Selenium speciation by coupling vesicle mediated HPLC with off-line ETAAS and on-line focused microwave digestion HG-AAS detection

A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C(18) reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 microg/L of Se. The detection limit using HPLC-"on line" focused microwave digestion-HG-AAS has been found to be 1 microg/L of Se, with a precision (repeatability) better than +/- 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes.     

Surface plasmon resonance biosensor for genetically modified organisms detection

The development of a surface plasmon resonance (SPR) affinity biosensor based on DNA hybridisation is described. This biosensor has been applied to genetically modified organisms (GMOs) detection. Single stranded DNA (ssDNA) probes were immobilised on the sensor chip of an SPR device and the hybridisation between the immobilised probe and the complementary sequence (target) was monitored. The probe sequences were internal to the sequence of 35S promoter and NOS terminator which are inserted sequences in the genome of GMO regulating the transgene expression. The system has been optimised using synthetic oligonucleotides, then applied to real samples analysis. Samples, containing the transgenic target sequences, were amplified by polymerase chain reaction (PCR) and then detected with the SPR biosensor.     

A natural scalar field in the einstein gravitational theory

In a Riemannian space-time, the difference between the third-order tensor potentialH of the Riemann tensor (presented in a precedent paper) and the Lanczos generating function of the Weyl tensor is here shown to be characterized by a vectorV , obtained by contractionH . The significant role of such a vector, in the context of general relativity, is then discussed. Particular attention is paid to the scalar potential which characterizes the irrotational part ofV : such a scalar field satisfies a space-time wave equation of the Poisson type. Weak fields are also considered: in the particular case of a static metric, the scalar is found to be proportional to the classic Newtonian potential.This work was done in the sphere of activity of the C.N.R. Groups for mathematical research.     

Formation of fluorinated nonionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

A structurally related series of fluorinated nonionic oxyethylene glycol surfactants of the type C(m)F(2m+1)(CH(2))(n)O[(CH(2)CH(2)O)(p)H], denoted C(m.n)E(p) (where m=4, 6, or 7, m=1 or 2, and p=4 or 6) were synthesized and their surface behavior in aqueous solution was characterized. The ability of these surfactants to form water-in-hydrofluorocarbon (HFC) propellant 134a microemulsions suitable for use in the aerosolized delivery of water-soluble drugs has been investigated. Phase studies showed that, regardless of the composition used, clear one-phase systems could not be prepared if a fluorinated nonionic surfactant was used alone, or in combination with a short or medium fluorocarbon alcohol cosurfactant. Clear one-phase systems could, however, be prepared if a short-chain hydrocarbon alcohol, such as ethanol, n-propanol, or n-pentanol, was used as cosurfactant, with the extent of the one-phase region increasing with decreased chain length of the alcohol cosurfactant. Light-scattering studies on a number of the hydrocarbon-alcoholcontaining systems in the propellant-rich part of the phase diagram showed that only systems prepared with C(4.2)E(6) and propanol contained microemulsion droplets (all other systems investigated were considered to be cosolvent systems).     

A Schiff base expanded porphyrin macrocycle that acts as a versatile binucleating ligand for late first-row transition metals

The coordination chemistry of the Schiff base polypyrrolic octaaza macrocycle 1 toward late first-row transition metals was investigated. Binuclear complexes with the divalent cations Ni(II), Cu(II), and Zn(II) and with the monovalent cation Cu(I) were prepared and characterized. Air oxidation of the Cu(I) ions in the latter complex to their divalent oxidation state resulted in a change in the coordination mode relative to the macrocycle.     

Fluorinated ionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

The factors influencing the formation of water-in-134a-propellant microemulsions using the fluorinated ionic surfactants ammonium perfluorooctanoate, ammonium perfluoroheptanoate, and sodium perfluorooctanoate has been determined. None of the fluorinated ionic surfactants could be used to prepare clear, one-phase systems when used as sole surfactant, but they could be when combined with a short-chain fluoro- or hydrocarbon alcohol in surfactant:cosurfactant weight-mixing ratios (K(m)) in the range 1:2 to 2:1. When hydrocarbon alcohols were used this clear region extended over a wide range of compositions and was confirmed by means of photon correlation spectroscopy (PCS) to contain microemulsion droplets in the propellant-rich part of the phase diagram. PCS studies performed in the presence of the water-soluble drug terbutaline sulfate showed that it was possible to solubilize the drug within water-in-propellant microemulsion droplets. These studies confirm for the first time that it is possible to prepare water-in-propellant 134a microemulsions using fluorinated ionic surfactants and to solubilize water-soluble drugs within these systems.     

Lipase production by solid-state fermentation

The production of lipase by Penicillium simplicissimum in solid-state fermentation was studied using babassu cake as the basal medium. Tray-type and packed-bed bioreactors were employed. In the former, the influence of temperature; content of the medium, and medium supplementation with olive oil, sugarcane molasses, corn steep liquor, and yeast hydrolysate was studied. For all combinations of supplements, a temperature of 30°C, a moisture content of 70%, and a concentration of carbon source of 6.25% (m/m, dry basis) provided optimum conditions for lipase production. When used as single supplements olive oil and molasses also were able to provide high lipase activities (20 U/g). Using packed-bed bioreactors and molasses-supplemented medium, optimum conditions for enzyme production were air superficial velocities above 55 cm/min and temperatures below 28°C. The lower temperature optimum found for these reactors is probably related to radial heat gradient formation inside the packed bed. Maximum lipase activities obtained in these bioreactors (26.4 U/g) were 30% higher than in tray-type reactors.     

Comparison between preparative methodologies of nanostructured carbon nitride and their use as selective photocatalysts in water suspension

Carbon nitride photocatalysts have been prepared by different methodologies, such as chemical ultrasonic irradiation (sonochemical treatment), hydrothermal and ball milling and thermoexfoliation, and have been used for the selective oxidation of 5-hydroxymethyl-2-furaldehyde (HMF) to form 2,5-furandicarboxyaldehyde (FDC) in water suspension both under UV and natural solar irradiation. The physico-chemical features of the photocatalysts have been studied by X-ray diffraction, infrared spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, scanning electron microscopy, and specific surface area measurements. The results indicate that exfoliation of carbon nitrides can increase the conversion of HMF and the selectivity to FDC. In particular, samples exfoliated by both thermal and acidic ultrasonic irradiation treatments showed the best photocatalytic performance.     

Mild and Efficient Synthesis of Benzo-Fused Seven- and Eight-membered Ring Lactams: A Convenient Approach to Biologically Interesting Chemotypes

A general and efficient method for the synthesis of benzo-fused 7- and 8-membered ring lactams via the Beckmann rearrangement of cyclic oximes is presented.

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