Biofunctionalization of Polyoxometalates with DNA Primers,Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products

The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW₁₁O₃₉{Sn(CH₂)₂CO}]^8? and [P₂W₁₇O₆₁{Sn(CH₂)₂CO}]^6? have been used to link to a 5′‐NH₂ terminated 21‐mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM‐labeled primers was demonstrated through hybridization with a surface‐immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.     

Water-soluble peptide-coated nanoparticles: control of the helix structure and enhanced differential binding to immune cells

The stabilizing action of C(α)-tetrasubstituted α-amino acids inserted into a sequence of short peptides allowed for the first time the preparation of water-soluble nanoparticles of different materials coated with a helix-structured undecapeptide. This peptide coating strongly favors nanoparticle uptake by human immune system cells.     

Radical-based grafting of GMA on sutures of different nature

Irradiation of a number of different sutures largely employed in the clinical practice with either high energy electrons or with γ-rays followed by quenching with glycidyl methacrylate (GMA) conveniently led to derivatization through a radical-based process. The radicals involved were detected by means of ESR spectroscopy and were characterized on the basis of their ESR spectral parameters which were also found to be consistent with the hfs constants predicted by DFT calculations. Evidence of the GMA derivatization of the sutures was obtained via(13)C CP-MAS NMR spectroscopy, while its extent was evaluated gravimetrically.     

Dynamics of pistachio oils by proton nuclear magnetic resonance relaxation dispersion

A number of pistachio oils were selected in order to test the efficacy of nuclear magnetic resonance relaxation dispersion (NMRD) technique in the evaluation of differences among oils (1) obtained from seeds subjected to different thermal desiccation processes, (2) retrieved from seeds belonging to the same cultivar grown in different geographical areas and (3) produced by using seed cultivars sampled in the same geographical region. NMRD measures relaxation rate values which are related to the dynamics of the chemical components of complex food systems. Results not only allowed to relate kinematic viscosity to relaxometry parameters but also were successful in the differentiation among the aforementioned oils. In fact, from the one hand, the larger the kinematic viscosity, the faster the rotational motions appeared as compared to the translational ones. On the other hand, relaxation rate curves (NMRD) varied according to the oxidative stresses and chemical composition of each sample. The present study showed for the first time that NMRD is a very promising technique for quick evaluations of pistachio oil quality without the need for time-consuming chemical manipulations.     

Experimental studies of surface reactions among OH radicals that yield H2O and CO2 at 40-60 K

We investigated the OH-related formation routes of two astrophysically important molecules, H(2)O and CO(2), under relatively warm astrophysical conditions. OH radicals, together with other neutral species such as H, O, H(2), and O(2), were produced in H(2)O microwave-discharge plasma and cooled to 100 K before being deposited on an Al substrate at 40-60 K. H(2)O formed at 40 and 50 K, but not at 60 K. Taking the experimental conditions into account, a possible route of H(2)O formation is via reactions involving OH + OH, which yield H(2)O(2) as the main reaction product. The present study is the first to show experimentally that surface reactions of two OH radicals can yield H(2)O at low temperatures. The products' branching ratio was 0.2 and 0.8 for H(2)O and H(2)O(2), respectively. When CO was co-deposited with neutral species that formed in the H(2)O plasma, CO(2) was formed at 40-60 K. H(2)CO(3) formed at 40 and 50 K. The present results may suggest that chemical reactions related to OH radicals are effective at yielding various molecules in relatively warm astrophysical environments, such as protostars.     

Changes in the morphology of interstellar ice analogues after hydrogen atom exposure

The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ?(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous.     

Resolution of (R,S)-flurbiprofen catalysed by dry mycelia in organic solvent

Mycelia of Aspergillus oryzae display high enantioselectivity towards (R)-flurbiprofen and can be efficiently used in pure organic solvent for the resolution of (R,S)-flurbiprofen through esterification. The use of the lyophilized mycelia facilitates the separation process so that in one step the two enantiomers of flurbiprofen, which are both valuable for pharmaceutical applications, can be easily separated. The biotransformation can be carried out in different apolar solvents using different primary alcohols as nucleophiles under very mild conditions.     

Determination of hexavalent chromium in welding fumes by GFAAS after liquid anion-exchange separation

Summary The interferences due to the presence of large amounts of atoms such as iron, sodium, cadmium, magnesium and potassium on the ETA-AAS determination of trace amounts of chromium(VI) in welding fumes are discussed. An ion-exchange liquid extraction separation procedure is proposed to overcome these interactions. Results obtained on international standards of welding fumes, distributed in two round robin experiments, are also presented.

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Bestimmung von Chrom(VI) in Schweißereidämpfen nach Abtrennung mit Hilfe eines flüssigen IonenaustauschersUntersuchung der Störungen

     

Signatures of short-range many-body effects in the dielectric function of silicon for finite momentum transfer

We present an investigation of the dynamic structure factor and of the dielectric function epsilonM(Q,omega) of the prototypical semiconductor silicon for finite momentum transfer, combining inelastic x-ray scattering experiments and ab initio calculations. In contrast with optical spectra, for finite momentum transfer time-dependent density-functional theory in the adiabatic local-density approximation together with lifetime broadening describes the physics of valence excitations correctly. Major structures in the spectra, governed by short-range crystal and exchange-correlation local-field effects, are strongly influenced by a mixing of transitions of positive and negative energies, in striking difference to spectra for vanishing momentum transfer. This mixing gives rise to a pronounced Fano asymmetry.     

Glaucopine C, a new diterpene from the fruiting bodies of Sarcodon glaucopus

In this work the mushroom Sarcodon glaucopus was studied. A new cyathane, glaucopine C (1), was isolated from the hexane extract and identified by 1H and 13C NMR spectra analysis. Glaucopine C showed anti-inflammatory acitvity.