Covalently immobilized aminonaphthalimide as fluorescent carrier for the preparation of optical sensors

By replacing the hydrogen of the 4-amino group of a 4-amino-1,8-naphthalimide derivative with an N-acryloxyethyl group, the fluorophore has been covalently immobilized on an optical sensor surface by UV photopolymerization. The optical sensor obtained can be used for the determination of picric acid. The linear range and detection limit of the sensor are 9.80x10(-7)-1.96x10(-4) mol L(-1) and 7.1x10(-7) mol L(-1), respectively. Leaching of the fluorophore from the membrane is effectively prevented by covalent immobilization, resulting in a sensor with a relatively long lifetime. The response time of the sensor is short, and the reproducibility and reversibility are good. The sensor has been used for the indirect determination of the chloroquine content of pharmaceutical tablets.     

Flow-injection determination of ornidazole by chemiluminescence detection based on a luminol-ferricyanide reaction.

A flow-injection analysis (FIA) with a chemiluminescence detection method was developed for the determination of ornidazole based on the inhibition intensity of chemiluminescence from the luminol-ferricyanide system. Under the condition of 1.0 x 10(-3) mol/L luminol and 5.0 x 10(-6) mol/L potassium ferricyanide, the response to the concentration of omidazole is linear from 0.2 microg ml(-1) to 10 microg ml(-1), and a detection limit of 0.05 microg ml(-1) can be obtained. This method has been successfully applied to the determination of omidazole in pharmaceutical preparations.     

A coumarin derivative covalently immobilized on sensing membrane as a fluorescent carrier for nitrofurazone

A coumarin derivative 4-methyl-8-methylacrylamide-2H, 5H-pyrano [3, 2-C] benzpyran 2, 5-dione (MMPBD) has been synthesized as a fluorescent carrier for preparing an optical chemical sensor. The carrier is immobilized on a quartz glass plate surface treated with a silanizing agent to prevent the leakage of the dye. This MMPBD sensor can be utilized for a nitrofurazone (NF) assay based on fluorescence quenching. The sensor shows good repeatability, a long lifetime and a fast response of less then 50 s. NF can be determined in the range between 1.0x10(-6)-1.0x10(-3 )mol L(-1) with a detection limit of 8.0x10(-7) mol L(-1 )at pH 7.0.     

Selective recognition of monohydrogen phosphate by fluorescence enhancement of a new cerium complex

Bis(8-hydroxy quinoline-5-solphonate) cerium(III) chloride (Ce(QS)(2)Cl) (L) was synthesized and then used as a novel fluorescent sensor for anion recognition. Preliminarily study showed that fluorescence of L enhanced selectively in the presence of HPO(4)(2-) ion. This enhancement is attributed to a 1:1 complex formation between L and HPO(4)(2-) anion. The association constant of 1:1 complex of L-HPO(4)(2-) was calculated as 3.0×10(6). Thus, L was utilized as a basis for a selective detection of HPO(4)(2-) anion in solution. The linear response range of the proposed fluorescent chemo-sensor covers a concentration range of HPO(4)(2-) from 3.3×10(-7) to 5.0×10(-6) mol L(-1) with a detection limit of 2.5×10(-8) mol L(-1). L showed selective and sensitive fluorescence enhancement response toward HPO(4)(2-) ion in comparison with I(3)(-), NO(3)(-), CN(-), CO(3)(2-), Br(-), Cl(-), F(-), H(2)PO(4)(-) and SO(4)(2-) ions. It was probably attributed to the higher stability of the inorganic complex between HPO(4)(2-) ion and L. The method was successfully applied for analysis of phosphate ions in some fertilizers samples.     

Fiber-optic sensor for iodine based on a covalently immobilized aminobenzanthrone Schiff base.

An aminobenzanthrone Schiff base has been synthesized as a new fluorescence carrier for the preparation of an optical chemical sensor for iodine. The response of the sensor is based on fluorescence quenching of the aminobenzanthrone Schiff base by iodine. The sensor shows a linear response toward iodine in the range of 1.0 x 10(-5) to 1.0 x 10(-3) mol l(-1), with a detection limit of 6.0 x 10(-6) mol l(-1) at pH 8.0. Leaching of the fluorophore from the membrane is effectively hindered by covalent immobilization, resulting in an enhanced sensor lifetime. In addition to satisfactory reproducibility and reversibility, the prepared sensor exhibits sufficient selectivity toward iodine with respect to other coexisting ions. The sensor has been applied to the determination of iodine in common salt samples.     

A novel water-soluble fluorescent probe for the determination of methylamine

A novel water-soluble fluorescent probe, monosodium 7-(4,6-dichloro-1,3,5-triazinylamino)-1,3-naphthalenedisulfonic acid (DTND), was synthesized by reacting cyanuric chloride with 7-amino-1,3-naphthalenedisulfonic acid monopotassium salt at 0-5 degrees C. This new reagent was used for the determination of methylamine. The linear range is 3x10(-6)-2x10(-4) mol L(-1) with a detection limit (S/N=3) of 7.2x10(-8) mol L(-1), and the relative S.D. is 1.3% for ten replicate determinations of 1x10(-5) mol L(-1) CH3NH2. Common species in the aqueous environment have no or only slight influence on the determination. The method can be used to determine methylamine in real water samples.     

Cesium-selective membrane electrode based on a recently synthesized 16-membered macrocyclic diamide

A PVC membrane sensor for the Cs+ ion based on 1,5-diaza-2,3,4-naphthyl-8,11,14-trioxacyclohexadecane-6,16-dione (L) has been prepared. The sensor has a linear dynamic range of 5.0 x 10(-1) - 6.9 x 10(-6) mol L(-1), a Nernstian slope of 59.5 +/- 0.8 mV decade(-1), and a detection limit of 4.7 x 10(-6) mol L(-1). It has a fast response time of <15 s and can be used for at least 8 weeks without any considerable divergence in potentials. The selectivity of the proposed electrode relative to alkali, alkaline earth, and transition metal ions was comparatively good. The electrode could be used in the pH range 4.5-11.0.     

A selective optical chemical sensor for o-nitrophenol based on fluorescence quenching of curcumin

An optical chemical sensor has been prepared for the selective determination of o-nitrophenol in aqueous solutions based on the fluorescence quenching of curcumin in PVC membrane. The sensing mechanism of the proposed sensor for o-nitrophenol has been discussed in detail. The fluorescence changes of sensing membrane resulted from an associated complex formation between curcumin and o-nitrophenol. In pH 4.8 buffer solution, the sensor responds linearly in the measuring range from 1.0 x 10(-2) mol 1(-1) to 1.5 x 10(-4) mol 1(-1), and the experimental detection limit is evaluated to be 8.0 x 10(-5) mol 1(-1). A stable signal was obtained within less than 1.5 min. Under the optimum conditions, the sequence of selective response to the sensing membrane is o-nitrophenol > 2,4-dinitrophenol > m-nitrophenol > p-nitrophenol > 2,4,6-trinitrophenol. Phenol, aniline as well as other ions have less effect on the fluorescence of the sensor. The reproducibility for the determination of o-nitrophenol is better than 1%, and the response is reversible. The sensor can be used for the determination of o-nitrophenol in water samples.     

Different Interactions between Isomeric Tetrakis-(N-Hexadecylpyridiniumyl) Porphyrins and CdS Nanoparticles

Using porphyrin amphiphiles TC(16)PyP(2), TC(16)PyP(3), and TC(16)PyP(4) as photosensitizers, the interaction between amphiphilic porphyrins and colloidal CdS nanoparticles was studied by observing their absorption spectra, fluorescence spectra, and fluorescence lifetimes. The experimental results reveal that upon addition of CdS nanoparticles to a TC(16)PyP(3) or TC(16)PyP(4) solution, TC(16)PyP(3) or TC(16)PyP(4) is adsorbed onto the surface of the colloidal nanoparticles due to electrostatic action. The absorption spectra display the characteristic absorption of metalloporphyrin. Moreover, this adsorption also leads to red-shifted fluorescence spectra and the quenching of fluorescence emission. These changes are related to the formation of complexes. Nearly 90% of the fluorescence emission of 5x10(-6) mol/L TC(16)PyP(4) can be quenched with 6.8x10(-4) mol/L CdS colloid nanoparticles. Only 60% of the fluorescence emission of 5x10(-6) mol/L TC(16)PyP(3) can be quenched with 6.8x10(-4) mol/L CdS nanoparticles. The fluorescence quenching is attributable mainly to static quenching. According to the fluorescence quenching curves, the apparent association constants of TC(16)PyP(4) and TC(16)PyP(3) with colloidal CdS nanoparticles are 1.42x10(3) (mol/L)(-1) and 6.76x10(2) (mol/L)(-1), respectively. However, TC(16)PyP(2) does not adsorb onto the surface of colloid nanoparticles due to its larger steric hindrance; its absorption and fluorescence spectra are unchanged. Copyright 2000 Academic Press.     

A selective PVC membrane for di- or trinitrophenol based on N,N-dibenzyl-3,3',5,5'-tetramethylbenzidine

A new fluorophore, N,N-dibenzyl-3,3',5,5'-tetramethylbenzidine (NBTMB), was prepared and shown to exhibit significant and analytical usefulness for optical sensing toward 2,4-dinitrophenol or 2,4,6-trinitrophenol (picric acid) when it was immobilized in a plasticized poly(vinyl chloride) (PVC) membrane. When the membrane was applied to aqueous nitrophenol solution, NBTMB was able to extract selectively nitrophenol into the membrane phase. Since the extraction equilibrium was accompanied by fluorescence quenching of NBTMB, the chemical recognition process could be directly translated into an optical signal. The sensor showed reversible response in the concentration range from 2.0 x 10(-7) to 6.0 x 10(-5) mol L(-1) for the detection of 2,4-dinitrophenol in NaOAc-HOAc buffer at pH 4.0. It also showed a fast response time (t95% < 1.5 min) when the sensor was applied to 2,4-dinitrophenol solution at concentration levels of 5.26 x 10(-6) and 2.10 x 10(-5) mol L(-1) alternatively. A working principle is proposed and the responses of this sensor to various kinds of nitrophenol were studied. The sensor was applied to the direct determination of 2,4-dinitrophenol in prepared water samples and the indirect assay of the drug cinchonine and the results obtained were satisfactory.     

N-allyl-4-(N-2'-hydroxyethyl)amino-1,8-naphthalimide as a fluorophore for optical chemosensing of nitrofurantoin

N-Allyl-4-(N-2'-hydroxyethyl)amino-1,8-naphthalimide (AHEAN), a naphthalimide derivative, was synthesized as a new fluorophore for optical chemical sensor preparation. To prevent leakage of the fluorophore, AHEAN was photo-copolymerized with 2-hydroxypropyl methacrylate on a glass surface treated with a silanizing agent. An optical chemical sensor based on AHEAN can be utilized for nitrofurantoin assay based on fluorescence quenching. The sensor shows sufficient repeatability, selectivity and a fast response of less than 30 s. Nitrofurantoin can be determined in the range between 1.00 x 10(-6) and 1.00 x 10(-3) mol l(-1) with a detection limit of 4.8 x 10(-7) mol l(-1). Most commonly co-existing drug substances and ions do not interfere with the nitrofurantoin assay. The sensor was applied to the analysis of pharmaceutical and urine samples.     

An optical fiber sensor for berberine based on immobilized 1,4-bis(naphth[2,1-d]oxazole-2-yl)benzene in a new copolymer

A new copolymer made of 8-quinolyl methacrylate, methyl methacrylate and n-butyl acrylate(PQMB) has been used as a solid substrate for the preparation of an optical fiber berberine sensor. The sensing is based on the fluorescence of 1,4-bis(naphth[2,1-d]oxazole-2-yl)benzene(BNOB) immobilized in the copolymer quenched by berberine with the formation of 1:1 complex between them. The membrane composition was optimized using the orthogonal experimental design. Using the sensor described above, berberine in a sample solution from 4.02x10(-7) mol l(-1) to 2.82x10(-4) mol l(-1) can be detected. The sensor has satisfactory reversibility and a short response time of less than 30 s. The relative standard deviations for repeated measurements (n=15) of 8.05x10(-6) mol l(-1) and 4.02x10(-5) mol l(-1) beberine are 0.43% and 0.33%, respectively. The sensor shows good selectivity over alkali and alkali-earth metal salts and some common pharmaceutical species and can be used for the determination of berberine in pharmaceutical preparations.     

Electrochemical behavior and electrocatalytic study of the methylene green coated on modified silica gel

The electrochemical behavior of methylene green (MG) adsorbed on a silica surface modified with niobium oxide (SN) was investigated, using modified carbon paste electrodes. It was also used in an electrocatalytic study of NADH oxidation. The electrode showed a high stability attributed to the presence of SN, which avoids the leaching of the mediator from the electrode surface. The formal potential (E(0')) of the adsorbed MG was -35 mV vs SCE, showing a shift of 30 mV toward more positive potential values, compared to the MG dissolved in aqueous solution. This shift was assigned to the interaction between the basic nitrogen of MG and the acid sites of SN. The variation of the solution pH between 4 and 8 did not affect the stability nor the formal potential. However, for solution pH lower than 4 the formal potential was affected by the acidity of the medium. The electrocatalytic oxidation of NADH at the electrode was investigated. In the solution pH between 5 and 8 the electrocatalytic activity remained almost constant, giving a response signal of 13.3 nA L micromol(-1) cm(-2) and a K(Mapp) of 1.4 x 10(-5) mol L(-1). The electrode gave a linear response range between 5.0 x 10(-4) and 4.0 x 10(-3) mol L(-1) NADH concentration at pH 7.0 at an applied potential of 50 mV vs SCE. Applying a flow injection analysis system, the electrode showed a better analytical performance for NADH detection, presenting a linear response range between 6.0 x 10(-5) and 1.0 x 10(-3) mol L(-1), with an analytical frequency of 30 determinations/h, a detection limit of 8.2 x 10(-6) mol L(-1), and a precision for 25 replicates of 1% expressed as a relative standard deviation.     

Fluorimetric study of the interaction between human serum albumin and quinolones-terbium complex and its application

A highly sensitive spectrofluorimetric method is proposed for determination of human serum albumin (HSA) and some quinolone drugs. Using quinolones-terbium (Tb3+) complex as a fluorescent probe, in the buffer solution of pH 7.8, HSA can remarkably enhance the fluorescence intensity of the quinolones-Tb3+ complex at 545 nm and the enhanced fluorescence intensity of Tb3+ ion is in proportion to the concentration of HSA and quinolone drugs. Optimum conditions for the determination of HSA were also investigated. The linear ranges and limits of detection are 8.0 x 10(-9) to 8.0 x 10(-8) mol L(-1), 4.20 x 10(-9) mol L(-1) (for HSA); 1.0 x 10(-6) to 4.0 x 10(-6) mol L(-1), 1.87 x 10(-8) mol L(-1) (for norfloxacin) and 1.0 x 10(-7) to 1.0 x 10(-6) mol L(-1), 4.82 x 10(-8) mol L(-1) (for enoxacine), respectively. This method is simple, practical and relatively free interference from coexisting substances, as well as much more sensitive than most of the existing assays.     

Simultaneous determination of trace of loxacin, ciprofloxacin, and sparfloxacin by micelle TLC-fluorimetry

The method of simultaneous determination of ofloxacin (OFLX), ciproflxacin (CPLX), and sparfloxacin (SPLX) by thin-layer chromatography is established, with micelle solutions as mobile phases. It is found that the optimum molar ratio of sodium dodecyl sulfate (SDS) to ethylene diamine tetraacetic acid is 0.01:0.1. On the polyamide thin-layer sheet, OFLX, CPLX, and SPLX are separated from each other, and the corresponding Rf values are 0.72, 0.55, and 0.32, respectively. The fluorescence spots are scanned with a spectrodensitometer at the excitation wavelength of 282 nm. The cut-off filter is set at 400 nm. The detection limits are 2 x 10(-6) mol/L for OFLX, 1.5 x 10(-6) mol/L for CPLX, and 1.6 x 10(-6) mol/L for SPLX, and the respective linear ranges correspondingly fell in the concentration of 1 x 10(-5) to 4 x 10(-4) mol/L for OFLX, 1 x 10(-5) to 4.5 x 10(-4) mol/L for CPLX, and 1 x 10(-5) to 4.2 x 10(-4) mol/L for SPLX. For all the three components, the relative standard deviations are in the range of 1.12-5.82%, and the recoveries are found to be 96.7-104.2% in urine and serum 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.     

On-line micellar-enhanced spectrofluorimetric determination of rhodamine dye in cosmetics

A simple FI-fluorimetric analytical methodology for the continuous and sequential determination of rhodamine B (RhB) in cosmetic products has been developed and evaluated in terms of sensibility and selectivity. The influence of several surfactant solutions on RhB fluorescence signal has been studied; particular attention was paid in the aggregation behavior of RhB-SDS system. Linear response has been obtained in the range of 1.6 x 10(-9) and 1 x 10(-6) mol L(-1), with a detection limit of 5 x 10(-10) mol L(-1). The novel technique provides a simple dissolution of sample, on-line filtration with sampling rate higher than 100 samples h(-1) and has been satisfactorily applied to the RhB determination in commercial lipsticks.     

Quenching effect of nickel ions on fluorescent gold nanoparticles

Herein, we reported the quenching effect of Ni(2+) on bovine serum albumin protected fluorescent gold nanoparticles (BSA-GNPs). The quenching mechanism was discussed and a static quenching mechanism was proposed. The number of binding sites (n), apparent stability constants (K) and corresponding thermodynamic parameters of BSA-GNPs-Ni(2+) complex were measured at different temperatures. Under optimum conditions, the fluorescence intensity of BSA-GNPs is linearly proportional to nickel concentration from 6.0x10(-8)mol/L to 8.0x10(-6)mol/L with a detection limit of 1.0x10(-8)mol/L. The result indicated that BSA-GNP was a potential Ni(2+) probe.     

Highly selective thiocyanate poly(vinyl chloride) membrane electrode based on a cadmium-Schiff's base complex

A PVC membrane electrode based on a cadmium-salen (N,N'-bis-salicylidene-1,2-ethylenediamine) complex as an anion carrier is described. The electrode has an anti-Hofmeister selectivity sequence with a preference for thiocyanate at pH 1.5-11.0. It has a linear response to thiocyanate from 1.0 x 10(-6) to 1.0 x 10(-1) mol L(-1) with a slope of 59.1 +/- 0.2 mV per decade, and a detection limit of 7 x 10(-7) mol L(-1). This electrode has high selectivity for thiocyanate relative to many common organic and inorganic anions. The proposed sensor has a fast response time of approximately 15 s. It was applied to the determination of thiocyanate in a milk sample.     

Amperometric determination of glutathione and cysteine on a Pd-IrO(2) modified electrode with high performance liquid chromatography in rat brain microdialysate

A Pd/IrO(2) co-electrodeposited glassy carbon electrode was prepared and the electrochemical behavior of glutathione (GSH) at this chemically modified electrode (CME) has been studied by cyclic voltammetry (CV). The results indicated that the modified electrode efficiently exhibited electrocatalytic oxidation for GSH with relatively high sensitivity, stability, and long-life. Coupled with high-performance liquid chromatography (HPLC), the Pd/IrO(2) modified electrode was utilized for the electrochemical detection (ECD) of the thiocompounds, glutathione and cysteine (Cys). The peak currents were linear with the substance concentrations in the range of 1.0 x 10(-5) mol L(-1) to 8.0 x 10(-4) mol L(-1) for GSH and 4.0 x 10(-6) mol L(-1) to 2.0 x 10(-4) mol L(-1) for Cys. The detection limits were 2.0 x 10(-6) mol L(-1) for GSH and 5.0 x 10(-7) mol L(-1) for Cys with S/N of 3. The method has been successfully applied to assess the contents of GSH and Cys in rat brain microdialysates.