High-voltage contactless conductivity detection of underivatized amino acids in capillary electrophoresis

High-voltage contactless conductivity detection of underivatized amino acids in both acidic and basic media is demonstrated. The suitability of different acidic buffer solutions at pH values of about 2.5 was investigated with 12 amino acids. Lactic acid as background electrolyte gave the best results in terms of detection limits for arginine, lysine and histidine, which were approximately 2 x 10(-7), 3 x 10(-7) and 4 x 10(-7) M, respectively. However, the sensitivity for other species was not quite as good and the detection limits in the order of 0.5-1 x 10 (-5) M. The use of basic conditions at pH 10-11 generally led to more stable baselines and more consistent sensitivities. A range of 20 amino acids was investigated with alkaline buffers and detection limits were typically about 10(-6) M. Urine and beer samples were analyzed. Nine and eleven amino acids could be identified, respectively.     

Direct determination of amino acids by pressurized capillary electrochromatography with chemiluminescence detection

A pressurized CEC (pCEC) coupled with on-column chemiluminescence (CL) detection was developed for direct determination of amino acids, which was based on the principle of an enhanced effect of Cu(II)-amino acid complexes on the CL reaction between luminol and hydrogen peroxide in alkaline solution. The effects of some important factors on pCEC separation and CL intensity were systemically investigated. Baseline separation of amino acids including L-histidine (L-His), L-threonine (L-Thr), and L-tyrosine (L-Tyr) was achieved by using a monolithic column with a mobile phase of 5.0x10(-3) mol/L phosphate buffer at pH 8.0 that contained 25% v/v methanol and 5.0x10(-4) mol/L luminol and 1.0x10(-5) mol/L Cu(II) at an applied voltage of -5 kV. The calibration curves of the analytes by plotting the peak height against corresponding concentration were linear over the range of 3.2x10(-6)-3.2x10(-4) mol/L for L-His, 4.1x10(-6)-4.1x10(-4) mol/L for L-Thr, and 6.0x10(-7)-3.0x10(-4) mol/L for L-Tyr. The LODs for L-His, L-Thr, and L-Tyr were 6.4x10(-7), 8.4x10(-7), and 3.0x10(-7) mol/L (S/N = 2), respectively. The proposed method was applied to the analysis of amino acid injection sample with satisfactory results. Mean recoveries for three amino acids were from 84.3 to 89.6%.     

Sequential determination of salicylic and acetylsalicylic acids by amperometric multisite detection flow injection analysis

An amperometric multisite detection flow injection analysis (FIA) system was developed for sequential determination of 2 analytes with a single sample injection and single detector. Tubular composite carbon electrodes with an inner diameter similar to that of the FIA manifold tubing were constructed so that measurements could be made without impairing the sample plug hydrodynamic characteristics. The electrochemical behavior of the tubular voltammetric cell in a low-dispersion FIA manifold and the behavior of the FIA system incorporating this type of voltammetric cell intended for multisite detection were evaluated by performing measurements with potassium hexacyanoferrate(II). Feasibility of the approach was demonstrated in the sequential determination of salicylic and acetylsalicylic acids in pharmaceutical products at a fixed potential of 0.98 V. The system allows sequential determination of salicylic acid concentrations ranging from 1.0 x 10(-5) to 5.0 x 10(-5) M and acetylsalicylic acid concentrations between 1.0 x 10(-3) and 5.0 x 10(-3) M with good precision on both detection sites and with relative standard deviations (RSDs) > or = 1.5% (n = 10) and 2.1% (n = 10), respectively. A comparison of these results with those of the U.S. Pharmacopeia procedure showed RSDs <5.0 and 1.0% for salicylic acid and acetylsalicylic acid, respectively. The proposed method enables 15 determinations per hour, which corresponds to the analysis of approximately 8 samples per hour. The detection limits of the methodology were approximately 3.5 x 10(-6) and 1.1 x 10(-5) M, respectively, for the first and second monitoring sites.     

A facile and sensitive chemiluminescence detection of amino acids in biological samples after capillary electrophoretic separation

It was found that native amino acids enhanced the chemiluminescence (CL) reaction between luminol and BrO(-) in an alkaline aqueous solution. This has led to the development of a facile and highly sensitive CL detection scheme for the determination of amino acids in biological samples after capillary electrophoretic (CE) separation. The CE-CL conditions were optimized. An electrophoretic buffer of 2.5 x 10(-2) M sodium borate (pH 9.4) containing 1 x 10(-4) M luminol was used. The oxidizer solution of 8 x 10(-4) M NaBrO in 0.1 M sodium carbonate buffer solution (pH 12.5) was introduced post-column. Under the optimal conditions, the detection limits were 1.0 x 10(-7) M for glutamic acid (Glu) and 1.3 x 10(-7) M (S/N = 3) for aspartic acid (Asp). The relative standard deviations (RSDs) of peak area and migration time were in the ranges of 3.8-4.3% and 1.4-1.6%, respectively. The present method was applied to the determination of excitatory amino acids (i.e., Asp and Glu) in rat brain tissue and monkey plasma. The levels of these major excitatory amino acids in monkey plasma were quantified for the first time and found to be 1.17 +/- 0.17 x 10(-5) M (mean +/- SD, n = 6) for Glu and 1.64 +/- 0.19 x 10(-6) M for Asp, which were comparable with the levels in human plasma.     

Voltammetric and amperometric determination of ascorbic acid at a chemically modified carbon fibre microelectrode

A carbon fibre microelectrode was modified by electrodeposition of a thin copper-heptacyanonitrosylferrate (CuHNF) film on its surface. The film showed the ability to catalyse electrochemical oxidation of ascorbic acid. The catalytic reaction was limited either by diffusion, or by the electrochemical reaction of the catalyst. A linear, cyclic voltammetric response for ascorbic acid was obtained between 5.0 x 10(-5) and 6.0 x 10(-3)M. By amperometric measurements the linear range could be extended to 8.0 x 10(-6)-2.0 x 10(-3)M. The modified electrode showed good stability and reproducibility.     

Titration of strong and weak acids by sequential injection analysis technique

A sequential injection analysis (SIA) titration method has been developed for acid-base titrations. Strong and weak acids in different concentration ranges have been titrated with a strong base. The method is based on sequential aspiration of an acidic sample zone and only one zone of the base into a carrier stream of distilled water. On their way to the detector, the sample and the reagent zones are partially mixed due to the dispersion and thereby the base is partially neutralised by the acid. The base zone contains the indicator. An LED-spectrophotometer is used as detector. It senses the colour of the unneutralised base and the signal is recorded as a typical SIA peak. The peak area of the unreacted base was found to be proportional to the logarithm of the acid concentration. Calibration curves with good linearity were obtained for a strong acid in the concentration ranges of 10(-4)-10(-2) and 0.1-3 M. Automatic sample dilution was implemented when sulphuric acid at concentration of 6-13 M was titrated. For a weak acid, i.e. acetic acid, a linear calibration curve was obtained in the range of 3x10(-4)-8x10(-2) M. By changing the volumes of the injected sample and the reagent, different acids as well as different concentration ranges of the acids can be titrated without any other adjustments in the SIA manifold or the titration protocol.     

The sensitive determination of nucleic acids using resonance light scattering quenching method

It is found that in hexamethylene tetramine (HMTA)-HCl buffer of pH 7.00, nucleic acids can quench the resonance light scattering (RLS) of europium (III) (Eu3+)-2-thenoyltrifluoroacetne (TTA)-1,10-phenanthroline (Phen) system. Based on this, a sensitive method for the determination of nucleic acids is proposed. The experiments indicate that under the optimum conditions, the quenched RLS intensity is in proportion to the concentration of nucleic acids in the range of 1.0x10(-10) to 2.0x10(-6) g ml-1 for fish sperm (fsDNA), 1.0x10(-11) to 1.0x10(-6) g ml-1 for yeast RNA (yRNA), 5.0x10(-11) to 5.0x10(-7) g ml-1 for calf thymus DNA (ctDNA). Their detection limits (S/N=3) are 0.03, 0.006 and 0.002 ng ml-1, respectively. Therefore, the proposed method is the most sensitive RLS method for the determination of nucleic acids so far. The interaction between nucleic acids and Eu3+-TTA-Phen is also discussed.     

Syntheses, structural properties and catecholase activity of copper(II) complexes with reduced Schiff base N-(2-hydroxybenzyl)-amino acids

A number of dicopper(II) complexes of reduced Schiff base ligands, N-(2-hydroxybenzyl)-amino acids [Cu2L2(H2O)x].yH2O (L = Sgly (1), D-Sala (2), L-Sala (3), DL-Sala (4), Sab2 (5), Sbal (6), Sab4 (7), Sval (8), Shis (9), Styr (10) and Stryp (11), x= 0-2 & y= 0-2) have been synthesized, and the solid-state structures of, and have been determined. The compounds and are binuclear in which the Cu(II) centres have square-pyramidal geometry with apical sites occupied by aqua ligands. In and one axial site is occupied by water and the other by an oxygen atom of the carboxylate group from the adjacent dimer through oxygen atoms to form 1D helical polymer. Variable temperature magnetic measurements of the dimer and helical polymer showed that they are typical for moderately strong antiferromagnetic coupling. All the complexes show significant catalytic activity on the oxidation of 3,5-di-tert-butylcatechol. The activity measured in terms of Kcat in the range 199-3800 h(-1) has been found to follow the order: 7>6>8>3>5 approximately 2 approximately 1>4 >10 >9 >11. The catalytic activity is found to increase with increasing the length of the methylene side chain of the amino acid in the reduced Schiff base ligands.     

Dissolution of kaolinite induced by citric, oxalic, and malic acids

Kaolinite is a dominant clay mineral in the soils in tropical and subtropical regions, and its dissolution has an influence on a variety of soil properties. In this work, kaolinite dissolution induced by three kinds of low-molecular-weight organic acid, i.e., citric, oxalic, and malic acids, was evaluated under far-from-equilibrium conditions. The rates of kaolinite dissolution depended on the kind and concentration of organic acids, with the sequence R(oxalate)>R(citrate)>R(malate). Chemical calculation showed the change in concentration of organic ligand relative to change in concentration of organic acid in suspensions of kaolinite and organic acid. The effect of organic acid on kaolinite dissolution was modeled by species of organic anionic ligand. For oxalic acid, L(2-)(oxalic) and HL(-)(oxalic) jointly enhanced the dissolution of kaolinite, but for malic and citric acids, HL(-)(malic) and H2L-(citric) made a higher contribution to the total dissolution rate of kaolinite than L(2-)(malic) and L(3-)(citric), respectively. For oxalic acid, the proposed model was R(Si)=1.89x10(-12)x[(25x)/(1+25x)]+1.93x10(-12)x[(1990x1)/(1+1990x1)] (R2=0.9763), where x and x1 denote the concentrations of HL(oxalic) and L(oxalic), respectively, and x1=10(-3.81)xx/[H+]. For malic acid, the model was R(Si)=4.79x10(-12)x[(328x)/(1+328x)]+1.67x10(-13)x[(1149x1)/(1+1149x1)] (R2=0.9452), where x and x1 denote the concentrations of HL(malic) and L(malic), respectively, and x1=10(-5.11)xx/[H+], and for citric acid, the model was R(Si)=4.73x10(-12)x[(845x)/(1+845x)]+4.68x10(-12)x[(2855x1)/(1+2855x1)] (R2=0.9682), where x and x1 denote the concentrations of H2L(citric) and L(citric), respectively, and [Formula: see text] .     

Re-evaluated data of dissociation constants of alendronic, pamidronic and olpadronic acids

The dissociation constants of (4-amino-1-hydroxybutylidene)bisphosphonic (alendronic) acid, (3-(dimethylamino)-1-hydroxypropylidene)bisphosphonic (olpadronic) acid and (3-amino-1-hydroxypropylidene)bisphosphonic (pamidronic) acid were obtained in aqueous solutions (0.10 M KCl) and micellar solutions of cetylpyridinium chloride (0.10 M CPC) at 25.0°C. With the exception of the third dissociation constant of alendronic acid, the dissociation constants of alendronic, olpadronic and pamidronic acids in aqueous solutions matched literature data. The possibility of sodium alendronate determination by acid-base titration by NaOH solution was theoretically grounded on the basis of re-evaluated data of alendronic acid dissociation constants.      

Interaction of cetylpyridine bromide with nucleic acids and determination of nucleic acids at nanogram levels based on the enhancement of resonance Rayleigh light scattering

Resonance Rayleigh light scattering (RRLS) spectra of cetylpyridine bromide (CPB)-nucleic acid system and their analytical application have been first studied. The effective factors and optimum conditions of the reaction have been investigated. After CPB and nucleic acid are mixed together, a new absorption peak located at 300 nm appeared, which is due to the formation of new ion associate of CPB-nucleic acid. The new associate can result in two apparent RRLS peaks at 310-400 and 460-480 nm. The RRLS peak of the corrected spectra located at 290-350 nm, which indicate that the RRLS is originated from the absorption of CPB-nucleic acid associate. The peak at 460-480 nm disappears in the corrected RRLS spectra, which indicated that this peak is originated from the strong line emission of the Xe lamp. Under the optimum conditions, the enhanced intensity of RRLS is proportional to the concentration of nucleic acid in the range of 5.0 x 10(-9)-5.0 x 10(-5) g ml(-1) for calf thymus DNA (ctDNA), 1.0 x 10(-8)-4.0 x 10(-5) g ml(-1) for fish sperm DNA (fsDNA) and 1.0 x 10(-8)-5.0 x 10(-5) g ml(-1) for yeast RNA (yRNA). The detection limits (S/N = 3) are 4.3, 8.7 and 7.4 ng ml(-1), respectively. Synthetic samples were determined satisfactorily.     

Spectrofluorimetric determination of anthranilic acid derivatives based on terbium sensitized fluorescence.

Terbium sensitized fluorescence was used to develop a sensitive and simple spectrofluorimetric method for the determination of the anthranilic acid derivatives furosemide and mefenamic and tolfenamic acids. The method makes use of radiative energy transfer from anthranilates to terbium ions in alkaline methanolic solutions. Optimum conditions for the formation of the anthranilate-Tb3+ complexes were investigated. Under optimized conditions, the detection limits are 6 x 10(-9), 1.4 x 10(-8) and 9.0 x 10(-9) mol l-1 for furosemide, mefenamic acids and tolfenamic acid, respectively. The range of application is 2.5 x 10(-8)-5.0 x 10(-5) mol l-1 for all three drugs. The method was successfully applied to the determination of furosemide and mefenamic and tolfenamic acids in serum after extraction of the samples with ethyl acetate, evaporation of the organic layer under a stream of nitrogen at 40 degrees C and reconstitution of the residue with alkaline methanolic terbium solution prior to instrumental measurement. The mean recoveries from serum samples spiked with furosemide (5.0 x 10(-7), 2.0 x 10(-6) and 8.0 x 10(-6) mol l-1), mefenamic acid (3.0 x 10(-6), 9.0 x 10(-6) and 3.0 x 10(-5) mol l-1) and tolfenamic acid (3.1 x 10(-6), 12.5 x 10(-6) and 2.5 x 10(-5) mol l-1) were 96 +/- 8, 101 +/- 5 and 98 +/- 7%, respectively. The within-run precision (RSD) for the method for two serum samples of each drug varied from 2 to 8% and the day-to-day precision for two concentration levels varied from 2 to 13%.     

Gamma2-, gamma3-, and gamma(2,3,4)-amino acids, coupling to gamma-hexapeptides: CD spectra, NMR solution and X-ray crystal structures of gamma-peptides

There are numerous possible gamma-amino acids with different degrees of substitution and with various constitutions and configurations. Of these the gamma4- and the like- and unlike-gamma(2,4)-amino acids have been previously used as building blocks in gamma-peptides. The synthesis of gamma2-, gamma3-, and gamma(2,3,4)-peptides is now described. The corresponding amino acids have been prepared by Michael addition of chiral N-acyl-oxazolidinone enolates to nitro-olefins, with subsequent reduction of the NO2 to NH2 groups. Such additions to E-2-methyl-nitropropene provide (2R,3R,4R)-2-alkyl-3-methyl-4-amino-pentanoic acid derivatives (9, 10, 11). Stepwise coupling and fragment coupling lead to gamma-di-, tri-, and hexapeptides (12-23), which were fully characterized. The crystal structures of one of the gamma-amino acids (2,3-dimethyl-4-amino-pentanoic acid x HCl, 9a), of a gamma(2,3,4)-di- and a gamma(2,3,4)-tetrapeptide (20, 22) are described, and the NMR solution structure in MeOH of a gamma(2,3,4)-hexapeptide (3) has been determined (using TOCSY, COSY, HSOC, HMBC and ROESY measurements and a molecular dynamics simulated-annealing protocol). A linear conformation (sheet-like), a novel (M) helix built of nine-membered hydrogen-bonded rings, and (M) 2.6(14) helices have thus been identified. NMR measurements at different temperatures (298-393 K) and H/D-exchange rates obtained for the gamma(2,3,4)-hexapeptide are interpreted as evidence for the stability of the 2.6(14) helix (no "melting") and for its non-cooperative folding mechanism. CD Spectra of the gamma-peptides have been measured in MeOH and CH3CN, indicating that only the protected and unprotected gamma(2,3,4)-hexapeptide is present as the 2.6(14) helix in solution. The structures of the gamma2- and gamma3-hexapeptides (1, 2) could not be determined.     

Electrocatalytic oxidation and highly selective voltammetric determination of L-cysteine at the surface of a 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone modified carbon paste electrode.

A carbon paste electrode (CPE) chemically modified with 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone (4-FEPEMCPE) was employed to study the electrocatalytic oxidation of L-cysteine using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry as diagnostic techniques. The diffusion coefficient (D = 7.863 x 10(-6) cm2 s(-1)) of L-cysteine was also estimated using chronoamperometry. The electron-transfer coefficient, alpha (= 0.40), for L-cysteine at the surface of 4-FEPEMCPE was determined using cyclic voltammetry technique. It was found that under an optimum pH (= 7.00), the oxidation of L-cysteine at the surface of such an electrode occurred at a potential of about 350 mV less positive than that of an unmodified CPE. The catalytic oxidation peak currents represented a linear dependence on the L-cysteine concentration. Linear analytical curves were obtained in the ranges of 9.0 x 10(-5) - 4.9 x 10(-3) M and 2.0 x 10(-5) - 2.8 x 10(-3) M of L-cysteine with correlation coefficients of 0.9981 and 0.9982 in cyclic voltammetry and differential pulse voltammetry, respectively. The detection limits (2 sigma) were determined to be 9.9 x 10(-6) M and 5 x 10(-6) M with cyclic voltammetry and differential pulse voltammetry, respectively. The influences of twenty other amino acids, such as glutamine, L-glutamic acid, L-glysine, L-histidine, L-isoleucine, L-leucine, L-arginine hydrochloride, L-aspargine, L-aspartic acid, S-carboxy methyl-L-cysteine, L-methionine, L-phenyl alanine, L-proline, L-serine, L-threonine, L-cystine, cysteamine and gluthathione, on the current response of the sensor were examined. The obtained results did not show any influence on the analytical signal of L-cysteine by these amino acids (except for cysteamine). The method was also used for the selective determination of L-cysteine in patient-blood plasma and some pharmaceutical preparations by using standard addition method.     

Simultaneous electrochemical determination of uric acid and ascorbic acid on a glassy carbon electrode modified with cobalt(II) tetrakisphenylporphyrin.

A cobalt(II) tetrakisphenylporphyrin (Co(II)TPP) film modified glassy carbon electrode (Co(II)TPP-GCE) was prepared by just coating Co(II)TPP solution on the surface of the electrode. It can be used for the simultaneous determination of ascorbic acid and uric acid. The anodic peaks of AA and UA can be separated well. Owing to the strongly hydrophobic property of porphyrin, the modified electrode has good stability and long life. The linear range for UA and AA were 2.0 x 10(-6)-1.0 x 10(-4) M and 9.0 x 10(-6)-2.0 x 10(-3) M with detection limits of 5.0 x 10(-7) and 5.0 x 10(-6) M, respectively. Furthermore, metalloporphyrins of other kinds were also used to construct modified electrodes. Their performances were inferior compared with that of the Co(II)TPP modified electrode.     

A 9,10-anthraquinone derivative having two propenyl arms as a neutral ionophore for highly selective and sensitive membrane sensors for copper(II) ion.

New polymeric membrane (PME) and coated graphite (CGE) copper(II)-selective electrodes based on 1-hydroxy-2-(prop-2'-enyl)-4-(prop-2'-enyloxy)-9,10-anthraquinone were prepared. The electrodes reveal linear emf-pCu2+ responses over wide concentration ranges (1.0 x 10(-5)-1.0 x 10(-1) M with a slope of 27.3 mV decade-1 for PME and 8.0 x 10(-8)-5.0 x 10(-2) M with a slope of 29.1 mV decade-1 for CGE) and very low limits of detection (8.0 x 10(-6) M for PME and 5.0 x 10(-8) M for CGE). The potentiometric response is independent of the pH of the test solution in the pH range 3.0-6.0. The proposed electrodes possess very good selectivities over a wide variety of other cations, including alkali, alkaline earth, transition and heavy metal ions, the selectivity coefficients for the CGE being much improved over those for the PME. The electrodes were used as indicator electrodes in the potentiometric titration of Cu2+ and in the recovery of copper ions from wastewater.     

One-electron reduction of methanesulfonyl chloride. The fate of MeSO2Cl(.)(-) and MeSO2(.) intermediates in oxygenated solutions and their role in the cis-trans isomerization of mono-unsaturated fatty acids

The one-electron reduction of methanesulfonyl chloride (MeSO2Cl) leads, in the first instance, to an electron adduct MeSO2Cl(.)(-) which lives long enough for direct detection and decays into sulfonyl radicals MeSO2(.) and Cl(-), with k = 1.5 x 10(6) s(-1). Both, MeSO2Cl(.)(-) and MeSO2(.) showed a similar absorption in the UV with lambdamax of 320 nm. In the presence of oxygen, MeSO2Cl(.)(-) transfers an electron to O(2) and establishes an equilibrium with superoxide. The rate constant for the forward reaction was measured to 4.1 x 10(9) M(-1) s(-1), while for the back reaction only an interval of 1.7 x 10(5) to 1.7 x 10(6) M(-1) s(-1) could be estimated, with a somewhat higher degree of confidence for the lower value. This corresponds to an equilibrium constant in the range of 2.4 x 10(3) to 2.4 x 10(4). With reference to E degrees (O2/O2(.)(-)) = -155 mV, the redox potential of the sulfonyl chloride couple, E degrees (MeSO2Cl/MeSO2Cl(.)(-)), thus results between being equal to -355 and -414 mV (vs NHE). MeSO2Cl(.)(-) reduces (besides O2) 4-nitroacetophenone. The underlying electron transfer took place with k = 1.5 x 10(9) M(-1) s(-1), corroborating an E degrees for the sulfonyl chloride couple significantly exceeding the above listed lower value. The MeSO2(.) radical added to oxygen with a rate constant of 1.1 x 10(9) M(-1) s(-1). Re-dissociation of O2 from MeSO2OO(.) occurred only very slowly, if at all, that is, with k < 10(5) s(-1). MeSO2(.) radicals can act as the catalyst for the cis-trans isomerization of several Z- and E-mono-unsaturated fatty acid methyl esters in homogeneous solution. The effectiveness of the isomerization processes has been addressed, and in the presence of oxygen the isomerization is completely suppressed.     

Mechanisms of reactions of flavin mononucleotide triplet with aromatic amino acids

Chemical reactions between the photoexcited triplet state of flavin mononucleotide and the aromatic amino acids, N-acetyl tryptophan (TrpH), N-acetyl tyrosine (TyrOH), and N-acetyl histidine (HisH) in aqueous solution have been studied in the pH range 2-12. Across the whole pH range, the principal mechanism of reaction of both TrpH and TyrOH is shown to be electron transfer. For HisH, the mechanism and rate of the reaction depend on the protonation state of the reactants. In acidic conditions (pH < 4), reaction does not occur. At 4 < pH < 11, the reaction proceeds via hydrogen atom abstraction with a rate constant varying from 3.0 x 10(6) to 2.5 x 10(8) M(-1) s(-1). In extremely basic solution (pH > 12) the mechanism switches to electron transfer.     

Modification of montmorillonite with cationic surfactant and application in electrochemical determination of 4-chlorophenol

Herein, montmorillonite calcium was exchanged with a cationic surfactant: cetyltrimethylammonium bromide (CTAB). The resulting CTAB-modified montmorillonite calcium (CTAB-MMT) shows higher accumulation efficiency to 4-chlorophenol compared with the unmodified MMT. At the CTAB-MMT-modified carbon paste electrode, the oxidation peak current of 4-chlorophenol remarkably increases. Based on this, a novel, sensitive and convenient electrochemical method was developed for the determination of 4-chlorophenol. The oxidation peak current of 4-chlorophenol is proportional to its concentration over the range from 5.0 x 10(-8) to 1.0 x 10(-5) mol L(-1). The limit of detection is evaluated to be 2.0 x 10(-8) mol L(-1) for 2 min accumulation. Finally this newly proposed method was successfully applied to determine 4-chlorophenol in water samples.     

Determination of trace amount of oxalic acid with zirconium(IV)-(DBS-arsenazo) by spectrophotometry

A novel method is proposed for the determination of trace amount of oxalic acid in the present article. In 1.0M hydrochloric acid medium, oxalic acid can react with the zirconium(IV) in Zr(IV)-(DBS-arsenazo) complex and replaces the DBS-arsenazo to produce a hyperchromic effect at 520 nm. The hyperchromic degree is proportional to the concentration of the oxalic acid added over a defined range. Based on this property, a new method for the spectrophotometric determination of trace oxalic acid was developed. Beer's law is held over the concentration range of 9.0 x 10(-6) to 5.0 x 10(-4)M for oxalic acid with a correlation coefficient of 0.9995. The apparent molar absorptivity of the method is epsilon520 nm = 1.16 x 10(3)L mol(-1)cm(-1) and the detection limit for oxalic acid is 0.815 microg/mL. The developed method was directly applied to the determination of oxalic acid in tomato samples with satisfactory results.