Micro-HPLC/TLC/FTIR

Identification problems often encountered in high performance liquid chromatography (HPLC)/Fourier transform infrared spectrometry (FTIR) can be circumvented through the use of a thin-layer chromatographic (TLC) plate as deposition and infra-red sampling medium. The combination of complementary separation modes is shown to demonstrate increased resolution of the components of complex mixtures. In this particular work, the effluent from a reversed-phase microcolumn is continuously deposited on a TLC plate with alumina stationary phase. The solute remains on the plate as a continuous record of the HPLC separation, which is then analyzed by diffuse reflectance FTIR. When the HPLC separation is inadequate for full separation of the components, the immobilized HPLC chromatogram serves as a starting point for subsequent TLC separation. A number of FTIR reconstructed chromatograms and spectra which are derived from the TLC plate aid in the interpretation.     

Supercritical fluid chromatography/Fourier transform infrared microspectrometry

The feasibility of supercritical fluid chromatography/Fourier transform-infrared (SFC/FT-IR) microspectrometry is presented. In this approach to SFC/FT-IR, the chromatographic eluates are aspirated from the restrictor directly onto the surface of a moving window which then passes into the beam focus of an infrared microscope. Because the mobile phase is gaseous at ambient conditions, elimination of the mobile phase is easily accomplished. Detection limits in all interfaces between a chromatograph and an FT-IR spectrometer in which the mobile phase is eliminated are determined in large part by the area over which the sample is deposited. We have shown that SFC eluates can be condensed at ambient temperature into spots of 100 to 200μm in diameter. The microscope interface therefore serves to increase the sensitivity of the SFC/FT-IR measurements of these spots and detection limits in the low nanogram range are possible. Preliminary results obtained before any real attempts were made to optimize the deposition process indicate that identifiable spectra can be obtained in real time at the 50 ng level for chromatographic separations performed with a 100μm i.d. wall coated open tubular column. Reproducible reconstructed chromatograms are obtained as each deposited eluate travels through the beam focus of the microscope. The concentration profile of deposited peaks was determined by IR measurements performed at 50 μm increments over the width of the peak to ascertain the deposition size. The results described in this paper, while not yet optimized, indicate the great potential of SFC/FT-IR microspectrometry.     

Nature of ThF bonding in crystalline and glassy states using EXAFS and XANES

A binary glass of thorium and hafnium tetrafluorides (with dopant concentrations of LaF₃) has been investigated using EXAFS and XANES analysis of the L_Ill edge spectra of thorium. Results of EXAFS analysis indicate that there is no change in the number of nearest neighbors of thorium ions. However, the intensity of the white line in XANES is significantly higher in the glass. This increase in intensity has been explained semiquantitatively in terms of enhanced covalency of ThF bonding. Since the coordination number of Th⁴⁺ remains constant in both crystalline and glassy states, covalency enhancement seems to be a general characteristic of glassy state of ionic materials.     

Hydrazine detection limits in the cigarette smoke matrix using infrared tunable diode laser absorption spectroscopy

Infrared absorption lines of hydrazine are broad and typically not baseline resolved, with line strengths approximately 100 times weaker than the more widely studied compound ammonia. Hardware and software improvements have been made to a two-color infrared tunable diode laser (IR-TDL) spectrometer in order to improve the limit of detection (LOD) of hydrazine (N2H4) in the cigarette smoke matrix. The detection limit in the smoke matrix was improved from 25 parts-per-million-by-volume (ppmv) to 4.2 ppmv using a 100 m pathlength cell with acquisition of background spectra immediately prior to each sample and 100 ms temporal resolution. This study did not detect hydrazine in cigarette smoke in the 964.4-964.9 cm(-1) spectral region, after mathematically subtracting the spectral contributions of ethylene, ammonia, carbon dioxide, methanol, acrolein, and acetaldehyde. These compounds are found in cigarette smoke and absorb in this spectral region. The LOD is limited by remaining spectral structure from unidentified smoke species. The pseudo random noise (root mean square) in the improved instrument was 2 x 10(-4) absorbance units (base e) which is equivalent to a 0.09 ppmv hydrazine gas sample in the multipass cell. This would correspond to a detection limit of 0.44 ppmv of hydrazine, given the dilution of the smoke by a factor of 5 by the sampling system. This is a factor of 10 less than the 4.2 ppmv detection limit for hydrazine in the smoke matrix, and indicates that the detection limit is primarily a result of the complexity of the matrix rather than the random noise of the TDL instrument.     

MINDO/3 Calculation of carbocation heats of formation

Heats of formation calculated by MINDO /3 are reported for 42 carbocations for which experimental heats of formation have been published. Errors associated with these calculations can be large, with an overall range of ±13 kcal/mol. Correction of systematic errors in the MINDO /3 calculations by means of hydrocarbon models and isodesmic relationships results in a reduction in the range of errors to ±8 kcal/mol. Comparison with experimental heats of reaction of hydride transfer equilibria minimizes experimental errors and gives an average absolute error of 2 kcal/mol with a range of ±3 kcal/mol.     

Interpretation of restricted diffusion in sandstones with internal field gradients.

We report on experiments to characterize internal magnetic field gradients that are caused by magnetic susceptibility differences between the solid phase and the fluids filling the pore space. Our measurements focus on low-field relaxometry of brine and oil in sandstones from various reservoirs around the world. Our results show the need to understand the dependence of internal field gradients on diffusion length, pore size- and fluid distribution in order to predict the impact of internal gradients on the interpretation of NMR experiments.     

Parametrization for mesoscale ocean transport through random flow models

We describe a mathematical approach based on homogenization theory toward representing the effects of mesoscale coherent structures on large-scale transport in the ocean. We demonstrate the approach on a deterministic and a random model flow. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Determination of dissolved thiols using solid-phase extraction and liquid chromatographic determination of fluorescently derivatized thiolic compounds

A method employing solid-phase extraction coupled with HPLC separation of thiol-monobromobimane (mBBr) derivatives was developed and optimized to quantify dissolved thiols at concentrations as low as 0.1 nM for glutathione (GSH) and gamma-glutamylcysteine (gammaEC) in natural waters. The reducing reagent, tri-n-butylphosphine (TBP), is needed for complete derivatization. At the optimal addition of TBP ([TBP]/[mBBr] = -0.4-1.6), no interference from copper was observed. The thiol fluorescence signal was totally suppressed if the mole ratio of TBP to mBBr was 2.6 or greater. Consistent recovery of thiols standards in a NaCl solution (0.5 M) was obtained using the Waters HLB reversed-phase resin, and blank levels of GSH and gammaEC were extremely low (less than 0.03 nM). The detection limits for GSH, gammaEC and phytochelatin-2 (PC-2) were 0.03, 0.03, and 0.06 nM, respectively.