A highly sensitive and simple method using HPLC-fluorescence detection with 7-chloro-N-[2-(dimethylamino)ethyl]-2,1,3-benzoxadiazole-4-sulfonamide (DAABD-Cl) as a fluorogenic reagent demonstrated the existence of the low-molecular-weight thiols in the extract of Caenorhabditis elegans (C. elegans). The method includes derivatization of the thiols with DAABD-Cl at 40 degrees C for 10 min in borate buffer (pH 9.0) containing TCEP, CHAPS and EDTA, separation of the derivatives on an ODS column and fluorometric determination of the derivatives at 510 +/- 15 nm with excitation at 400 +/- 15 nm. The identification of the thiols was made by HPLC-electrospray ionization mass spectrometry (LC-MS) following isolation of the derivatives using HPLC-fluorescence detection. Low-molecular-weight thiols were found to exist in the extract of C. elegans, such as cysteine, cysteinylglycine, gamma-glutamylcysteine, reduced glutathione and two other unidentified thiol compounds, confirming the existence of the 'glutathione cycle' in C. elegans similar to the mammalian body.
Porous cellulose beads were quaternized with glycidyltrimethylammonium chloride (GTMAC) to explore a potential use of them as an adsorbent for removal of humic acid (HA) from aqueous medium. The introduction of quaternary ammonium groups was confirmed by FT-IR and XPS analysis. The content of introduced quaternary ammonium groups increased with an increase in the GTMAC concentration. The adsorption capacity increased with a decrease in the initial pH value and attained the maximum value at pH 3 and increased with an increase in the content of quaternary ammonium groups. The removal % increased with the dose of quaternized cellulose beads at both pH 3.0 and 6.0. The adsorption process obeyed the pseudo-second order kinetic model and exhibited a better fit to the Langmuir isotherm model, suggesting that the adsorption of HA is accomplished through the electrostatic interaction between a quaternary ammonium group introduced and a dissociated carboxy group of a HA molecule. The maximum adsorption capacity obtained in this study is comparable to or higher than those published by other articles. HA loaded was completely released to NaOH solutions at higher than 100 mM to regenerate the quaternized cellulose beads. The above-mentioned results clearly show that the quaternized cellulose beads prepared in this study can be used as a regenerable adsorbent with high capacity for removal of HA from aqueous medium.
Polyethylene (PE) plates grafted with a neutral monomer, 2-hydroxyethyl methacrylate (HEMA), and a cationic monomer, 2-(dimethylamino)ethyl methacrylate (DMAEMA), (PE-g-PHEMA)-g-PDMAEMA plates were prepared by the two-step photografting. The Cr(VI) ion adsorption behavior of the (PE-g-PHEMA)-g-PDMAEMA plates was investigated as a function of the amounts of grafted HEMA, amount of grafted DMAEMA, initial pH value, and temperature. The adsorption capacity of the DMAEMA-grafted PE (PE-g-PDMAEMA) and (PE-g-PHEMA)-g-PDMAEMA plates had the maximum value at the initial pH value of 3.0, independent of the temperature. The adsorption capacity of (PE-g-PHEMA)-g-PDMAEMA plates increased with the amount of grafted HEMA (G) in the first-step grafting. The increase in the water absorptivity of the grafted layers and thereby the increase in the degree of protonation of dimethylamino groups on grafted PDMAEMA chains were found to lead to the increase in the adsorption capacity. This adsorption capacity was higher than or comparable to those of other polymeric adsorbents for Cr(VI) ions. The Cr(VI) ion adsorption behavior on both PE-g-DMAEMA and (PE-g-PHEMA)-g-PDMAEMA plates obeyed the mechanism of the pseudo-second-order kinetic model and was well expressed by Langmuir isotherm. The high values of the Langmuir constant suggest that the adsorption of Cr(VI) ions occurs through an electrostatic interaction between protonated dimethylamino groups on grafted PDMAEMA chains and [Formula: see text]ions. Cr(VI) ions were successfully desorbed from PE-g-PDMAEMA and (PE-g-PHEMA)-g-PDMAEMA plates in eluents such as NaCl, NaCl containing NaOH, NHCl, NHCl containing NaOH, and NaOH.
The hexavalent chromium (Cr(VI)) ion adsorption properties were conferred to porous silica beads by introducing alkylamine chains through functionalization with an aminosilane coupling agent, [3-(2-aminoethylamino)propyl]triethoxysilane (AEAPTES), or with an epoxysilane coupling agent, (3-glycidyloxypropyl)triethoxysilane (GOPTES), and polyfunctional amine compounds or poly-ethylenimines (PEIs). The presence of amino groups on the silica beads was confirmed by XPS and the amount of amino groups increased to 0.270 mmol/g by increasing the AEAPTES concentration and/or reaction time. The adsorption capacity of the silica beads functionalized with AEAPTES was the maximum at the initial pH value of 3.0 and the initial adsorption rate increased with an increase in the temperature. The adsorption capacity increased with an increase in the amount of amino groups at pH 3.0 and 30 °C. The adsorption behavior obeyed the pseudo-second order kinetic model and was well expressed by the Langmuir isotherm. These results support that Cr(VI) ion adsorption is accomplished through the electrostatic interaction between protonated amino groups and HCrO4- ions. In addition, the adsorption capacity further increased to 0.192–0.320 mmol/g by treating the GOPTES-treated silica beads with triethylenetetramine, pentaethylenehexamine, or PEI. These empirical, equilibria, and kinetic aspects obtained in this study support that the porous silica-based adsorbents prepared in this study can be applied to the removal of Cr(VI) ions.
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