Detection of Methyl Radicals in a Flat Flame by Degenerate Four-Wave Mixing

We report the spatially resolved detection of methyl radicals in a methane–air f lat flame, using degenerate four-wave mixing (DFWM). A frequency-tripled dye laser pumped with a frequency-doubled Nd:YAG laser was used to access the Herzberg b1 band of methyl near 216 nm. Using a nearly phase-conjugate geometry, we detected methyl with high spatial resolution [0.2 mm (0.3 mm) vertical (horizontal) and ,6 mm longitudinal] and with good signal-to-noise ratio in a rich sf _ 1.55d flame. Compared with laser absorption spectra, DFWM spectra were much less influenced by a broad featureless background. From the absorption data, we measured the peak methyl concentration to be 650 parts in 106, resulting in an estimated DFWM detection limit of 65 parts in 106.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/86762/1/Sick48.pd

Two-pulse rapid remote surface contamination measurement.

This project demonstrated the feasibility of a 'pump-probe' optical detection method for standoff sensing of chemicals on surfaces. Such a measurement uses two optical pulses - one to remove the analyte (or a fragment of it) from the surface and the second to sense the removed material. As a particular example, this project targeted photofragmentation laser-induced fluorescence (PF-LIF) to detect of surface deposits of low-volatility chemical warfare agents (LVAs). Feasibility was demonstrated for four agent surrogates on eight realistic surfaces. Its sensitivity was established for measurements on concrete and aluminum. Extrapolations were made to demonstrate relevance to the needs of outside users. Several aspects of the surface PF-LIF physical mechanism were investigated and compared to that of vapor-phase measurements. The use of PF-LIF as a rapid screening tool to 'cue' more specific sensors was recommended. Its sensitivity was compared to that of Raman spectroscopy, which is both a potential 'confirmer' of PF-LIF 'hits' and is also a competing screening technology

Dual-Pump Coherent Anti-Stokes Raman Scattering Temperature and CO2 Concentration Measurements

Measurements of temperature and CO2 concentration using dual-pump coherent anti-Stokes Raman scattering, (CARS) are described. The measurements were performed in laboratory flames,in a room-temperature gas cell, and on an engine test stand at the U.S. Air Force Research Laboratory, Wright-Patterson Air Force Base. A modeless dye laser, a single-mode Nd:YAG laser, and an unintensified back-illuminated charge-coupled device digital camera were used for these measurements. The CARS measurements were performed on a single-laser-shot basis. The standard deviations of the temperatures and CO2 mole fractions determined from single-shot dual-pump CARS spectra in steady laminar propane/air flames were approximately 2 and 10% of the mean values of approximately 2000 K and 0.10, respectively. The precision and accuracy of single-shot temperature measurements obtained from the nitrogen part of the dual-pump CARS system were investigated in detail in near-adiabatic hydrogen/air/CO2 flames. The precision of the CARS temperature measurements was found to be comparable to the best results reported in the literature for conventional two-laser, single-pump CARS. The application of dual-pump CARS for single-shot measurements in a swirl-stabilized combustor fueled with JP-8 was also demonstrated

Measuring individual overpotentials in an operating solid-oxide electrochemical cell

We use photo-electrons as a non-contact probe to measure local electrical potentials in a solid-oxide electrochemical cell. We characterize the cell in operando at near-ambient pressure using spatially-resolved X-ray photoemission spectroscopy. The overpotentials at the interfaces between the Ni and Pt electrodes and the yttria-stabilized zirconia (YSZ) electrolyte are directly measured. The method is validated using electrochemical impedance spectroscopy. Using the overpotentials, which characterize the cell's inefficiencies, we compare without ambiguity the electro-catalytic efficiencies of Ni and Pt, finding that on Ni H_2O splitting proceeds more rapidly than H2 oxidation, while on Pt, H2 oxidation proceeds more rapidly than H2O splitting.Comment: corrected; Phys. Chem. Chem. Phys., 201

Mechanisms for charge-transfer processes at electrode/solid-electrolyte interfaces.

This report summarizes the accomplishments of a Laboratory-Directed Research and Development (LDRD) project focused on developing and applying new x-ray spectroscopies to understand and improve electric charge transfer in electrochemical devices. Our approach studies the device materials as they function at elevated temperature and in the presence of sufficient gas to generate meaningful currents through the device. We developed hardware and methods to allow x-ray photoelectron spectroscopy to be applied under these conditions. We then showed that the approach can measure the local electric potentials of the materials, identify the chemical nature of the electrochemical intermediate reaction species and determine the chemical state of the active materials. When performed simultaneous to traditional impedance-based analysis, the approach provides an unprecedented characterization of an operating electrochemical system

Surveillance of Sentinel Node-Positive Melanoma Patients with Reasons for Exclusion from MSLT-II:Multi-Institutional Propensity Score Matched Analysis

BACKGROUND: In sentinel lymph node (SLN)-positive melanoma, two randomized trials demonstrated equivalent melanoma-specific survival with nodal surveillance vs completion lymph node dissection (CLND). Patients with microsatellites, extranodal extension (ENE) in the SLN, or >3 positive SLNs constitute a high-risk group largely excluded from the randomized trials, for whom appropriate management remains unknown. STUDY DESIGN: SLN-positive patients with any of the three high-risk features were identified from an international cohort. CLND patients were matched 1:1 with surveillance patients using propensity scores. Risk of any-site recurrence, SLN-basin-only recurrence, and melanoma-specific mortality were compared. RESULTS: Among 1,154 SLN-positive patients, 166 had ENE, microsatellites, and/or >3 positive SLN. At 18.5 months median follow-up, 49% had recurrence (vs 26% in patients without high-risk features, p 3 positive SLN constitute a high-risk group with a 2-fold greater recurrence risk. For those managed with nodal surveillance, SLN-basin recurrences were more frequent, but all-site recurrence and melanoma-specific mortality were comparable to patients treated with CLND. Most recurrences were outside the SLN-basin, supporting use of nodal surveillance for SLN-positive patients with microsatellites, ENE, and/ or >3 positive SLN

Active surveillance of patients who have sentinel node positive melanoma:An international, multi-institution evaluation of adoption and early outcomes after the Multicenter Selective Lymphadenectomy trial II (MSLT-2)

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/168248/1/cncr33483.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/168248/2/cncr33483_am.pd

Molecular-scale measurements of electric fields at electrochemical interfaces.

Spatially resolved measurements of electric fields at electrochemical interfaces would be a critical step toward further understanding and modeling the detailed structure of electric double layers. The goal of this project was to perform proof-of-principle experiments to demonstrate the use of field-sensitive dyes for optical measurements of fields in electrochemical systems. A confocal microscope was developed that provides sensitive detection of the lifetime and high resolution spectra of excited fluorescence for dyes tethered to electrically conductive surfaces. Excited state lifetimes for the dyes were measured and found to be relatively unquenched when linked to indium tin oxide, but strongly quenched on gold surfaces. However, our fluorescence detection is sufficiently sensitive to measure spectra of submonolayer dye coatings even when the fluorescence was strongly quenched. Further work to create dye labeled interfaces on flat, uniform and durable substrates is necessary to make electric field measurements at interfaces using field sensitive dyes

Report on the Accuracy of Hydsys Generated Flow Data for Gauging Stations in the Daly River Catchment

Date:2004-01Made available via the Publications (Legal Deposit) Act 2004 (NT