Hexachloroantimonate(V) mit Nitroderivaten als Liganden, 3. Mitt.: Komplexe Verbindungen mit dreiwertigen Metallen

Complex compounds of trivalent metal chlorides (AlCl₃, CrCl₃, FeCl₃) are described, which had been obtained in a double complexation reaction in CCl₄ as a solvent with nitro compounds and SbCl₅:M ^III(C₆H₅NO₂) _m (SbCl₆)₃ (m=3,6),M ₂ ^III(C₆H₅NO₂)₄(SbCl₆)₄ and Al(-C₁₀H₇NO₂)₃(SbCl₆)₃. Synthesis, analytical results and i.r. spectra are discussed.     

Bioanalysis of pentoxifylline and related metabolites in plasma samples through LC‐MS/MS

Analytical aspects related to the assay of pentoxifylline (PTX), lisofylline (M1) and carboxypropyl dimethylxanthine (M5) metabolites are discussed through comparison of two alternative analytical methods based on liquid chromatography separation and atmospheric pressure electrospray ionization tandem mass spectrometry detection. One method is based on a ‘pure’ reversed‐phase liquid chromatography mechanism, while the second one uses the additional polar interactions with embedded amide spacers linking octadecyl moieties to the silicagel surface (C‐18 Aqua stationary phase). In both cases, elution is isocratic. Both methods are equally selective and allows separation of unknowns (four species associated to PTX, two species associated to M1) detected through specific mass transitions of the parent compounds and owning respective structural confirmation. Plasma concentration–time patterns of these compounds follow typical metabolic profiles. It has been advanced that in‐vivo formation of conjugates of PTX and M1 is possible, such compounds being cleaved back to the parent ones within the ion source. The first method was associated with a sample preparation procedure based on plasma protein precipitation by strong organic acid addition. The second method used protein precipitation by addition of a water miscible organic solvent. Both analytical methods were fully validated and used to assess bioequivalence between a prolonged release generic formulation and the reference product, under multidose and single dose approaches. Copyright © 2009 John Wiley & Sons, Ltd.     

Dielectric properties and thermal stability of γ-irradiated inorganic nanofiller modified PVC

The dielectric characteristics of polyvinyl chloride nanocomposites containing titania, silica and alumina at the concentration of 5% were investigated by dielectric spectroscopy. The sharp modification in the permittivity and dielectric loss of neat and irradiated PVC samples over the low frequency range may be explained by the interaction between external electrical field and the dipoles formed during high energy exposure. The material characterization is completed by the thermal stability assay based on the accumulation of carbonyl units in the sample matrices, which provides the differences in the molecular level contact between host polymer and fillers.     

New basic catalysts obtained from layered double hydroxides nanocomposites

A new route for the preparation of basic mixed oxides using nanocomposite precursors obtained from layered double hydroxides (LDH) was investigated. These nanocomposites have been prepared by intercalation of negatively charged guest entities containing Ca²⁺, Sr²⁺, Ba²⁺ or La³⁺ cations in the interlayer space of host Mg/Al LDH by anionic exchange. The guest entities have been previously prepared by complexation of the required cations in the presence of edta or citrate chelating anions. Intercalation of [Mⁿ⁺(edta)]^(4?n)? or [La(cit)OH]^? complexes is proved by elemental analysis, XRD analysis and FT-IR spectroscopy. However, in order to satisfy the charge equilibrium in the materials, (edta)^4? and (citrate)^3? species are also co-intercalated in the nanocomposites. The basic properties of the mixed oxides obtained after thermal decomposition of the nanocomposites precursors were evaluated in the disproportionation of 2-methyl-3-butyn-2-ol (MBOH) and the transesterification of 1-phenylethanol with diethylcarbonate (DEC). The Sr- and Ba-containing mixed oxides exhibit basicity close to the one of MgO and Mg(La)O mixed oxides. A comparative study of the reactivity of La-containing mixed oxides obtained following different preparation routes, i.e. coprecipitation or anionic exchange, allows to conclude that the nanocomposite route led to the most active samples.     

Synthesis of Enantiopure Sulfonimidamides and Elucidation of Their Absolute Configuration by Comparison of Measured and Calculated CD Spectra and X‐Ray Crystal Structure Determination

Straightforward syntheses of enantiopure N‐benzoyl‐ and N‐tert‐butyloxycarbonyl‐protected sulfonimidamides, which can be used as building blocks in newly designed catalysts, are presented. Key synthetic step is a dynamic resolution of a racemic sulfinic acid sodium salt. All subsequent transformations proceed stereospecifically. The absolute configurations at the sulfur atoms of both sulfonimidamides were determined by comparison of measured and calculated CD spectra. An X‐ray crystal structure determination of a sulfonimidoylguanidine derivative confirmed this result.     

Microfluidics in macro-biomolecules analysis: macro inside in a nano world

Use of microfluidic devices in the life sciences and medicine has created the possibility of performing investigations at the molecular level. Moreover, microfluidic devices are also part of the technological framework that has enabled a new type of scientific information to be revealed, i.e. that based on intensive screening of complete sets of gene and protein sequences. A deeper bioanalytical perspective may provide quantitative and qualitative tools, enabling study of various diseases and, eventually, may offer support for the development of accurate and reliable methods for clinical assessment. This would open the way to molecule-based diagnostics, i.e. establish accurate diagnosis and disease prognosis based on identification and/or quantification of biomacromolecules, for example proteins or nucleic acids. Finally, the development of disposable and portable devices for molecule-based diagnosis would provide the perfect translation of the science behind life-science research into practical applications dedicated to patients and health practitioners. This review provides an analytical perspective of the impact of microfluidics on the detection and characterization of bio-macromolecules involved in pathological processes. The main features of molecule-based diagnostics and the specific requirements for the diagnostic devices are discussed. Further, the techniques currently used for testing bio-macromolecules for potential diagnostic purposes are identified, emphasizing the newest developments. Subsequently, the challenges of this type of application and the status of commercially available devices are highlighted, and future trends are noted.     

Microorganism response to atmospheric pressure helium plasma DBD treatment

The effect of an atmospheric pressure plasma dielectric barrier discharge on some microorganisms was investigated, due to the possible extent of plasma applications in controlling microbial contamination. The present investigation involved both Gram-positive and Gram-negative germs – bacteria and yeasts – treated in helium plasma (asymmetric dielectric barrier discharge) for various time durations between 25 s and 100 s. Circular growth inhibition zones were measured for two distances between the discharge electrodes, the correlations with the plasma treatment time being analyzed. Differences between the sensitivities of the four tested microorganisms to helium plasma in open atmosphere were discussed.     

Chemiluminescence study on the oxidation of several polyolefins—I. Thermal-induced degradation of additive-free polyolefins

Chemiluminescence (CL) has been applied to evaluate the oxidation susceptibility of various polyolefins: low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and isotactic polypropylene (i-PP). The intensity of CL emission in inert atmosphere could be related to the previous oxidation level. The thermal stability at 170 °C of the hydroperoxides in LDPE seems to be lower than that in LLDPE or HDPE. The kinetic parameters of the oxidation at 170 °C in oxygen, calculated from CL data, suggest the following stability order: HDPE > LLDPE > LDPEi-PP. The intensity of CL emission was related to the CH₃ content as evaluated by Fourier transform infra-red spectroscopy.     

Jets of nuclear matter in He-A T inelastic collisions at 4.5 A GeV/c

The problem of the nuclear matter jets in nucleus-nucleus collisions at 4.5 A GeV/c is discussed. The global analysis of experimental data, namely the sphericity tensor, is used to evidence such jets. The experimental results are compared with those obtained in the same collisions for hydrodynamic flow and thrust. The experiments have been performed in the frame of the SKM 200 Collaboration from JINR Dubna. Received: 20 March 1997 / Revised version: 20 July 1997