Synergy between pyroelectric and photovoltaic effects for optoelectronic nanoparticle manipulation.

The combined action of the pyroelectric (PY) and photovoltaic (PV) effects, exhibited by z-cut LiNbO3:Fe substrates, has been investigated for particle trapping and patterning applications. The novel hybrid procedure provides new possibilities and versatility to optoelectronic manipulation on LiNbO3 substrates. It has allowed obtaining periodic and arbitrary 2D patterns whose particle density distribution is correlated with the light intensity profile but can be tuned through ΔT according to the relative strength of the PV and PY effects. A relevant result is that the PY and PV contributions compete for a ΔT range of 1-20 °C, very accessible for experiments. Moreover, the synergy of the PY and PV has provided two additional remarkable applications: i) A method to measure the PV field, key magnitude for photovoltaic optoelectronic tweezers. Using this method, the minimum field needed to obtain a particle pattern has been determined, resulting relatively high, E~60 kV/cm, and so, requiring highly doped crystals when only using the PV effect. ii) An strategy combining the PY and PV to get particle patterning in samples inactive for PV trapping when the PV field value is under that threshold.

Biocatalytic synthesis of polypyrrole powder, colloids, and films using horseradish peroxidase.

Polypyrrole was synthesized in high yield by a biocatalytic method in mild aqueous media using hydrogen peroxide as oxidizer. A redox mediator, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) diammonium salt, was used to oxidize the pyrrole. ABTS is a very effective peroxidase substrate, which was enzymatically oxidized to generate a radical cation that in turn was able to chemically oxidize pyrrole. This indirect biocatalytic method was implemented because pyrrole is not a substrate of horseradish peroxidase, however, the polymerization process was successfully optimized and later adapted to prepare also polypyrrole thin films and water dispersible polypyrrole colloids. The polypyrrole powder and colloids were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, electrical conductivity, and thermogravimetric analysis. In addition, the deposition of the polypyrrole thin film was monitored using a quartz-crystal microbalance and its morphology studied by optical and scanning electron microscopy. The biocatalytic polymerization of pyrrole results in a polymer spectroscopically very similar to chemically synthesized polypyrrole.

Reactivity of Cl-P(+)-Cl toward cyclic organic ethers.

The dichlorophosphenium ion (Cl-P(+)-Cl) undergoes a variety of reactions with cyclic organic ethers in the gas phase in a Fourier-transform ion cyclotron resonance mass spectrometer. Most of the reactions are initiated by Cl-P(+)-Cl-induced heterolytic C-O bond cleavage. However, the observed final products depend on the exact structure of the ether. For saturated ethers, e.g., tetrahydropyran, tetrahydrofuran, and 2-methyltetrahydrofuran, the most abundant ionic product corresponds to hydroxide abstraction by Cl-P(+)-Cl. This unexpected reaction is rationalized by a multistep mechanism that involves an initial heterolytic C-O bond cleavage accompanied by a 1,2-hydride shift, and that ultimately yields a resonance-stabilized allyl cation and HOPCl2. The process is estimated to be highly exothermic (AM1 calculations yield delta H = -(33-38) kcal mol(-1) for the ethers mentioned above). However, the adducts formed from most of the unsaturated ethers are unable to undergo hydride shifts and hence cannot react via this pathway. In some of these cases, e.g., for 2,5-dihydrofuran and 2,5-dihydro-3,4-benzofuran, the C-O bond heterolysis is followed by oxygen/chlorine exchange to yield the O=PCl radical and a resonance-stabilized carbocation (AM1 calculations yield delta H = -14 kcal mol(-1) for the reaction of 2,5-dihydro-3,4-benzofuran). Hydride abstraction by Cl-P(+)-Cl also yields an abundant product for these two ethers. On the other hand, the ethers with low ionization energies, such as 2,3-dihydrofuran and 2,3-dihydrobenzofuran, react with Cl-P(+)-Cl by electron transfer. Finally, a unique pathway, addition followed by elimination of HCl, dominates the reaction with furan. The observed reactions are rationalized by thermochemical data obtained from semiempirical molecular orbital calculations.

Lifetimes of thermally fixed holograms in LiNbO(3):Fe crystals.

The thermal erasure decay at different temperatures of holographic gratings thermally fixed in iron-doped lithium niobate has been exhaustively studied. An activation energy of 0.94 eV was found to be independent of the grating fringe spacing. At a given temperature the decay time is strongly dependent on the grating spacing. This dependence is well fitted to a square fringe spacing law, as predicted theoretically. From the experimental data the room-temperature hologram lifetime under illumination is extrapolated, giving as a result t(years)=(5.2+/-0.2)?(2) , with the grating spacing ? in micrometers.

Spatial frequency filtering in holographic image reconstruction.

We show that reconstructing a hologram by its object beam leads to spatial filtering, namely, to the suppression of spatial frequency components that are perpendicular to the plane of the recording beams. We conduct experiments by rotating the transparencies of Ronchi gratings and crossed gratings and measuring the corresponding diffraction efficiencies. Good agreement is found with a theory based on image reconstruction with a beam that does not quite satisfy the Bragg condition.

Location of tumoral antigens in L5178Y murine lymphoma cells.

Location of neoplasia specific tumoral antigens (ANE) were investigated in L5178Y murine cells. Cells were treated by means of concanavalin A (CoA), Vibrio cholerae neuraminidase (NVC) or a combination of both (Coa-NVC) and were inactivated by 6,000 rad irradiation. With 5 x 10(6) treated cells four groups, 15 mice in each group of the BALB/c strain were immunized weekly and 10 days latter immunity to L5178Y lymphoma cells was tested by means of intraperitoneal inoculation of 5 x 10(7) intact, viable L5178Y cells. None of the mice immunized with concanavalin A treated and irradiated cells developed the inoculated lymphoma. However all mice immunized with cells treated with CoA or CoA-NVC developed a lymphoma. Electron microscopy studies of normal L5178Y cells, irradiated or treated with NVC showed the exterior cell coating or glycocalix that was absent in those treated with CoA or CoA-CoA-NVC. These results allowed us to conclude that ANE of L5178Y cells susceptible to modification by NVC as if to induce an immunologic rejection response are located in the glycocalix of these cells.