A Novel Method for the Assessment of Cortisol Hormone in Different Body Fluids Using A New Photo Probe Thiazole Derivative

A low cost and accurate method for the detection and analytical determination of the cortisol in pharmaceutical preparation, blood serum and urine was developed. The method was based upon the enhancement of fluorescence intensity of the band at 424 nm of the photo probe by different cortisol concentrations in acetonitrile at (pH 5.7, λ_ex?=?320 nm). The influence of the different parameters, e.g. pH, solvent, cortisol concentration and foreign ions concentrations that control the enhancement process of fluorescence intensity of the band of photo probe was critically investigated. The remarkable enhancement of the fluorescence intensity at 424 nm in acetonitrile by various concentrations of cortisol was successfully used as a photo- probe for the assessment of cortisol concentration. The calibration plot was achieved over the concentration range 8.0?×?10^?6–5.5?×?10^?9 mol L^?1 cortisol with a correlation coefficient of 0.998 and a detection limit of 4.7?×?10^?9 mol L^?1. The developed method is simple and proceeds without practical artifacts compared to the other determination methods.     

Study on the Cofluorescence Effect of Europium (III)–Yttrium (III)–Balofloxacin–Sodium Dodecyl Sulfate System and Its Analytical Application

A new fluorescence enhancement phenomenon in the europium(III)–balofloxacin–sodium dodecyl sulfate system was observed when yttrium(III) was added. Based on this, a sensitive cofluorescence assay for the estimation of balofloxacin was established. Under the optimized conditions, the enhanced fluorescence signal was linear over the concentration of balofloxacin ranging from 3.0 × 10^?9 to 7.0 × 10^?6 mol L^?1 with a correlation coefficient of 0.9993. The detection limit (3 σ) was determined as 8.3 × 10^?10 mol L^?1. The presented method was successfully applied to determination of balofloxacin in pharmaceutical preparations, human serum, and urine. The possible fluorescence enhancement mechanism was also discussed.     

Determination of Rosuvastatin in Urine by Spectrofluorimetry After Liquid–Liquid Extraction and Derivatization in Acidic Medium

Statins are a class of drugs mostly used for treating hyperlipidemia, and rosuvastatin is the newest drug in the market belonging to this class. In this present work, a method was developed based on the molecular fluorescence technique, with the objective to quantify rosuvastatin in urine samples. For this purpose, the study of several parameters was made to achieve the maximum analytical signal (under reaction with sulfuric acid during 40 min). Also, a previous step to avoid matrix interference was carried out (liquid–liquid extraction). The limit of detection (LOD) and the limit of quantification (LOQ) were 0.38 and 1.28 mg L^?1, respectively. Linear relationship between rosuvastatin concentration and it’s fluorescence intensity was found until 5.0 mg L^?1. The proposed method was tested in several samples spiked with rosuvastatin and recovery was found in the range of 90?±?10 %.     

Spectrofluorimetric Determination of Nickel (ΙΙ) with Murexide

A very sensitive and selective spectrofluorimetric method has been developed for nickel (ΙΙ) determination in environmental samples. The method is based on measuring the decrease in fluorescence intensity of murexide after nickel (ΙΙ) binding. The intensity of the fluorescence emission peak was measured at ex/em 345/431 nm in several solutions with pH interval 3.0–7.0. The fluorescence intensity decrease was found to be linear in the concentration range of 0.007 mg.L^?1 to 0.1 mg.L^?1 and 0.1 mg.L^?1 to 20 mg.L^?1 of nickel (ΙΙ) by using 10^?4 M murexide at pH 3. The detection limit was found 0.004 mg.L^?1. Relatively large excesses of over 20 cations and anions do not interfere. The method was successfully applied to the analysis of nickel (ΙΙ) in sea, rain and ground water. This method is very precise and accurate (R.S.D.?=?0.42 % for the determination of 0.05 mg.L?¹ nickel in 10 replicates).     

A Validated Spectrofluorimetric Method for the Determination of Citalopram in Bulk and Pharmaceutical Preparations Based on the Measurement of the Silver Nanoparticles-Enhanced Fluorescence of Citalopram/Terbium Complexes

A simple, sensitive, and accurate spectrofluorimetric method was developed for the determination of citalopram in bulk and pharmaceutical preparations. The method is based on the enhancement of the weak fluorescence signal (FL) of the Tb (III)-citalopram system in the presence of silver nanoparticles. Fluorescence intensities were measured at 555 nm after excitation at 281 nm. Prepared silver nanoparticles (AgNPs) were characterized by UV-Visible spectra and transmission electron microscopy (TEM). Various factors affecting the formation of citalopram-Tb (III)-AgNPs complexes were studied and optimized. The fluorescence intensity versus concentration plot was linear over the range 0.02–14 μg?mL^?1, with an excellent correlation coefficient of 0.9978. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 7.15?×?10^?6?μg?mL^?1 and 2.38?×?10^?5?μg?mL^?1 respectively. The proposed method was found to have good reproducibility with a relative standard deviation of 3.66 % (n?=?6). The interference effects of common excipients found in pharmaceutical preparations were studied. The developed method was validated statistically by performing recoveries studies and successfully applied for the assay of citalopram in bulk powder and pharmaceutical preparations. Percent recoveries were found to range from 98.98 % to 100.97 % for bulk powder and from 96.57 % to 101.77 % for pharmaceutical preparations.     

Synthesis and Characterization of New Light Emitter Symmetrical Phenoxazinium Salt and Its Potential Application as Sensor for Assessment of Hg2+

The sensitization of the excited triplet state of a novel symmetrical Bis(dialkylamino)phenoxazinium salt was developed in the presence of Hg²⁺. This effect was used to determine the concentration of Hg²⁺ in different water samples. The phenoxazinium salt sensor was characterized by different spectroscopic tools such as: UV, FTIR, NMR and fluorescence spectra. The sensor has an emission band at 347 nm in DMSO. Hg²⁺ in DMSO at pH 5.6 can remarkably quench the fluorescence intensity of the sensor at 347 nm and a new band was appeared at 436 nm due to the strong complex formation between Hg²⁺ and sensor. The quenching of the band intensity at 347 and the enhancement of the intensity of the new band at 436 were used to determine the Hg²⁺ in different waste water samples. The dynamic range found for the determination of Hg²⁺ concentration is 8.7?×?10^-10 – 1.4?×?10^-6 mol L^?1 with a detection limit of 5.8?×?10^?10 mol L^?1 and quantification detection limit of 1.8?×?10^-9 mol L^-1.     

SPECTROPHOTOMETRIC DETERMINATION OF ZINC IN PHARMACEUTICAL SAMPLES USING DI-2-PYRIDYL KETONE SALICYLOYLHYDRAZONE

ABSTRACT

A highly sensitive procedure for spectrophotometric determination of zinc has been developed. At pH 4.5, in 50% (V/V) ethanol-water medium and in the presence of di-2-pyridyl ketone salicyloylhydrazone (DPKSH), zinc forms a yellow complex which has maximum absorption at 376 nm The molar absorptivity is 4.82×10⁴ L mol^?1 cm^?1. The detection limit of this method is 62.1 nM for Zn(II).

The method has been applied to the spectrophotometric determination of zinc in pharmaceutical formulations and the results comply with those obtained by AAS. The proposed method is simple, rapid and accurate.     

Study on the Fluorescence Quenching Reaction of Amitriptyline and Clomipramine Hydrochlorides with Eosin Y and its Analytical Application

Amitriptyline.HCl (AMI) and clomipramine.HCl (CMI) react with eosin Y (EY) in pH 3.8 NaAc-AcH buffer solution to form ion association complex which results in quenching of fluorescence of EY and appearance of a new resonance Rayleigh scattering (RSS) spectrum at 620 nm. The spectral characteristics of absorption, fluorescence and RSS spectra have been investigated. The factors influencing the reaction were studied and optimum conditions for the reaction have been determined. Based on fluorescence quenching, a simple and sensitive spectrofluorimetric method for determination of AMI and CMI has been developed. The fluorescence quenching intensity was measured at 550 nm using an excitation wavelength of 310 nm. The calibration graph was found to be rectilinear in the range 0.08–2.0 μg?mL^?1 with detection limit of 0.017 μg?mL^?1 for AMI and 0.06–2.0 μg?mL^?1 with detection limit of 0.015 μg?mL^?1 for CMI. The method can be satisfactorily applied to the determination of AMI and CMI in tablets without interference from commonly occurring exicipients. The recovery and RSD values obtained indicate good accuracy and precision of the method. The mechanism of the reaction and fluorescence quenching has also been discussed.     

Hydrodynamic Sequential Injection Spectrophotometric System for Determination of Manganese in Soil

ABSTRACT

A novel hydrodynamic sequential injection (HSI) spectrophotometric system for determination of manganese was developed. It is based on the complexation of Mn(II) with formaldoxime in basic solution (pH ≥ 10) to produce product that could be monitored spectrophotometrically at 450 nm. Based on the HSI concept, both sample and reagents were aspirated through solenoid valves to fill a defined volumes conduit between 3-way connectors connected in series, forming stacked zones of solutions similar to those in normal SI. The concept was successfully demonstrated for manganese determination. A linear calibration graph over a range of 0.5 to 30 mg L^?1 Mn(II) with a detection limit of 0.2 mg L^?1 was obtained. Relative standard deviations for 11 replicated injections of 5 and 20 mg Mn L^?1 were 5.6% and 2.4%, respectively. A sample throughput of 45 h^?1 was achieved. The results from investigation of exchangeable manganese in soil samples by the developed method were found to be in good agreement with the results obtained by a batch spectrophotometric method, despite the proposed system employed simpler and more cost-effective devices/instruments, had higher degrees of automation with full microcontroller control of the operation, and consumed smaller amounts of chemicals (250 µL each of hydroxylamine, sample, and formaldoxime solutions and 2.5 mL of buffer carrier solution per operation cycle).     

Cloud point extraction-fluorimetric combined methodology for the determination of trace warfarin based on the sensitization effect of supramolecule

Compared to the fluorescence spectra of warfarin in pure ethanol and in the presence of the nonionic surfactant Tergitol 15-S-7 after cloud point extraction (CPE), it can be seen that the fluorescence emission peak underwent an obvious red shift and the fluorescence intensity of warfarin was significantly increased in the presence of Tergitol 15-S-7. In order to confirm Tergitol 15-S-7-induced supramolecular effects, the investigations on the fluorescence quantum yields of warfarin in the micellar medium and pure ethanol were performed. The experimental results showed that the supramolecular interactions between Tergitol 15-S-7 and the warfarin excimers played a key role for improving the warfarin fluorescence properties.Based on these facts, a simple fluorometric method combined with CPE for the determination of trace warfarin was developed for the first time. Under optimized experimental conditions, the linear concentration range for warfarin was 3.0×1.0^?9–1.0×10^?6 mol L^?1 and the detection limit was 3.3×10^?10 mol L^?1. And, the proposed method was approved to be appropriate for monitoring warfarin in actual pharmaceutical formulations and biological fluid samples by recovery test, in comparison with other reported methods being satisfactory.     

Supramolecular Study on the Interaction Between Ofloxacin and Methyl β-Cyclodextrin by Fluorescence Spectroscopy and its Analytical Application

The supramolecular interaction of ofloxacin (Oflo) and methyl β-cyclodextrin (Mβ-CD) has been examined by UV–vis, IR and fluorescence spectroscopy. The formation of inclusion complex has been confirmed based on the changes of the spectral properties. The results showed that Mβ-CD reacted with Oflo to form an inclusion complex. The Oflo and Mβ-CD complex formed a host-guest complex in 1:1 stoichiometry and inclusion constant (K?=?7.8?×?10^?3 L mol^?1) was ascertained by the typical double reciprocal plots. Furthermore, the thermodynamic parameters (?H°, ?S° and ?G°) associated with the inclusion process were also determined. In addition, solid inclusion complex was synthesized. Based on the significant enhancement of the fluorescence intensity of Oflo produced through complex formation, a simple, accurate, rapid and highly sensitive spectrofluorometric method for the determination of Oflo in pharmaceutical formulation was developed. The measurement of relative fluorescence intensity was carried out at 497 nm with excitation at 296 nm. The factors affecting the inclusion complex formation were studied and optimized. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9995) were in the concentration range of 50–350 ng/mL for spectrofluorimetry. The limit of detection (LOD) was 11.5 ng/mL. The proposed method was successfully applied to the analysis of Oflo in pharmaceutical preparation.     

Selective Determination of Atropine Using poly Dopamine-Coated Molecularly Imprinted Mn-Doped ZnS Quantum Dots

In this study, a selective method for the determination of atropine in pharmaceutical formulations was proposed. L-cysteine capped Mn-doped ZnS quantum dots (QDs) were prepared in an in-situ method using sodium thiosulfate precursor and characterized by spectrofluorometer, Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope (TEM) and X-ray diffractometer (XRD). Dopamine hydrochloride was used as a precursor for preparation of poly dopamine-coated molecularly imprinted Mn-doped ZnS quantum dots. Finally, these prepared molecularly imprinted Mn-doped ZnS quantum dots were used for determination of atropine in pharmaceutical formulations. The obtained linear range for determination of atropine was in the range of 2 × 10^?8 – 7 × 10^?6 M, with a correlation coefficient (R²) of 0.9889; and the detection limit (S/N = 3) was 3.2 nM.     

A Novel Pyrene Fluorescent Sensor Based on the π–π Interaction Between Pyrene and Graphene of Graphene–Cadmium Telluride Quantum Dot Nanocomposites

In this article, water-soluble graphene–cadmium telluride quantum dot nanocomposites were fabricated through the synthesis of cadmium telluride quantum dots in the presence of graphene aqueous dispersion. It was found that pyrene could remarkably quench fluorescence of graphene–cadmium telluride quantum dot nanocomposites. On this basis, a novel method for the determination of pyrene was developed. Factors affecting the pyrene detection were investigated, and the optimum conditions were determined. Under the optimum conditions, a linear relationship could be established between the quenching of fluorescence intensity of graphene–cadmium telluride quantum dot nanocomposites and the pyrene concentration in the range of 6.00 × 10^?8–2.00 × 10^?6 mol L^?1 with a correlation coefficient of 0.9959. The detection limit was 4.02 × 10^?8 mol L^?1. Furthermore, the nanocomposites were applied to practical determination of pyrene in different water samples with satisfactory results.     

Study on the Interaction Between Oxymatrine and Tungstosilicic Acid by Resonance Rayleigh Scattering and Its Analytical Applications

In the 0.1 mol · L^?1 hydrochloric acid solution, oxymatrine reacted with tungstosilicic acid to form a 2:1 ion-association complexes. This results in a great enhancement of resonance Rayleigh scattering. The maximum resonance Rayleigh scattering wavelength was located at 393 nm. Resonance Rayleigh scattering intensity was proportional to the concentration of oxymatrine in the range of 1.5–26.4 µg · mL^?1, and the detection limit (3σ) was 0.23 µg · mL^?1. The optimum conditions and the effects of coexisting substances on the reaction were investigated. The method shows a wide linear range and high sensitivity, and was applied to the determination of oxymatrine in marine capsules and human urine samples with satisfactory results. Therefore, a highly sensitive, simple, and quick method has been developed for the determination of oxymatrine.     

Determination of Protoporphyrin IX Disodium Salt Based on Fluorescence Quenching of Glutathione-Capped Cadmium/Tellurium Quantum Dots

ABSTRACT

Aqueous glutathione-capped cadmium/tellurium quantum dots with a diameter of about 3 nm were synthesized. The fluorescence was quenched in the presence of protoporphyrin IX disodium salt, with the excitation wavelength at 320 nm. Under the optimal conditions, the quenched fluorescence intensity was linear in the range of 0.096–16 µg · mL^?1 with a concentration of protoporphyrin IX disodium salt, and the detection limit (3σ) was 2.8 × 10^?2 µg · mL^?1. The proposed method has been applied to the determination of protoporphyrin in serum samples with satisfactory results. The interaction mechanism was investigated.     

Fluorimetric Method Based on Diazotization-Coupling Reaction for Determination of Clenbuterol

A novel fluorimetric method based on diazotization-coupling reaction (DCR) for the determination of clenbuterol is described. In acidic solution, clenbuterol was first diazotized with sodium nitrite, followed by coupling with bisphenol A to produce an azo-compound in NH₃- NH₄Cl buffer. It has found the diazotized clenbuterol- bisphenol A- NH₃- NH₄Cl (DCBN) system has strong fluorescence efficiency compare with the bisphenol A solution. There is a linear relationship between the increased intensity of the fluorescence emission spectra (λ_ex/λ_em?=?276 nm/306 nm) and the concentration of clenbuterol. The effects of the amount of sodium nitrite, diazo reaction time, the amount of bisphenol A, coupling reaction time and coupling reaction temperature have been examined. Under the optional conditions, clenbuterol can be determined over the concentration range of 0.02 to 2.0 μg mL^?1 with a correlation coefficient of 0.9953. The detection limit is 0.01 μg mL^?1 at a signal-to-noise ratio of 3. The relative standard deviation (RSD) for 11 repetitive determinations of 0.9 μg mL^?1 clenbuterol is 0.22 %. The utility of this method was demonstrated by determining clenbuterol in meat samples.     

Automated Flow Injection Method for Monitoring Total Cyanide Concentration in Petroleum Refinery Effluents Using Ninhydrin as Color Reagent

Abstract

An automated flow injection system was developed for monitoring cyanide concentration in effluents from petroleum refineries. The method takes advantage of the reaction of cyanide ions with ninhydrin in basic medium in a flow injection system. A linear range of 0.01 to 0.04 µg mL^?1 was obtained with a detection limit of 1.5 ng mL^?1 by using 500 µL sample injection, with an analytical throughput of 30 samples hr^?1, excluding sample pretreatment by distillation if required. Regarding interferences, cyanide can be determined in the presence of 100 mg L^?1 of thyocianate and sulfide, both species normally found in industrial effluents. For total cyanide determination, strong acid distillation is recommended due to the presence of cyano‐metallic complexes in the refinery effluents. The method was validated by analyte addition and results compared with the standard methodology proposed by the American Public Health Association (APHA). The more significant advantage of the proposed method is the lack of use of carcinogenic reagent such as pyridine and psychotropic compound such as barbituric acid, both used in the recommended method by APHA. Thus, the proposed method is really a friendly analytical procedure.     

Simultaneous Determination of Ritodrine and Isoxsuprine Using Coupling Technique of Synchronous Fluorimetry and H-Point Standard Addition Method

Simultaneous determination of two structurally related ß₂ adrenergic receptor agonists namely, Ritodrine HCl (RTH) and Isoxsuprine HCl (ISP) was performed using coupling technique of synchronous fluorimetry and H-point standard addition method. Under optimum conditions, linear determination ranges were 1.48 – 14.80?×?10^?6 mol L^?1 and 1.54 – 15.44?×?10^?6 mol L^?1 for ISP and RTH respectively. RTH and ISP could be determined simultaneously without interference from each other when their concentration ratio varies from 5:1 to 1:5 in the mixed sample. The proposed method was applied to the determination of RTH and ISP in synthetic mixture of pharmaceutical samples, the accuracy and precision of the results were satisfactory.     

Fluorimetric Determination of Ketorolac in Urine by Stopped-Flow Sequential Injection Analysis

ABSTRACT

An automatic fluorescence method was developed for the determination of ketorolac tromethamine. The method is based on the direct oxidation of the analyte by an acidic solution of permanganate, being the resulting fluorescence measured at 227 nm/320 nm (λ_ex/λ_em). The reaction is carried out online due to the use of the Sequential Injection Analysis methodology. A detection limit of 0.12 µ g mL^?1 and a R.S.D. lower than 3% (n = 10) were obtained under optimum conditions. The analyte was satisfactorily determined in pharmaceuticals and urine samples. Recovery experiments were carried out on human urine, with recoveries in the range 92–108%.     

Native Fluorescence Determination of Pyridoxine Hydrochloride (Vitamin B6) in Pharmaceutical Preparations After Sorption on Sephadex SP C‐25

A simple, batch mode, solid phase spectrofluorimetric procedure has been developed for the determination of pyridoxine hydrochloride (PY) (vitamin B₆). The method is based on the measurement of the native fluorescence of the analyte at 395 nm (λ_exc = 295 nm) sorbed on Sephadex SP C‐25 beads. The cation‐exchange gel, previously equilibrated with the sample solution, is packed in a 1‐mm quartz cell in which the measurements are performed (diffuse transmitted fluorescence).

The method responds linearly in the measuring range of 50–500, 10–100 and 5–40 μg·l^? 1 with detection limits of 9.5, 2.3 and 0.60 μg·l^? 1 for 10, 25 and 50 ml of sample volume, respectively.

The relative standard deviation (n = 10) for the determination of 100 (10 ml), 60 (25 ml) and 30 μg·l^? 1 (25 ml) of PY is 1.3%, 2.2% and 3.7%, respectively. The method, which shows increasing sensitivity as the sample volume increases, was satisfactorily applied to the determination of vitamin B₆ in pharmaceutical preparations using the procedure for 10 ml of sample.