Gold-activated luminol chemiluminescence for the selective determination of cysteine over homocysteine and glutathione.

This work reports a chemiluminescence assay for the highly selective determination of cysteine in biological fluids without separation techniques. The method is based on the ability of cysteine to selectively enhance the metal-catalyzed chemiluminescence generated by the oxidation of luminol from gold tetrachloride anions under alkaline conditions. The selectivity of the method stems from the fact that, under strongly alkaline conditions, the formation of the four-membered ring transition state of cysteine is less favorable as compared to the formation of the respective 5- and 9- membered ring transition states of homocysteine and glutathione, respectively. These transition states exert stronger hindrance and hydrophobic interactions repelling the negatively charged luminol dianion and possibly exhibit lower reducing ability for dissolved oxygen, towards the formation of superoxide radicals, thus reducing the oxidation of luminol. Under the optimum experimental conditions, the linear range of the method extended from 0.5 to 20 µΜ while cysteine could be determined at concentrations as low as 0.5 µM, with good reproducibility (<3.5%) and recoveries between 80 and 93% in artificial and real biological fluids.

Chemometric procedure for the study of fractionated wastewater ingredients using RP-HPLC/diode array spectrophotometer.

A fast screening method of domestic wastewater is reported based on fractionation with RP-HPLC and diode array absorption detection implemented by chemometric treatment of the spectra using cluster analysis, deconvolution, simulation, and multiple regression statistical techniques. The proposed method is limited to constituents that absorb in the UV-Vis region which include most of the toxic organic pollutants.

Removal and recovery of p-phenylenediamines developing compounds from photofinishing lab-washwater using clinoptilolite tuffs from Greece.

Clinoptilolite tuffs from areas in Thrace region of Greece are compared with synthetic zeolites NaY and NH4Y for the uptake of N4-ethyl-N4-(2-methansulphonamidoethyl)-2-methyl-1,4-phenylenediamin (sesquisulphate, monohydrate) with the trade name CD-3 for the purpose to be used for clean-up and recycling photo-finishing and photo-developing washwaters. The cation-exchange capacity is found to be 6.15-11.1 mg/g for zeoliferous tuffs at equilibrium concentration of 50 ppm CD-3 in aqueous solution compared to 65.0 mg/g of NaY and 48.2 mg/g for NH4Y synthetic zeolites corresponding to the removal of CD-3 from 120 to 2001 of 50 ppm aqueous solution per kg of natural zeoliferous tuff; this capacity is only 6-10 times lower than type-Y synthetic zeolite. Initial rates of uptake are 20.8 mg/l/min for natural and 38.5 mg/l/min for synthetic zeolites. Regeneration levels of 55, 23, 35, and 33% are obtained for MCH, SF, NaY, and NH4Y, respectively. The rapid and almost complete uptake of CD-3 from its aqueous solutions at low CD-3 concentrations by the natural zeolites is promising for such an application.

Chemiluminescence (CL) emission generated during oxidation of pyrogallol and its application in analytical chemistry. I. Effect of oxidant compound.

An investigation of chemiluminescence (CL)-emission generated by the oxidation of pyrogallol using various inorganic oxidant compounds is reported in this F.I.A.-merging zone application. The oxidant compounds that showed measurable CL-emission were permanganate, periodate, hypochlorite anions, cerium(IV) and hydrogen peroxide. The different oxidant compounds showed CL-emissions at different pH-ranges. The CL-emission was limited by the inner filter effect and this was more intense for oxidants of selective oxidation. Kinetic effects were also found in the case of oxidation by permanganate. Plots of CL-emission against pH give evidence of speciation and or deactivation mechanism effects. The analytical parameters for the determination of the oxidants are given. Sensitivities of 895 600, 19 500, 33 723, 10 680 and 56 703 mV M(-1) were found for the determination of permanganate, cerium(IV), periodate, hypochlorite and hydrogen peroxide, respectively. The calibration curves of the oxidant determination were generally S-shaped; the S-shaped calibration curve of periodate was closer to a straight line relationship while that of hypochlorite was almost a straight line; detection limits in the range of 10(-4) M oxidant concentration were found for nearly all oxidants. The analytical parameters for determination of pyrogallol by the CL-emission generated through oxidation by the different oxidants at optimum conditions were 1.16x10(6) mV M(-1) for permanganate; 0.086x10(6) mV M(-1) for cerium(IV); 0.91x10(6) mV M(-1) for periodate; 0.012x10(6) mV M(-1) for hypochlorite; and 0.25x10(6) mV M(-1) for hydrogen peroxide. The detection limit was 1.0x10(-4) M. The nearly straight-line relationship (initial part of the plot) for CL-emission with oxidant concentration gives an indication that the CL-reaction of pyrogallol oxidation by hypochlorite proceeds through a process that involves energy transfer while the pronounced S-shaped curve produced by permanganate gives the indication that the reaction proceeds through a process that does not involve energy transfer according to the mathematical model of CL-emission that controls the F.I.A.-merging zone technique of the flow apparatus used in this work. The sequence of completeness of the oxidation process by each oxidant was MnO(4)(-)>H(2)O(2)>IO(4)(-)>OCl(-); the stoichiometric quantity of the oxidant per pyrogallol molecule for the rapid part of the overall oxidation by each different oxidant was attempted; this is an index-value of the oxidation state of the fluorescent excited molecule. Finally, the impact of the above findings for further analytical applications is discussed.