Effects of substrate polarity and chain length on conformational and thermal properties of phosphonic acid self-assembled bilayers

Conformational and thermal behavior of self-assembled structures of three phosphonic acids, OPA (octadecylphosphonic acid), TPA (tetradecylphosphonic acid), and OcPA (octylphosphonic acid), with different alkyl chain lengths are investigated and compared. The orientation of self-assembled bilayers depends on whether the substrate is nonpolar (graphite) or polar (mica). For nonpolar substrates, bilayers lay parallel to the surface, and for polar substrates, bilayers lay perpendicular to the surface. Thermal behaviors of these structures on mica and graphite are also investigated, showing that, depending on the temperature they are submitted to, molecules stack, unstack, or agglomerate on mica and form larger domains on graphite.     

Synthesis of structurally defined scaffolds for bivalent ligand display based on glucuronic acid anilides. The degree of tertiary amide isomerism and folding depends on the configuration of a glycosyl azide

[structures: see text] Syntheses and structural analyses of bivalent carbohydrates based on anilides of glucuronic acid are described. Secondary anilides predominantly adopted the Z-anti structure; there is also evidence for population of the Z-syn isomer. Bivalent tertiary anilides displayed two signal sets in their NMR spectra, consistent with the presence of (i) a major isomer where both amides have E configurations (EE) and (ii) a minor isomer where one amide is E and the other Z (EZ). Qualitative NOE/ROE spectroscopic studies in solution support the proposal that the anti conformation is preferred for E amides. The crystal structure of one bivalent tertiary anilide showed E-anti and E-syn structural isomers; intramolecular carbohydrate-carbohydrate stacking was observed and mediated by carbonyl-pyranose, azide-azide, and pyranose-aromatic interactions. The EE to EZ isomer ratio, or the degree of folding, for tertiary amides, was greatest for a bivalent compound containing two alpha-glycosyl azide groups; this was enhanced in water, suggesting that hydrophobic interactions are partially but not wholly responsible. Computational methods predicted azide-aromatic (N...H-C interaction) and azide-azide interactions for folded isomers. The close contact of the azide and aromatic protons (N...H-C interaction) was observed upon examination of the close packing in the crystal structure of a related monomer. It is proposed that the alpha-azide group is more optimally aligned, compared to the beta-azide, to facilitate interaction and minimize the surface area of the hydrophobic groups exposed to water, and this leads to the increased folding. The alkylation of bivalent secondary anilides induces a switch from Z to E amide that alters the scaffold orientation. The synthesis of a bivalent mannoside, based on a secondary anilide scaffold, for investigation of mannose-binding receptor cross-linking and lattice formation is described.     

Characterization of wax manufactures of historical and artistic interest

Purpose of this scientific research is the physic and chemical characterization of two historical wax manufactures, made at the end of XIX century by Francesco Bianchi, a papal engraver. The chemical and analytical investigation was necessary to complete and to confirm the restorer's work. The IR Spectroscopy, X-Ray and GC-MS, the best technique to characterise wax, allowed us to obtain the following results. The two manufactures were made with commercial beeswax: in fact, the relative chromatograms showed unchanged peaks about esters of palmitic acid with C24 to C32 alcohol molecules; using standard beeswax we determined the same amount of hydrocarbons present in the wax manufactures. We found several hydrocarbons in these beeswax materials so that it is reasonable to think about successive modifications. ZnO (white zinc), a pigment, was added, probably due to its colour and covering capacity. Sb2S3, Anthimoniun vermilion, a red-orange pigment, was added to these manufactures to give them a soft pink-orange colour. By all used techniques we determined some modifications in the original beeswax; surely they were made to get a more malleable, mouldable, and then more able to be modelled wax.     

Circular dichroism of the photoreceptor pigment oxyblepharismin

Circular dichroism (CD) was used to study the structure of oxyblepharismin (OxyBP), the photoreceptor chromophore for the photophobic response of the blue form of Blepharisma japonicum. Both the chromophore associated to its native protein and the free chromophore in ethanol solution were investigated. CD spectra in the far-UV range indicate that OxyBP induces a slight increase in the alpha-helix content of the protein matrix. CD spectra in the near-UV and visible region of the spectrum show that OxyBP adopts a chiral conformation with a preferential geometry not only when associated to its protein matrix, but also when isolated and dissolved in ethanol. This experimental result is related to the existence of a high-energy interconversion barrier between two enantiomeric structures of the molecule and discussed on the basis of an asymmetric biosynthesis of its precursor, blepharismin.     

Midpoint potentials of hemes a and a3 in the quinol oxidase from Acidianus ambivalens are inverted

The aa3 type B oxygen reductase from the thermophilic archaeon Acidianus ambivalens (QO) was immobilized on silver electrodes and studied by potential-dependent surface-enhanced resonance Raman (SERR) spectroscopy. The immobilized enzyme retains the native structure at the level of the heme pockets and exhibits reversible electrochemistry. From the potential dependence of specific spectral marker bands, the midpoint potentials of hemes a and a3 were unambiguously determined for the first time, being 320 +/- 20 mV for the former and 390 +/- 20 mV for the latter. Both hemes could be treated as independent one-electron Nernstian redox couples, indicating that the interaction potential is smaller than 50 mV. The reversed order of the midpoint potentials compared to those of type A (mitochondrial-like) oxidases, as well as the lack of substantial Coulombic interactions, suggests a different mechanism of electroprotonic energy transduction. In contrast to type A enzymes, a-a3 intraprotein electron transfer in QO is already guaranteed by the order of the midpoint potentials at the onset of enzyme reduction and, therefore, does not require a complex network of cooperativities to ensure exergonicity. In the immobilized state, conformational transitions of the QO a3-CuB active site, which are believed to be essential for proton translocation, are drastically slowed compared to those in solution. We ascribe this finding to the effect of the interfacial electric field, which is of the same order of magnitude as in biological membranes. These results suggest that the membrane potential may play an active role in the regulation of the enzymatic activity of QO.     

Influence of the electrical field applied during thermal cycling on the conductivity of LLDPE/CNT composites

The effect of the electrical field on the conductivity of linear low-density polyethylene/carbon nanotubes/ (LLDPE/CNT) composites during temperature cycling has been investigated. Under applied voltage a positive resistivity temperature coefficient was observed during heating already at low (2–3 wt%) CNT content, followed by a large negative temperature coefficient during cooling whose value depends on the applied voltage. The resistivity values after thermal cycling were markedly lower, while they slightly increased in the absence of an electrical field. The effects of thermal cycling on structural and physical properties of the composites have been evaluated by X-ray diffraction and differential scanning calorimetry.     

Future trends in the market for electrochemical biosensing

Schematic representation of the path that electrochemical biosensing is following in terms of future market trends.

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