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Pretreatment of wastewater from triazine manufacturing by coagulation, electrolysis, and internal microelectrolysis.

We studied the pretreatment of concentrated wastewater from triazine manufacturing by coagulation, electrolysis, and internal microelectrolysis. Results show that coagulation by polyaluminum chloride at dosage of 0.5 g/L could remove up to 17.2% chemical oxygen demand (COD) from the wastewater. Electrolysis using iron electrode achieved 33.2% COD removal at current of 2A in 180 min, which was attributed to coagulation and oxidation of the organic contaminants in the wastewater by the radicals (OH and O) and oxidants (O2, O3, and H2O2) produced in electrochemical reactions. Internal microelectrolysis using iron chips and granular activated carbon (GAC) showed that up to 60.5% COD could be removed under the conditions of iron/GAC/wastewater volumetric ratio of 3:2:490, sparge ratio (ratio of air flow rate to volume of wastewater) of 2:490 min(-1), and reaction time of 132 h. COD reduction in internal microelectrolysis was attributed to a combination of chemical and physical processes, mainly oxidation by radicals and oxidants formed in electrochemical reactions, adsorption on, co-precipitation with, and enmeshment in ferrous and ferric hydroxides resulted from Fe2+ released during anode oxidation. The results suggest that internal microelectrolysis using iron chips and GAC is a promising, low-cost alternative for pretreating concentrated wastewater from pesticide manufacturing.

Aluminum Hydroxide↗

Synthesis, properties and thermal studies of oxorhenium(V) complexes with 3-hydrazino-5,6-diphenyl-1,2,4-triazine, benzimidazolethione and 2-hydrazinobenzimidazole. Mixed ligand complexes, pyrolytical products and biological activity.

A series of biologically active complexes of oxorhenium(V), were prepared by using the organic ligands 3-hydrazino-5,6-diphenyl-1,2,4-triazine (HL1), benzimidazolethione (H2L2) and 2-hydrazinobenzimidazole (H2L3). The mixed ligand complexes of oxorhenium(V) with the previous ligands and one of the following ligands: NH4SCN, 1,10-phenanthroline (1,10-phen), 8-hydroxyquinoline (8-OHquin) or glycine (Gly), were isolated. All the binary and mixed ligand complexes have monomeric structures and exist in the octahedral configuration. Thermal studies on these complexes showed the possibility of structural transformation from mononuclear into binuclear ones. The structures of all complexes and the corresponding thermal products were elucidated by elemental analyses, IR, electronic absorption and 1H NMR spectra, magnetic moments, conductance and TG-DSC measurements. The antifungal activities of the metal complexes towards Alternaria alternata and Aspergilus niger were tested and showed comparable behaviour with some well known antibiotics.

Alternaria↗

A study of peroxyoxalate-chemiluminescence of 4,4'-bis{[4,6-bis (2-hydroxyethyl)amino-1,3,5-triazin-2-yl]amino}stilbene-2,2'-disulfonic acid-disodium salt as a novel blue fluorescer.

The chemiluminescence arising from the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in the presence of brightener 4,4'-bis{[4,6-bis(2-hydroxyethyl)amino-1,3,5-triazin-2-yl]amino}stilbene-2,2'-disulfonic acid-disodium salt (Triazinyl) has been studied. The influence of concentration of TCPO, hydrogen peroxide, Triazinyl, base catalysts and temperature on the resulting chemiluminescence was investigated. The kinetic parameters for the peroxyoxalate-chemiluminescence (PO-CL) of Triazinyl were evaluated from computer fitting of the resulting intensity-time plots. The activation energies, E(a), were evaluated from temperature dependence of the corresponding rise and fall rate constants.

Fluorescence↗

Immunomodulation of human natural killer cell cytotoxic function by triazine and carbamate pesticides.

Triazine (atrazine) and carbamates (maneb, metiram, and ziram) are used as pesticides on a variety of crops around the world. To our knowledge, there have been no studies dealing with the effects of these compounds on human natural killer (NK) cells cytotoxic function. NK cells play a central role in immune defense against tumor development and viral infections. Thus, any agent that interferes with the ability of NK cells to lyse their targets could increase the risk of tumor incidence and/or viral infections. In this study, we examined the effects of atrazine, maneb, metiram, zineb, and ziram on the ability of human NK cells to lyse tumor cells. The compounds were tested in both purified NK cells as well as a cell preparation that contained both T and NK lymphocytes (T/NK cells). Lymphocytes were exposed to the compounds for periods of time ranging from 1 h to 6 days. Exposure of highly purified NK cells to 10 microM atrazine, maneb, or metiram inhibited K562 tumor cell lysis by 63+/-25, 95+/-4, and 50+/-6%, respectively, after a 24 h exposure and by 83+/-21, 70+/-39, and 48+/-41% after a 6-day exposure. Exposure to 2.5 microM ziram for 24 h caused a 99+/-2% decrease in lytic function and at 1 microM for 6 days caused a 96+/-4% decrease. However, when T/NK cells were exposed to atrazine, maneb, or metiram for 24 h only 10 microM atrazine and maneb caused a significant decreases in lytic function (61+/-13 and 38+/-18%) and after 6 days only atrazine was inhibitory (54+/-12%). A 24-h exposure to 2.5-microM ziram caused a 41+/-51% decrease in function, but a 6-day exposure to 1 microM ziram caused no inhibition of lytic function. The results provide evidence of relative toxic potential for the five compounds and the immunomodulatory effects on both T and NK lymphocyte function.

Adjuvants, Immunologic↗

Serum iron determination using ferene triazine.

The synthesis and characterisation of a new colorimetric reagent for iron, 3-(2-pyridyl)-5,6-bis(2-furyl)-1,2,4-triazine are described. Peak assignments and chemical shifts of the high resolution 13C nmr spectrum are given. The reagent forms a tris iron(II) complex with epsilon max of 32000 Lcm-1 mol-1 at 577 nm. The results of precision, linearity and recovery studies for use of the reagent in direct serum iron determinations are reported. Thiourea effectively suppresses copper interference for the serum iron determinations. With the procedure used, the presence of hemolysed cells in the serum had no effect on serum iron levels recorded.

Chromogenic Compounds↗

Detection of the cyclic nitramine explosives hexahydro-1,3,5-trinitro- 1,3,5-triazine (RDX) and octahydro- 1,3,5,7-tetranitro- 1,3,5,7-tetrazine (HMX) and their degradation products in soil environments.

The cyclic nitramine explosives hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine (HMX) were examined in field and microcosm soil samples to determine their patterns of degradation and environmental fates. A number of analytical techniques, including solid-phase microextraction with on-fiber derivatization, gas chromatography-mass spectrometry, gas chromatography with electron-capture detection, liquid chromatography-mass spectrometry, and micellar electrokinetic chromatography were required for the analyses. Two different classes of intermediates were detected, both of which lead ultimately to the formation of nitrous oxide (N2O) and carbon dioxide (CO2). The first class was identified as the nitroso derivatives formed by the sequential reduction of -NO2 functional groups. The second class of intermediates, which was favored at higher humidities and in the presence of anaerobic sludge amendments, consisted of ring cleavage products including bis-(hydroxymethyl)-nitramine and methylenedinitramine. Rye-grass (Lolium perenne) present in field samples was found to extract and accumulate HMX from soil without further degradation. In all cases (excepting the plant samples), the indigenous microbes or amended domestic anaerobic sludge consortia degraded the cyclic nitramine explosives eventually to produce N2O and CO2.

Azocines↗

On-line concentration of s-triazine herbicides in micellar electrokinetic chromatography using a cationic surfactant.

On-line concentration of neutral species of s-triazine herbicides in micellar electrokinetic chromatography using tetradecylammonium bromide (TTAB) as a cationic surfactant was investigated. Factors affecting the stacking of analytes were examined. The results indicate that the stacking efficiency is markedly improved with addition of phosphate buffer in the sample matrix. It was found that, depending on the nature of the analytes, the most effective stacking of these analytes occurs when the ratio of the conductivity of buffer electrolyte to that of sample matrix is in the range 1.4-1.2, with sample matrix containing phosphate buffer. Micelle concentration in the separation buffer is also a crucial factor to enhance the stacking efficiency and detection sensitivity of analytes. Moreover, the stacking efficiency of each individual analyte depends on its binding constant to TTAB micelles. The concentration effect is primarily based on sweeping mechanism which is operated in a normal stacking mode with reversed electrode polarity in the presence of reversed electroosmotic flow. As a result of concentration enhancement, the detection limits of these herbicides can reach about 9-15 ng/ml with UV detection.

Chromatography, Micellar Electrokinetic Capillary↗

Use of immobilized triazine dyes in the purification of DNA topoisomerase I (Topo I) and terminal deoxynucleotidyl transferase (TdT) from calf thymus.

The interaction between TdT and Topo I, and twelve various triazine dyes immobilized on Sepharose CL-6B was studied. Yellow lightproof 2KT-Sepharose and Bordeaux 4ST-Sepharose were used to purify TdT and Topo I, respectively. The principal role of copper ions, complexed to the dye molecules, in the dye-protein interaction was evaluated.

Animals↗

Determination of triazines and organophosphorus pesticides in water samples using solid-phase extraction.

Octadecyl (C18)-bonded porous silica was evaluated for the extraction of triazine and organophosphorus pesticides from natural water. The extraction results showed an effective performance when 11 of water was passed through small glass columns containing 500 mg of 50-100-microns C18 bonded porous silica. The adsorbed compounds were removed with ethyl acetate, evaporated to 200 microliters and determined by gas chromatography. The overall average recoveries were greater than 85% except for dimethoate and trichlorfon. Application of this procedure to the analysis of natural water samples gave results that agree well with those obtained by solvent extraction methods.

Chromatography, Gas↗

Parameters determining affinity partitioning of yeast enzymes using polymer-bound triazine dye ligands.

Triazine dyes, bound to polyethylene glycol, have been used to influence the partition of some enzymes within a dextran-polyethylene glycol-water two-phase system. The enzymes, present in a protein extract from baker's yeast, included glucose 6-phosphate dehydrogenase, glyceraldehyde phosphate dehydrogenase, 3-phospho-glycerate kinase and alcohol dehydrogenase. The partition coefficients of the enzymes could be changed by a factor of 10-500 in favour of the polyethylene glycol-rich phase, while the partition of bulk protein was much less affected. The influence of the concentration of polymer-bound dye and phase-forming polymers, temperature, pH, kind and concentration of salt and the presence of nucleotides on this affinity partitioning effect was studied. The extraction was effective even at high concentrations of dye and protein (40 g/l). A partial purification (32-fold) of glucose 6-phosphate dehydrogenase was carried out by an extraction in five steps.

Chromatography, Affinity↗

Membrane-assisted solvent extraction of triazines and other semi-volatile contaminants directly coupled to large-volume injection-gas chromatography-mass spectrometric detection.

A simple device was developed for in-vial liquid-liquid extraction using a polymer membrane (nonporous polypropylene) to separate an aqueous sample from an organic extractant. The membrane consisted of tubing with an internal diameter of 6 mm and a wall thickness of 0.05 mm, which was heat-sealed at the lower end and filled with 500 microl hexane. This membrane bag was incorporated into a conventional 20 ml headspace vial suitable for a multi-purpose sampler (MPS 2, Gerstel, Mülheim, Germany) directly interfaced to a gas chromatograph with a mass-selective detector. The sampler enabled the extraction vial to be mixed at a defined temperature with subsequent large-volume injection of the organic extract taken from the membrane bag. The method was evaluated using several triazines, 2,4-dichloroaniline, alpha-hexachlorocyclohexane and phenanthrene as model compounds. Extraction parameters such as temperature, agitation speed, and extraction time were optimised. Recoveries of 60-90% were achieved after 30 min extraction. By increasing the injection volume to 100 microl, detection limits of 1-10 ng/l were determined.

Gas Chromatography-Mass Spectrometry↗

New triazine spectroscopic reagent for the separation of DL-amino acids by micellar electrokinetic chromatography.

An approach to the chiral separation of racemic mixtures of amino acids by means of micellar electrokinetic chromatography after derivatization with a new triazine spectroscopic reagent, 3-(4,6-dichloro-1,3,5-triazinylamino)-7-dimethylamino-2-methylphenazine (DTDP), has been evaluated. It was found that the derivatives of the aliphatic amino acids such as serine, valine and arginine, could produce a strong UV absorption at 282 nm, whose apparent molar absorptivities are of 10(-4) M(-1) cm(-1), and thus the concentration of the amino acids down to 3 x 10(-7) M can still give a detectable signal (S/N = 3). Beta-Cyclodextrin (beta-CD) added to the buffer system was used as a chiral selector, and separation conditions were optimized. The presence of an organic modifier (2-propanol) was also a prerequisite for the chiral separation. The best results for the chiral separation of DTDP-amino acids were achieved in a mixed sodium dodecylsulfate-beta-CD-borate-2-propanol medium at pH 9.0. Compared to some of the commonly used derivatization methods, the present one offers a relatively stable derivative and strong UV absorption for the spectroscopically inert amino acids, thus enabling amino acids to be separated and detected by CE even with a simpler UV detector.

Amino Acids↗

Correlation of retention parameters of pesticides in normal- and reversed-phase systems and their utilization for the separation of a mixture of 14 triazines and urea herbicides by means of two-dimensional thin-layer chromatography.

The selectivities of TLC systems were compared by use of correlations between RF(II) and RF(I) (by analogy with two-dimensional TLC). The greatest spread of points, indicative of individual selectivity, was obtained for nonaqueous mobile phases on silica and aqueous mobile phases on octadecyl silica adsorbent wettable with water (RP-18 W). The correlation of RF values in normal- and reversed-phase systems was utilized in the practical separation of a mixture of 14 triazines and urea herbicides using two-dimensional thin-layer chromatography on a Multi-K CS5 dual phase (3 cm strip of octadecyl silica parallel to silica layer). The plate was videoscanned showing the real picture of the plate.

Chromatography, Thin Layer↗

Synthesis of a silica-bonded bovine serum albumin s-triazine chiral stationary phase for high-performance liquid chromatographic resolution of enantiomers.

A novel method of synthesizing protein chiral stationary phase (protein-CSP) is proposed with 2,4,6-trichloro-1,3,5-triazine as the activator. The bovine serum albumin (BSA) based chiral columns (150 x 4.6 mm I.D.) were prepared successfully within 8 h. With tryptophan as the probe solute, it was observed that the BSA immobilized by this method had a better ability to distinguish enantiomers than that activated by glutaric dialdehyde. This may be due to the well-maintained BSA conformation and the larger amount of BSA immobilized on the silica gel. The BSA-CSP prepared by this method was relatively stable under experimental conditions, and the resolution of 13 chiral compounds was achieved. The coupling reaction in this method is mild, reliable and reproducible; it is also suitable for the immobilization of various biopolymers in the preparation of bioreactor, biosensor and affinity chromatography columns.

Chromatography, High Pressure Liquid↗

Use of solid-phase extraction and high-performance liquid chromatography for the determination of triazine residues in water: validation of the method.

A method for determination of some triazine residues in water has been developed. The method involves concentration with C18 solid-phase extraction cartridges followed by high-performance liquid chromatographic analysis using a C18 column with UV detection at 230 nm, a mobile phase of methanol-water (60:40, v/v) at pH 4.6 (phosphoric acid) and a flow-rate of 0.8 ml/min. After optimization of the extraction and separation conditions, the method was validated. The method can be used for determination of atrazine, simazine, cyanazine and ametryn in water, within the international limits of 0.1 microg/l.

Chromatography, High Pressure Liquid↗

Determination of triazine herbicides in natural waters by solid-phase extraction and non-aqueous capillary zone electrophoresis.

Capillary zone electrophoresis (CZE) in an organic medium was used to analyse triazines at sub-ppb concentration levels in natural waters after a preconcentration step using conventional C18 cartridges and new Oasis HLB devices. With both sorbents, satisfactory results were obtained on analysing deionized water. However, on analysing natural waters, both sorbents showed very different types of behaviour. The different variables affecting the elution of both sorbents were studied, resulting in the choice of Oasis HLB as the most suitable for later separation by CZE in non-aqueous medium. Combination of a preconcentration step with electrokinetic injection revealed that capillary electrophoresis with simple UV detection can also be used satisfactorily for the quantification of micropollutants in natural waters. The detection limits obtained varied between 0.01 and 0.05 microg l(-1), depending on the type of matrix analysed. The day-to-day precision varied between 0.9% and 2.3%, expressed as the relative standard deviation.

Electrophoresis, Capillary↗

Hindered amine stabilizers investigated by the use of packed capillary temperature-programmed liquid chromatography. I. Poly((6-((1,1,3,3-tetramethylbutyl)-amino)-1,3,5-triazine-2,4- diyl)(2,2 ,6,6-tetramethyl-4-piperidyl)imino)-1,6-hexanediyl ((2,2,6,6-tetramethyl-4-piperidyl)imino)).

Three different trademarks of a hindered amine stabilizer with the IUPAC name poly((6-((1,1,3,3-tetramethylbutyl)-amino)-1,3,5-triazine-2,4-d iyl)(2,2,6,6-tetramethyl-4-piperidyl)imino)-1,6-hexanediyl(( 2,2 ,6,6-tetramethyl-4-piperidyl)imino)), have been analyzed and compared to each other by the use of non-aqueous packed capillary temperature-programmed liquid chromatography and light scattering detection. The analysis by this method has shown that the products contained almost 40 different homologues and other components. This is in contrast to what has been assumed earlier based on results achieved with size exclusion chromatography. The method demonstrated significant differences between the products from different manufacturers.

Amines↗