The Application of Gibberellic Acid to the Determination of Trace Amounts of Lead by Spectrofluorimetry

The ionization constant of fluorescent reagent gibberellic acid (GA) was established spectrophotometrically. The fluorescent reaction of this reagent with lead was studied. Based on this chelation reaction, a sensitive, direct spectrofluorimetric method for the determination of trace lead with use of GA has been developed. The reaction conditions for the fluorescence system of lead with GA were studied. The lead ion can form a stable binary chelate with GA, having a ratio of 1:2 in the pH range 7.0‐8.0. The maximum excitation and emission wavelengths are 205.0 nm and 308.8 nm for the lead chelate, respectively. The reaction is instantaneous and the fluorescence intensity of the lead chelate remains stable from 20 to 150 min. Under the optimal experimental conditions the fluorescence intensity is a linear function of concentration in the range 1.0‐10.0 ng/mL of lead and the detection limit is 0.52 ng/mL of lead. Interferences of other ions were studied. The method has been successfully applied to the determination of lead in common paint.     

The new fluorescence enhancement system Tb-N-(2-pyridinyl) ketoacetamide-Et(3)N-Zn and its application

A sensitive fluorescence enhancement system was developed for the determination of terbium. The fluorescence intensity of the Tb-N-(2-pyridinyl) ketoacetamide (PKAA) system was greatly enhanced by the addition of triethylamine (Et(3)N) and zinc nitrate in the methanol solution. The excitation and emission wavelengths were 329 and 546 nm, respectively. Under optimal conditions, the fluorescence intensities varied linearly with the concentration of Tb(3+) in the range of 7.5 x 10(-8)-8.2 x 10(-6)M with a detection limit of 6.4 x 10(-8)M. The interferences of some rare earth ions were described. This method was applied to the determination of trace amounts of terbium (III) in a synthetic rare earth oxide and a high purity Y(2)O(3) matrix. The mechanism of fluorescence enhancement was also studied.     

Enhancement of fluorescence of terbium/trimesic acid/cyclodextrin system by zirconate and its application to the determination of terbium

A new approach of fluorescence enhancement for the determination of terbium based on the formation of a new fluorescence system of Tb-TMA-beta-CD (benzene-1,3,5-tricarboxylic acid (TMA), beta-cyclodextrin (beta-CD)) in an aqueous medium of pH 5.0 provided by a HAc-NaAc buffer in the presence of an oxy-acid of transition metal, zirconate acid, is reported. The maximum excitation and emission wavelengths are 301 nm and 545 nm for the terbium complex, respectively. Under the optimal conditions, the method allows the determination of terbium over the range of 0.508-521 ng ml(-1) with a S.D. of 0.392, and the recovery is in the range of 99.0-100.1%. The emulsion formed by Tb-TMA-beta-CD with zirconate acid makes the determinate system more stable than the system of Tb-TMA-beta-CD. The proposed method has been employed for the determination of some international standard reference or samples with a good precision (RSD < 1.7%, n = 5).     

微量铽的萤光光度测定——铽与吡啶-2,6-二羧酸螯合物的萤光

铽与吡啶-2,6-二羧酸(以下简称DPA)形成螯合物的萤光有人从生物化学角度作过一些研究^[1],但对测定稀土氧化物中微量铽的研究未见报导。本文系统地研究了Tb³⁺-DPA螯合物萤光产生的条件,拟订了测定稀土氧化物中微量铽的萤光光度法,探讨了螯合物萤光强度与其组成的关系。     

Enhanced fluorescence of 3-tryptimino-1-phenyl-butan-1-one–Tb with 1,10-phenanthroline ternary system, and its analytical application

A new Schiff base ligand, 3-tryptimino-1-phenyl-butan-1-one (TPB), was synthesized. The fluorescence intensity of its terbium(III) complex was greatly enhanced by addition of 1,10-phenanthroline to an acetonitrile solution. Spectrofluorimetric determination of trace amounts of Tb³⁺ was performed based on this effect. The excitation and emission wavelengths are 293 and 546 nm, respectively. Under optimal conditions, the fluorescence intensities varied linearly with the concentration of Tb³⁺ in the range of 2.0 × 10⁻⁶ to 7.0 × 10⁻⁶ M with a detection limit of 2.4 × 10⁻⁹ M. Interference by some rare earth ions is described. This method was applied to the determination of trace amounts of terbium(III) in a high purity Y₂O₃ matrix. The mechanism of fluorescence enhancement was also studied.     

Determination of trace terbium(III) with N, N', N"-tri(3-indolemethanal)triaminotriethylamine based on a new fluorescence enhancement system.

A new Schiff-base ligand with a tripodal structure, N,N',N"-tri(3-indolemethanal)triaminotriethylamine (TTAIM), was synthesized. Its fluorescence intensity with terbium(III) was increased by about two orders of magnitude in the present of sodium acetate (NaAc). After the adding of the organic solvent dimethyl sulfoxide (DMSO) to the above system, leading to Tb3+ the fluorescence was further enhanced by about 16 fold. The spectrofluorimetric determination of a trace amount of Tb3+ based on this phenomenon was carried out. The excitation and emission wavelengths were 330 nm and 545 nm, respectively. Under the optimal conditions, the fluorescence intensities varied linearly with the concentration of Tb3+ in the range of 5.7 x 10(-11) - 6.3 x 10(-6) mol L(-1) with a detection limit of 5.0 x 10(-11) mol L(-1). The interferences of some rare earth metals and other inorganic ions were described. The method is a selective, sensitive, rapid and simple analytical procedure for the determination of terbium(III) in a high-purity yttrium oxide and synthetic sample. The mechanism for the fluorescence enhancement was also studied.     

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.     

Highly Sensitive Spectrofluorimetric Determination of Trace Amounts of Folic Acid using a Oxytetracycline-Terbium(III) Probe

Abstract

A new spectrofluorimetric method was developed for the determination of trace amounts of folic acid using oxytetracycline–terbium ion complex as a fluorescent probe. In the buffer solution of pH 6.00, folic acid remarkably reduced the fluorescence intensity of the oxytetracycline–terbium complex at λ = 545 nm. The reduced fluorescence intensity of the Tb³⁺ ion was proportional to the concentration of folic acid. Optimum conditions for the determination of folic acid were investigated. This method was simple, practical, and relatively free of interference from coexisting substances. Furthermore, it was successfully applied to assess folic acid in tablet, injection, and urine samples.     

Fluorimetry determination of trace Ce3+ with EDTP

The use of ethylenediaminetetrakis(methylphosphonic) acid (EDTP) in the fluorimetry determination of trace amounts of Ce3+ ions is described. The fluorescence intensity of Ce3+ was greatly enhanced when an 1:1 complex with EDTP in solution of pH 7-8 formed. The apparent excitation and emission wavelength used were 313 and 397 nm, respectively. The fluorescence intensity varied linearly with the concentration of Ce3+ in the range of 1 x 10(-8) -1 x 10(-4) mol l(-1). The quenching effects of coexist ions (other rare earth ions, Fe3+ and some inorganic anions) were studied. This technique has unique advantage in eliminating disturb of coexist.     

Simultaneous determination of samarium, europium and terbium with quinaldic acid and phenanthroline by synchronous derivative fluorimetry

Synchronous derivative fluorescence of samarium, europium and terbium complexes with quinaldic acid and phenanthroline was examined in aqueous solution. The composition of these complexes was determined. The maximum emission wavelengths are 645 nm, 617 nm and 545 nm for samarium, europium and terbium, respectively. Under the optimal experimental conditions, the fluorescence intensity was a linear function of concentration in the range of 10-250 ppm for samarium, 0.5-50 ppm for europium and 0.5-300 ppm for terbium. Simultaneous determination of samarium, europium and terbium was successfully carried out for samarium oxide and middle rare earth mixture. The precision of the method, expressed as relative standard deviation, is within 1.1-2.5%.     

Determination of proteins by fluorescence quenching of Magdala Red

Magdala Red (MR) binding to protein causes a decrease in the fluorescence intensity of MR at 556 nm. Based on this, a new quantitative determination method for proteins is developed. The linear range of this assay is 0.1-4.0 microg ml(-1) of Bovine Serum albumin (BSA). The measurements can be made easily on a common fluorimeter. The reaction between MR and proteins is completed in 1 min, and the fluorescence intensity is stable for at least 2 h. There is little or no interference from amino acids and most metal ions. The proposed method has been applied to the determination of protein in milk powder and soybean milk powder and the results are in agreement with the results by the other methods.     

Terbium (III) chelate complexes as fluorescence energy transfer donor in the determination of formaldehyde in aqueous solutions

The sensitized fluorescence intensity of the terbium (III) ion can be notably enhanced in the presence of sodium hexametaphosphate (SHMP). Based on this, water-soluble Tb-SHMP chelate complexes were synthesized in aqueous solutions, and characterized by spectrofluorometry. 6-Mercapto-5-triazole[4,3-b]-S-tetrazine was generated by the quantitative reaction of HCHO with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole under alkaline conditions at room temperature. The spectral overlap between the emission of Tb-SHMP chelate complexes and absorption of 6-mercapto-5-triazole[4,3-b]-S-tetrazine meets the prerequisite for fluorescence energy transfer. Based on this, a novel efficient fluorescence energy transfer system between Tb-SHMP chelate complexes as donor and 6-mercapto-5-triazole[4,3-b]-S-tetrazine as acceptor was developed for the determination of HCHO in aqueous solutions. Under the optimal experimental conditions, this method is capable of detecting HCHO concentrations from 2.06×10(-5) to 6.18×10(-3) mg mL(-1) and the limit of detection was 7.11×10(-6) mg mL(-1). Compared with other general methods for the determination of HCHO, the proposed method improved the sensitivity and selectivity. Moreover, the proposed method was successfully applied to the determination of HCHO in water samples.     

Improved detection of salicylic acids using terbium-sensitized luminescence in aqueous micellar solutions of cetyltrimethylammonium chloride

The determination of salicylic, p-aminosalicylic and 5-fluorosalicylic acids was investigated using terbium-sensitized luminescence in aqueous solutions. Formation of a ternary chelate between terbium, EDTA and the salicylic acid requires dissociation of the phenol group which is adjacent to the dissociated carboxylic group. The reaction is obtained in alkaline solutions and is enhanced in the presence of cetyltrimethylammonium chloride. As evidenced by absorbance and fluorescence measurements, the cationic surfactant plays an important role in the formation of the ternary chelate and then terbium luminescence depends mainly on the extent of chelate formation. Linearity is found over more than four orders of magnitude and detection limits are in the range (2-4) x 10(-10) mol l-1 for the three acids.     

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.     

Photochemical fluorescence enhancement of the terbium-lomefloxacin complex and its application

The sensitized fluorescence intensity of the terbium ion (Tb(3+)) can be notably enhanced after the Tb(3+)-lomefloxacin(LFLX) complex system was irradiated by 365nm ultraviolet light. A photochemical reaction occurs to the irradiated Tb(3+)-LFLX complex. A new Tb(3+)system with intense fluorescence is obtained. On this basis a new sensitive and selective photochemical fluorimetry for the determination of LFLX was established. Under the optimal experimental conditions, the linear range of the determination is 2.0-500x10(-8) mol l(-1) for LFLX, and the detection limit is 6.0x10(-9) mol l(-1).Without any pre-treatment the recoveries of LFLX in human urine and serum were determined.     

Spectrofluorometric trace determination of cerium(III) in sodium hexametaphosphate solutions

The use of sodium hexametaphosphate in the spectrofluorometric determination of trace amounts of cerium(III) ions is described. Sodium hexametaphosphate acts as a specific reagent for enhancing the fluorescence intensity of cerium(III) in aqueous solutions. The apparent excitation and fluorescence wavelength used are 304 and 344 nm, respectively. Maximum fluorescence intensity is obtained by irradiating Ce(III) dissolved in 5.346 g/l sodium hexametaphosphate solution at room temperature. The fluorescence varies linearly with the concentration of cerium(III) in the range of 0.001-60 microg/ml. The coefficient of variation for 45 microg/ml Ce(III) in 5.346 g/l sodium hexametaphosphate solution is 1. The quenching effects of other lanthanides and some inorganic anions are given. This technique permits a direct and rapid determination of cerium(III) in rare earth mixtures and cerium concentrates.     

A new Fluorimetric Reagent for Highly Selective and Sensitive Determination of Terbium Ion

 In this work, a new ligand, 2,9-bis[N,N-bis(carboxymethyl)-aminomethyl]-1,10-phenanthroline (BBCAP), was synthesized and used to establish a novel fluorimetric method for the determination of trace amounts of terbium in a binary system. Its luminescence mechanism was studied. The excitation and emission wavelengths are 284 nm and 547 nm, respectively. Other rare-earth metal ions in 100-fold excess caused no interference. The fluorescence intensity was a linear function of the concentration of terbium in the range of 5.0 × 10⁻¹⁰–1.0 × 10⁻⁶ mol/L. The detection limit was 2.0 × 10⁻¹¹ mol/L (n = 12). The standard addition method was used to determine the terbium in a synthetic rare-earth sample with satisfactory results. This method represents a direct, rapid, selective and sensitive analytical procedure with a widely linear range. Received November 29, 2001 Revision February 9, 2002     

The resonance Rayleigh scattering of the interaction of copper(II)-bleomycinA2 with DNA and its analytical application

The forming of bleomycinA2-Cu(II) cationic chelate and the interaction of the chelate with DNA have been investigated by using resonance Rayleigh scattering (RRS), molecular absorption and fluorescence spectra. The result shows that in aqueous solution, bleomycinA2 (BLMA2) can react with Cu(II) to form 1:1 cationic chelate which contributes to the changes of the absorption spectra and the quenched fluorescence of BLMA2. When the cationic chelate further bound with DNA to form ternary ion-association complexes, the remarkable enhancement of the RRS intensity was observed. In this work, the optimum conditions for the coordination reaction of BLMA2 with Cu(II) and some influencing factors have been investigated. The reaction mechanism of BLMA2-Cu(II) binding with DNA was suggested and a binding model was proposed. In addition, the fluorescence quenching type of BLMA2 was investigated. A highly sensitive, simple and rapid new method for the determination of DNA by using BLMA2-Cu(II) as RRS probe has been developed. The detection limits (3σ) are 7.2 ng/mL for ctDNA, 7.1 ng/mL for sDNA and 18 ng/mL for hsDNA. The method can be applied to the determination of trace amounts of DNA.     

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.     

Spectrophotofluorometric determination of terbium and europium in potassium carbonate solution

The conditions for the spectrophotofluorometric determination of terbium and europium, in solutions of potassium carbonate, have been established. The apparent excitation and fluorescence wavelengths used, respectively, are 245 mmu and 550 mmu for terbium and 400 mmu and 620 mmu for europium. The fluorescence varies linearly with the concentration of terbium and europium in the range 0.3-70 mug, of terbium/ml and 4-800 mug of europium/ml. Large amounts of gadolinium, lutetium and yttrium do not interfere. Cerium(IV) interferes seriously.