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Electric field induced desorption of bacteria from a conditioning film covered substratum.

Desorption of three oral bacterial strains from a salivary conditioning film on an indium tin oxide electrode during application of a positive (bacterial adhesion to the anode) or a negative electric current was studied in a parallel plate flow chamber. Bacterial adhesion was from a flowing suspension of high ionic strength, after which the bacterial suspension was replaced by a low ionic strength solution without bacteria and currents ranging from -800 to +800 microA were applied. Streptococcus oralis J22 desorbed during application of a positive and negative electric current with a desorption probability that increased with increasing electric current. Two actinomyces strains, however, could not be stimulated to desorb by the electric currents applied. The desorption forces acting on adhering bacteria are electroosmotic in origin and working parallel to the electrode surface in case of a positive current, whereas they are electrophoretic and electrostatic in origin and working perpendicular to the surface in case of a negative current. By comparison of the effect of positive and negative electric currents, it can be concluded that parallel forces are more effective in stimulating bacterial desorption than perpendicular forces. The results of this study point to a new pathway of cleaning industrial and biomedical surfaces without the use of detergents or biocides.

Actinomyces↗

Electrochemical optical waveguide lightmode spectroscopy (EC-OWLS): a pilot study using evanescent-field optical sensing under voltage control to monitor polycationic polymer adsorption onto indium tin oxide (ITO)-coated waveguide chips.

A new technique has been developed that combines evanescent-field optical sensing with electrochemical control of surface adsorption processes. This new technique, termed "electrochemical optical waveguide lightmode spectroscopy" (EC-OWLS), proved efficient in monitoring molecular surface adsorption and layer thickness changes of an adsorbed polymer layer examined in situ as a function of potential applied to a waveguide in a pilot study. For optical sensing, a layer of indium tin oxide (ITO) served as both a high-refractive-index waveguide and a conductive electrode. In addition, an electrochemical flow-through fluid cell was provided, which incorporated working, reference, and counter electrodes, and was compatible with the constraints of optical sensing. Poly(L-lysine)-grafted-poly(ethylene glycol) (PLL-g-PEG) served as a model, polycation adsorbate. Adsorption of PLL-g-PEG from aqueous buffer solution increased from 125 to 475 ng/cm(2 )along a sigmoidal path as a function of increasing potential between 0 and 1.5 V versus the Ag reference electrode. Upon buffer rinse, adsorption was partially reversible when a potential of >/=0.93 V was maintained on the ITO waveguide. However, reducing the applied potential back to 0 V before rinsing resulted in irreversible polymer adsorption. PLL-g-PEG modified with biotin demonstrated similar adsorption characteristics, but subsequent streptavidin binding was independent of biotin concentration. Applying positive potentials resulted in increased adsorbed mass, presumably due to polymer chain extension and reorganization in the molecular adlayer.

Adsorption↗

Functionalizing nanocrystalline metal oxide electrodes with robust synthetic redox proteins.

De novo designed synthetic redox proteins (maquettes) are structurally simpler, working counterparts of natural redox proteins. The robustness and adaptability of the maquette protein scaffold are ideal for functionalizing electrodes. A positive amino acid patch has been designed into a maquette surface for strong electrostatic anchoring to the negatively charged surfaces of nanocrystalline, mesoporous TiO(2) and SnO(2) films. Such mesoporous metal oxide electrodes offer a major advantage over conventional planar gold electrodes by facilitating formation of high optical density, spectroelectrochemically active thin films with protein loading orders of magnitude greater (up to 8 nmol cm(-2)) than that achieved with gold electrodes. The films are stable for weeks, essentially all immobilized-protein display rapid, reversible electrochemistry. Furthermore, carbon monoxide ligand binding to the reduced heme group of the protein is maintained, can be sensed optically and reversed electrochemically. Pulsed UV excitation of the metal oxide results in microsecond or faster photoreduction of an immobilized cytochrome and millisecond reoxidation. Upon substitution of the heme-group Fe by Zn, the light-activated maquette injects electrons from the singlet excited state of the Zn protoporphyrin IX into the metal oxide conduction band. The kinetics of cytochrome/metal oxide interfacial electron transfer obtained from the electrochemical and photochemical data obtained are discussed in terms of the free energies of the observed reactions and the electronic coupling between the protein heme group and the metal oxide surface.

Crystallization↗

Controlled nanozeolite-assembled electrode: remarkable enzyme-immobilization ability and high sensitivity as biosensor.

An enzyme-immobilized nanozeolite-assembled electrode was prepared by controlled assembly of nanometer-sized Linder type-L zeolite (nano-LTL-zeolite) on an indium tin oxide (ITO) glass electrode surface, and subsequent immobilization of cytochrome c. Cyclic voltammetric (CV) and amperometric experiments showed that, relative to other reported electrodes, the enzyme-immobilized electrodes possess fast electron-transfer rates (2.2 s(-1)), a broad linear range (15-540 micromol L(-1)), a low detection limit (3.2 nmol L(-1)), a remarkably long lifetime (5 months), and high stability in the pH range 5-10. These characteristics could be due to the fact that nanozeolites assembled on ITO have high immobilization ability and facilitate interaction with enzymes. The function controllability of these enzyme electrodes, resulting from the facile manipulability of nanozeolite-assembled layers, may provide a possibility to rationally design biosensors.

Biosensing Techniques↗

Efficient charge injection from the S2 photoexcited state of special-pair mimic porphyrin assemblies anchored on a titanium-modified ITO anode.

A novel surface fabrication methodology has been accomplished, aimed at efficient anodic photocurrent generation by a photoexcited porphyrin on an ITO (indium-tin oxide) electrode. The ITO electrode was submitted to a surface sol-gel process with titanium n-butoxide in order to deposit a titanium monolayer. Subsequently, porphyrins were assembled as monolayers on the titanium-treated ITO surface via phosphonate, isophthalate, and thiolate groups. Slipped-cofacial porphyrin dimers, the so-called artificial special pair at the photoreaction center, were organized through imidazolyl-to-zinc complementary coordination of imidazolylporphyrinatozinc(II) units, which were covalently immobilized by ring-closing olefin metathesis of allyl side chains. The modified surfaces were analyzed by means of X-ray photoelectron spectroscopy. Photoirradiation of the porphyrin dimer generated a large anodic photocurrent in aqueous electrolyte solution containing hydroquinone as an electron sacrificer, due to the small reorganization energy of the dimer. The use of different linker groups led to significant differences in the efficiencies of anodic photocurrent generation. The apparent flat-band potentials evaluated from the photocurrent properties at various pH values and under biased conditions imply that the band structure of the ITO electrode is modified by the anchoring species. The quantum yield for the anodic photocurrent generation by photoexcitation at the Soret band is increased to 15 %, a surprisingly high value without a redox cascade structure on the ITO electrode surface, while excitation at the Q band is not so significant. Extensive exploration of the photocurrent properties has revealed that hot injection of the photoexcited electron from the S2 level into the conduction band of the ITO electrode takes place before internal conversion to the S1* state, through the strong electronic communication of the phosphonyl anchor with the sol-gel-modified ITO surface.

Dimerization↗

Glycosidation-anomerisation reactions of 6,1-anhydroglucopyranuronic acid and anomerisation of beta-D-glucopyranosiduronic acids promoted by SnCl(4).

The reaction of silylated nucleophiles with 6,1-anhydroglucopyranuronic acid (glucuronic acid 6,1-lactones) catalysed by tin(IV) chloride provides 1,2-trans or 1,2-cis (deoxy)glycosides in a manner dependent on the donor structure. The alpha-glycoside was obtained for reactions of the donor with the 2-acyl group and 2-deoxydonors, whereas the 2-deoxy-2-iodo donor gave the beta-glycoside. Experimental evidence shows that when 1,2-cis-glycoside formation occurs, the anomerisation of initially formed 1,2-trans-glycosides catalysed by SnCl(4) is possible. The anomerisation of beta-D-glucopyranosiduronic acids was found to be faster, in some cases, than anomerisation of related beta-D-glucopyranosiduronic acid esters and beta-D-glucopyranoside derivatives and the rates are dependent on the structure of the aglycon. Moreover, the rates of anomerisation of beta-D-glucopyranuronic acid derivatives can be qualitatively correlated with rates of hydrolysis of beta-D-glucopyranosiduronic acids. Mechanistic possibilities for the reactions are considered.

Glycosylation↗

Prolactin increases HO-1 expression and induces VEGF production in human macrophages.

The pituitary hormone prolactin (PRL) is a multifunctional polypeptide which exerts a role on cell proliferation and may also contribute to cell differentiation. PRL is also produced by immune cells and is regarded as a key component of the neuroendocrine-immune loop and as a local regulator of macrophage response. The involvement of PRL in regulating monocyte/macrophage functions is suggested by the presence of PRL receptors in these cells. It has been shown that PRL possess both angiogenic and antiangiogenic effects. Recently, we revealed that augmentation of HO-1 activity enhances PRL-mediated angiogenesis in human endothelial cells. Since macrophages are key participants in angiogenesis our objective was to investigate the effect of PRL also in human macrophages. In vitro treatment of macrophages with PRL was found to increase both heme oxygenase-1 (HO-1) expression and protein synthesis in a time and dose dependent manner as quantified respectively by reverse-transcriptase real-time polymerase chain reaction and Western blot analysis. PRL-treated macrophages also showed an enhanced release of vascular endothelial growth factor (VEGF) as demonstrated by ELISA assay. Furthermore, to determine whether PRL-induced HO-1 activity was required for VEGF production by macrophages, the effect of PRL on the induction of VEGF was studied in the presence of an inducer stannic chloride (SnCl(2)) and of an inhibitor stannic mesoporphyrin (SnMP) of HO activity. Our observations suggest that PRL may regulate monocyte activation and influences not only immune function but also angiogenesis.

Blotting, Western↗

Tailor-made nanoparticles via gas-phase synthesis.

Gas-phase synthesis is a well-known chemical manufacturing technique for an extensive variety of nanoscale particles. Since the potential of ultrafine and, in particular, nanoscale particles in high-performance applications has been identified, scientific and commercial interest has increased immensely, thus identifying this field as a most important technology of the future. However, nanomaterials can perform their multifunctional tasks only if they are customized in terms of chemical composition, size, and morphology to suit the application at hand. Profound knowledge of the synthesis and precise process control is crucial in meeting the stringent specifications. Although the gas-phase synthesis of ultrafine materials has been known and commercially exploited for decades, existing knowledge is based almost exclusively on empirical know-how. Process simulation is a very suitable tool for expanding the understanding of the synthesis-relevant processes, particle formation mechanisms, and operating parameters. Based on the resulting expertise some special nanoscale gas-phase products of high innovative potential have been developed.

Electric Conductivity↗

Thermally driven interfacial dynamics of metal/oxide bilayer nanoribbons.

Solid-solid interfacial processes greatly affect the performance of electronic and composite materials, but probing the dynamics of buried interfaces is challenging and often involves lengthy or invasive sample preparation. We show that bilayer nanoribbons-made here of tin dioxide and copper-are convenient structures for observing as-made interfaces as they respond to changing temperature in a transmission electron microscope (TEM). At low temperatures (<200 degrees C), differential thermal expansion causes the bilayers to bend when heated or cooled, with the motion determined by the extent of Cu-SnO(2) epitaxy. At higher temperatures, we are able to watch-in real time and with nanometer resolution-a progression of grain growth, interdiffusion, island formation, solid-state chemical reactions, and melting. This novel TEM geometry is readily applicable to other nanoribbon/coating combinations and is well suited to observing interfacial phenomena driven thermally or by the application of mechanical, electrical, or magnetic forces.

Alloys↗

Beaklike SnO2 nanorods with strong photoluminescent and field-emission properties.

Beaklike SnO2 nanorods were synthesized by a vapor-liquid-solid approach using Au as a catalyst. The nanorods grow along the [10 1] direction and the beak is formed by switching the growth direction to [1 12] through controlling the growth conditions at the end of the synthesis. The photoluminescence (PL) spectrum of the nanorods exhibits visible light emission with a peak at 602 nm. The field-emission (FE) properties of the nanorods have been measured to exhibit a turn-on field of 5.8 V microm(-1). A comparative study of FE measurements between SnO2 nanorods with uniform diameters and these beaklike nanorods suggests that the shape and curved tips are important factors in determining the FE properties.

Crystallization↗