The Co-luminescence Effect of Eu–Gd–Ofloxacin–SDBS System and its Analytical Application

A fluorescence enhancement phenomenon in the europium (Eu)–Ofloxacin (OF)–Sodium Dodecyl Benzene Sulfonate (SDBS) fluorescence system was observed when Gd³⁺ was added. The fluorescence intensity of the systems was measured (λ _ex/λ _em = 280/612 nm) at pH 7.8. Under optimum conditions, a linear relationship between the enhanced fluorescence intensity and the Eu³⁺ concentration in the range of 5.0 × 10⁻¹⁰ ∼ 2.0 × 10⁻⁷ mol·L⁻¹ was observed. The detection limit of Eu³⁺ was 1.46 × 10⁻¹⁰ mol·L⁻¹ (S/N = 3). This method was used for the determination of trace amounts of europium in synthetic rare earth samples with satisfactory results. In addition, the interaction mechanism is also studied.     

Fluorescence of N,N-di(2-carboxyethyl)-<Emphasis Type="Italic">p</Emphasis>-anisidine in solution and crystalline states

The fluorescence properties of N,N-di(2-carboxyethyl)-p-anisidine (I) in solvents of various nature and in the crystalline state have been studied at room temperature (273 K) and at the boiling point of liquid nitrogen (77 K). Fluorescence in aqueous solutions of I with protonated (λ _ex /λ _fl ^max = 225/290 nm) and unprotonated (λ _ex /λ _fl ^max = 270/380 nm) amino nitrogen has been detected. On going from aqueous solutions to nonaqueous, the fluorescence band of unprotonated I experiences a blue shift and its intensity rises. The fluorescence intensity of the band in aprotic polar solvents is higher than that in protic solvents. A linear dependence of the fluorescence intensity of deprotonated I on Cu(II) concentration (ranging from 1.0 to 5.0 mg/dm³) in aqueous solution has been found. The fluorescence intensity of I in aqueous solutions at 77 K and pH 1–6 has been shown to increase in the presence of Zn(II) (1–170 mg/dm³) and Cd(II) (2–330 mg/dm³) although a similar dependence is not observed at 293 K.     

Fluorescence assay of tyrosine in blood plasma

A more simple and sensitive assay for the quantitative determination of tyrosine in blood plasma is developed on the basis of a modification of the method of S. Udenfriend (1962). A volume of 0.2 ml of plasma is used in the analysis; after its deproteinization with trichloroacetic acid, it is reacted with sodium nitride, nitrous acid, and 1-nitroso-2-naphthol at 65°C, and the content of the reaction product is measured by the fluorescence at λ_ex/λ_em=460/570 nm. The consumption of plasma and reagents is reduced by a factor of 5–10 compared to the original method; in addition, the stage of extraction with an organic solvent is excluded. The linear dependence of the fluorescence signal on the tyrosine concentration within the range of 2–60 μg/ml, high specificity, accuracy, and reproducibility of the assay are shown. The importance of tyrosine determination in monitoring of glucocorticoid therapy and protein catabolism is discussed. Institute of Photobiology, National Academy of Sciences of Belarus, 27, Akademicheskaya St., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 366–371, May–June, 1998.     

Spectral and kinetic properties of fluorescence of immunoactive steroids in the gas phase

We have used steady-state fluorescence spectroscopy and pulsed kinetic fluorimetry with high time resolution to experimentally study the spectral and temporal characteristics of luminescence of immunoactive 8-aza-D-homogona-1,3,5(10), 13-tetraene-12,17a-dione (8-aza-D-homogonane) molecules in the gas phase. We have established the existence of several centers emitting long-wavelength and short-wavelength fluorescence. The fluorescence of high-temperature 8-aza-D-homogonane vapor (T = 550 K) when excited by radiation with λ_ex = 266 nm is represented by two spectrally separated emission bands with maxima λ _max ^fl = 465 nm and λ _max ^fl = 365 nm. Analysis of the distribution of fluorescence decay times for 8-aza-D-homogonane showed that in the spectral range of the emission wavelengths 360–590 nm, the fluorescence decay kinetics contains three components with average lifetimes <200 psec, 2.8 nsec and 13.5 nsec. The multicenter nature of luminescence of 8-aza-D-homogonane was confirmed by direct measurements of instantaneous fluorescence spectra in different stages of luminescence decay. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 309–314, May–June, 2006.     

Fluorimetric Determination of Some Sulfur Containing Compounds Through Complex Formation with Terbium (Tb<Superscript>+3</Superscript>) and Uranium (U<Superscript>+3</Superscript>)

Two simple, sensitive and specific fluorimetric methods have been developed for the determination of some sulphur containing compounds namely, Acetylcysteine (Ac), Carbocisteine (Cc) and Thioctic acid (Th) using terbium Tb⁺³ and uranium U⁺³ ions as fluorescent probes. The proposed methods involve the formation of a ternary complex with Tb⁺³ in presence of Tris-buffer method (I) and a binary complex with aqueous uranyl acetate solution method (II). The fluorescence quenching of Tb⁺³ at 510, 488 and 540 nm (λ_ex 250, 241 and 268 nm) and of uranyl acetate at 512 nm (λ_ex 240 nm) due to the complex formation was quantitatively measured for Ac, Cc and Th, respectively. The reaction conditions and the fluorescence spectral properties of the complexes have been investigated. Under the described conditions, the proposed methods were applicable over the concentration range (0.2–2.5 μg ml⁻¹), (1–4 μg ml⁻¹) and (0.5–3.5 μg ml⁻¹) with mean percentage recoveries 99.74±0.36, 99.70±0.52 and 99.43±0.23 for method (I) and (0.5–6 μg ml⁻¹), (0.5–5 μg ml⁻¹), and (1–6 μg ml⁻¹) with mean percentage recoveries 99.38±0.20, 99.82±0.28 and 99.93±0.32 for method (II), for the three cited drugs, respectively. The proposed methods were successfully applied for the determination of the studied compounds in bulk powders and in pharmaceutical formulations, as well as in presence of their related substances. The results obtained were found to be in agree statistically with those obtained by official and reported ones. The two methods were validated according to USP guidelines and also assessed by applying the standard addition technique.     

A Non-fluorescent Derivative from Derivatizing <Emphasis Type="BoldItalic">trans</Emphasis>, <Emphasis Type="BoldItalic">trans</Emphasis>-Muconic Acid with 2-(2-Naphthoxy)ethyl-2-(piperidino)ethanesulfonate

trans, trans-Muconic acid (MA) is a polar metabolite of benzene and used as a biomarker for monitoring human exposure to benzene. Because MA is a trace metabolite, sensitive method is required for its detection. In addition, MA is a highly polar compound with dicarboxyl functions that could incur unfavorable adsorption on silica-based stationary phase usually used for separation. To address these problems, we planned to derivatize MA with a fluorescent reagent 2-(2-naphthoxy)ethyl-2-(piperidino)ethanesulfonate to give a naphthoxy derivative of MA for improving detection sensitivity and chromatographic properties. Surprisingly, the resulting derivative shows no fluorescent activity (λ_ex: 226 nm; λ_em: 350 nm). The negative results could be used as an instructive example for discussing on fluorescence quenching.     

FIA-Fluorimetric Determination of the Pesticide 3-Indolyl Acetic Acid

The paper presents the determination of the pesticide 3-indolyl acetic acid based on its native fluorescence; the method has been optimised either in a flow injection analysis (FIA) assembly or in batch. Maximum fluorescence intensity was observed at basic pH solutions at λ_exc = 280 nm and λ_em = 364 nm. The influence of different empirical parameters as pH, surfactants presence, solvent polarity, solved oxygen amount, and temperature was studied; highest outputs only required the pH in aqueous solutions to be adjusted over the range 9.5–10.5. Different calibration ranges were obtained by working with three different sensitivity scales of the fluorimeter either in flow injection analysis or batch. With the high sensitivity scale and FIA, the linear dynamic range was from 0.005 to 0.6 mg L⁻¹ 3-indolyl acetic acid; with an relative standard deviation (RSD) of 4.9% inter-day reproducibility. A large series of potential interferents was studied and finally, the method was applied to several water samples.     

Absorption,fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives

We have obtained and analyzed the absorption, fluorescence, and fluorescence excitation spectra of indole vapor, N-acetyl-L-tryptophan vapor, and 3-indole aldehyde vapor. From analysis of the dependence of the fluorescence spectrum of the free indole molecules on the wavelength of the exciting radiation λ_ex, it follows that emission of fluorescence occurs when the molecules undergo a transition from the one electronically excited state ¹L_b. The fluorescence spectra of the studied compounds are insignificantly different, suggesting a major role for the indole chromophore in formation of the compounds. The absorption spectrum of N-acetyl-L-tryptophan, in which the group of atoms is added to the indole ring through a-C-C bond, is similar to the spectrum of indole, while the spectrum of 3-indole aldehyde is significantly different from the indole spectrum due to the effect of the C=O group conjugated with the indole ring. The fluorescence excitation spectra are considerably different from the absorption spectra. This is associated with the strong dependence of the quantum yield for the free molecules on λ_ex. Qualitatively, they are mirror-symmetric to the fluorescence spectra of the stodied compounds. Analysis of the data obtained provides a basis for assuming that in the case of free molecules of indole and its derivatives, the ¹L_a absorption in the extreme long-wavelength region of the spectrum does not overlap ¹L_b absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 218–222, March–April, 2007.     

Terbium Sensitized Luminescence for the Determination of Ketoprofen in Pharmaceutical Formulations

This paper explores an ultra-sensitive luminescence method for the determination of Ketoprofen (KP) in pharmaceutical formulations. The technique is indirect and exploits the luminescence enhancement of terbium (Tb³⁺) by complexation with KP (Tb³⁺–KP), which was monitored at respective excitation and emission wavelengths of λ _ex = 258 nm and λ _em = 549 nm. The effect of varying the Tb³⁺ concentration and using multiple solvents was examined to determine optimal experimental conditions. Maximum sensitization was accomplished in the presence of methanol where the most favourable condition for the formation of the complex was recorded at a level of 1.0 × 10⁻⁵ M of Tb³⁺. Under these optimum experimental conditions, linear calibration curve was obtained in the range of 2.8 × 10⁻⁷–3.1 × 10⁻⁶ M with a detection limit of 8.7 × 10⁻⁸ M. The technique was validated with ‘working’ reference standards and produced relative standard deviations < 2% indicating that the reproducibility was highly acceptable. The proposed method was successfully applied to assays of KP in pharmaceutical formulations with average recoveries of 92–98%. The results were found to be in good agreement with those obtained by HPLC. The method is highly suited for general applications of this nature.     

Donor-Acceptor Compound Based on Rhodanineacetic Acid-Pyrene Derivative: Red-Light Emitting Fluorescent Organic Nanoparticles

A donor-acceptor compound based on Rhodanineacetic acid-pyrene derivative (RAAP), which emits weak yellow-green fluorescence in the methanol solution, was investigated. RAAP nanoparticles with a mean diameter of 50–60 nm were prepared by a simple reprecipitation method without surfactants. The observation of RAAP nanoparticles were undertaken through SEM and TEM method. The emission spectra of RAAP nanoparticles are red-shifted (Δ λ_em = 86 nm) to red region and the intensity is 40-fold higher than that in the methanol solution. Both the J-aggregation and aggregation-induced intramolecular planarization are considered to be the probable mechanism of strong emission for RAAP nanoparticles. The excellent sensibility toward organic vapor which profits from its fluorescence switching behavior is well demonstrated by vapor experiment.     

Synthesis,Electrochemical, and Optical Properties of New Fluorescent,Substituted Thieno[3,2-b][1]Benzothiophenes

The synthesis, electrochemical and optical properties of three fluorescent substituted thieno[3,2-b][1]benzothiophenes (TBT) derivatives, including 3-methoxythieno[3,2-b][1]benzothiophene (3-MeO-TBT), 2,3-dimethylthieno[3,2-b][1]benzothiophene (2,3-diMe-TBT), and 6-methoxythieno[3,2-b][1]benzothiophene-2-carboxylate (6-MeO-TBT-2-COOMe), were investigated. The oxidation potential values varied between 1.40 and 1.20 V/SCE according to the electronic substituent effect, and electropolymerization attempts, performed in 0.1 M LiClO₄ acetonitrile solution, led to the formation of very thin films of poly(3-MeO-TBT) and poly(2,3-di-Me-TBT). Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (Φ_F) , lifetimes (τ_F), and other photophysical parameters of the three new TBT derivatives were measured in DMSO solutions at room temperature. For the methyl-and methoxy-substituted TBT derivatives, the fluorescence emission peak were slightly red shifted relative to that of unsubstituted TBT (Δλ_em = 1–12 nm) whereas, in the case of 6-MeO-TBT-2-COOMe, a rather strong red-shift (Δλ_em = 73 nm) was attributed to the existence of a “push-pull” electronic interaction of the MeO and COOMe groups. All Φ_F values were rather high, varying between 0.11 and 0.35, according to the substituent effect. Fluorescence decays were mono-exponential and τ_F values were very short, ranging between 0.11 and 0.30 ns for the substituted TBT derivatives until study.     

Radiative properties of organic molecules in strong photon fields

We have experimentally investigated the dependence of the luminescence intensity of ethanol solutions of 2-(4-pyridyl)-5-phenyloxazole on the intensity of the exciting radiation from an XeCl laser (λ_ex = 308 nm, τ_p = 10 nsec, E_ex=10²²–10²⁶ photons/cm²·sec). We discuss the measurement technique and possible reasons for the change in radiative properties of the investigated solutions under the given conditions. V. D. Kuznetsov Siberian Physicotechnical Institute at Tomsk State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 69–74, April, 1997.     

Development of Flow Injection Spectrofluorimetric Detection System for the Determination of Homocysteine

In this work, a new simple and sensitive flow injection method is developed for the determination of homocysteine with spectrofluorimetric detection technique. This method is based on the oxidation of homocysteine with Tl (III) in acidic media, producing fluorescence reagent, TlCl₃^2- (λ_ex = 237 nm, λ_em = 419 nm). The effects of chemical parameters (including pH of the solutions, the buffer, Tl (III) and potassium chloride concentrations), instrumental parameters (such as flow rate of the solutions, reaction coil length, and sample loop volume) and temperature on the fluorescence intensity as an analytical signal are studied and optimized. In the optimum conditions of the above variables, homocysteine can be determined in the range 4.0 × 10^-7–40.0 × 10^-6 M with the LDR from 4.0 × 10^-7 to 25.0 × 10^-6 M. The detection limit (with S/N = 3) is 6.0 × 10^-8 M of homocysteine and precision for the injection of 5.0, 10.0 and 15.0 μM of homocysteine are 0.8%, 1.5% and 2.5% (n = 10) respectively. The rate of analysis is 90 samples per hour. The influence of potential interfering substances, including amino acids and carbohydrates is also studied. The proposed method has been successfully used for the determination of homocysteine in the real sample (blood serum and tap water) matrix.     

Determination of Meloxicam Using Europium Sensitized Luminescence in the Presence of Co-Luminescence Reagents

A sensitive time- resolved luminescence method for the determination of meloxicam (MX) in methanol and in aqueous solution is described. The method is based on the luminescence sensitization of europium (Eu³⁺) by formation of ternary complex with MX in the presence of 1,10- phenanthroline as coligand, Tween-80 as surfactant and gadolinium ion as a co-luminescence reagent. The signal for Eu- MX-1, 10- phenanthroline is monitored at λ_ex = 360 nm and λ_em = 620 nm. Optimum conditions for the formation of the complex in aqueous system were 0.01 M TRIS buffer, pH 8.0, 1,10- phenanthroline (6.0 × 10⁻⁶ M) , Gd³⁺ (7.0 × 10⁻⁶ M), Tween-80 (0.28%) and 1.75 mM of Eu³⁺ which allows the determination of 20–800 ppb of MX with limit of detection (LOD) of 7 ppb. The relative standard deviations of the method range between 0.1 and 1.1% indicating excellent reproducibility of the method. The proposed method was successfully applied for the assay of MX in pharmaceutical formulations, plasma and in urine samples. Average recoveries of 99.8 ± 1.1%, 100.2 ± 0.9% and 100.9 ± 1.1% were obtained for MX in tablet, plasma and urine sample respectively.     

Absorption spectra of benzene-isooctane mixtures in the wavelength range 1620–1820 nm

Experimental absorption spectra of benzene, isooctane, and their mixtures are obtained in the wavelength range λ = 1620–1820 nm in which the first overtones of vibrational frequencies of CH, CH₂, and CH₃ hydrocarbon groups are located. Positions of fundamental absorption bands of benzene are refined. Absorption spectra of benzene-isooctane mixtures are shown to intersect in a narrow area near λ ≈ 1695 nm. The main maximum of benzene absorption at λ = 1671.5 ± 0.5 nm, where the influence of isooctane absorption is practically absent, is proposed for determining the content of benzene in benzene-isooctane mixtures. A linear calibration curve for λ = 1671.5 nm that encompasses the full range of benzene concentrations (0–100%) is presented. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 631–634, September–October, 2008.     

Investigation of Rb <Emphasis Type="Italic">D</Emphasis><Subscript>1</Subscript> atomic lines in strong magnetic fields by fluorescence from a half-wave-thick cell

It has been experimentally demonstrated that the use of the effect of significant narrowing of the fluorescence spectrum from a nanocell that contains a column of atomic Rb vapor with a thickness of L = 0.5λ (where λ = 794 nm is the wavelength of laser radiation, whose frequency is resonant with the atomic transition of the D ₁ line of Rb) and the application of narrowband diode lasers allow the spectral separation and investigation of changes in probabilities of optical atomic transitions between levels of the hyperfine structure of the D ₁ line of ⁸⁷Rb and ⁸⁵Rb atoms in external magnetic fields of 10–2500 Gs (for example, for one of transitions, the probability increases ∼17 times). Small column thicknesses (∼390 nm) allow the application of permanent magnets, which facilitates significantly the creation of strong magnetic fields. Experimental results are in a good agreement with the theoretical values. The advantages of this method over other existing methods are noted. The results obtained show that a magnetometer with a local spatial resolution of ∼390 nm can be created based on a nanocell with the column thickness L = 0.5λ. This result is important for mapping strongly inhomogeneous magnetic fields.     

A Simple and Sensitive Spectrofluorimetric Method for Analysis of Some Nitrofuran Drugs in Pharmaceutical Preparations

A simple, rapid, selective and sensitive spectrofluorimetric method was described for the analysis of three nitrofuran drugs, namely, nifuroxazide (NX), nitrofurantoin (NT) and nitrofurazone (NZ). The method involved the alkaline hydrolysis of the studied drugs by warming with 0.1 M sodium hydroxide solution then dilution with distilled water for NX or 2-propanol for NT and NZ. The formed fluorophores were measured at 465 nm (λ _Ex 265 nm), 458 nm (λ _Ex 245 nm) and 445 nm (λ _Ex 245 nm) for NX, NT and NZ, respectively. The reaction pathway was discussed and the structures of the fluorescent products were proposed. The different experimental parameters were studied and optimized. Regression analysis showed good correlation between fluorescence intensity and concentration over the ranges 0.08–1.00, 0.02–0.24 and 0.004–0.050 μg ml⁻¹ for NX, NT and NZ, respectively. The limits of detection of the method were 8.0, 1.9 and 0.3 ng ml⁻¹ for NX, NT and NZ, respectively. The proposed method was validated in terms of accuracy, precision and specificity, and it was successfully applied for the assay of the three nitrofurans in their different dosage forms. No interference was observed from common pharmaceutical adjuvants. The results were favorably compared with those obtained by reference spectrophotometric methods.     

A method to study polydispersity of humic acid from fluorescence quenching by Cu<Superscript>2+</Superscript> ions

The spectral dependence of Stern–Volmer constants (K_SV^lK_{SV}^{\lambda} ) for fluorescence quenching by Cu²⁺ ions in a standard sample of humic acid (HA) (IHSS) with monochromatic excitation (λ_ex = 337.1 nm) conditions has been studied in the spectral range 400–600 nm. This is interpreted within a concept implying that HA macromolecules possess the property of polydispersity, which means that fluorophore-containing sites are different in terms of chemical nature and spatial accessibility. Modeling data show that the minimum number of spectral components required for the simulated spectral dependence of K_SV^lK_{SV}^{\lambda} to agree as closely as possible with that observed experimentally is three.     

Photo-induced Fluorescence of Fluometuron in a Continuous-flow Multicommutation Assembly

This paper deals with the photo-induced fluorimetric determination of the herbicide Fluometuron with the aid of a continuous-flow assembly of the emergent and new methodology known as Multicommutation which was provided with an on-line photoreactor. Maximum fluorescence intensity was observed at basic pH solutions, 1×10⁻⁴ mol l⁻¹ NaOH, after 1.4 min of irradiation and being the maximum at λ_exc 247.0 nm and λ_em 325.0 nm. The influence of different experimental parameters either chemical (pH, surfactants presence, solvent polarity and temperature) or hydrodynamic (time of photo-degradation, size and number of different segments and flow-rate) was tested. The linear dynamic range was from 0.01 to 4.0 mg l⁻¹ of Fluometuron; the inter-day reproducibility (as R.S.D.) of the slope was 0.001% and 1.7% from the peaks intra-day reproducibility. A large series of potential interferents was studied and finally the method was applied to human urine, soil, formulation and water samples.     

Micelle-Enhanced Spectrofluorimetric Method for Determination of Cholesterol-Reducing Drug Ezetimibe in Dosage Forms

A simple and sensitive spectrofluorimetric method was developed for the determination of ezetimibe in its pharmaceutical formulations. The proposed method is based on investigation of the fluorescence spectral behavior of ezetimibe in sodium dodecyl sulfate (SDS) micellar system. In aqueous solution of acetate buffer pH 5.0, the fluorescence intensity of ezetimibe was greatly enhanced, 200% enhancement, in the presence of SDS. The fluorescence intensity of ezetimibe was measured at 380 nm after excitation at 268 nm. The fluorescence-concentration plot was rectilinear over the range of 0.03–3.0 μg/mL with lower detection limit of 3.08 × 10⁻³ μg/mL. The method was successfully applied to the analysis of ezetimibe in its commercial tablets; the results were in good agreement with those obtained with the reported method. The application of the proposed method was extended to the stability studies of ezetimibe after exposure to different forced degradation conditions, such as acidic, alkaline, photo and oxidative conditions, according to ICH guidelines.