A fluorescent probe for zinc ions based on N-methyltetraphenylporphine with high selectivity

N-methyl-alpha,beta,gamma,delta-tetraphenylporphine (NMTPPH) has been used to detect trace amount of zinc ions in ethanol-water solution by fluorescence spectroscopy. The fluorescent probe undergoes a fluorescent emission intensity enhancement upon binding to zinc ions in EtOH/H(2)O (1:1, v/v) solution. The fluorescence enhancement of NMTPPH is attributed to the 1:1 complex formation between NMTPPH and Zn(II) which has been utilized as the basis for the selective detection of Zn(II). The linear response range covers a concentration range of Zn(II) from 5.0x10(-7) to 1.0x10(-5)mol/L and the detection limit is 1.5x10(-7)mol/L. The fluorescent probe exhibits high selectivity over other common metal ions except for Cu(II).     

Determination of ATP as a fluorescence probe with europium(III)-doxycycline.

A new spectrofluorimetric method has been developed for the determination of adenosine disodium triphosphate (ATP). We studied the interactions between the doxycycline (DC)-Eu3+ complex and adenosine disodium triphosphate (ATP) by using UV-visible absorption and fluorescence spectra. Using doxycycline (DC)-Eu3+ as a fluorescence probe, under the optimum conditions, ATP could remarkably enhance the fluorescence intensity of the DC-Eu3+ complex at lambda = 612 nm. The enhanced fluorescence intensity of the Eu3+ ion was in proportion to the concentration of ATP. The optimum conditions for the determination of ATP were also investigated. The linear ranges for ATP were 1.00 x 10(-7) - 2.00 x 10(-6) mol L(-1) with detection limits of 4.07 x 10(-8) mol L(-1). This method is simple, practical and relatively free of interference from coexisting substances, and can be successfully applied to the determination of ATP in samples. The mechanism of fluorescence enhancement between the doxycycline (DC)-Eu3+ complex and ATP was also studied.     

Determination of adenosine disodium triphosphate (ATP) using oxytetracycline-Eu3+ as a fluorescence probe by spectrofluorimetry

A new spectrofluorimetric method was developed for determination of adenosine disodium triphosphate (ATP). We studied the interactions between oxytetracycline (OTC)-Eu3+ complex and adenosine disodium triphosphate (ATP) by using UV-vis absorption and fluorescence spectra. Using oxytetracycline (OTC)-Eu3+ as a fluorescence probe, under the optimum conditions, ATP can remarkably enhance the fluorescence intensity of the OTC-Eu3+ complex at lambda = 612 nm and the enhanced fluorescence intensity of Eu3+ ion is in proportion to the concentration of ATP. Optimum conditions for the determination of ATP were also investigated. The linear ranges for ATP are 8.00 x 10(-8)-1.50 x 10(-6) mol L(-1) with detection limits of 2.67 x 10(-9) mol L(-1). This method is simple, practical and relatively free interference from coexisting substances and can be successfully applied to determination of ATP in samples. The mechanism of fluorescence enhancement between oxytetracycline (OTC)-Eu3+ complex and ATP was also studied.     

Thermal lens studies of the reaction of iron (II) with 1,10-phenanthroline at the nanogram level

The determination of iron(II) with 1,10-phenanthroline in aqueous solutions was carried out exemplarily by thermal lens spectrometry. The peculiarities of analytical reactions at the nanogram level of reactants can be studied using this method. Under the conditions of the competing reaction of ligand protonation, the overall stability constant for iron(II) chelate with 1,10-phenanthroline was determined at a level of n x 10(-7) mol L(-1), logbeta3 = 21.3+/-0.1. The rates of formation and dissociation of iron(II) tris-(1,10-phenanthrolinate) at a level of n x 10(-8) mol L(-1) were found to be (2.05+/-0.05) x 10(-2) min(-1) and (3.0+/-0.1) x 10(-3) min(-1), respectively. The conditions for the determination of iron(II) with 1,10-phenanthroline by thermal lensing were reconsidered, and ascorbic acid was shown to be the best reducing agent, which provided minimum and reproducible sample pretreatment. Changes in the conditions at the nanogram level improved both the selectivity and sensitivity of determination. The optimum measurement conditions for thermal lensing were determined not only by the absorption of the analyte and reagents, but also by the background absorption of the solvent. The limits of detection and quantification of iron(II) at 488.0 nm (excitation beam power 140 mW) are 1 x 10(-9) and 6 x 10(-9) mol L(-1), respectively; the reproducibility RSD for the range n x 10(-8)-n x 10(-6) mol L(-1) is 2-5%.     

Fluorescence enhancement assay for trace iron(II) using Pyr-tempo as a spin label fluorescent probe

Pyrene-tetramethylpiperidinyl (Pyr-Tempo) as a spin label fluorescent probe for iron(II) was synthesized. It exhibited weak fluorescence (λ_exc/λ_em = 346/399 nm) in aqueous solution due to an intramolecular quenching pathway. A method for determination of iron(II) was proposed based on the fluorescence enhancement of the probe in the presence of iron(II) in acidic medium. Under optimum conditions, the fluorescence enhancement of Pyr-Tempo is linearly proportional to the iron(II) concentration range of 6.0 × 10⁻⁸ to 9.6 × 10⁻⁶ mol L⁻¹ with a detection limit of 8.0 × 10⁻⁹ mol L⁻¹. The relative standard deviation (RSD) of six replicate measurements is 1.95% for 3.0 × 10⁻⁷ mol L⁻¹ iron(II). The developed spin label fluorescence probe is found to be rapidly and sensitively responsive to iron(II) with high selectivity compared to existing fluorescence methods. The proposed method was successfully applied to iron(II) detection in five real samples with satisfactory results obtained by manual UV/Vis spectrophotometry (standard method) with 1,10-phenanthroline.     

Facile synthesis of water-soluble and size-homogeneous cadmium selenide nanoparticles and their application as a long-wavelength fluorescent probe for detection of Hg(II) in aqueous solution

Highly luminescent uncoated water-soluble and mono-disperse CdSe nanoparticles (NPs) have been prepared facilely. Uncoated CdSe core NPs possessing a good size distribution was accompanied with long wavelength of fluorescence emission. It is interesting to note that these functionalized NPs are soluble in water medium stably for more than 1 month, and no significant changes were found in the optical characteristics in comparison with fresh CdSe NPs prepared. The functionalized CdSe NPs exhibited strong specific affinity for mercury(II) through their surface functional groups. Based on the significant quenching of fluorescence emission of functionalized CdSe NPs with a long-wavelength 630nm, a simple, rapid and specific detection for Hg(II) was proposed. Under optimum conditions, the response of linearly proportional to the concentration of Hg(II) is between 0mol/L and 1.25x10(-6)mol/L, and the limit of detection is 4.50x10(-9)mol/L. The relative standard deviation (R.S.D.) of six replicate measurements is 2.0% for 2.0x10(-7)mol/L of Hg(II). In terms of fluorescence quenching at 630nm of CdSe NPs, no obvious wavelength shift or no new emission band in presence of Hg(II) at pH 7.50 of phosphate buffer solution were found; furthermore, a significant reduction in absorbance at 230nm of CdSe NPs was first observed in our work. We could speculate that Hg(II) as an effective quencher (even at low concentration) for functionalized CdSe NPs emission suggests that it is capable of directly intercepting one of the charge carriers, thus disrupting the recombination process.     

Influence of Cu(II) on the interaction between sulfite and horseradish peroxidase in vitro

This paper discussed the quantitative influence of Cu(II) on the interaction between horseradish peroxidase (HRP) and sulfite (SO3(2-)), which is a derivate of sulfite dioxide in human bodies, by using fluorescence spectrum and ultraviolet (UV) absorption spectrometry in vitro. The results show that under the conditions of physiological pH and room-temperature, Cu(II) can bind strongly with both the protein part and the ferroporphyrin part in HRP at a low concentration (10(-4) mol L(-1)), and the combination constants are 2.047 x 10(3) and 7.66 x 10(2) L mol(-1), respectively. Under the same conditions, SO3(2-) at low concentrations (<0.15 mol L(-1)) has little quenching for the fluorescence of HRP at 330 nm, and the combination constant is 0.108 L mol(-1). While the fluorescence intensity at 440 nm enhance gradually with the increased concentration of SO3(2-) (<0.1 mol L(-1)), and the combination constant is 8.219 L mol(-1). These indicate that SO3(2-) at low concentration has little reaction with the enzyme protein part in HRP but obvious reaction with the ferroporphyrin part in HRP. After SO3(2-) at low concentrations is added into the HRP-Cu(II) binary system, the reaction constants between SO3(2-) and the enzyme protein part in HRP increase rapidly. Compared with the absence of Cu(II), the combination constant of SO3(2-) with the enzyme protein part in HRP increases nearly 70 times with a certain Cu(II) concentration (5.0 x 10(-4) mol L(-1)) in the system. However, the presence of Cu(II) in the system has little effect on the reaction constants between SO3(2-) and the ferroporphyrin part in HRP.     

Determination of carbamazepine by chemiluminescence detection using chemically prepared tris(2,2'-bipyridine)ruthenium(III) as oxidant.

A new chemiluminescence method for the determination of carbamazepine (CBZ) has been developed. The method is based on the chemiluminescence produced in the reaction of tris(2,2'-bipyridine)ruthenium(III) and CBZ in an acidic medium. The chemiluminescence intensity was enhanced by organic solvents in the reaction system. Under the optimum experimental conditions, the calibration curve was linear over the range 4.0 x 10(-3)-8.6 x 10(-7) mol/L for CBZ. The detection limit (S/N = 3) was 2.5 x 10(-7) mol/L and the relative standard deviation of six replicate measurements was 2.6% for 4.0 x 10(-4) mol/L of CBZ. The possible reaction mechanism were also discussed. The chemiluminescence method was successfully applied to assay the CBZ contents in pharmaceutical tablets.     

Flow injection analysis for oxidation state speciation of vanadium(IV) and vanadium(V) in natural water.

A sensitive and simultaneous spectrophotometric flow injection method for the determination of vanadium(IV) and vanadium(V) is proposed. The method is based on the effect of ligands such as 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ) and diphosphate on the conditional redox potential of iron(III)/iron(II) system. A four-channel flow system is assembled. In this flow system, diluted hydrochloric acid (1.0 x 10(-2) mol dm(-3)) as a carrier for standard/sample, acetate buffer (pH 5.5) as a carrier for diphosphate solution, an equimolar mixed solution of iron(III) and iron(II) and a TPTZ solution are delivered, so that the baseline absorbance can be established by forming a constant amount of iron(II)-TPTZ complex (lambda(max) = 593 nm). Vanadium(IV) and/or vanadium(V) (400 microL) and diphosphate (200 microL) solutions are simultaneously introduced into the flow system; in this system the diphosphate solution passes through a delay coil. The potential of the iron(III)/iron(II) system increases in the presence of TPTZ, and therefore vanadium(IV) is easily oxidized by iron(III) to vanadium(V) to produce an iron(II)-TPTZ complex (a positive peak for vanadium(IV) appears). On the other hand, the potential of the redox system decreases in the presence of diphosphate, so that vanadium(V) can be easily reduced by iron(II) to vanadium(IV). In this case, the amount of iron(II) decreases according to the amount of vanadium(V). As a result, the produced iron(II)-TPTZ complex decreases (a negative peak for vanadium(V) appears). In this manner, two peaks for vanadium(IV) and vanadium(V) can be alternately obtained. The limits of detection (S/N = 3) are 1.98 x 10(-7) and 2.97 x 10(-7) mol dm(-3) for vanadium(IV) and vanadium(V), respectively. The method is applied to the simultaneous determination of vanadium(IV) and vanadium(V) in commercial bottled mineral water samples.     

Direct fluorescence quantification of chromium(VI) in wastewater with organic nanoparticles sensor.

Under ultrasonic irradiation, organic fluorescence nanoparticles have been prepared by a reprecipitation method. Compared with single organic fluorophores, these nanoparticles are brighter, more stable against photobleaching and more water-soluble. They also have high room-temperature fluorescence quantum yields (approximately 20%) and a long fluorescence lifetime (approximately 0.2 micros). Based on the fluorescence quenching of nanoparticles by chromium(VI), a method for the selective determination of chromium(VI) without the separation of chromium(III) in water was developed. Under the optimal conditions, the linear range of the calibration curve was 7.0 x 10(-6) - 1.0 x 10(-4) mol L(-1). The detection limit was 2.8 x 10(-6) mol L(-1). The method is characterized by a short reaction time, stable fluorescence signals, simplicity and high selectivity. The present assay has been applied to the selective quantification of Cr(VI) in wastewater with satisfactory results.     

Determination of platinum(IV) by UV spectrophotometry

A simple, rapid and sensitive spectrophotometric procedure for the determination of platinum has been elaborated. Pt traces were determined in the form of the PtCl(6)(2-) complex in hydrochloric acid solution whose concentration varies from 0.01 to 2 mol L(-1) by measuring the absorbance at 260 nm. The detection limit is 4.7 x 10(-7) mol L(-1), the linearity range from 2 x 10(-6) mol L(-1) to 7 x 10(-6) mol L(-1), and the correlation coefficient is r=0.9990. No significant interferences were observed from a majority of the investigated ions, such as Zn(II), Pb(II), Mn(II), Cd(II), Co(II) and Ni(II) with the exception of Cu(II), Sb(III), Fe(III), Pd(II), Sn(II) and I(-) ions. The method was successfully applied for the determination of Pt traces in different solid samples and the recovery from inorganic materials was studied.     

Use of surface-modified CdTe quantum dots as fluorescent probes in sensing mercury (II)

Thioglycolic acid (TGA)-capped CdTe quantum dots (QDs) were synthesized in aqueous medium, and their interaction with metal cations was studied with UV-vis absorption, steady-state and time-resolved fluorescence spectra. The results demonstrated that Hg(II), Cu(II) and Ag(I) could effectively quench the QD emission based on different action mechanisms: Cu(II) and Ag(I) quenched CdTe QDs because they bound onto particle surface and facilitated non-radiative electron/hole recombination annihilation of QDs; electron transfer process between the capping ligands and Hg(II) was mainly responsible for the remarkable quenching effect of Hg(II). To prevent the approach of metal cations to QD core, the original TGA-capped CdTe QDs were further coated by denatured bovine serum albumin (dBSA). It was found that the dBSA-coated CdTe QDs could be quenched effectively by Hg(II), but Cu(II) and Ag(I) could hardly quench the QDs even at fairly higher concentration levels because the dBSA shell layer effectively prevented the binding of metal cations onto the QD core. On the basis of this fact, a simple, rapid and specific method for Hg(II) determination was proposed. Under optimal conditions, the quenched fluorescence intensity increased linearly with the concentration of Hg(II) ranging from 0.012 x 10(-6) to 1.5 x 10(-6) mol L(-1). The limit of detection for Hg(II) was 4.0 x 10(-9) mol L(-1). The developed method was successfully applied to the detection of trace Hg(II) in real samples.     

Determination of ulifloxacin by terbium-sensitized fluorescence with second-order scattering and its applications.

This paper reports the determination of ulifloxacin (UFX) by terbium-sensitized fluorescence using a second-order scattering method. UFX and Tb(III) ion form a fluorescence complex in aqueous solution, and its maximum excitation and emission wavelengths are located at 273 and 545 nm, respectively. In optimum conditions, the relative intensity at 545 nm has a linear relationship to the concentration of UFX in the range of 2.0 x 10(-8) - 1.0 x 10(-5) mol L(-1) and the detection limit is 3.9 x 10(-9) mol L(-1). The proposed method was applied to the determination of UFX in spiked human serum and urine satisfactorily. The luminescence property of UFX is also discussed by comparing with norfloxacin (NFLX) and ofloxacin (OFLX).     

A fluorescence quenching method for the determination of nitrite with Rhodamine 110

A simple and sensitive fluorescence quenching method for the determination of trace nitrite has been developed. The method is based on the reaction of Rhodamine 110 with nitrite in acidic medium to form a new compound, which has much lower fluorescence. The optimum experimental conditions were studied. The linear range was obtained at a nitrite concentration of 1.0 x 10(-8)-3.0 x 10(-7)mol l(-1) with a detection limit of 7.0 x 10(-10) mol l(-1) (S/N=3). The proposed method has been successfully applied to the determination of nitrite in tap water and lake water without extraction.     

Characteristic redox potential-time curve in the iron(II)/nitric acid autocatalytic reaction and its application to a time measurement-determination of folic acid.

A characteristic redox potential-time curve of the iron(II)/nitric acid autocatalytic reaction was applied to a time measurement-determination for sub-microM levels of folic acid. The determination range was 7.5 x 10(-7) - 1.5 x 10(-5) M, the detection limit (3 sigma) was 5.9 x 10(-7) M, and the relative standard deviation was 3.6% (n = 5).     

Separation and determination of trace amounts of aluminium(III), vanadium(V), iron(III), copper(II) and nickel(II) with CALKS and PAR by RP-HPLC.

An RP-HPLC method for the separation and determination of aluminium(III), vanadium(V), iron(III), copper(II) and nickel(II) with CALKS (Chromazol KS) and PAR ([4-(2-pyridylazo)resorcinol]) chelating on a YWG-ODS column was developed. A mixture of methanol-tetrahydrofuran(THF)-water (60:5:35 v/v) containing 0.2 mol/L LiCl, 5 x 10(-5) mol/L CALKS, 5 x 10(-5) mol/L PAR and acetate buffer solution (pH 4.9) was selected as mobile phase. The method has high sensitivity, with the detection limits being 6 ng/mL for aluminium(III), 3.5 ng/mL for vanadium(V), 10.4 ng/mL for iron(III), 6.3 ng/mL for copper(II) and 8.7 ng/mL for nickel(II). It also has good selectivity, so that most foreign metal ions do not interfere under the optimum conditions. The method can be applied to the simultaneous determination of trace amounts of aluminium, vanadium, iron, copper and nickel in rice and flour samples.     

Sequential flow-injection spectrophotometric determination of iron(II) and iron(III) by copper(II)-catalyzed reaction with Tiron

A flow injection method for the sequential determination of iron(II) and iron(III) was developed. It is based on the differential reaction kinetics of iron(II) and iron(III) with Tiron in a double-injection FI system. The proposed method employs the accelerating action of copper(II) for the oxidation of iron(II) in the presence of Tiron. A linear calibration graph is obtained for iron (II) and iron(III) in the concentration range 1.8 × 10^–5– 1.8 × 10^–4 mol/L; the throughput of samples is 30 injections/h. Received: 22 October 1996 / Revised: 4 December 1996 / Accepted: 10 December 1996     

Evaluation of luminol-H(2)O(2)-KIO(4) chemiluminescence system and its application to hydrogen peroxide, glucose and ascorbic acid assays

A novel chemiluminescence (CL) system was evaluated for the determination of hydrogen peroxide, glucose and ascorbic acid based on hydrogen peroxide, which has a catalytic-cooxidative effect on the oxidation of luminol by KIO(4). Hydrogen peroxide can be directly determined by luminol-KIO(4)-H(2)O(2) CL system. The detection limit was 3.0x10(-8) mol l(-1) and the calibration graph was linear over the range of 2.0x10(-7)-6.0x10(-4) mol l(-1). The relative standard deviation of H(2)O(2) was 1.1% for 2.0x10(-6) mol l(-1) (N=11). Glucose was indirectly determined through measuring the H(2)O(2) generated by the oxidation of glucose in the presence of glucose oxidase at pH 7.6. The present method provides a source for H(2)O(2), which, in turn, coupled with the luminol-KIO(4)-H(2)O(2) CL reaction system. The CL was linearly correlated with glucose concentration of 0.6-110 mug ml(-1). The relative standard deviation was 2.1% for 10 mug ml(-1) (N=11). Detection limit of glucose was 0.08 mug ml(-1). Ascorbic acid was also indirectly determined by the suppression of luminol-KIO(4)-H(2)O(2) CL system. The calibration curve was linear over the range of 1.0x10(-7)-1.0x10(-5) mol l(-1) of ascorbic acid. The relative standard deviation was 1.0% for 8.0x10(-7) mol l(-1) (N=11). Detection limit of ascorbic acid was 6.0x10(-8) mol l(-1). These proposed methods have been applied to determine glucose, ascorbic acid in tablets and injection.     

利用salen型荧光探针测定Cr3+

研究了salen型席夫结构的荧光探针N,N’-二(2-羟基-1-萘甲醛)-l,2-苯二胺(NAPPDIH)对Cr3+的响应。Cr3+能够使该探针的荧光猝灭。研究表明,在pH3.5(乙酸胺-盐酸)和DMSO/H2O(V/V,8:2)的条件下,8.0×10-6 mol/L的Cr3+可以导致NAPPDIH 65%的荧光猝灭。并且,Cr3+的浓度在5.0×10-7～8.0×10-6 mol/L的范围内,与荧光强度的变化值呈良好的线性关系,检出限为3.7×10-7 mol/L。方法可用于直接检测水样中的Cr3+。     

一种基于形成杂多核配合物的荧光增敏效应的研究Ⅰ.锰(Ⅱ)-7-(8-羟基-3,6-二磺基萘偶氮)-8-羟基喹啉-5-磺酸-硼(Ⅲ)三元体系的荧光性质及其分析应用

本文报道了一种新发现的荧光增敏效应.在7-(8-羟基-3,6-二磺基萘偶氮)-8-羟基喹啉-5-磺酸-硼(Ⅲ)配位反应体系的非平衡状态下加入微量Mn^2+,体系荧光强度大为增加,三元体系特征荧光峰波长与原二元体系相同.研究表明,荧光增敏同Mn^2+参与形成杂多核配合物有关.据此建立了Mn^2+的高灵敏分析方法, Mn^2+线性范围0～2.9×10^-7mol.L^-1,检出下限3×10^-9mol·L^-1.方法选择性亦好,大多数共存离子的干扰都比较小.以此法测定合成样和粮食试样中的微量锰.结果满意.