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Various S = 3/2 EPR signals elicited from wild-type and variant Azotobacter vinelandii nitrogenase MoFe proteins appear to reflect different conformations assumed by the FeMo-cofactor with different protonation states. To determine whether these presumed changes in protonation and conformation reflect catalytic capacity, the responses (particularly to changes in electron flux) of the alpha H195Q, alpha H195N, and alpha Q191 K variant MoFe proteins (where His at position 195 in the alpha subunit is replaced by Gln/Asn or Gln at position alpha-191 by Lys), which have strikingly different substrate-reduction properties, were studied by stopped-flow or rapid-freeze techniques. Rapid-freeze EPR at low electron flux (at 3-fold molar excess of wild-type Fe protein) elicited two transient FeMo-cofactor-based EPR signals within 1 s of initiating turnover under N-2 with the alpha H195Q and alpha H195N variants, but not with the alpha Q191K variant. No EPR signals attributable to P cluster oxidation were observed for any of the variants under these conditions. Furthermore, during turnover at low electron flux with the wild-type, alpha H195Q or alpha H195N MoFe protein, the longer-time 430-nm absorbance increase, which likely reflects P cluster oxidation, was also not observed (by stopped-flow spectrophotometry); it did, however, occur for all three MoFe proteins under higher electron flux. No 430-nm absorbance increase occurred with the alpha Q191K variant, not even at higher electron flux. This putative lack of involvement of the P cluster in electron transfer at low electron flux was confirmed by rapid-freeze Fe-57 Mossbauer spectroscopy, which clearly showed FeMo-factor reduction without P cluster oxidation. Because the wild-type, alpha H195Q and alpha H195N MoFe proteins can bind N-2, but alpha Q195K cannot, these results suggest that P cluster oxidation occurs only under high electron flux as required for N-2 reduction. (C) 2007 Elsevier Inc. All rights reserved.

The simultaneous separation and quantification of two casein peptides (IPP, VPP) presenting potent inhibitory activity of angiotensin-converting-enzyme (ACE) and casein in fermented milks was developed. Gradient elution was carried out at a flow-rate of 1 mL/min, using a mixture of two solvents. Solvent A was 0.1% TFA in water and solvent B was acetonitrile-water-trifluoracetic acid 95:5:0.1. The effluent was monitored by UV detector at 214 nm. Calibration curves were constructed in the interval of 0.01-1.0 mg/mL for VPP, 0.005-1.0 mg/mL for IPP, and 0.05-3.0 mg/mL for casein. R 2 invariably exceeded 0.999. The detection limits were 0.004 for VPP, 0.002 mg/mL for IPP, and 0.02 mg/mL for casein. Repeatability of the method was evaluated by six consecutive injections of two standard solutions containing VPP, IPP, and casein. The RSD values for concentration were all below 5.08%. Recovery studies were carried out to determine the accuracy of the method. Recoveries ranged between 88 and 98.2%. The methodology was applied, not only, for the monitorization of VPP, IPP, and casein in commercial fermented milks labeled as presenting anti hypertensive properties, but also, in milk with different degrees of fermentation by L Helveticus, and in other commercial functional fermented milks, such as, those presenting cholesterol lowering properties.

Indium molybdenum oxide thin films were RF sputtered at room temperature on glass substrates with a reference base pressure of 7.5 × 10- 4 Pa. The electrical and optical properties of the films were studied as a function of oxygen partial pressures (OPP) ranging from 1.5 × 10- 3 Pa to 3.5 × 10- 3 Pa. The obtained data show that the bulk resistivity of the films increased by about 4 orders of magnitude (from 7.9 × 10- 3 to 7.6 × 101 Ω-cm) when the OPP increased from 1.5 × 10-3 to 3.5 × 10- 3 Pa, and the carrier concentration decreased by about 4 orders (from 1.77 × 1020 to 2.31 × 1016 cm- 3). On the other hand, the average visible transmittance of 30.54% of the films (brown colour; OPP = 1.5 × 10- 3 Pa) was increased with increasing OPP to a maximum of 80.47% (OPP = 3.5 × 10- 3 Pa). The optical band gap calculated from the absorption edge of the transmittance spectra ranges from 3.77 to 3.88 eV. Further, the optical and electrical properties of the films differ from those deposited at similar conditions but with a base pressure lower than 7.5 × 10- 4 Pa. © 2007 Elsevier B.V. All rights reserved.

Cork is a natural cellular and electrically insulating material which may have the capacity to store electric charges on or in its cell walls. Since natural cork has many voids, it is difficult to obtain uniform samples with the required dimensions. Therefore, a more uniform material, namely commercial cork agglomerate, usually used for floor and wall coverings, is employed in the present study. Since we know from our previous work that the electrical properties of cork are drastically affected by absorbed and adsorbed water, samples were protected by means of different polymer coatings (applied by spin-coating or soaking). Corona charging and isothermal charging and discharging currents were used to study the electrical trapping and detrapping capabilities of the samples. A comparison of the results leads to the conclusion that the most promising method for storing electric charges in this cellular material consists of drying and coating or soaking with a hydrophobic, electrically insulating polymer such as polytetraflouroethylene (Teflon (R)).

Thin films of molybdenum-doped indium oxide (IMO) were prepared by a 3-source, cylindrical radio-frequency magnetron sputtering at room temperature. The films were post-annealed and were characterized by their structural (X-ray diffraction) and optical (UV-VIS-NIR spectrophotometer) properties. The films were studied as a function of oxygen volume percentage (O2 vol.%) ranging from 3.5 to 17.5. The structural studies revealed that the as-deposited amorphous films become crystalline on annealing. In most cases, the (222) reflection emerged as high intensive peak. The poor visible transmittance of the films as-deposited without oxygen was increased from ∼ 12% to over 80% on introducing oxygen (3.5 O2 vol.%). For the films annealed in open air, the average visible transmittance in the wavelength ranging 400-800 nm was varied between 77 and 84%. The films annealed at high temperatures (> 300 °C) decreased the transmittance to as low as < 1%. The optical band gap of the as-deposited films increased from the range 3.83-3.90 to 3.85-3.98 eV on annealing at different conditions. © 2007 Elsevier B.V. All rights reserved.

Cross-linked polyethylene (XLPE) is currently widely used as an insulating material for power cables due to its good physical properties, however when in use it undergoes an electrical ageing process. Its ability to trap electric charge can give rise to space charge accumulation in the bulk of the polymer and produce localised electric stresses that can lead to cable failure, since the electric field will be increased above the design stress in some regions favouring the initiation of degradation there. In this work the PEA (pulsed electro-acoustic) method was used to compare the charge dynamics in three samples (XLPE cable peelings) aged in different ways (electrothermally in the laboratory, field aged in service and thermally aged in the laboratory). Very different transient behavior was found depending upon the ageing history. This is related to differences in the migration of chemical species in the insulation layer, which are known to act as charge traps. All materials showed heterocharge peaks when the space charge reached stability, the magnitude of which seems to be related to the severity of the ageing.

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Various S = 3/2 EPR signals elicited from wild-type and variant Azotobacter vinelandii nitrogenase MoFe proteins appear to reflect different conformations assumed by the FeMo-cofactor with different protonation states. To determine whether these presumed changes in protonation and conformation reflect catalytic capacity, the responses (particularly to changes in electron flux) of the alpha H195Q, alpha H195N, and alpha Q191 K variant MoFe proteins (where His at position 195 in the alpha subunit is replaced by Gln/Asn or Gln at position alpha-191 by Lys), which have strikingly different substrate-reduction properties, were studied by stopped-flow or rapid-freeze techniques. Rapid-freeze EPR at low electron flux (at 3-fold molar excess of wild-type Fe protein) elicited two transient FeMo-cofactor-based EPR signals within 1 s of initiating turnover under N-2 with the alpha H195Q and alpha H195N variants, but not with the alpha Q191K variant. No EPR signals attributable to P cluster oxidation were observed for any of the variants under these conditions. Furthermore, during turnover at low electron flux with the wild-type, alpha H195Q or alpha H195N MoFe protein, the longer-time 430-nm absorbance increase, which likely reflects P cluster oxidation, was also not observed (by stopped-flow spectrophotometry); it did, however, occur for all three MoFe proteins under higher electron flux. No 430-nm absorbance increase occurred with the alpha Q191K variant, not even at higher electron flux. This putative lack of involvement of the P cluster in electron transfer at low electron flux was confirmed by rapid-freeze Fe-57 Mossbauer spectroscopy, which clearly showed FeMo-factor reduction without P cluster oxidation. Because the wild-type, alpha H195Q and alpha H195N MoFe proteins can bind N-2, but alpha Q195K cannot, these results suggest that P cluster oxidation occurs only under high electron flux as required for N-2 reduction. (C) 2007 Elsevier Inc. All rights reserved.

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The bacterial cytochroine c peroxidases contain an electron-transferring haem c (E) and a peroxidatic haem c (P). Many are isolated in an inactive oxidised state. Reduction of the E baem promotes Ca2+-dependent spin state and coordination changes at the P haem rendering it accessible to ligand. Recent crystallographic work on the oxidised and mixed valence enzymes has suggested a mechanism by which an electron entering the E haem remotely triggers this activation of the P haem. Binding of hydrogen peroxide at the activated P haem leads to an intermediate catalytic form containing two oxidising equivalents, one of which is a ferryl oxene. This form of the enzyme is then reduced by two single electron transfers to the E haem delivered by small redox proteins such as cytochromes or cupredoxins. The binding of these small redox proteins is dominated by global electrostatic forces but the interfaces of the electron transfer complexes that are formed are largely hydrophobic and relatively non-specific. These features allow very high electron transfer rates in the steady state. (c) 2006 Elsevier Inc. All rights reserved.

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Thin films of indium molybdenum oxide (IMO) were rf sputtered onto glass substrates at room temperature. The films were studied as a function of sputtering power (ranging 40-180 W) and sputtering time (ranging 2.5-20 min). Thickness of the films found varied between 50-400 nm. The films were characterized for their structural (XRD), electrical (Hall measurements) and optical (Transmittance spectra) properties. XRD studies revealed that the films are amorphous for the sputtering power ≤ 100 W and deposition time ≤ 5 min. All the other films are polycrystalline and the strongest refection along (222) plane showing a preferential orientation. A minimum bulk resistivity of 2.65 × 10-3 Ω-cm and a maximum carrier concentration of 4.16 × 1020 cm-3 have been obtained for the films sputtered at 180 W (10 min). Whereas maximum mobility (19.5 cm2 V-1 s-1) has been obtained for the films sputtered at 80 W (10 min). A maximum visible transmittance of 90% (500 nm) has been obtained for the films sputtered at 80 W (10 min) with a minimum of 27% for those sputtered at 180 W. The optical band gap of the films found varying between 3.75 and 3.90 eV for various sputtering parameters. © 2006 Materials Research Society.

Thin films of molybdenum doped indium oxide (IMO) were rf sputtered onto glass substrates at room temperature. The films were studied as a function of oxygen volume percentage (OVP) ranging 1.4 - 10.0% in the sputtering chamber. The thickness of the films found varying between 180 and 260 nm. The X-ray diffraction pattern showed the films are polycrystalline with the peaks corresponding to (222) and (400) planes and one among them showing as a preferential orientation. It is observed that the preferred orientation changes from (222) plane to (400) as the OVP increases from 1.4 to 10.0%. The transmittance spectra were found to be in the range of 77 to 89%. The optical band gap calculated from the absorption coefficient of transmittance spectra was around 3.9 eV. The negative sign of Hall coefficient confirmed the films were n-type conducting. The bulk resistivity increased from 2.26×10 -3 to 4.08×-1 Ωcm for the increase in OVP from 1.4 to 4.1%, and thereafter increased dramatically so as the Hall coefficients were not detectable. From the AFM morphologies it is evaluated that the RMS roughness of the films ranges from 0.9 to 3.2 nm. © 2006 Materials Research Society.

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