Toward the Optimization of an e-Tongue System Using Information Visualization: A Case Study with Perylene Tetracarboxylic Derivative Films in the Sensing Units

The wide variety of molecular architectures used in sensors and biosensors and the large amount of data generated with some principles of detection have motivated the use of computational methods, such as information visualization techniques, not only to handle the data but also to optimize sensing performance. In this study, we combine projection techniques with micro-Raman scattering and atomic force microscopy (AFM) to address critical issues related to practical applications of electronic tongues (e-tongues) based on impedance spectroscopy. Experimentally, we used sensing units made with thin films of a perylene derivative (AzoPTCD acronym), coating Pt interdigitated electrodes, to detect CuCl(2) (Cu(2+)), methylene blue (MB), and saccharose in aqueous solutions, which were selected due to their distinct molecular sizes and ionic character in solution. The AzoPTCD films were deposited from monolayers to 120 nm via Langmuir-Blodgett (LB) and physical vapor deposition (PVD) techniques. Because the main aspects investigated were how the interdigitated electrodes are coated by thin films (architecture on e-tongue) and the film thickness, we decided to employ the same material for all sensing units. The capacitance data were projected into a 2D plot using the force scheme method, from which we could infer that at low analyte concentrations the electrical response of the units was determined by the film thickness. Concentrations at 10 mu M or higher could be distinguished with thinner films tens of nanometers at most-which could withstand the impedance measurements, and without causing significant changes in the Raman signal for the AzoPTCD film-forming molecules. The sensitivity to the analytes appears to be related to adsorption on the film surface, as inferred from Raman spectroscopy data using MB as analyte and from the multidimensional projections. The analysis of the results presented may serve as a new route to select materials and molecular architectures for novel sensors and biosensors, in addition to suggesting ways to unravel the mechanisms behind the high sensitivity obtained in various sensors.

Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

An extensive investigation of strontium titanate, SrTiO3 (STO), nanospheres synthesized via a microwave-assisted hydrothermal (MAH) method has been conducted to gain a better insight into thermodynamic, kinetic, and reaction phenomena involved in STO nucleation and crystal growth processes. To this end, quantum chemical modeling based on the density functional theory and periodic super cell models were done. Several experimental techniques were employed to get a deep characterization of structural and optical features of STO nanospheres. A possible formation mechanism was proposed, based on dehydration of titanium and strontium clusters followed by mesoscale transformation and a self-assembly process along an oriented attachment mechanism resulting in spherical like shape. Raman and XANES analysis renders a noncentrosymmetric environment for the octahedral titanium, while infrared and first order Raman modes reveal OH groups which are unsystematically incorporated into uncoordinated superficial sites. These results seem to indicate that the key component is the presence of distorted TiO6 clusters to engender a luminescence property. Analysis of band structure, density Of states, and charge map shows that there is a close relationship among local broken symmetry, polarization, and energy split of the 3d orbitals of titanium. The interplay among these electronic and structural features provides necessary conditions to evaluate its luminescent properties under two energy excitation.

CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

Ceria (CeO2) plays a vital role in emerging technologies for environmental and energy-related applications. The catalytic efficiency of ceria nanoparticles depends on its morphology. In this study, CeO2 nanoparticles were synthesized by a microwave-assisted hydrothermal method under different synthesis temperatures. The samples were characterized by X-ray diffraction, transmission electron microscopy, Raman scattering spectroscopy, electron paramagnetic resonance spectroscopy and by the Brunauer-Emmett-Teller method. The X-ray diffraction and Raman scattering results indicated that all the synthesized samples had a pure cubic CeO2 structure. Rietveld analysis and Raman scattering also revealed the presence of structural defects due to an associated reduction in the valence of the Ce4+ ions to Ce3+ ions caused by an increasing molar fraction of oxygen vacancies. The morphology of the samples was controlled by varying the synthesis temperature. The TEM images show that samples synthesized at 80 degrees C consisted of spherical particles of about 5 nm, while those synthesized at 120 degrees C presented a mix of spherical and rod-like nanoparticles and the sample synthesized at 160 degrees C consisted of nanorods with 10 nm average diameter and 70 nm length. The microwave-assisted method proved to be highly efficient for the synthesis of CeO2 nanoparticles with different morphologies.

On the optical properties of copper nanocubes as a function of the edge length as modeled by the discrete dipole approximation

This Letter reports an investigation on the optical properties of copper nanocubes as a function of size as modeled by the discrete dipole approximation. In the far-field, our results showed that the extinction resonances shifted from 595 to 670 nm as the size increased from 20 to 100 nm. Also, the highest optical efficiencies for absorption and scattering were obtained for nanocubes that were 60 and 100 nm in size, respectively. In the near-field, the electric-field amplitudes were investigated considering 514, 633 and 785 nm as the excitation wavelengths. The E-fields increased with size, being the highest at 633 nm. (c) 2012 Elsevier B.V. All rights reserved.

Mapping the Energy Distribution of SERRS Hot Spots from Anti-Stokes to Stokes Intensity Ratios

The anomalies in the anti-Stokes to Stokes intensity ratios in single-molecule surface-enhanced resonance Raman scattering were investigated. Brilliant green and crystal violet dyes were the molecular probes, and the experiments were carried out on an electrochemically activated Ag surface. The results allowed new insights into the origin of these anomalies and led to a new method to confirm the single-molecule regime in surface-enhanced Raman scattering. Moreover, a methodology to estimate the distribution of resonance energies that contributed to the imbalance in the anti-Stokes to Stokes intensity ratios at the electromagnetic hot spots was proposed. This method allowed the local plasmonic resonance energies on the metallic surface to be spatially mapped.

Looking at Chemistry in Hard to See Places: Understanding Energy Conversion at 1400° Celsius

Solid oxide fuel cells (SOFCs) are promising devices for stationary and portable power and heat generation, because they can use complex fuels such as hydro-carbons, CO, and alcohols. Extreme, non-equilibrium conditions and high tem-peratures (≥ 700 ˚C) required for SOFC operation hamper efforts to understand the mechanisms of component degradation in SOFCs. This talk focuses on new insights into SOFC chemistry and the conversion of carbon-containing fuels (both hydrocarbons and oxygenated) into electricity, carbon dioxide and water, gleaned from a combination of techniques including electrochemical impedance spectroscopy, voltammetry, and vibrational Raman scattering.

Pressure-enhanced ortho-para conversion in solid hydrogen up to 58 GPa

We measured the ortho-para conversion rate in solid hydrogen by using Raman scattering in a diamond-anvil cell, extending previous measurements by a factor of 60 in pressure. We confirm previous experiments that suggested a decrease in the conversion rate above about 0.5 GPa. We observe a distinct minimum at 3 GPa followed by a drastic increase in the conversion rate to our maximum pressure of 58 GPa. This pressure enhancement of conversion is not predicted by previous theoretical treatments and must be due to a new conversion pathway.

Real-time visualization of intracellular hydrodynamics in single living cells

Intracellular water concentrations in single living cells were visualized by nonlinear coherent anti-Stokes Raman scattering (CARS) microscopy. In combination with isotopic exchange measurements, CARS microscopy allowed the real-time observation of transient intracellular hydrodynamics at a high spatial resolution. Studies of the hydrodynamics in the microorganism Dictyostelium discoideum indicated the presence of a microscopic region near the plasma membrane where the mobility of water molecules is severely restricted. Modeling the transient hydrodynamics eventuated in the determination of cell-specific cytosolic diffusion and plasma membrane permeability constants. Our experiments demonstrate that CARS microscopy offers an invaluable tool for probing single-cell water dynamics.

Spectroelectrochemical Study of the Photoinduced Catalytic Formation of 4,4′-Dimercaptoazobenzene from 4-Aminobenzenethiol Adsorbed on Nanostructured Copper

Surface-enhanced raman scattering (SERS) spectra of self-assembled monolayers of 4-aminobenzenethiol (4-ABT) on copper (Cu) and silver (Ag) surfaces decorated with Cu and Ag nanostructures, respectively, have been obtained with lasers at 532, 632.8, 785, and 1064 nm. Density functional theory (DFT) has been used to obtain calculated vibrational frequencies of the 4-ABT and 4,4′-dimercaptoazobenzene (4,4′-DMAB) molecules adsorbed on model Cu surfaces. The features of the SERS spectra depend on the electrode potential and the type and power density of the laser. SERS spectra showed the formation of the 4,4′-DMAB on the nanostructured Cu surface independently of the laser employed. For the sake of comparison SERS spectra of a self-assembled monolayer of the 4-ABT on Ag surfaces decorated with Ag nanostructures have been also obtained with the same four lasers. When using the 532 and 632.8 nm lasers, the 4,4′-DMAB is formed on Cu surface at electrode potentials as low as −1.0 V (AgCl/Ag) showing a different behavior with respect to Ag (and others metals such as Au and Pt). On the other hand, the surface-enhanced infrared reflection absorption (SEIRA) spectra showed that in the absence of the laser excitation the 4,4′-DMAB is not produced from the adsorbed 4-ABT on nanostructured Cu in the whole range of potentials studied. These results point out the prevalence of the role of electron–hole pairs through surface plasmon activity to explain the obtained SERS spectra.

Double-walled carbon nanotubes synthesized using carbon black as the dot carbon source

Double- walled carbon nanotubes (DWNTs) were synthesized used carbon black as the dot carbon source by a semi-continuous hydrogen arc discharge process. High-resolution transmission electron microscopy (HRTEM) observations revealed that most of the tubes were DWNTs with outer and inner diameters in the range of 2.67 - 4 nm and 1.96 - 3.21 nm, respectively. Most of the DWNTs were in a bundle form of about 10 - 30 nm in diameter with high purity ( about 70%) from thermal gravimetric analysis (TGA), resonant laser Raman spectroscopy, scanning electron microscopy (SEM) and TEM characterizations. It was found that carbon black as the dot carbon source could be easy controlled to synthesize one type of nanotube. A simple process combining oxidation and acid treatment to purify the DWNT bundles was used without damaging the bundles. The structure of carbon black, as the key element for influencing purity, bundle formation and purification of DWNTs, is discussed.

Switching and generation of ultrashort pulses using all-fibre devices

Serial and parallel interconnection of photonic devices is integral to the construction of any all-optical data processing system. This thesis presents results from a series of experiments centering on the use of the nonlinear-optical loop mirror (NOLM) switch in architectures for the manipulation and generation of ultrashort pulses. Detailed analysis of soliton switching in a single NOLM and cascade of two NOLM's is performed, centering on primary limitations to device operation, effect of cascading on amplitude response, and impact of switching on the characteristics of incident pulses. By using relatively long input pulses, device failure due to stimulated Raman generation is postponed to demonstrate multiple-peaked switching for the first time. It is found that while cascading leads to a sharpening of the overall switching characteristic, pulse spectral and temporal integrity is not significantly degraded, and emerging pulses retain their essential soliton character. In addition, by including an asymmetrically placed in-fibre Bragg reflector as a wavelength selective loss element in the basic NOLM configuration, both soliton self-switching and dual-wavelength control-pulse switching are spectrally quantised. Results are presented from a novel dual-wavelength laser configuration generating pulse trains with an ultra-low rms inter-pulse-stream timing jitter level of 630fs enabling application in ultrafast switching environments at data rates as high as 130GBits/s. In addition, the fibre NOLM is included in architectures for all-optical memory, demonstrating storage and logical inversion of a 0.5kByte random data sequence; and ultrafast phase-locking of a gain-switched distributed feedback laser at 1.062GHz, the fourteenth harmonic of the system baseband frequency. The stringent requirements for environmental robustness of these architectures highlight the primary weaknesses of the NOLM in its fibre form and recommendations to overcome its inherent drawbacks are presented.

Picosecond soliton transmission using concatenated nonlinear optical loop-mirror intensity filters

The issues involved in employing nonlinear optical loop mirrors (NOLMs) as intensity filters in picosecond soliton transmission were examined in detail. It was shown that inserting NOLMs into a periodically amplified transmission line allowed picosecond solitons to be transmitted under conditions considered infeasible until now. The loop mirrors gave dual function, removing low-power background dispersive waves through saturable absorption and applying a negative feedback mechanism to control the amplitude of the solitons. The stochastic characteristics of the pulses that were due to amplifier spontaneous-emission noise were investigated, and a number of new properties were determined. In addition, the mutual interaction between pulses was also significantly different from that observed for longer-duration solitons. The impact of Raman scattering in the computations was included and it was shown that soliton self-frequency shifts may be eliminated by appropriate bandwidth restrictions.

1.14Tb/s DP-QPSK WDM polarization-diverse optical phase conjugation

Optical phase conjugation (OPC) of a polarization-multiplexed comb of 10x114Gb/s DP-QPSK signals has been demonstrated for the first time, occupying a spectral bandwidth of >1THz (~9nm). The nonlinear element employed for the OPC was highly nonlinear fiber (HNLF) optimized for the suppression of stimulated Brillouin scattering (SBS) and configured in a bi-directional loop offering polarization diversity. Pump power (each way about the loop) and input signal power to the OPC subsystem were optimized at 29.7dBm and + 3dBm respectively producing a Q2 penalty of ≤0.9dB over all conjugate wavelengths, polarizations and output OSNR (up to 20dB).

High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Relative intensity noise transfer in higher-order distributed amplification through ultra-long fiber cavities

Among the different possible amplification solutions offered by Raman scattering in optical fibers, ultra-long Raman lasers are particularly promising as they can provide quasi-losless second order amplification with reduced complexity, displaying excellent potential in the design of low-noise long-distance communication systems. Still, some of their advantages can be partially offset by the transfer of relative intensity noise from the pump sources and cavity-generated Stokes to the transmitted signal. In this paper we study the effect of ultra-long cavity design (length, pumping, grating reflectivity) on the transfer of RIN to the signal, demonstrating how the impact of noise can be greatly reduced by carefully choosing appropriate cavity parameters depending on the intended application of the system. © 2010 Copyright SPIE - The International Society for Optical Engineering.