Showing papers by "Purnendu K. Dasgupta published in 2014"

Light-Emitting Diodes for Analytical Chemistry

Abstract: Light-emitting diodes (LEDs) are playing increasingly important roles in analytical chemistry, from the final analysis stage to photoreactors for analyte conversion to actual fabrication of and incorporation in microdevices for analytical use. The extremely fast turn-on/off rates of LEDs have made possible simple approaches to fluorescence lifetime measurement. Although they are increasingly being used as detectors, their wavelength selectivity as detectors has rarely been exploited. From their first proposed use for absorbance measurement in 1970, LEDs have been used in analytical chemistry in too many ways to make a comprehensive review possible. Hence, we critically review here the more recent literature on their use in optical detection and measurement systems. Cloudy as our crystal ball may be, we express our views on the future applications of LEDs in analytical chemistry: The horizon will certainly become wider as LEDs in the deep UV with sufficient intensity become available.

Capillary scale admittance detection.

Abstract: Techniques that have been variously termed oscillometric detection or (capacitively coupled) contactless conductivity detection (C4D) are known actually to respond to the admittance. It is not often appreciated that the frequency range (f) over which such systems respond (quasi)linearly with the cell conductance decreases acutely with increasing cell resistance. Guidance on optimum operating conditions for high cell resistance, such as for very small capillaries/channels and/or solutions of low specific conductance (σ), is scant. It is specially necessary in this case to take the capacitance of the solution into account. At high frequencies and low σ values, much of the current passes through the solution behaving as a capacitor and the capacitance is not very dependent on the exact solution specific conductance, resulting in poor, zero, or even negative response. We investigated, both theoretically and experimentally, capillaries with inner radii of 5–160 μm and σ ≈ 1–1400 μS/cm, resulting in cell resist...

Admittance Detector for High Impedance Systems: Design and Applications

Abstract: We describe an admittance detector for high impedance systems (small capillary bore and/or low solution specific conductance). Operation in the low frequency range (≤1 kHz, much lower than most relevant publications) provides optimum response to conductance changes in capillaries ≤20 μm in bore. The detector design was based on studies described in a preceding companion paper (Zhang, M.; Stamos, B. N.; Amornthammarong, N.; Dasgupta, P. K. Anal. Chem. 2014, 86, DOI 10.1021/ac503245a.). The highest S/N for detecting 100 μM KCl (5.5 μM peak concentration, ∼0.8 μS/cm) injected into water flowing through a capillary of 7.5 μm inner radius (r) was observed at 500–750 Hz. A low bias current operational amplifier in the transimpedance configuration permitted high gain (1 V/nA) to measure pA–nA level currents in the detection cell. Aside from an oscillator, an offset-capable RMS-DC converter formed the complete detection circuitry. Limits of detection (LODs) of KCl scaled inversely with the capillary cross section...

Formaldehyde content of atmospheric aerosol.

Abstract: Formaldehyde (HCHO) is a highly soluble polar molecule with a large sticking coefficient and thus likely exists in both gaseous and particulate forms. Few studies, however, address particulate HCHO (HCHO(p)). Some report that HCHO(p) concentrations (obtained only with long duration sampling) are very low. The lack of data partly reflects the difficulty of specifically measuring HCHO(p). Long duration filter sampling may not produce meaningful results for a variety of reasons. In this work, gaseous HCHO (HCHO(g)) and (HCHO(p)) were, respectively, collected with a parallel plate wet denuder (PPWD) followed by a mist chamber/hydrophilic filter particle collector (PC). The PPWD quantitatively removed HCHO(g) and the PC then collected the transmitted aerosol. The collected HCHO from either device was alternately analyzed by Hantzsch reaction-based continuous flow fluorometry. Each gas and particle phase measurement took 5 min each, with a 10 min cycle. The limits of detection were 0.048 and 0.0033 μg m(-3), respectively, for HCHO(g) and HCHO(p). The instrument was deployed in three separate campaigns in a forest station in western Japan in March, May, and July of 2013. Based on 1296 data pairs, HCHO(p), was on the average, 5% of the total HCHO. Strong diurnal patterns were observed, with the HCHO(p) fraction peaking in the morning. The relative humidity dependence of the partition strongly suggests that it is driven by the liquid water content of the aerosol phase. However, HCHO(p) was 100× greater than that expected from Henry's law. We propose that the low water activity in the highly saline droplets lead to HCHO oligomerization.

An open tubular ion chromatograph.

Abstract: We describe an open tubular ion chromatograph (OTIC) that uses anion exchange latex coated 5 μm radius silica and 9.8 μm radius poly(methyl methacrylate) tubes and automated time/pressure based hydrodynamic injection for pL–nL scale injections. It is routinely possible to generate 50 000 plates or more (up to 150 000 plates/m, columns between 0.3 and 0.8 m have been used), and as such, fast separations are possible, comparable to or in some cases better than the current practice of IC. With an optimized admittance detector, nonsuppressed detection permits LODs of submicromolar to double digit micromolar for a variety of analytes. However, large volume injections are possible and can significantly improve on this. A variety of eluents, the use of organic modifiers, and variations of eluent pH can be used to tailor a given separation. The approach is discussed in the context of extraterrestrial exploration, especially Mars, where the existence of large amounts of perchlorate in the soil needs to be confirme...

Electrochemical arsine generators for arsenic determination.

Abstract: Arsine generation is the gateway for several sensitive and selective methods of As determination. An electrochemical arsine generator (EAG) is especially green: we report here the use of two electrode materials, aluminum and highly oriented (ordered) pyrolytic graphite (HOPG) never before used for this purpose. The first is operated on a novel constant voltage mode: current flows only when the sample, deliberately made highly conductive with acid, is injected. As a result, the cathode, despite being a highly active metal that will self-corrode in acid, lasts a long time. This EAG can be made to respond to As(III) and As(V) in an equivalent fashion and is fabricated with two readily available chromatographic T-fittings. It permits the use of a wire roll as the cathode, permitting rapid renewal of the electrode. The HOPG-based EAG is easily constructed from ion chromatography suppressor shells and can convert As(III) to AsH3 quantitatively but has significantly lower response to As(V); this difference can b...

Cavity-enhanced absorption measurements across broad absorbance and reflectivity ranges.

Abstract: Cavity-enhanced spectrometry constitutes an important and highly sensitive technique for absorbance measurements. The current practice generally involves very high reflectivity mirrors and hence intense light sources (typically lasers) to have enough light transmitted. Available theory describes the situation only for high-finesse cavities (high-reflectance mirrors) and generally for systems with very low absorbances. We develop the general expression for absorbance regardless of mirror reflectivity or the absorbance and show that in the limit of high reflectivities and low absorbances it predicts the same numerical values as that derived by O’Keefe (Chem. Phys. Lett. 1998, 293, 331−336; Chem. Phys. Lett. 1999, 307, 343–349). Signal to noise in any photometric system is also dependent on the amount of light reaching the detector because of shot noise limitations. We show that a small aperture in the entrance mirror greatly improves light throughput without significant departure from the theoretically pred...

What Can In Situ Ion Chromatography Offer for Mars Exploration

Abstract: The successes of the Mars exploration program have led to our unprecedented knowledge of the geological, mineralogical, and elemental composition of the martian surface. To date, however, only one mission, the Phoenix lander, has specifically set out to determine the soluble chemistry of the martian surface. The surprising results, including the detection of perchlorate, demonstrated both the importance of performing soluble ion measurements and the need for improved instrumentation to unambiguously identify all the species present. Ion chromatography (IC) is the state-of-the-art technique for soluble ion analysis on Earth and would therefore be the ideal instrument to send to Mars. A flight IC system must necessarily be small, lightweight, low-power, and have low eluent consumption. We demonstrate here a breadboard system that addresses these issues by using capillary IC at low flow rates with an optimized eluent generator and suppressor. A mix of 12 ions known or plausible for the martian soil,...

Method and apparatus for scanning detection

Abstract: An apparatus (30) for scanning and detecting analytes in real time as they move through a separation conduit is provided. The apparatus generally comprises a stationary base (32), a separation conduit (33) mounted on said base, a carriage (35) movably supported on said base and configured to move along a length of said separation conduit, an integrated detector (37) mounted on the carriage and located immediately adjacent to the separation conduit, and a driver (39) moving the carriage relative to the base so that the integrated detector moves back and forth along the length of the separation conduit. A method for real time analysis of analytes as they move through a separation conduit is also provided.