Sensitive assay for catecholamines in pharmaceutical samples and blood plasma using flow injection chemiluminescence analysis.

A rapid and sensitive chemiluminescence (CL) method using flow injection analysis was described for the determination of three catecholamines: dopamine, adrenaline and dobutamine, based on their greatly enhancing effects on the CL reaction of luminol-potassium periodate in basic solutions. Under the optimized conditions, the calibration graphs relating the increase of CL intensity to the concentration of the analytes were linear. The present method allows for the determination of dopamine, adrenaline, and dobutamine over the range of 1.0 x 10(-10) - 1.0 x 10(-7) g/ml. The relative standard deviations for measurements (n=11) of dopamine, adrenaline and dobutamine were 2.9, 2.3 and 1.8% when the concentrations of three catecholamines were at 1.0 x 10(-9) g/ml, respectively. The detection limits of the method were 2.0 x 10(-11) g/ml dopamine, 1.0 x 10(-11) g/ml adrenaline and 4.0 x 10(-11) g/ml dobutamine. The method was successfully applied to the determination of three catecholamines in pharmaceutical samples and blood plasma.     

Flow-injection determination of trace amounts of dopamine by chemiluminescence detection

A flow-injection analysis (FIA) for the determination of dopamine has been developed. The method is based on the inhibition effect of dopamine on the iron(II)-induced chemiluminescence (CL) of 10,10'-dimethyl-9,9'-biacridinium dinitrate (lucigenin). The presence of a non-ionic surfactant, polyoxyethylene (23) lauryl ether (Brij 35), caused an increase in the inhibition effect. The present method allows the determination of dopamine over the range 1x10(-8)-2x10(-7) mol dm(-3). The relative standard deviation was 0.7% for eight determinations of 6x10(-8) mol dm(-3) dopamine. The detection limit (S/N=3) was 2x10(-9) mol dm(-3) with the sampling rate of 40 samples h(-1). The effect of other catecholamines and compounds of similar structure on the lucigenin CL reaction was studied: quinone, hydroquinone, norepinephrine, pyrocatechol and l-dopa suppressed the CL intensity.     

Determination of catecholamines by CE with direct chemiluminescence detection

A rapid and sensitive method to detect three catecholamines, isoprenaline, epinephrine, and dopamine, by CE coupled with direct luminol-potassium periodate chemiluminescence (CL) detection is described. The conditions for CE separation and CL reaction were systematically optimized. Under the optimum conditions, the baseline separation of three catecholamines was achieved within 6.5 min. The LODs obtained in standard solution were 5.3 x 10(-8 )mol/L for isoprenaline, 4.7 x 10(-8 )mol/L for epinephrine, and 1.5 x 10(-7 )mol/L for dopamine. The RSD of the migration time and peak area were less than 1.8 and 3.6% (n = 5), respectively. The present method was applied to the determination of the dopamine in urine samples of cigarette smokers and nonsmokers. The results obtained indicate that there is a close relationship between the content of dopamine in human urine and the amount of cigarettes smoked daily; the level of dopamine in smokers is higher than in nonsmokers.     

Trace and ultratrace analysis of purified water samples and hydrogen peroxide solutions for phosphorus by flow-injection method.

A highly sensitive fluorescence-quenching method for the determination of phosphorus based on the formation of an ion associate between molybdophosphate and Rhodamine B (RB) was developed. A simple flow-injection system coupled with a fluorescence detector was used to measure the fluorescence intensity at 560 nm and 580 nm as an excitation and an emission wavelength, respectively. The calibration graph for phosphorus showed a good linearity in the range of (0 - 1) x 10(-7) M (1 M = 1 mol L(-1)), and a detection limit of 1 x 10(-9) M (S/N = 3). The proposed method was successfully applied to the determination of ultratrace amounts of phosphorus in ultrapurified and purified water samples, and to the determination of trace amounts of phosphorus in commercially-available hydrogen peroxide solutions with satisfactory results.     

Spectrophotometric determination of methyldopa and dopamine in pharmaceutical formulations using a crude extract of sweet potato root (Ipomoea batatas (L.) Lam.) as enzymatic source

A rapid, precise and low cost spectrophotometric method is proposed for the determination of methyldopa and dopamine in pharmaceutical formulations. The crude extract of sweet potato root (Ipomoea batatas (L.) Lam.) was used as an enzymatic source of polyphenol oxidase (PPO; EC.1.14.18.1). This enzyme catalyses the oxidation of catecholamines to the corresponding methyldopaquinone and dopaminequinone. Those compounds are converted by a rapid spontaneous auto-oxidation to methyldopachrome and dopaminechrome which have a strong absorption at 480 or 470 nm, respectively. The calibration graphs are linear from 2.0x10(-4) to 6.0x10(-3) M. The results obtained by the proposed enzymatic method are in close agreement with those obtained using a Pharmacopoeia procedure and also with the label values. The detection limit (three times the signal blank/slope) was 3.4x10(-5) and 3.0x10(-5) M for methyldopa and dopamine, respectively, the recovery of methyldopa and dopamine from three samples ranged from 97.5 to 102.9% of the added amount.     

Determination of catecholamines and serotonin by micellar electrokinetic chromatography with laser-induced fluorescence detection

6-Oxy-(N-succinimidyl acetate)-9-(2'-methoxycarbonyl) fluorescein, a new synthesized fluorescent reagent, was established for the first time as a label for the sensitive analysis of catecholamines (CAs) and serotonin (5-HT) by micellar electrokinetic chromatography (MEKC) with laser-induced fluorescence detection. After careful study on the derivatization conditions such as pH value, reagent concentration, temperature and reaction time, the labeling reaction was accomplished as quickly as 7 min with stable yield. The separation parameters for the CAs and 5-HT were also optimized in detail. The derivatives were baseline separated in a running buffer containing 30 mM boric acid and 15 mM sodium dodeculsulfate at pH 9.0. The detection limits ranged from 5 x 10(-10) to 2 x 10(-9) M (signal-to-noise ratio = 3). The rapid and sensitive method was also applied to the determination of the CAs and 5-HT of urine samples.     

Simultaneous determination of Cd, Pb, Cu, Sb, Bi, Se, Zn, Mn, Ni, Co and Fe in water samples by differential pulse stripping voltammetry at a hanging mercury drop electrode

A highly sensitive and selective voltammetric procedure is described for the simultaneous determination of eleven elements (Cd, Pb, Cu, Sb, Bi, Se, Zn, Mn, Ni, Co and Fe) in water samples. Firstly, differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) is used for the direct simultaneous determination of Cd, Pb, Cu, Sb and Bi in 0.1 M HCI solution (pH = 1) containing 2 M NaCl. Then, differential pulse cathodic stripping voltammetry (DPCSV) is used for the determination of Se in the same solution. Zn is subsequently determined by DPASV after raising the pH of the same solution to pH 4. Next, the pH of the medium is raised to pH 8.5 by adding NH3/NH4Cl buffer solution for the determination of Mn by DPASV. Ni and Co are determined in the same solution by differential pulse adsorptive stripping voltammetry (DPAdSV) after adding DMG (1 x 10(-4) M). Finally, 1 x 10(-5) M 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) is added to the solution for the determination of Fe by DPAdSV. The optimal conditions are described. Relative standard deviations and relative errors are calculated for the eleven elements at three different concentration levels. The lower detection limits for the investigated elements range from 1.11 x 10(-10) to 1.05 x 10(-9)M, depending on the element determined. The proposed analysis scheme was applied for the determination of these eleven elements in some ground water samples.     

Simultaneous determination of phosphonate, phosphate, and diphosphate by capillary electrophoresis using in-capillary complexation with Mo(VI)

This study describes the simultaneous determination of phosphonate, phosphate, and diphosphate by CE with direct UV detection, based on in-capillary complexation with Mo(VI). When a mixture of phosphonate, phosphate, and diphosphate was injected into a capillary containing 3.0 mM Mo(VI), 0.05 M malonate buffer (pH 3.0) and 45% v/v CH3CN, three well-defined peaks, due to the migration of the corresponding polyoxomolybdate anions, were separated. The respective calibration graphs were linear in the concentration range of 2 x 10(-6)-2 x 10(-4) M for phosphonate, 1 x 10(-6)-5 x 10(-5) M for phosphate, and 1 x 10(-6)-2 x 10(-4) M for diphosphate; the correlation coefficients were better than 0.9990. The present CE method is successfully applied to the simultaneous determination of phosphonate, phosphate, and diphosphate in tap water.     

Differential pulse voltammetric indirect determination of aluminium in drinking waters, blood, urine, hair, and medicament samples using L-dopa under alkaline conditions

The differential pulse voltammetric (DPV) indirect determination of aluminium using L-dopa under alkaline conditions on a glassy carbon working electrode was studied. The proposed method relies on the linear decrease of the DPV anodic peak current of L-dopa with increase in the concentration of aluminium added. Under the optimum experimental conditions (pH 8.5, 0.08 M NH4Cl-NH3.H2O buffer solution, and 4 x 10(-4) M L-dopa), the linear range is 2-18 x 10(-7) M AlIII. The detection limit is 7.6 x 10(-8) M and the relative standard deviation for 8 x 10(-7) M AlIII is 3.5% (n = 8). A number of foreign species were examined as potential interferents. The method was applied to the determination of aluminium in drinking waters, synthetic renal dialysate, sodium chloride injection, sucrafate, hydrothorax, blood, urine and hair samples. The physiological significance is discussed.     

Paracetamol voltammetric microsensors based on electrocopolymerized-molecularly imprinted film modified carbon fiber microelectrodes

A molecularly imprinted polymer is presented as a carbon fiber microelectrode coating for determining the presence of paracetamol. The polymeric film was obtained by electrocopolymerization of o-phenylenediamine and aniline in the presence of the template molecule, through the use of cyclic voltammetry. After removing the template, the signals of the microsensor were converted into physical ones by a voltammetric transductor using square wave voltammetry. Various parameters influencing the electropolymerization and voltammetric determination processes were examined and optimized. The response of the imprinted microsensor to paracetamol was linearly proportional to its concentration over the range 6.5 x 10(-6) to 2.0 x 10(-3) mol l(-1), with good stability and reproducibility (RSD < 5.6%). The detection limit was 1.5 microM. Under the experimental conditions used the voltammetric microsensor was able to differentiate between paracetamol and other closely structurally-related compounds present in biological fluids, such as certain catecholamines.     

Ultratrace determination of europium in high-purity lanthanum, praseodymium and dysprosium oxides by luminescence spectrometry

A luminescence spectrometric method was developed for the determination of ultra trace amounts of europium (down to 1 x 10(-13) M) in high purity lanthanum, praseodymium and dysprosium oxides. This is based on the enhanced luminescence of europium-thenoyltrifluoroacetone (TTA)-dibenzo-18-crown-6 (DBC)-Triton X-100 in the presence of terbium. The fluorescence intensity is linear with europium concentration in the range 1 x 10(-11) - 1 x 10(-6) M under the recommended conditions. The optimized procedure is successfully utilized for the determination of ultratrace amounts of europium in lanthanium, praseodymium and dysprosium oxides.     

PVC membrane ion selective electrode for the determination of pentachlorophenol in water, wood and soil using tetrazolium pentachlorophenolate

A novel PVC membrane electrode selective for the determination of pentachlorophenolate (PCP) ion based on 2,3,5-triphenyl-2H-tetrazolium (TPT) pentachlorophenolate ion pair as an electroactive material is described. The electrode shows a linear response for PCP ion over the concentration range of 6x10(-5) to 1x10(-2) M with lower detection limit of 4x10(-5) M at 25 degrees C. The electrode posses a Nernstian slope of -55.0+/-1.0 mV/decade and a fast potential response of 45 s, which is almost constant over a pH range of 5.5-10.5. Selectivity coefficient data for some common ions show negligible interference, however, 2,4,6-trichlorophenolate and cetylpyridinium ions interfere. An average recovery of 96.2% with relative standard deviation of 2.3% has been achieved for the determination of 75.0 ppm PCP in wastewater samples. The determination of PCP in soil and wood samples gave results that compare favorably with those obtained by gas chromatography. The electrode has been utilized as an end point indicator electrode for the determination of PCP using potentiometric titration.     

Molecular imprinting-chemiluminescence determination of trimethoprim using trimethoprim-imprinted polymer as recognition material

A new molecular imprinting-chemiluminescence method for the determination of trimethoprim was developed, in which trimethoprim-imprinted polymer was used as the molecular recognition material and the CL reaction of trimethoprim with potassium permanganate in acidic medium was used as the detection system. The CL intensity responds linearly to the concentration of trimethoprim within the 5.0 x 10(-8)-5.0 x 10(-6) g mL(-1) range (r= 0.9983) with a detection limit of 2 x 10(-8) g mL(-1). The relative standard deviation for the determination of 1.0 x 10(-7) g mL(-1) trimethoprim solutions is 4.8% (n= 9). The method has been applied to the determination of trimethoprim in pharmaceutical preparations and body fluids, and satisfactory results were obtained.     

A new red-region substrate, tetra-substituted amino aluminium phthalocyanine, for the fluorimetric determination of H2O2 catalyzed by mimetic peroxidases

A new red-region fluorogenic substrate, tetra-substituted amino aluminium pthalocyanine, was developed for the selective determination of H2O2 based on the catalytic effect of mimetic peroxidases, viz., hemin or iron tetrasulfonatophthalocyanine (FeTSPc). Under the optimum conditions, the linearity of the calibration graph for the determination of H2O2 with hemin (or FeTSPc) as the catalyst was in the range from 0.0 to 3.0 x 10(-7) mol L-1 (or from 0.0 to 2.0 x 10(-6) mol L-1). The detection limits were 3.7 x 10(-9) and 4.9 x 10(-9) mol L-1 H2O2, respectively. The relative standard deviation (n = 7) was within 1.5% in the middle of the linear range. The peroxidase activity of the mimetic enzymes hemin and FeTSPc, the effects of some experimental conditions and the influence of foreign substances were investigated. With this substrate, 0.0-7.5 x 10(-8) mol L-1 hemin and 0.0-2.0 x 10(-6) mol L-1 FeTSPc can be determined with an accuracy and precision of about 1.3%. The potential application of the reagent was tested by the determination of H2O2 in rainwater.     

Spectrofluorometric determination of trace amounts of terbium with 4-chlorosalicylic acid, EDTA, and cetyltrimethylammonium bromide.

The quadruple complex formed by terbium with 4-chlorosalicylic acid (CSA), EDTA and cetyltrimethylammonium bromide (CTMAB) has been used for the sensitive spectrofluorometric determination of terbium in mixed rare earths. The effect of the experimental conditions on the fluorescence intensity was defined. Under the optimum conditions selected, the fluorescence intensity was linear with the terbium concentration in the range of 3.0 x 10(-8)-1.0 x 10(-5) mol/L with a detection limit of 8.0 x 10(-9) mol/L (S/N = 3). It has been satisfactory for the determination of terbium in mixed rare earths with good recovery.     

Differential pulse polarographic determination of dicrotophos, crotoxyphos and chlorfenvinphos in grains and soils

A simple, sensitive and rapid differential pulse polarographic method has been developed for the quantitative determination of organophosphorus pesticides such as dicrotophos, crotoxyphos and chlorfenvinphos in agricultural formulations in universal buffers of a pH range 2.0-12.0. The sample is treated with ethanol to facilitate the dissolution of these pesticides. Both standard addition and calibration methods can be used for the analyses. The lower detection limits are 1.25x10(-9), 1.05x10(-9) and 1.0x10(-9) M, respectively. The method can be applied successfully to determination of these pesticides in grains and soil.     

Simultaneous determination of N,N-dimethylaniline and phenol in wastewater by high-performance liquid chromatography with chemiluminescence detection.

A method using HPLC-CL linkage was developed for simultaneous determination of N,N-dimethylaniline and phenol in wastewater, based on the strong sensitive chemiluminescence of the luminol-K3Fe(CN)6 systems in alkaline medium. The separation was carried out on a Hypersil ODS column with a mobile phase of ethanol-0.01% triethylamine (2:1, v/v). The linear ranges for N,N-dimethylaniline determinations were 2.0 x 10(-7) - 2.5 x 10(-5) g/mL and 4.0 x 10(-5) - 1.5 x 10(-4) g/mL with a detection limit (3sigma) of 1.20 x 10(-8) g/mL; the relative standard deviation (3sigma) for 5.0 x 10(-6) g/mL N,N-dimethylaniline was 1.4% (n = 6). The range for phenol was from 5.1 x 10(-7) to 1.3 x 10(-4) g/mL, and a detection limit (3sigma) of 2.5 x 10(-8) g/mL could be obtained. The method can be useful for the determination of N,N-dimethylaniline and phenol in some environmental samples.     

Colorimetric determination of benzocaine, lignocaine and procaine hydrochlorides in pure form and in pharmaceutical formulations using p-benzoquinone.

A simple, accurate and sensitive method for the microdetermination of benzocaine, lignocaine and procaine hydrochlorides in pure forms and in pharmaceutical formulations is described. The procedure is based on the reaction of those drugs in an aqueous acidic medium with p-benzoquinone to form charge-transfer complexes. The method has been used for the determination of 5.0-70, 5.0-60 and 5.0-90 microg ml(-1) of benzocaine, lignocaine HCl and procaine HCl, respectively. The complexes have apparent molar absorptivities of 1.70 x 10(3), 2.79 x 10(3) and 2.42 x 10(3) L mol(-1) cm(-1) and Sandell sensitivities of 9.72, 10.34 and 11.25 ng cm(-2), respectively. The proposed procedure of analysis is as accurate as the British Pharmacopoeial method (2003). The method was successfully used for the determination of those drugs in the presence of their degradation products, additives and excipients, which were normally encountered in pharmaceutical formulations.     

Analysis of various very slightly water soluble drugs in micellar medium

A potentiometric and/or visual method for the determination of sulphamethoxazole (SULF) in pure form in the range of 5.3 x 10(-5) to 5.0 x 10(-4) mol/L is proposed. To enhance the solubility, the determination has been carried out in a micellar medium formed by an aqueous 5.0 x 10(-2) mol/L N-hexadecyl-N,N,N-trimethyl ammonium bromide (CTAB) solution which increases the dissociation constant K(alpha) of SULF about tenfold. The titration is performed with NaOH (2.5 x 10(-3) or 5.0 x 10(-2) mol/L) and the end-point is determined by the second derivative graph. The results agree with those obtained by the official method of the USP XXIII. The method is simple, accurate, economical and can successfully replace the more complicated, more expensive and time-consuming existent procedures which are carried out in a non-aqueous medium.     

Flow injection electrogenerated chemiluminescence determination of vanadium and its application to environmental water sample

A selective flow injection electrogenerated chemiluminescence(CL) method for the determination of vanadium is described in this paper. It was based on the chemiluminescence reaction of luminol with vanadium(II), which was on-line electrogenerated from vanadate using a flow-through carbon electrolytic cell. Under the optimal conditions, the CL intensity was linear to the concentration of vanadium in the range of 5.0x10(-10)-1.0x10(-7) gml(-1) with a detection limit of 2x10(-10) gml(-1) vanadium. The relative standard deviation was 4% for 5.0x10(-8) gml(-1) vanadium in 11 repeated measurements. The method has been successfully applied to the determination of vanadium in environmental water samples.