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Purnendu K Dasgupta

Publications and source records attributed to Purnendu K Dasgupta.

32 records · Page 2Linked to original sources
PubMed2004

Mid-ultraviolet light-emitting diode detects dipicolinic acid.

Dipicolinic acid (DPA, 2,6-pyridinedicarboxylic acid) is a substance uniquely present in bacterial spores such as that from anthrax (B. anthracis). It is known that DPA can be detected by the long-lived fluorescence of its terbium chelate; the best limit of detection (LOD) reported thus far using a large benchtop gated fluorescence instrument using a pulsed Xe lamp is 2 nM. We use a novel AlGaN light-emitting diode (LED) fabricated on a sapphire substrate that has peak emission at 291 nm. Although the overlap of the emission band of this LED with the absorption band of Tb-DPA (lambda(max) doublet: 273, 279 nm) is not ideal, we demonstrate that a compact detector based on this LED and an off-the-shelf gated photodetection module can provide an LOD of 0.4 nM, thus providing a basis for convenient early warning detectors.

Aerosols↗
PubMed2003

A continuous analyzer for soluble anionic constituents and ammonium in atmospheric particulate matter.

A new continuous soluble particle collector (PC) that does not use steam is described. Preceded by a denuder and interfaced with an ion chromatograph, this compact collector (3 in. o.d., approximately 5 in. total height) permits collection and continuous extraction of soluble components in atmospheric particulate matter. The PC is mounted atop a parallel plate wetted denuder for removal of soluble gases. The soluble gas denuded air enters the PC through an inlet. One version of the PC contained an integral cyclone-like inlet. For this device, penetration of particles as a function of size was characterized. In the simpler design, the sampled air enters the PC through a nozzle, and deionized water flows through a capillary tube placed close to the exit side of the nozzle by Venturi action or is forcibly pumped. Some growth of the aerosol occurs in the highly humid mist-chamber environment, but the dominant aerosol capture mechanism involves capture by the water film that forms on the hydrophobic PTFE membrane filter that constitutes the top of the PC and the airflow exit. Water drops coalesce on the filter and fall below into a purpose-machined cavity equipped with a liquid sensor. The water and the dissolved constituents are aspirated by a pump onto serial cation and anion preconcentrator columns. NH4+ captured by the cation preconcentrator is eluted with NaOH and is passed across an asymmetric membrane device. NH3 diffuses from the alkaline donor stream into a deionized water flowing countercurrent; the conductivity of the latter provides a measure of ammonium. The anions on the anion preconcentrator column are eluted and measured by a fully automated ion chromatography system. The total system thus provides automated semicontinuous measurement of soluble anions and ammonium. With a 15 min analytical cycle and a sampling rate of 5 L/min, the limit of detection (LOD) for ammonium is 8 ng/m3 and those for sulfate, nitrate, and oxalate are < or = 0.1 ng/m3. The system has been extensively field tested.

Air Pollutants↗
PubMed2003

Silver-induced enhancement of thiochrome-based peroxide measurements.

Thiamine is presently one of the most attractive substrates used for sensitive fluorometric measurements of peroxides. Thiochrome (TC), a highly fluorescent product, is formed in enzyme-mediated oxidations. It is assumed that H(2)O(2) is nearly quantitatively converted to TC. The reaction cannot differentiate H(2)O(2) from many other peroxides such as methylhydroperoxide (MHP); to perform differential measurements, H(2)O(2) can first be selectively destroyed by a suitable catalyst such as MnO(2). In substituting Ag(2)O for MnO(2) to accomplish the selective destruction of H(2)O(2), we achieved the stated objective but were puzzled by a 3-fold increase in the MHP response in the presence of Ag(2)O. It was soon discovered that traces of dissolved Ag(+) and Hg(2+) can dramatically increase the yield of TC in this reaction from either H(2)O(2) or MHP; the normal yield in fact is only 20%. We present here a reaction scheme and kinetic model that adequately describes this behavior and should provide a path to substantially increase the sensitivity of this important assay method.

Flow Injection Analysis↗
PubMed2003

Chemiluminometric measurement of atmospheric ozone with photoactivated chromotropic acid.

A highly sensitive, robust, fast, affordable measurement system based on interfacial gas-liquid chemiluminescence (CL) on a wetted transparent screen directly on top of a miniature photomultiplier tube provides the basis of an attractive method for ozone (O(3)). Alkaline chromotropic acid (CA, 4,5-dihydroxynaphthalene-2,7-disulfonic acid) chemiluminesces upon exposure to ozone. No light emission is observed from exposure of alkaline CA to NO(2) or H(2)O(2). However, response to ozone is highly dependent on the age and storage condition of the CA solution. As such, quantitative analysis will require frequent calibration, and the method will not be attractive. We have discovered that photoactivation plays the key role in producing (a) compound(s) from chromotropic acid that appear(s) to be the primary agent(s) responsible for the CL reaction with O(3). We thus devised a method wherein a flowing solution of CA (that is stable in neutral/acidic solutions) is rendered alkaline and then exposed for a few seconds on-line to UV radiation. The solution then reacts with ozone on a screen consisting of an "invisible" nylon stocking that provides for low liquid residence time and high light throughput and results in an LOD of 40 pptv, a determination range at least up to 230 ppbv, and 10-90% and 90-10% response times of 130 and 80 ms, respectively. Intra- and interday repeatabilities at the same concentration were 0.32 and 3.8% in relative standard deviation. On the basis of aging, CL, chromatography, and chromatography-mass spectrometry studies, we suggest that the primary CL-active species are likely dimeric semiquinone species derived from CA by a series of radical reactions.

Journal Article↗
PubMed2003

Perchlorate in milk.

Perchlorate was unambiguously detected by ion chromatography-suppressed conductivity (IC-CD) and/or ion chromatography-electrospray mass spectrometry (IC-MS) in seven of seven supermarket milk samples bought randomly in Lubbock, TX. Quantitation by IC-MS and IC-suppressed conductivity detection in conjunction with a preconcentration-preelution method provided comparable results. With a sample cleanup procedure that involved protein removal by ethanol and sequential passage though activated alumina and C-18 silica, the limit of detection for perchlorate in milk was 0.5 microg/L. The levels found ranged from 1.7 to 6.4 microg/L. An evaporated milk sample contained perchlorate at 1.1 +/- 0.6 microg/L level, while we did not find detectable levels in a reconstituted powdered milk sample.

Animals↗
PubMed2003

Trace gas measurement with an integrated porous tube collector/long-path absorbance detector.

Porous membrane tubes filled with an absorbing solution that change colors upon selective reactions with specific gases provide high sensitivity inexpensive gas sensors. These can be routinely used for ambient monitoring in a fully automated manner. We consider both stopped and continuous flow operations and show the superiority of the stopped flow mode theoretically and experimentally. Light throughput through various membrane tubes is presented, and superior performance of such tubes over Teflon AF is shown. Sensors for NO2 and for O3 were based on Griess-Saltzman and indigotrisulfonate chemistries, respectively. A computer-controlled two-LED absorbance measurement system (one wavelength monitors the signal, the other references the system) that also governs automated reagent refilling was implemented. Sub-parts-per-billion-volume detection limits are attainable within a few minutes for both gases. Comparative data with a commercial UV-photometry-based ozone monitor showed excellent agreement with the response pattern of the present instrument. Low cost, ready applicability to the measurement of different gases by merely changing the light source and chemistry, and high sensitivity makes this instrument attractive for both pedagogic and practical purposes.

Journal Article↗
PubMed2003

An energy-efficient self-regulating heater for flow-through applications.

In many experiments, a flow-through heating arrangement is needed to reduce reaction time. Often the reaction conditions require inertness of the wetted material. Heated reactors based on polymeric tubing, notably PTFE, are the most common, and such reactors are typically used in a manner in which they are put in a heated bath or an otherwise thermally conductive potting in which a heater and a temperature sensor are embedded for heating and temperature control. Polymeric tubes are poor conductors of heat; as such, most reactors of this type have very poor energy utilization. We describe here heated flow-through reactors where a wire runs through the entire length of the tubular reactor and where the wire is directly electrically heated. The wire may or may not be electrically insulated. If the exterior of the tube is well insulated, the energy efficiency of such a reactor in heating the fluid of interest is nearly unity. This makes it most suitable for battery-powered applications. If an appropriate wire with a significant temperature coefficient of resistance is chosen, monitoring the current through the device at constant applied voltage indicates the effective mean temperature of the device and thus allows effective temperature control without an additional sensor/controller with essentially instantaneous response. Temperature control within +/- 0.4 degrees C at a mean temperature of 65 degrees C and within +/- 0.9 degrees C at 87 degrees C have been achieved.

Journal Article↗
PubMed2003

A nanoinjector for microanalysis.

We describe a simple miniature injection device that can be used for introduction of nanoliter sample volumes in microfluidic systems. The hybrid microstructure consists of two hydraulically connected parts, a pulse micropump, and a multilevel cross-flow injector. Sample injection is accomplished by creating a transient pressure pulse in the sample line by means of the solenoid-based micropump. The sample line is aligned at right angles to the main carrier flow line. The two flow channels are located in two different parallel planes. The cross section of the two channels is defined by a self-sealing aperture in an elastomer. During the pressure pulse, the sample is introduced through this aperture directly into the main flow stream. Fast impulse-based injection causes rapid mixing of the injected sample with the main flow stream. This permits simple single-line manifold micro flow injection (MFI) systems. The deformation/relaxation of the elastomer is fast and repeatable; as such, rapid serial actuations essentially result in a larger injected sample volume without significantly affecting the peak shape. In the present form, 2-40-nL samples are easily injected by single injection, and the injected volume can be chosen by system parameters. The injection repeatability as observed by a photometric detector is better than 1.2% (n = 100).

Journal Article↗
PubMed2003

Pulsed excitation source multiplexed fluorometry for the simultaneous measurement of multiple analytes. Continuous measurement of atmospheric hydrogen peroxide and methyl hydroperoxide.

Presently, solid-state sources such as light-emitting diodes (LEDs) provide for intense, nearly monochromatic light. They are available over a broad range of emission wavelengths. Unlike incandescent and discharge lamps, LEDs can be turned on and off at high speeds. The resulting light pulses are highly reproducible. This allows the use of a single photomultiplier tube (PMT), often the most expensive component in a high-sensitivity measurement system, as a multiplexed detector with multiple, fiber-optic-coupled, fluorescence-detection cells excited by solid-state sources. A time resolution of 1 min is adequate in many continuous detection schemes. This enables multiple-channel single-detector multiplexed measurement without any loss of S/N. On the basis of this principle, we describe a new automated continuous instrument for the simultaneous measurement of atmospheric hydrogen peroxide and methyl hydroperoxide (MHP). A Nafion membrane diffusion scrubber (DS) is used with hematin-catalyzed oxidation of thiamine to thiochrome for the measurement of H2O2, and an expanded poly(tetrafluoroethylene) (ePTFE) DS is used with a H2O2 destruction catalyst and horseradish peroxidase-catalyzed oxidation of thiamine to thiochrome for the measurement of MHP. The respective limits of detection are 25 pptv and 15 pptv. Design, performance details, and illustrative results from a field campaign (Philadelphia NEO3PS study, 2001) are presented.

Journal Article↗
PubMed2003

Determination of trace perchlorate in high-salinity water samples by ion chromatography with on-line preconcentration and preelution.

A simple, automated system for the determination of trace perchlorate by ion chromatography (IC) with an online preconcentration technique is reported. The sample is preconcentrated, and less strongly held ions preeluted before the analyte is transferred to the principal separation system. This approach provides low limits of detection (LOD) and is particularly robust toward the effect of high concentrations of common anions, such as those present in groundwater samples. It compares favorably with currently promulgated EPA method 314.0. The LOD (S/N = 3) is 0.77 microg/L for a 2-mL reagent water sample and decreases more-or-less proportionately with increasing sample volume, at least up to 20 mL. Even with a sample of conductivity 14.7 mS/cm (approximately that of 0.1 M Na2SO4), the recovery of added perchlorate at the 25.0 microg/L level was still 92%. The concentration of added perchlorate in the range of 1-400 microg/L was linearly correlated to the peak area, with an r2 value of 0.9997. The recovery of perchlorate from artificial samples with different conductivity by the present method compares favorably with those from the currently recommended EPA Method. The ability of this approach to remove matrix interferences suggests that it would be also promising for perchlorate analysis in other challenging samples.

Fresh Water↗
PubMed2003

Selective measurement of gaseous hydrogen peroxide with light emitting diode-based liquid-core waveguide absorbance detector.

Atmospheric H2O2 is typically determined by enzymatically mediated fluorogenic reactions that do not discriminate between H2O2 and organic peroxides. Reactions of Ti(IV) with H2O2 has also been the basis of colorimetric measurements of H2O2 but is too insensitive. A more sensitive determination is possible with the Ti(IV)-4-(2-pyridylazo)resorcinol (PAR) complex, however, unreacted PAR must be chromatographically separated. A titanium(IV)porphyrin complex, oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato]titanium(IV) [TiO(tpypH4)4+], (TiTPyP) was introduced for the measurement of aqueous H2O2. In this paper, we show that TiTPyP can be used for measuring H2O2(g)), it does not respond to CH3HO2. With a proper membrane collector, practically there is no interference from concurrently present gaseous SO2 and O3. The approach permits a S/N = 3 limit of detection (LOD) of 26 pptv with a 50 mm path liquid core waveguide (LCW) absorbance detector and a light emitting diode based light source. This is adequate for real atmospheric measurements.

Journal Article↗
PubMed2002

Microscale continuous ion exchanger.

A microscale continuous ion exchanger based on two liquid streams flowing in parallel is presented. The ion exchange reaction occurs through diffusional transfer of molecules between the ion exchanger phase and the eluent phase and is applied for conductivity suppression. Two approaches are demonstrated. In the first approach, a liquid ion exchanger (i.e. a strongly basic compound, e.g., tetraoctylammonium hydroxide, or a secondary amine, e.g., Amberlite IA-2) is dissolved in an organic solvent immiscible with the aqueous eluent. The system allows for sensitive suppressed conductivity detection of various inorganic cations. When the weakly basic secondary amine is used, conductometric detection of heavy metals is possible. In the second approach, a suspension of finely ground ion-exchange resin is used as the ion exchanger phase. In this case, the suspension need not involve an organic solvent. Theoretical models and computations are presented along with experimental results. The potential of such a system as a chip-scale post-separation suppressor/reactor is evident.

Cations↗
PubMed2002

Oxygen-independent poly(dimethylsiloxane)-based carbon-paste glucose biosensors.

Several silicone oils have been assessed and compared as an internal source of oxygen in connection to their use as binders for carbon-paste glucose biosensors. All four poly(dimethylsiloxane) (PDMS) oils tested a dramatic increase in the oxygen capacity of carbon-paste enzyme electrodes to allow convenient biosensing under severe oxygen-deficit conditions. The resulting oxygen independence is better than that exerted by perfluorocarbon binders or that displayed by mediator-based bioelectrodes. The resistance to oxygen effects is indicated from the identical response (observed in the presence and absence of oxygen) up to 2 x 10(-2) M glucose and the slight (12%) sensitivity loss at 4 x 10(-2) M. The influence of the viscosity of the PDMS binder upon the internal oxygen supply is examined. The PDMS carbon-paste enzyme electrode displays a stable glucose response over prolonged (15 h) operation in an oxygen-free solution. On-line continuous testing indicates favorable dynamic properties with no carry-over effects over the physiological and pathophysiological range (3-12 mM glucose).

Biosensing Techniques↗