Showing papers by "Purnendu K. Dasgupta published in 2012"

Iron(III) modification of Bacillus subtilis membranes provides record sorption capacity for arsenic and endows unusual selectivity for As(V).

Abstract: Bacillus subtilis is a spore forming bacterium that takes up both inorganic As(III) and As(V). Incubating the bacteria with Fe(III) causes iron uptake (up to ∼0.5% w/w), and some of the iron attaches to the cell membrane as hydrous ferric oxide (HFO) with additional HFO as a separate phase. Remarkably, 30% of the Bacillus subtilis cells remain viable after treatment by 8 mM Fe(III). At pH 3, upon metalation, As(III) binding capacity becomes ∼0, while that for As(V) increases more than three times, offering an unusual high selectivity for As(V) against As(III). At pH 10 both arsenic forms are sorbed, the As(V) sorption capacity of the ferrated Bacillus subtilis is at least of 11 times higher than that of the native bacteria. At pH 8 (close to pH of most natural water), the arsenic binding capacity per mole iron for the ferrated bacteria is greater than those reported for any iron containing sorbent. A sensitive arsenic speciation approach is thus developed based on the binding of inorganic arsenic species by the ferrated bacteria and its unusual high selectivity toward As(V) at low pH.

A Capacitance Sensor for Water: Trace Moisture Measurement in Gases and Organic Solvents

Abstract: The determination of water in various matrices is one of the most important analytical measurements. We report on a high-resolution capacitance-based moisture sensor utilizing a thin film of a perfluorosulfonate ionomer (PFSI)-H(3)PO(4) composite in a flow-through configuration, for both gas and liquid samples. Incorporation of H(3)PO(4) into a PFSI sensing film improved the limit of detection (LOD) (signal-to-noise ratio, S/N = 3) by a factor of 16 in the gas phase to 0.075% relative humidity (RH) (dew point = -56 °C). The response time was dependent on the sensing film thickness and composition and was as low as ∼60 ms. The temperature dependence of the sensor response, and its relative selectivity over alcohol and various other solvents, are reported. Measurement of water in organic solvents was carried out in two different ways. In one procedure, the sample was vaporized and swept into the detector (e.g., in a gas chromatograph (GC) without a column); it permitted a throughput of 80 samples/h. This is well-suited for higher (%) levels of water. In the other method, a flow injection analysis system integrated to a tubular dialysis membrane pervaporizer (PV-FIA) was used; the LOD for water in ethanol was 0.019% (w/w). We demonstrated the temporal course of drying of ethanol by Drierite; the PV-FIA results showed excellent correspondence (r(2) > 0.99) with results from GC-thermal conductivity detection. The system can measure trace water in many types of organic solvents; no reagent consumption is involved.

Electrodialytic ion isolation for matrix removal

Abstract: We report a fully automated online sample pretreatment system for ionic analytes that extracts the ionic analytes from the sample and largely removes the nonionic sample matrix and can preconcentrate the analyte. Sample pretreatment is a key analytical process; conventional pretreatment is conducted in a difficult to automate batchwise manner. The present system relies on the transport of ions induced by an electric field to a water acceptor. Cations and anions are simultaneously and separately collected into individual acceptor streams which can be directly introduced to a chemical analyzer. Common inorganic ions (≤10 meq/L) are quantitatively transferred from samples within a few seconds. Small nonionic molecules are transferred by 0.5–10%, and proteins are not transferred at all. The method has been successfully applied to drinking water, urine, and cow’s milk with 3.7 ± 2.5, 3.8 ± 2.6, and 4.6 ± 2.6%, respectively, in variance (n = 10). Present results agreed well with those from conventional pretreat...

Resolving DNA in free solution

Abstract: DNA molecules are usually separated by gel electrophoresis. While gels help resolve DNA, the polymers bring problems to the analysis (e.g., difficulty in automating and poor reproducibility). One way to eliminate these problems completely is to separate DNA in free solutions. However, DNA fragments cannot normally be resolved in a free solution by electrophoresis because the electrophoretic mobilities of these molecules have similar charge-to-mass ratios, especially when the fragments are large. Efforts have been invested in free-solution DNA separations and a number of approaches (e.g., high-performance liquid chromatography, end-labeled free-solution electrophoresis, entropic traps, and DNA prism) have been successfully developed. Very recently, a new technique, called bare narrow capillary-open tubular chromatography (BaNC-OTC), was developed and can resolve a wide range of sizes of DNA in a few minutes. In this article, we review the significant progress on free-solution DNA separations, with emphasis on the most recent, advanced developments.

pH- and Concentration-Programmable Electrodialytic Buffer Generator

Abstract: We have presented in a companion paper a suppressor-based electrodialytic buffer generator (EBG) that can produce programmable pH gradients. Here we demonstrate a three-electrode EBG. In this three-compartment flow-through device, the central compartment is separated from the outer compartments with a cation-exchange membrane (CEM) and an anion-exchange membrane (AEM), respectively. One platinum electrode is disposed in each compartment. The flows through each compartment are independent. With appropriate solutions in each compartment, independent potentials are applied to the CEM and AEM electrodes with respect to the grounded central electrode. The CEM current and the AEM current can be independently manipulated to generate buffers with variable concentration and pH in the central compartment. Both the CEM and AEM currents can be positive or negative. For the CEM, a positive current (icatin) indicates that cations are coming in from the CEM channel to the center. A negative current (icatout) takes catio...

Electrodialytic Membrane Suppressors for Ion Chromatography Make Programmable Buffer Generators

Abstract: The use of buffer solutions is immensely important in a great variety of disciplines. The generation of continuous pH gradients in flow systems plays an important role in the chromatographic separation of proteins, high-throughput pKa determinations, etc. We demonstrate here that electrodialytic membrane suppressors used in ion chromatography can be used to generate buffers. The generated pH, computed from first principles, agrees well with measured values. We demonstrate the generation of phosphate and citrate buffers using a cation-exchange membrane (CEM) -based anion suppressor and Tris and ethylenediamine buffers using an anion-exchange membrane (AEM) -based cation suppressor. Using a mixture of phosphate, citrate, and borate as the buffering ions and using a CEM suppressor, we demonstrate the generation of a highly reproducible (avg RSD 0.20%, n = 3), temporally linear (pH 3.0–11.9, r2 > 0.9996), electrically controlled pH gradient. With butylamine and a large concentration (0.5 M) of added NaCl, we ...

Confeito-like assembly of organosilicate-caged fluorophores: ultrabright suprananoparticles for fluorescence imaging

Abstract: We report ultrabright, photostable, sub-25 nm nanoparticle agglomerates (suprananoparticles) assembled from a few hundred 3.3 ± 0.9 nm units, each hosting on average a single rhodamine 6G (Rh6G) dye molecule encased in a thin organosilicate cage. These individual Rh6G-doped nanoparticle (DOSNP) units consist of a hydrophobic core containing the dye and an ultrathin, conformal silicate shell modified by CO2 plasma to confer a beneficial “cage effect” as well as surface hydrophilicity. The isolation of the dye within individual DOSNP units in the final 22 ± 5 nm agglomerate avoids dimerization and related spontaneous molecular interactions that otherwise lead to self-quenching in closely co-localized fluorophores. The resulting suprananoparticles are over 200 times brighter than the free Rh6G molecules in the same volume. There is no observable dye leaching, and the labels are 20-fold more resistant to photobleaching than free Rh6G in solution. We demonstrate the attractive features of DOSNPs as labels in bioimaging applications.

Breastfed infants metabolize perchlorate.

Abstract: Bifidobacteria are the dominant intestinal bacteria in breastfed infants. It is known that they can reduce nitrate. Although no direct experiments have been conducted until now, inferred pathways for Bifidobacterium bifidum include perchlorate reduction via perchlorate reductase. We show that when commercially available strains of bifidobacteria are cultured in milk, spiked with perchlorate, perchlorate is consumed. We studied 13 breastfed infant-mother pairs who provided 43 milk samples and 39 infant urine samples, and 5 formula-fed infant-mother pairs who provided 21 formula samples and 21 infant urine samples. Using iodine as a conservative tracer, we determined the average urinary iodine (UI) to milk iodine (MI) concentration ratio to be 2.87 for the breastfed infants. For the same samples, the corresponding perchlorate concentration ratio was 1.37 (difference significant, p < 0.001), indicating that perchlorate is lost. For the formula fed infant group the same ratios were 1.20 and 1.58; the difference was not significant (p = 0.68). However, the small number of subjects in the latter group makes it more difficult to conclude definitively whether perchlorate reduction does or does not occur.

Electrolytic buffer generator

Abstract: Buffer generators are described based on electrodialytic devices. The methods of using these devices can generate buffers for diverse applications, including separations, e.g., HPLC and ion chromatography. Also provided are chromatographic devices including the buffer generators, generally located upstream from a chromatography column, sample injector valve or both.

Three- electrode buffer generator and method

Abstract: An electrodialytic buffer generator is described. The buffer generator may include a central buffer-generating channel having an inlet and outlet, a second chamber, and a third chamber. The buffer-generating channel, the second chamber, and the third chamber may each include an electrode. The buffer generator may also include a first ion exchange barrier and a second ion exchange barrier. The first ion exchange barrier can be disposed between the second chamber and the buffer- generating channel. The second ion exchange barrier can be disposed between the third chamber and the buffer-generating channel.