Electrochromic materials are characterized by their colour changes upon applied voltage. Colour can mean many things: a certain kind of light, its effect on the human eye, or the result of this effect in the mind of the viewer. Since the electrochromic materials are developed towards real life applications it is relevant to characterize them with the usual commercial colour standards. A colorimetric study of electrogenerated Prussian blue and electrogenerated polymers based on salen-type complexes of Cu(II), Ni(II) and Pd(H) deposited over transparent flexible electrodes of polyethylene terephthalate coated with indium tin oxide (PET/ITO electrodes) was carried out using the CIELAB coordinates. A cuvette with a designed adapter to allow potentiostatic control was placed on an integrating sphere installed in the sample compartment of a spectrophotometer to run the colorimetric measurements. The colour evolution in situ was measured through the transmittance of the films by potentiostatic control. Chronocoutometry/chronoabsorptometry was used to evaluate maximum coloration efficiencies for the coloration step: 184 (Pd), 161 (Cu) and 83 cm(2)/C (Ni) and for bleaching: 199 (Pd), 212 (Cu) and 173 cm(2)/C (Ni) of the Pd, Cu and Ni polymer films, respectively. The Prussian Blue/Prussian White states over the PET/ITO films were relatively reversible while the reversibility and stability of the polymers based on the metals salen-type complexes depends on the metal, Pd being the most stable. (c) 2008 Elsevier B.V. All rights reserved.

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Progresses made in bacterial genome sequencing show a remarkable profusion of multiheme c-type cytochromes in many bacteria, highlighting the importance of these proteins in different cellular events. However, the characterization of multiheme cytochromes has been significantly retarded by the numerous experimental challenges encountered by researchers who attempt to overexpress these proteins, especially if isotopic labeling is required. Here we describe a methodology for isotopic labeling of multiheme cytochromes c overexpressed in Escherichia coli, using the triheme cytochrome PpcA from Geobacter sulfurreducens as a model protein. By combining different strategies previously described and using E. coli cells containing the gene coding for PpcA and the cytochrome c maturation gene cluster, an experimental labeling methodology was developed that is based on two major aspects: (i) use of a two-step culture growth procedure, where cell growth in rich media was followed by transfer to minimal media containing 15N-labeled ammonium chloride, and (ii) incorporation of the heme precursor delta-aminolevulinic acid in minimal culture media. The yields of labeled protein obtained were comparable to those obtained for expression of PpcA in rich media. Proper protein folding and labeling were confirmed by UV–visible and NMR spectroscopy. To our knowledge, this is the first report of a recombinant multiheme cytochrome labeling and it represents a major breakthrough for functional and structural studies of multiheme cytochromes.

The biaxial nematic phase was recently observed in different thermotropic liquid crystals, namely bent-core compounds, side-chain polymers, bent-core dimers, and organosiloxane tetrapodes. In this work, a series of experiments with a nematic organosiloxane tetrapode where nuclear magnetic resonance (NMR) spectra are collected while the sample is continuously rotating around an axis perpendicular to the magnetic field, are discussed in conjunction with the analysis of a deuterium NMR experiment on the same system reported earlier. The sample used is a mixture of a deuterated probe with the tetrapode. The mixture exhibits a nematic range between -40 degrees C and 37 degrees C. The results of the two independent, but complementary deuterium NMR experiments confirm the existence of a biaxial nematic phase for temperatures below 0 degrees C with high values of the asymmetry parameter at low temperatures. The presence of slow movements of the tetrapode mesogenic units in the low-temperature regime could also be detected through the analysis of the NMR spectra. Simulations indicate that these movements are mainly slow molecular reorientations of the mesogenic units associated with the presence of collective modes in the nematic phases of this compound. In the case of tetrapodes, recent investigations attribute the origin of biaxiality to the hindering of reorientations of the laterally attached mesogenic units which constitute the tetrapode. This study relates the molecular movements with the nematic biaxial ordering of the system.

We carry out a detailed deuterium nuclear magnetic resonance (NMR) study of local nematic ordering in polydomain nematic elastomers. This system has a close analogy to the random-anisotropy spin glass. We find that, in spite of the quadrupolar nematic symmetry in three dimensions requiring a first-order transition, the order parameter in the quenched "nematic glass" emerges via a continuous phase transition. In addition to this remarkable effect, by a careful analysis of the NMR line shape, we deduce that the local director fluctuations grow in a critical manner around the transition point. This could become an essential experimental evidence for the quenched disorder changing the order of discontinuous transition.

In order to contribute to the understanding of the origin of biaxial nematic ordering in tetrapodes, a deuterium NMR study was performed on mixtures of monomers from organosiloxane tetrapodes with a deuterated nematic probe. Contrary to the tetrapode system previously studied, which exhibits a biaxial nematic phase, the results for monomers are compatible, within the experimental error, with uniaxial nematic ordering in the whole nematic range. The data are in agreement with the conjecture that the nematic biaxial behaviour is related to hindering of the mesogenic units' rotational movements, arising from interdigitation and connection to the central silicon core.

In this letter, we report for the first time the use of a sheet of cellulose-fiber-based paper as the dielectric layer used in oxide-based semiconductor thin-film field-effect transis- tors (FETs). In this new approach, we are using the cellulose– fiber-based paper in an “interstrate” structure since the device is built on both sides of the cellulose sheet. Such hybrid FETs present excellent operating characteristics such as high channel saturation mobility (> 30 cm2/Vs), drain–source current on/off modulation ratio of approximately 104, near-zero threshold voltage, enhance- ment n-type operation, and subthreshold gate voltage swing of 0.8 V/decade. The cellulose-fiber-based paper FETs’ character- istics have been measured in air ambient conditions and present good stability, after two months of being processed. The obtained results outpace those of amorphous Si thin-film transistors (TFTs) and rival with the same oxide-based TFTs produced on either glass or crystalline silicon substrates. The compatibility of these devices with large-scale/large-area deposition techniques and low– cost substrates as well as their very low operating bias delin- eates this as a promising approach to attain high-performance disposable electronics like paper displays, smart labels, smart packaging, RFID, and point-of-care systems for self-analysis in bioapplications, among others.

Three ultrasonic energy sources were studied to speed up the sample treatment for in-solution protein identification by peptide mass fingerprint using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Protein reduction, alkylation, and enzymatic digestion steps were done in 15 min. Nine proteins, including zinc resistance-associated protein precursor from Desulfovibrio desulfuricans strain G20 and split-soret cytochrome c from D. desulfuricans ATCC27774 were successfully identified with the new protocol.

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.

This study describes the characterisation of whey protein hydrolysates obtained from tryptic hydrolysis to assess their application as ingredients with angiotensin-converting-enzyme (ACE) inhibitory action. The levels of a-lactalbumin (alpha-la) and P-lactoglobulin (beta-lg) remaining after hydrolysis were quantified. Peptides were separated by RP-HPLC, and Ala-Leu-Pro-Met-His-Ile-Arg (ALPMHIR), the most potent beta-lg-derived ACE-inhibitory peptide was monitored. A correlation curve was established for the production of this peptide as a function of hydrolysis time. Heat-induced gelation of hydrolysates was studied by small-deformation rheology. The gelation times and the strength of the final gels were highly dependent on the degree of hydrolysis. Smaller peptides liberated by hydrolysis contributed to the inability of whey protein hydrolysates to gel. (c) 2006 Elsevier Ltd. All rights reserved.

Reactive oxygen species (ROS), when in excess, are among the most deleterious species an organism can deal with. The physiological effects of ROS include amino acid chain cleavage, DNA degradation and lipid oxidation, among others. They can be formed in the cytoplasm in a variety of ways, including autooxidation reactions (FMN- and FAD-containing enzymes) and Fenton reactions as a result of the cytoplasmatic pool of iron ions. The superoxide anion (021, despite its short half-life in solution, is particularly pernicious as it can form other reactive ROS (such as the strong oxidant peroxynitrite) or oxidize and/or reduce cellular components. For strict anaerobic or microaerophilic bacteria it is of particular importance to be able to dispose of ROS in a controlled manner, especially if these organisms are temporarily exposed to air. This review aims to describe the structural characteristics of superoxide reductases (SORs) and mechanistic aspects of biological superoxide anion reduction. SORs can be considered the main class of enzymes behind the oxygen detoxification pathway of anaerobic and microaerophilic bacteria. The geometry of the active site (three classes have been described), the possible electron donors in vivo and the current hypothesis for the catalytic mechanism will be discussed. Some phylogenetic considerations are presented, regarding the primary structure of SORs currently available in genome databases. ((c) Wiley-VCH Verlag GmbH \& Co. KGaA, 69451 Weinheim, Germany, 2007).

Amorphous/nanocrystalline silicon pi'ii'n devices fabricated on micromachined glass substrates are integrated with oligonucleotide-derivatized gold nanoparticles for a colorimetric detection method. The method enables the specific detection and quantification of unamplified nucleic acid sequences (DNA and RNA) without the need to functionalize the glass surface, allowing for resolution of single nucleotide differences between DNA and RNA sequences-single nucleotide polymorphism and mutation detection. The detector's substrate is glass and the sample is directly applied on the back side of the biosensor, ensuring a direct optical coupling of the assays with a concomitant maximum photon capture and the possibility to reuse the sensor. (c) 2007 American Institute of Physics.