Placement and characterization of pairs of luminescent molecules in spatially separated regions of nanostructured thin films

Methods of making mesostructured sol-gel silicate thin films containing two different molecules deliberately placed in two different spatially separated regions in a one-step, one-pot preparation are developed and demonstrated. When the structure-directing agent is the surfactant cetyltrimethylammonium bromide, the structure is 2-D hexagonal with lattice spacings between 31.6 and 42.1 angstroms depending on the dopant molecules and their concentrations. The three general strategies that are used to place the molecules are philicity (like dissolves like), bonding, and bifunctionality. These strategies take advantage of the different chemical and physical properties of the regions of the films. These regions are the inorganic silicate framework, the hydrophobic organic interior of the micelles, and the ionic interface between them. Luminescent molecules that possess the physical and chemical properties appropriate for the desired strategies are chosen. Lanthanide and ruthenium complexes with condensable trialkoxysilane groups are incorporated into the silicate framework. 1,4-Naphthoquinone, pyrene, rhodamine 6G and coumarin 540A, and lanthanides with no condensable trialkoxysilanes occupy the hydrophobic core of micelles by virtue of their hydrophobicity. The locations of the molecules are determined by luminescence spectroscopy and by luminescence lifetime measurements. In all cases, the long-range order templated into the thin film is verified by X-ray diffraction. The simultaneous placement of two molecules in the structured film and the maintenance of long-range order require a delicate balance among film preparation methodology, design of the molecules to be incorporated in specific regions, and concentrations of all of the species.     

Optical Single-Sideband Modulators and Their Applications

We review our recent work in the implementation of optical single-sideband (OSSB) modulation and in the application of this modulation format to microwave photonics and optical testing systems. We have developed an enhanced OSSB modulator for wide-band operation, the so-called bidirectional OSSB modulator, and a simplification of this scheme for narrow-band applications. These OSSB modulators are based on the use of a standard single-electrode Mach-Zehnder electro-optic modulator (MZ-EOM) and passive fiber-optic components. In both designs, the OSSB operation is shown to be independent of the MZ-EOM bias. Therefore, the optical modulation depth at the output of the device can be enhanced using minimum transmission biasing to provide suppression of the optical carrier. Finally, we demonstrate the application of OSSB modulators to the improvement of microwave/millimeter-wave subcarrier multiplexing fiber-optic links and to narrow-band fiber radio systems. In addition, we analyzed the feasibility and the limitations of an optical vector network analysis technique based on OSSB modulation that can provide sub-picometer wavelength resolution.     

Characterization of the surface structure of gold nanoparticles and nanorods using structure sensitive reactions

The surface structure of gold nanorods has been determined by studying the behavior of electrochemical reactions sensitive to the structure and compared to that obtained by other structure characterization techniques. Lead underpotential deposition (UPD) reveals that the surface of the nanorods is composed by (111) and (110) domains, while (100) domains are practically absent from the surface. In the case of the oxygen reduction reaction, the formation of hydrogen peroxide as a final product of the reaction in the whole potential range also indicates that (100) domains are absent on the surface of the nanoparticles, corroborating the previous result. These results are compared with other surface structure information provided by other techniques.     

Polarity effects on ZnO films grown along the nonpolar [1120] direction

The surface electrical properties of ZnO thin films grown along the nonpolar [1120] direction have been investigated by Kelvin probe microscopy on a nanometer scale. Two different charge domains, with a 75 meV work function difference, coexist within the ZnO surface, which is covered by rhombohedral pyramids whose sidewalls are shown to be {1011}-type planes. The presence and relative orientation of the two kinds of charge domains are explained in terms of the atomic arrangement at the {1011} polar surfaces.     

Nucleation time of nanoscale water bridges

Water capillaries bind together grains of sand. They also can bind an atomic force microscope tip to a substrate. The kinetics of capillary condensation at the nanoscale is studied here using friction force microscopy. At 40% relative humidity we find that the meniscus nucleation times increase from 0.7 to 4.2 ms when the temperature decreases from 332 to 299 K. The nucleation times grow exponentially with the inverse temperature 1/T obeying an Arrhenius law. We obtain a nucleation energy barrier of 7.8 x 10(-20) J and an attempt frequency ranging between 4 and 250 GHz, in excellent agreement with theoretical predictions. These results provide direct experimental evidence that capillary condensation is a thermally activated phenomenon.     

Slow-light six-wave mixing at low light intensities

We report an experimental study of resonant six-wave mixing in coherently prepared Rb atoms. Electromagnetically induced transparency in a four-level atomic system suppresses the linear susceptibility and enhances the nonlinear susceptibilities, which leads to the resonantly enhanced, slow-photon six-wave mixing at low light intensities. The light emission in the six-wave mixing process can be viewed as resulting from diffraction of slow light off a resonant nonlinear grating induced in the four-level system by a standing-wave pump field.     

Dynamic processes in the Venice region outlined by environmental isotopes

Research carried out in the last 40 years has shown the scientific importance of groundwater circulation both in the Northern Adriatic sea bed and within the uppermost sedimentary layers of the Venice lagoon and of the Venice plain. Hydrodynamic processes are strictly controlled by a well-cemented sedimentary horizon lying under and around Venice ('caranto'), which plays the role of regional aquitard. This layer was attributed to the subaerial cementation of the Flandrian (8-10 ka Before Present) sedimentary surface. The caranto is generalised as a continuum horizon, being an easy explanation for several environmental, hydrogeological and geotechnical problems, e.g., a base layer for landfills, a confining layer for deep aquifers and the best substratum for locating the oak wooden pile-dwelling needed to support the largest buildings. The preservation of the isotope signal within the deep aquifers and aquiclude system records the changes in surface and groundwater characteristics and suggests the present and past recharge regimes. In this region, the heavily perturbed hydrodynamic conditions do not allow for the use of isotopic signals to derive a correct reconstruction of the present recharge. The perturbations induced by the intensive anthropogenic activity force to follow climate evolution by considering deep groundwater and pore waters. In addition, the presence of carbonatic rocks inside terrigeneous sediments affects the reconstruction of the past. Results indicate that carbonatic rocks are created by seepage, through the sediments, of gaseous carbon compounds from decaying organic layers. The gas interactions with the intra-sedimentary saline and fresh waters produce CO2, inducing the cementation of the sediments.     

Ferrocenyl-substituted α,β-unsaturated ketones in synthesis of tetrahydropyrimidinones

Ferrocenyltetrahydropyrimidin-2-ones were prepared by reactions of linear and cyclic ,-unsaturated ketones of the ferrocene series with urea in i-PrOH in the presence of t-BuOK. The structures of the compounds prepared were studied by ¹H and ¹³C NMR and IR spectroscopy, and also by single crystal X-ray diffraction.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1887–1893.Original Russian Text Copyright © 2004 by E. Klimova, Lorez, T. Klimova, Garcia, Hernandez, Ramirez.This revised version was published online in April 2005 with a corrected cover date.