor targeting for three injected doses of SiNc (0.5, 1, 2 mg/kg). However, upon 776 nm light irradiation (300 mW/cm²; 520 J/cm²), the delay in the rate of tumor growth was maximal (7-8 days) for the highest naphthalocyanine dose. On the other hand, a remarkable improvement in the tumor response was obtained by inducing an intratumoral temperature increase to 44°C immediately after PDT. The thermal effect appeared to be due to photoexcitation of melanin by 776 nm light (550 mW/cm²; 520 J/cm²) and subsequent partial conversion of absorbed energy into heat.     

Optimization of the separation of a group of antifungals by capillary zone electrophoresis

Two simple, rapid, and efficient methods for the analysis of seven antifungal compounds have been developed by capillary zone electrophoresis. Resolutions higher than 1.5 were obtained using 0.025 M phosphate buffer (pH 2.30) (analysis time close to 9 min) or 0.2 M formic acid (pH 2.15) (analysis time close to 6 min), with an applied voltage of 20 kV and a temperature of 30 degrees C. The highest sensitivity and selectivity can be obtained using phosphate buffer but the shortest analysis times are achieved in the formic system. The analytical characteristics of the optimized methods were investigated. The reproducibility obtained for migration times (RSD(n = 10) < or = 1.0%) and peak areas (RSD(n = 10) < or = 4.3%) was acceptable, but better reproducibilities were obtained when verapamil was used as internal standard (RSD(n = 10) < 0.4% for relative migration times and RSD(n = 10) < or = 2.2% for peak area ratios). The lowest limit of detection was obtained for clotrimazole (0.12 microg/ml) and the highest for fluconazole and voriconazole (0.90 microg/ml). The lowest and the highest limits of quantitation were, respectively, 0.40 microg/ml for clotrimazole and 3.00 microg/ml for fluconazole and voriconazole.     

13C hyperfine coupling constants in o-benzosemiquinones

The ¹³C hyperfine splitting constants of the tetrachloro-o-benzosemiquinone radical anion are measured for naturally occurring ¹³C nuclei in all the possible positions in the molecule. Their assignment is based on the linewidth analysis of the single hyperfine components and this is discussed with reference to the reported spin density distribution in o-semiquinones.     

An efficient synthesis of 6-formyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid and some carbonyl derivatives of it and its 6-acetyl homologue

Starting with 1,1-dimethoxy-2-propanone ( 1 ), 6-formyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid ( 5a ) has been prepared in large quantities by a highly efficient, 4-step synthesis. This compound, along with its one carbon homologue, 6-acetyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acid ( 5b ) has been reacted with several carbonyl derivative forming reagents to provide a series of side chains for β-lactams. Among these carbonyl derivatives are styrylamides which were prepared from Wittig and Horner-Emmons reagents. The preparation of the phosphonium salts and phosphonate esters is also described.     

Determination of molybdenum by atomic-absorption spectrometry after separation by 5,5'-methylenedisalicylohydroxamic acid extraction and further reaction with thiocyanate and tin (II)

A method is described for the determination of molybdenum down to the microgram level, in samples of soil, steels, fertilizers and pharmaceuticals. After attack with acids, this element is separated from matrix elements by extraction of its 5,5'-methylenedisalicylohydroxamic acid (MEDSHA) complex from 4M hydrochloric acid, into methyl isobutyl ketone. Molybdenum is determined by atomic-absorption spectrometry (AAS), after conversion of the Mo-MEDSHA complex into the MoSCN(-) complex in the organic phase. The detection limit is 0.03 microg/ml, with a relative standard deviation not exceeding 1.5% at a level of 2 microg/ml. The method is highly selective and suffers only from interference by tungsten.     

Benzocoumarins from the rhizomes of Juncus acutus

Investigation of the ethyl acetate extract of Juncus acutus rhizomes revealed seven benzocoumarins, probably derived from oxidation of phenanthrenes already isolated from the plant. The structures were determined by means of spectroscopic methods. The anti-algal activity of the isolated compounds tested on the green alga Pseudokirchneriella subcapitata are reported here.     

Preparative high-performance liquid chromatography of peptides on a new reversed-phase packing material, Kromasil C18

Preparative reversed-phase high-performance liquid chromatography has found wide use in the production of peptides for pharmaceutical formulations. Purity of the substance and overall economy of the chromatographic system are the most important criterias. In this sense optimized, silica particles and production process with capability to separately control parameters important to chromatography, are essential to high-performance chromatography. Kromasil C18 packing material was tested and evaluated in respect of its selectivity, flow and pressure properties, resolution, load capacity, recovery, adsorption effects, mechanical strength and chemical degradation.