Direct monitoring of absorption in solution by cavity ring-down spectroscopy

Cavity ring-down spectroscopy is applied to the liquid phase by placing the target solution directly into the optical cavity. We demonstrate that solutions in the cavity can be stirred and more importantly monitored in a flow. We report a minimum detectable absorption of 10(-6) cm(-1) for a range of organic solvents. This detection limit corresponds to picomolar concentrations for strong absorbers.     

High-speed characterization and analysis of orange oils with tandem-column stop-flow GC and time-of-flight MS

High-speed GC with time-of-flight (TOF) MS detection is used for the characterization and analysis of oils rendered from the peel of five diverse species of orange including bergemot orange, bitter orange, tangerine, mandarin orange, and sweet orange. With a user-defined signal-to-noise threshold of 100, 44 peaks were found and 36 compounds identified in the various oils. Some major constituent components show large concentration ranges over the five species. A 14-m-long, 0. 18-mm-i.d. column ensemble consisting of 7.0-m lengths of a trifluoropropylmethyl polysiloxane and a 5% phenyl dimethyl polysiloxane column was temperature-programmed at 50 degrees C/min starting at the time of injection to achieve analysis times under 140 s. The TOFMS was operated with a spectral acquisition rate of 25 spectra/s, and automated peak finding software successfully found all of the components, with the exception of one severely overlapping peak pair in bitter-orange oil. Of the 44 peaks, 25 were identified by use of a TOFMS library created for this study; another 11 were identified with a commercial terpene library, and 8 were not identified. A quantitative comparison (percent of total peak area) is presented for 16 components, which comprise 98.8-99.5% of the total peak area for the five orange species. Stop-flow operation of the column ensemble is used to enhance selectivity for targeted component pairs to facilitate single-channel detection for QA/ QC analysis of characterized samples and to enhance column selectivity for TOFMS characterization in cases in which peak overlap is so severe that only a single peak is observed.     

Wave-front sensing from defocused images by use of wave-front slopes

We describe a novel technique for deriving wave-front aberrations from two defocused intensity measurements. The intensity defines a probability density function, and the method is based on the evolution of the cumulative density function of the intensity with light propagation. In one dimension, the problem is easily solved with a histogram specification procedure, with a linear relationship between the wave-front slope and the difference in the abscissas of the histograms. In two dimensions, the method requires use of a Radon transform. Simulation results demonstrate that good reconstructions can be attained down to 100 photons in each detector. In addition, the method is insensitive to scintillation at the aperture.     

Fixed three-dimensional holographic images

Three-dimensional holograms were recorded in a cerium-doped, strontium barium niobate (SBN:75) photorefractive crystal. These holograms are shown to not degrade after more than one week of continuous readout and to reconstruct reproductions of the original object with an observable field of view of approximately 35 degrees.     

Stabilization of anionic adducts in negative ion electrospray mass spectrometry

Attachment of small anions to neutral molecules is an important ionization mechanism in negative ion electrospray mass spectrometry. In this report, the tendency for different anions to remain attached to selected analyte compound classes has been systematically investigated. A rationale for the formation and stability of preferred anionic adducts is proposed in light of thermodynamic considerations. A series of collision-induced dissociation experiments reveals that the gas-phase basicities of the deprotonated analyte molecule ([M - H]-) and the anion moiety play important roles in determining the stability of anionic adducts. Adducts of the form [M - H]-...H+...[anion]- manifest increased stability when the two anions have similar gas-phase basicities. Within certain limitations, the difference in deltaG degrees values for proton combination with [M - H]- and with [anion]- can be used as a first-order predictor of adduct stability. In addition, stability increases with the rising gas-phase basicities of the two moieties. The specific interaction between a small inorganic anion (bisulfate) and a neutral analyte molecule (alpha-D-glucose) in the form of multiple hydrogen bonding has also been affirmed by computer modeling to contribute to the stability of some anionic adducts. Last, the gas-phase basicity of deprotonated alpha-D-glucose (i.e., the gas-phase acidity of alpha-D-glucose) is determined by a "bracketing method" to be in the range of 1373-1407 kJ/mol.     

Three-dimensional imaging laser radar with a photon-counting avalanche photodiode array and microchip laser

We have developed a threedimensional imaging laser radar featuring 3-cm range resolution and single-photon sensitivity. This prototype direct-detection laser radar employs compact, all-solid-state technology for the laser and detector array. The source is a Nd:YAG microchip laser that is diode pumped, passively Q-switched, and frequency doubled. The detector is a gated, passively quenched, two-dimensional array of silicon avalanche photodiodes operating in Geigermode. After describing the system in detail, we present a three-dimensional image, derive performance characteristics, and discuss our plans for future imaging three-dimensional laser radars.     

Assessment of the Wiener-Retinex process

We assess the performance of the Retinex transformation, the Wiener restoration, and the combined Wiener-Retinex process in the context of the end-to-end model of color visual-communication channels for near-surface acquisition. We extend the formulations of panchromatic imaging for the nonlinear Retinex transformation and the linear Wiener and Wiener-Retinex restoration filters to color imaging. We further assess the accuracy by which colors are restored in the cases of uniform and spatially varying irradiance levels, and the shadow depth for which color consistency is still possible with reasonable accuracy. Finally, we assess the sensitivity of these processes to perturbations in the visual channel, including the image-gathering design and the spatial support of the Retinex transformation.     

Gas temperature measurements in weakly ionized glow discharges with filtered Rayleigh scattering

We report the first gas temperature measurements in plasmas to our knowledge obtained by filtered Rayleigh scattering (FRS). A narrow-linewidth Ti:sapphire laser is used as the illumination source, and a mercury filter provides strong suppression of elastic background. We perform measurements in weakly ionized glow discharges in pure argon and in an argon-plus-1%-nitrogen mixture. Where possible, we verify the FRS technique by comparing filtered measurements with unfiltered measurements. We present point measurements of axial temperature with uncertainties of less than 5%. We use a planar scheme to obtain radial temperature profiles with uncertainties of 10%.     

Retrieval of the ultraviolet aerosol optical depth during a spring campaign in the Bavarian Alps

A measurement campaign was organized in March 1999 in the Bavarian Alps as part of the European project, Characteristics of the UV Radiation Field in the Alps (CUVRA), to analyze the effect of altitude, aerosols, and snow cover on ground-level UV spectral irradiance. We present the results of simultaneous measurements of aerosol optical depth (AOD) made at various sites on two cloudless days in March 1999. The two days exhibited different aerosol conditions. Results derived from spectral measurements of UV irradiance are compared with data from filter radiometer measurements made at discrete wavelengths extending from the UV to the near IR. The different methods generated values for the AOD that were in good agreement. This result confirms that one can use either method to retrieve the AOD with an uncertainty of approximately 0.03-0.05. On 18 March, high turbidity was observed at low altitude (400-nm AOD approximately 0.5 at 700 m above sea level), and the AOD decreased regularly with altitude; on 24 March, the turbidity was much less (0.11 at 700 m above sea level). On both days very low AODs (0.05-0.09) were measured at 3000 m above sea level. The spectral dependence of the AOD is often parameterized by the angstrom relationship; the alpha parameter is generally difficult or impossible to retrieve from spectral measurements because of the relatively narrow wavelength range (320-400 nm), and only one of the spectro-radiometers used during the campaign permits this retrieval. In most cases, during this field campaign, alpha was found by filter sunphotometers to be 1.1-1.5.     

Selectively grouping neurons in recurrent networks of lateral inhibition

Winner-take-all networks have been proposed to underlie many of the brain's fundamental computational abilities. However, not much is known about how to extend the grouping of potential winners in these networks beyond single neuron or uniformly arranged groups of neurons. We show that competition between arbitrary groups of neurons can be realized by organizing lateral inhibition in linear threshold networks. Given a collection of potentially overlapping groups (with the exception of some degenerate cases), the lateral inhibition results in network dynamics such that any permitted set of neurons that can be coactivated by some input at a stable steady state is contained in one of the groups. The information about the input is preserved in this operation. The activity level of a neuron in a permitted set corresponds to its stimulus strength, amplified by some constant. Sets of neurons that are not part of a group cannot be coactivated by any input at a stable steady state. We analyze the storage capacity of such a network for random groups--the number of random groups the network can store as permitted sets without creating too many spurious ones. In this framework, we calculate the optimal sparsity of the groups (maximizing group entropy). We find that for dense inputs, the optimal sparsity is unphysiologically small. However, when the inputs and the groups are equally sparse, we derive a more plausible optimal sparsity. We believe our results are the first steps toward attractor theories in hybrid analog-digital networks.