Cavity ring-down spectroscopy as a detector for liquid chromatography

We have demonstrated the use of cavity ring-down spectroscopy (CRDS) as a detector for high performance liquid chromatography (HPLC). For this use, we have designed and implemented a Brewster's angle flow cell such that cavity ring-down spectroscopy can be performed on microliter volumes of liquids. The system exhibits a linear dynamic range of 3 orders of magnitude (30 nM to 30 microM quinalizarin at 470 nm) for static measurements and 2 orders of magnitude (0.5 microM to 50 microM) for HPLC measurements. For the static measurements, the baseline noise is 2.8 x 10(-6) AU rms and 1.0 x 10(-5) AU peak-to-peak, and for the HPLC separations, it is 3.2 x 10(-6) AU rms and 1.3 x 10(-5) AU peak-to-peak. The baseline noise is determined after the data are smoothed by an 11-point boxcar average. The peak areas detected from HPLC separations are reproducible to within 2-3%. The HPLC mass detection limit for a molecule with epsilon = 9 x 10(3) M(-1) cm(-1) in a 300-microm path length cell (illuminated volume, 0.5 microL) is reported as 2.5 x 10(-8) g/mL. These results were obtained using a simple pulsed CRDS system and are comparable to, if not better than, a high-quality commercial UV-vis absorption detector for the same path length.     

An Inter-Comparison of Two Black Carbon Aerosol Instruments and a Semi-Continuous Elemental Carbon Instrument in the Urban Environment

Aerosol absorption coefficients were obtained using two versions of the Magee Scientific Aethalometer and a Particle Soot Absorption Photometer (PSAP) in Riverside, California during July and August of 2005. These measurements were subsequently compared to each other and to hourly elemental carbon (EC) mass concentrations as determined by a Sunset Labs semi-continuous OCEC analyzer. Measurements from all four instruments were shown to be highly correlated (R ² = 0.83 to 0.92). Differences between absorption values measured by the PSAP and the Aethalometer were found to be dominated by differences in the filter media used by the respective instruments. Comparison of optical and thermal measurements revealed that the specific attenuation cross section (σ _ATN ) of light absorbing carbon (LAC) varied as a function of the time of the day, most notably during weekdays. Minimum σ _ATN values were observed during morning rush hour when EC concentrations were at their greatest and maxima were seen in the late afternoon. These variations correlated with changes in the OC/EC ratio and the Angstrom exponent for absorption, which is consistent with changes in the mixing state of elemental carbon associated with secondary aerosol condensation on primary EC particles.     

Dimensional analysis of ionic transport problems in hydrated cement systems: Part 1. Theoretical considerations

The validity of the local equilibrium assumption in hydrated cement systems that a particular chemical reaction is instantaneous with respect to transport is examined using a dimensional analysis of electrochemical transport in cementitious materials. The transport equation parameters are scaled, resulting in a dimensionless equation. The dimensionless coefficient for each reaction/transport term determines its relative contribution to the overall process. The diffusion of ions in a reactive porous medium can be fully described on the basis of six independent dimensionless numbers. The analysis demonstrates that the kinetics of the reaction determine the appropriate time constant for the analysis. The formalism is applied to the dissolution of calcium hydroxide under an electrochemical potential gradient. The results are in agreement with previous observations and demonstrate quantitatively the local equilibrium hypothesis is valid in most practical cases where ions are transported by diffusion through a saturated material.     

Simple Equation to Estimate Reference Evapotranspiration from Evaporation Pans Surrounded by Fallow Soil

Reliable estimates of reference evapotranspiration (ET0) are key elements for efficient water resource management, and estimating ET0, based on “Class ‘A’ pan evaporation” data is common in arid climates. A pan coefficient (Kp), which depends on the distance (or fetch) of green vegetation or fallow soil around the pan (F), wind run (U), and relative humidity (RH), is used to convert from pan evaporation to ET0. Several researchers have developed models for estimating Kp values for pans surrounded by green vegetated fetch, but there is only one equation to estimate Kp values for dry fetch conditions. The equation is complex, so the objective of this research was to develop a new simple equation to estimate Kp under fallow soil fetch conditions. The new Kp equation and the more complex equation were compared with tabular values published by the United Nations Food and Agriculture Organization. The new equation performed slightly better at matching the tabular Kp values than the complex equation. The equation derivation and evaluation are presented.     

The Zintl Compound Ca5Al2Sb6 for Low‐Cost Thermoelectric Power Generation

Understanding transport in Zintl compounds is important due to their unusual chemistry, structural complexity, and potential for good thermoelectric performance. Resistivity measurements indicate that undoped Ca₅Al₂Sb₆ is a charge‐balanced semiconductor with a bandgap of 0.5 eV, consistent with Zintl–Klemm charge counting rules. Substituting divalent calcium with monovalent sodium leads to the formation of free holes, and a transition from insulating to metallic electronic behavior is observed. Seebeck measurements yield a hole mass of ～2m_e, consistent with a structure containing both ionic and covalent bonding. The structural complexity of Zintl compounds is implicated in their unusually low thermal conductivity values. Indeed, Ca₅Al₂Sb₆ possesses an extremely low lattice thermal conductivity (0.6 W mK^?1 at 850 K), which approaches the minimum thermal conductivity limit at high temperature. A single parabolic band model is developed and predicts that Ca_4.75Na_0.25Al₂Sb₆ possesses a near‐optimal carrier concentration for thermoelectric power generation. A maximum zT > 0.6 is obtained at 1000 K.Beyond thermoelectric applications, the semiconductor Ca₅Al₂Sb₆ possesses a 1D covalent structure which should be amenable to interesting magnetic interactions when appropriately doped.     

Self-monitoring: Appraisal and reappraisal.

Theory and research on self-monitoring have accumulated into a sizable literature on the impact of variation in the extent to which people cultivate public appearances in diverse domains of social functioning. Yet self-monitoring and its measure, the Self-Monitoring Scale, are surrounded by controversy generated by conflicting answers to the critical question, Is self-monitoring a unitary phenomenon? A primary source of answers to this question has been largely neglected—the Self-Monitoring Scale's relations with external criteria. The authors propose a quantitative method to examine the self-monitoring literature and thereby address major issues of the controversy. Application of this method reveals that, with important exceptions, a wide range of external criteria tap a dimension directly measured by the Self-Monitoring Scale. The authors discuss what this appraisal reveals about what self-monitoring is and is not. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Natural organic matter and sunlight accelerate the degradation of 17ß-estradiol in water

Nanomolar concentrations of steroid hormones such as 17β-estradiol can influence the reproductive development and sex ratios of invertebrate and vertebrate populations. Thus their release into surface and ground waters from wastewater facilities and agricultural applications of animal waste is of environmental concern. Many of these compounds are chromophoric and susceptible to photolytic degradation. High intensity UV-C radiation has been demonstrated to degrade some of these compounds in engineered systems. However, the degradation efficacy of natural solar radiation in shallow fresh waters is less understood. Here photolytic experiments with 17β-estradiol demonstrated modest photodegradation (~ 26%) when exposed to simulated sunlight between 290 and 720 nm. Photodegradation significantly increased (~ 40-50%) in the presence of 2.0-15.0 mg/l of dissolved organic carbon (DOC) derived from humic acids of the Suwannee River, GA. However, rates of photodegradation reached a threshold at approximately 5.0 mg/l DOC. Observed suppression of photolysis in the presence of a radical inhibitor (i.e. 2-propanol) indicated that a significant proportion of the degradation was due to radicals formed from the photolysis of DOC. Although photodegradation was greatest in full sunlight containing UV-B (290-320 nm), degradation was also detected with UV-A (320-400 nm) and visible light (400-720 nm) alone.     

Diffusion and transfer of antibody proteins from a sugar-based hydrogel

Diffusion of antibody protein from hydrogel films and hydrogel encapsulated in a microcapillary was studied. Thin hydrogel films were formed by crosslinking 6-acryloyl-B-O-methylgalactoside with N,N'-methylene-bis-acrylamide and the diffusive transport of monoclonal antimouse IgG-FITC into and out of the hydrate films was measured. Diffusion coefficients in 2 and 4% crosslinked hydrogel films were measured. The measured diffusion constants determined for IgG in both the 2 and 4% hydrogel films were comparable to the free diffusion of IgG in bulk water (Dmean approximately 10(-7) cm2/s). In addition, 2% crosslinked hydrogels were prepared in a capillary tube and the transport of antimouse IgG-FITC into and out of the hydrated hydrogel was measured. Kinetic analysis indicated that the protein transport through the capillary hydrogel was faster than would be expected for a simple diffusion process. Finally, by utilizing the diffusion of antibody from the capillary hydrogel, transfer of antibody to a silica surface was demonstrated. A capillary hydrogel loaded with antimouse IgG-FITC was used to transfer the protein to a silica surface forming a 30-micron spot of antibody, which was imaged using fluorescence microscopy. These results may lead to the development of a nonlithographic method of patterning antibodies on surfaces for use in integrated microimmunosensors.