Resonance Rayleigh Scattering,Second-Order Scattering and Frequency Doubling Scattering Spectra of Copper(II)-Flutamide System with Anionic Surfactants and its Analytical Application

A simple, sensitive, and rapid method based on ion association, for the determination of FLD has been developed. Flutamide (FLD) can react with Cu(II) to form 1:1 cationic chelate at pH 2.2–7.0 Mclivaine buffer medium, which can further react with anionic surfactants (AS) such as sodium dodecyl sulfate (SDS), sodium lauryl sulfonate (SLS) and sodium dodecylbenzene sulfonate (SDBS) to form 1:1 ion-association complexes. As a result, the resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency doubling scattering (FDS) were enhanced to the highest degree. The maximum RRS, SOS and FDS wavelengths of three ion-association complexes were located at 345/345 nm, 610/305 nm and 430/860 nm, respectively. The increments of scattering intensity (ΔI) were directly proportional to the concentration of FLD in certain ranges. The detection limits (3σ) of FLD for SDS, SLS and SDBS systems were 1.9 ng ml⁻¹, 2.1 ng ml⁻¹ and 2.2 ng ml⁻¹(RRS method), 2.4 ng ml⁻¹, 2.7 ng ml⁻¹ and 2.6 ng ml⁻¹ (SOS method) and 2.3 ng ml⁻¹, 2.4 ng ml⁻¹ and 2.5 ng ml⁻¹ (FDS method), separately. The sensitivity of RRS method was higher than those of FDS and SOS methods. The optimum conditions of RRS method and the influence factors, the composition and the reaction mechanism have been discussed. Since the method is highly selective, it does not interference concomitant substances. These methods were applied successfully for the determination of FLD in pharmaceutical formulation and urine samples.     

Chemiluminescence Determination of Sodium New Houttuyfonate in Pharmaceutical Preparations Based on Tween 80—Rhodamine B System

Strong chemiluminescence (CL) emission was observed when sodium new houttuyfonate (SNH) was mixed with Tween 80 in sulfuric acid medium in the presence of rhodamine B. Base on this phenomenon, a sensitive flow injection-CL method for the determination of SNH was developed. Under the optimum conditions, the CL emission is linearly with SNH concentration in the range 8.0–4000 ng mL⁻¹, with a detection limit of 2.7 ng mL⁻¹ (3σ). As a preliminary application, the proposed method was successfully applied to the determination of SNH in pharmaceutical preparations. The possible CL mechanism was also discussed in this paper.     

A Simple Flow-injection Spectrofluorimetric Method for the Determination of Mercury

A highly sensitive flow-injection spectrofluorimetric method is presented for the rapid and simple determination of Hg (II) in environmental and pharmaceutical samples. Murexide (ammonium purpurate) was used as the fluorescence reagent in the carrier stream. An emission peak of murexide, which is decreased linearly by addition of Hg (II), occurs at 435 nm in aqueous solution with excitation at 335 nm. A linear calibration was obtained for 5–200 ng ml⁻¹ Hg (II) with the relative standard deviation 2.5% (n = 5) for a 20 μl injection volume Hg (II). The limit of the detection was 1 ng ml⁻¹ and the sampling rate was 80 h⁻¹. No significant interference was found by the ions commonly found in the most environmental samples. The proposed method was successfully applied for the determination of trace mercury in real samples and the validation of the proposed methodology is provided.     

Preparation and Characterization of CdHgTe Nanoparticles and Their Application on the Determination of Proteins

CdHgTe nanoparticles (NPs) with the emission in the near-infrared regions were prepared in aqueous solution, and were characterized by transmission electron microscopy, X-ray diffraction spectrometry, spectrofluorometry and ultraviolet-visible spectrometry. Based on the fluorescence quenching of CdHgTe NPs in the presence of proteins, a novel method for the determination of proteins with CdHgTe NPs as a near-infrared fluorescence probe was developed. Maximum fluorescence quenching was observed with the excitation and emission wavelengths of 500 and 693 nm, respectively. Under the optimal conditions, the calibration graphs were linear in the range of 0.04 × 10⁻⁶–5.6 × 10⁻⁶ g ml⁻¹ for lysozyme (Lyz) and 0.06 × 10⁻⁶–6.1 × 10⁻⁶ g ml⁻¹ for bovine hemoglobin (BHb), respectively. The limits of detection were 13 ng ml⁻¹ for Lyz and 27 ng ml⁻¹ for BHb, respectively. Four synthetic samples were determined and the results were satisfied.     

Solid Substrate–Room Temperature Phosphorimetry for the Determination of Trace Terbutaline Sulfate Based on Its Inhibition Oxidation of Rhodamine 6G by Sodium Periodate

When 1.00 mol l⁻¹ I⁻ is used as ion perturber, rhodamine 6G (Rh 6G) can emit strong and stable room temperature phosphorescence (RTP) on filter paper substrate in KHC₈H₄O₄–HCl buffer solution (pH = 3.50), heated at 70 °C for 10 min. NaIO₄ can oxidize Rh 6G, which makes the RTP signal quench. Terbutaline sulfate (TBS) can inhibit NaIO₄ from oxidizing Rh 6G, which makes the RTP signal of Rh 6G enhance sharply. The content of TBS is linear correlation to ΔIp of the system. Based on the facts above, a new inhibition solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace TBS has been established. The linear range of this method is 0.0104–2.08 pg spot⁻¹ (corresponding concentration: 0.026–5.2 ng ml⁻¹, with a sample volume of 0.4 μl) with a detection limit (L.D.) of 2.6 fg spot⁻¹ (corresponding concentration: 6.5 × 10⁻¹² g ml⁻¹), and the regression equation of working curve is ΔIp = 2.040 + 54.54 m_TBS (pg spot⁻¹), n = 6, correlation coefficient is 0.9994. For the samples containing 0.0104 pg spot⁻¹ and 2.08 pg spot⁻¹ TBS, the relative standard deviation (RSD) are 3.8% and 2.3% (n = 8), respectively, indicating good precision. This method has been applied to determination of trace TBS in the practical samples with satisfactory results. The reaction mechanism of NaIO₄ oxidizing Rh 6G to inhibit SS-RTP for the determination of trace TBS is also discussed.     

A Chemosensing Ensemble for the Detection of Cysteine Based on the Inner Filter Effect Using a Rhodamine B Spirolactam

A fluorescent chemosensing ensemble for the detection of cysteine is designed based on the fluorescence inner filter effect. The method employs the coordination of Cu²⁺ ion with salicylaldehyde rhodamine B hydrazone (I), a colorless and non-fluorescent rhodamine B spirolactam derivative to form I-Cu(II), a pink color but weakly fluorescent complex. When rhodamine B was introduced to the I-Cu(II) complex solution, the fluorescence signal of rhodamine B is dramatically decreased because of the fluorescence inner filter effect (IFE). Upon adding cysteine to the above solution, it can complex preferentially to Cu²⁺ compared to I, and the I-Cu(II) complex dissociates, which thus decreases the fluorescence IFE of the solution, and in turn leading to the fluorescence increase of the chemosensing system. Based on the above mechanism, a fluorescent chemosensing ensemble for cysteine is developed. The fluorescence increase is linearly with cysteine concentration up to 10.0 μ mol L⁻¹, with a detection limit of 1.4 × 10⁻⁷ mol L⁻¹ (3σ). The optimal conditions of the proposed method were studied and the selectivity of the proposed method was investigated in this paper.     

Simultaneous Determination of Acetylsalicylic Acid and Caffeine in Pharmaceutical Formulation by First Derivative Synchronous Fluorimetric Method

A sensitive, rapid, and specific assay has been developed for the simultaneous determination of acetylsalicylic acid and caffeine in commercial tablets based on their natural fluorescence. The mixture of these drugs was resolved by first derivative synchronous fluorimetric technique using two scans. At Δλ=106 nm, using first derivative synchronous scanning, only acetylsalicylic acid yields a detectable signal at 316 nm (peak to zero method) which is unaffected by caffeine. At Δλ=30 nm, the signal of caffeine at 288 nm (peak to zero method) is not affected by acetylsalicylic acid. The range of application is between 0.021 and 41.62 μg ml⁻¹ (correlation coefficient, R=0.9995) for acetylsalicylic acid and between 0.4486 and 44.86 μg ml⁻¹ (correlation coefficient, R=0.99786) for caffeine. The recovery range of 98.40–102% for acetylsalicylic acid and 90–100.5% for caffeine from their synthetic mixture was reported. Overall recovery of both compounds about 97–99% for acetylsalicylic acid and 97–98% for caffeine was obtained from real sample analysis. The detection limits are 0.0013 μg ml⁻¹ and 0.0306 μg ml⁻¹ for acetylsalicylic acid and caffeine, respectively. The relative standard deviation (n=10) for 20 μg ml⁻¹ of acetylsalicylic acid is 2.75% and for 2.2 μg ml⁻¹of caffeine is 1.7%.     

Spectrofluorimetric Determination of Oxamniquine in Dosage Forms and Spiked Human Plasma through Derivatization with 1-dimethylaminonaphthalene-5-sulphonyl chloride

A sensitive, simple and selective spectrofluorimetric method was developed for the determination of oxamniquine (OXM) in pharmaceutical formulations and biological fluids. The method is based on the reaction between the drug and 1-dimethylaminonaphthalene-5-sulphonyl chloride (dansyl chloride) in presence of 0.5 M sodium carbonate (pH 10) to yield a highly fluorescent derivative that is measured at 445 nm after excitation at 335 nm. The different experimental parameters affecting the development and stability of the reaction product were carefully studied and optimized. The fluorescence concentration plot was rectilinear over the range of 0.02–0.2 μg ml⁻¹ with a lower detection limit (LOD) of 0.007 μg ml⁻¹ and limit of quantitation (LOQ) of 0.02 μg ml⁻¹. The proposed method was successfully applied to the analysis of commercial capsules. The results obtained were in good agreement with those obtained using the official spectrophotometric method. Furthermore, the method was applied for the determination of oxamniquine in spiked human plasma, the mean % recovery (n = 4) is 97.77 ± 1.19. A proposal of the reaction pathway was presented.     

Spectrofluorimetric Determination of Fluvoxamine in Dosage Forms and Plasma Via Derivatization with 4-Chloro-7-Nitrobenzo-2-Oxa-1,3-Diazole

A highly sensitive and simple spectrofluorimetric method has been developed and validated for the determination of the antidepressant fluvoxamine (FXM) in its dosage forms and plasma. The method was based on nucleophilic substitution reaction of FXM with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole in an alkaline medium (pH 8) to form a highly fluorescent derivative that was measured at 535 nm after excitation at 470 nm. The factors affecting the reaction was carefully studied and optimized. The kinetics of the reaction was investigated, and the reaction mechanism was presented. Under the optimized conditions, linear relationship with good correlation coefficient (0.9995) was found between the fluorescence intensity and FXM concentration in the range of 65–800 ng ml⁻¹. The limits of detection and quantitation for the method were 21 and 64 ng ml⁻¹, respectively. The precision of the method was satisfactory; the values of relative standard deviations did not exceed 2.17%. The proposed method was successfully applied to the determination of FXM in its pharmaceutical tablets with good accuracy; the recovery values were 97.8–101.4 ± 1.08–2.75%. The results obtained by the proposed method were comparable with those obtained by the official method. The high sensitivity of the method allowed its successful application to the analysis of FXM in spiked human plasma. The proposed method is superior to the previously reported spectrofluorimetric method for determination of FXM in terms of its simplicity. The proposed method is practical and valuable for its routine application in quality control and clinical laboratories for analysis of FXM.     

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.     

Kinetic Fluorimetric Measurement of Trace Resorcinol1 in Phenol Mixtures

A kinetic spectrofluorimetric method was studied to measure the concentration of trace resorcinol. The proposed method is based on the inhibitory effect of resorcinol on the oxidation of rhodamine B by potassium bromate in the medium of dilute sulfuric acid. The detection limit and linear range of the proposed resorcinol measurement method are 12 μg L⁻¹ and 24∼280 μg L⁻¹, respectively. Relative standard derivations of eleven measurements for 80 μg L⁻¹ and 200 μg L⁻¹ resorcinol solutions are 2.12% and 1.08%, respectively. The trace of resorcinol can be determined directly by the proposed method without any pre-separation process when phenol and many other phenolic compounds are present.     

Validated Spectrofluorimetric Method for the Determination of Lamotrigine in Tablets and Human Plasma Through Derivatization with <Emphasis Type="BoldItalic">o</Emphasis>-phthalaldehyde

A sensitive, simple and selective spectrofluorimetric method was developed for the determination of Lamotrigine (LMT) in pharmaceutical formulations and biological fluids. The method is based on reaction of LMT with o-phthalaldehyde in presence of 2-mercaptoethanol in borate buffer of pH 9.8 to yield a highly fluorescent derivative that is measured at 448 nm after excitation at 337 nm. The different experimental parameters affecting the development and stability of the reaction product were carefully studied and optimized. The fluorescence-concentration plot was rectilinear over the range of 0.1–1.0 μg ml⁻¹ with lower limit of detection (LOD) 0.02 μg ml⁻¹ and limit of quantification (LOQ) 0.06 μg ml⁻¹ respectively. The proposed method was successfully applied to the the analysis of commercial tablets. Statistical comparison of the results obtained by the proposed and reference method revealed no significant difference in the performance of the two methods regarding the accuracy and precision respectively. The proposed method was further extended to the in-vitro and in-vivo determination of the drug in spiked and real human plasma. The mean percentage recoveries in spiked and real human plasma (n = 3) were 95.78 ± 1.37 and 90.93 ± 2.34 respectively. Interference arising from co-administered drugs was also studied. A proposal for the reaction pathway with o-phthalaldehyde was postulated.     

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.     

Sensitive Determination of Norfloxacin by the Fluorescence Probe of Terbium (III)- Sodium Dodecylbenzene Sulfonate and Its Luminescence Mechanism

The fluorescence system of the norfloxacin-Tb³⁺- sodium dodecylbenzene sulfonate (SDBS) was investigated in this paper. The experiments indicated that the fluorescence intensity of the Tb³⁺-SDBS was greatly enhanced by the norfloxacin. On the basis of the above findings, a sensitive fluorimetric method for determining the norfloxacin was established. The fluorescence intensity was measured by a 1-cm quartz cell with the excitation wavelength of 290 nm and the emission wavelength of 545 nm. The enhanced fluorescence intensity of the system (Δ F) showed a good linear relationship with the concentration of norfloxacin in the range of 5.0×10⁻⁹ mol L⁻¹–2.0×10⁻⁶ mol L⁻¹, its correlation coefficient was 0.9991 and the detection limit (S/N=3) was 1.2×10⁻⁹ mol L⁻¹. The presented method was used to determine the norfloxacin in real pharmaceutical samples. The luminescence mechanism was also discussed in detail. In the fluorescence system of the norfloxacin-Tb³⁺-SDBS, the SDBS not only acted as the surfactant, but also acted as the energy donor.     

New fluorimetric reagents, sodium pyrophosphate, sodium trimetaphosphate, and sodium tetrametaphosphate, for the determination of cerium(III)

Three sensitive and selective new alternatives for fluorometric determination of cerium(III) are described in this study. Ce(III) is highly fluorescent in sodium pyrophosphate, sodium trimetaphosphate, and sodium tetrametaphosphate solutions. For these reagents, the maximum excitation/emission wavelengths are 300/350, 297/340, and 299/352 nm, respectively. Maximum fluorescence intensities are obtained by irradiating Ce(III) dissolved in 0.033 g L⁻¹ sodium pyrophosphate, 41.4 g L⁻¹ sodium trimetaphosphate, and 0.96 g L⁻¹ sodium tetrametaphosphate at room temperature. The fluorescence intensities are linear over the range 0.001–30, 0.001–75, and 0.001–70 μg ml⁻¹. The detection limits are calculated as 9.5 × 10⁻³, 1.1/10⁻³, and 3.8 × 10^-3 μg ml⁻¹ Ce(III), respectively. The relative standard deviations for 15/0.05 Μg ml⁻¹ Ce(III) are 1.1/1.2, 1/1.1, and 1.2/1.3%, respectively. Quenching effects of other lanthanides and some inorganic anions were investigated. The methods have been applied to rare earth mixtures with a good accuracy.     

Fluorophotometric Determination of Hydrogen Peroxide with Fluorescin in the Presence of Cobalt (II) and Reaction Against Other Reactive Oxygen Species

A fluorophotometric method for the determination of hydrogen peroxide (H₂O₂) using fluorescin was developed. This method was based on the oxidative reaction of fluorescin, a colorless, non-fluorescent lactoid fluorescein, by H₂O₂ to give highly fluorescein fluorescence emission. In the determination of H₂O₂, the calibration curve exhibited linearity over the H₂O₂ concentration range of 1.5–310 ng mL⁻¹ at an emission wavelength of 525 nm with an excitation of 500 nm and with relative standard deviations (n = 6) of 2.51%, 2.48%, and 1.31% for 3.1 ng mL⁻¹, 30.8 ng mL⁻¹, and for 308 ng mL⁻¹ of H₂O₂, respectively. The detection limit for H₂O₂ was 1.9 ng mL⁻¹ six blank determinations was performed (ρ = 6). This proposed method was applied to detection of other reactive oxygen species and nitrogen species (ROS/RNS) such as singlet oxygen (¹O₂), hydroxyl radical (^•OH), peroxynitrite (ONOO⁻) etc., and it was possible to detect them with a high sensitivity. In addition, this proposed method was applied to the recovery tests of H₂O₂ in calf serum, human saliva, rain water, and wheat noodles; the results were satisfactory.     

Simple and Sensitive Spectrofluorimetric Method for the Determination of Oseltamivir Phosphate in Capsules Through Derivatization with Fluorescamine

A new, simple and sensitive spectrofluorimetric method has been developed for the determination of oseltamivir phosphate (OSP) in capsules. The method is based on the reaction between oseltamivir and fluorescamine in borate buffer solution of pH 8.50 to give highly fluorescent derivatives that are measured at 483 nm using an excitation wavelength of 381. The different experimental parameters effecting the development and stability of the reaction product were carefully studied and optimized. The fluorescence intensity concentration plot is rectilinear over the range 50–450 ng mL⁻¹ with a lower detection limit (LOD) of 1.219 ng mL⁻¹ and limit of quantitation (LOQ) of 4.064 ng mL⁻¹. Selectivity was validated by subjecting stock solution of OSP to acidic, basic, oxidative, and thermal degradation. No interference was observed from excipients present in formulations. The developed method was successfully applied to determination of the drug in capsules. The mean % recovery (n = 6) was 100.08. The results obtained were in good agreement with those obtained using a reported spectrophotometric method.     

A Fluorescent Probe for Diacetyl Detection

A water-soluble fluorescent probe, rhodamine B hydrazide (RBH), was prepared and its properties for recognition of diacetyl were studied. The method employs the reaction of diacetyl with RBH, a colorless and non-fluorescent rhodamine B spiro form derivative to give a pink-colored fluorescent substance. In weakly acidic media, RBH reacts more selectively with diacetyl than with other carbonyls, causing a large increase in fluorescence intensity and thereby providing an easy assay for the determination of diacetyl.     

Simple and sensitive spectrophotometric methods for determination of amantadine hydrochloride

Three simple and sensitive spectrophotometric methods (A–C) for determination of amantadine hydro-chloride have been developed and validated. The first method (A) is based on the oxidation of the drug by ammonium molybdate. The second method (B) was based on the charge-transfer complexation reaction between the amantadine base as an electron donor and iodine as a σ-acceptor. The third method (C) is based on the reaction of N-alkylvinylamine formed from the interaction of the free amino group in amantadine molecule and acetalde-hyde with chloranil to give colored vinylamino-substituted benzoquinone. The colored products of these reactions were measured at their corresponding maximum absorption peaks. Different variables affecting the reactions were carefully studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients 0.9993–0.9998 were found between the reading and the corresponding concentration of the drug in the range 2–90 μg·ml⁻¹. The limits of detection ranged from 0.16 to 1.91 μg·ml⁻¹. The precision of the methods was satisfactory: the values of relative standard deviation did not exceed 1.63%. The proposed methods were successfully applied to the analysis of amantadine HCl in its capsules with good accuracy and precision; the label claim percentages ranged from 99.8 to 100.5 ± (0.52–1.22) %. The results obtained by the proposed spectrophotometric methods were comparable with those obtained by the official method. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 707–712.     

Spectrofluorimetric Determination of Pentachlorophenol Based on Its Inhibitory Effect on The Redox Reaction Between Hydroxyl Radicals and Fluorescent Dye Rhodamine B

Hydroxyl radicals that is generated by Fenton reagent reacts with rhodamine B, which makes the fluorescence quenching of rhodamine B. However, there is an inhibitory effect of pentachlorophenol on the reaction. Based on this observation, an inhibitory fluorimetric method is reported for the determination of trace pentachlorophenol. The fluorescent inhibition of rhodamine B is measured by fix-time method. On the optimum conditions of experimentation, the detection limit for pentachlorophenol is 3.0 ng/ml and the linear range of the determination is 4.0–240 ng/ml. Combined with the samples treating with ion exchange resins and XDA-1 absorption resin, the method has been used for the determination of pentachlorophenol in synthetic samples and natural water samples with satisfactory results. We have also discussed the possible mechanism of the reaction.