Sensitive determination of enoxacin by its enhancement effect on the fluorescence of terbium(III)-sodium dodecylbenzene sulfonate and its luminescence mechanism

The fluorescence system of enoxacin-Tb³⁺-sodium dodecylbenzene sulfonate (SDBS) was investigated in this paper. The experiments indicated that the fluorescence intensity of Tb³⁺-SDBS was greatly enhanced by enoxacin. Accordingly, a sensitive fluorimetric method for determining enoxacin was established. The fluorescence intensity was measured by a 1-cm quartz cell with an excitation wavelength of 290 nm and an emission wavelength of 545 nm. The enhanced fluorescence intensity of the system (ΔF) showed a good linear relationship with the concentration of enoxacin in the range of 5.0×10⁻⁹ to 2.0×10⁻⁶ mol L⁻¹, its correlation coefficient was 0.9992 and the detection limit (S/N=3) was 2.8×10⁻⁹ mol L⁻¹. The presented method was used to determine enoxacin in real pharmaceutical samples. The luminescence mechanism was also discussed in detail. In the fluorescence system of enoxacin-Tb³⁺-SDBS, SDBS not only acted as the surfactant but also acted as the energy donor.     

氧化还原荧光法测定痕量亚硝酸根

建立了碘化钾与亚硝酸根氧化还还原反应生成游离碘使异硫氰酸荧光素荧光猝灭测定痕量亚硝酸根的新方法,其线性范围为25－100ug/L,回归方程为ΔF＝7．98C－10．5,r=0.990,方法的检测限为12ug/L。本法快速,灵敏,操作简便,用于水样中痕量亚硝酸根的测定,结果良好。     

荧光法研究PTB与白蛋白的结合

利用药物对蛋白的荧光猝灭作用,用荧光法研究了N-苯酰甲噻唑溴(PTB)与牛血清白蛋白(BSA)及人血清白蛋白(HSA)的相互作用。测定发现BSA溶液的最大激发波长为280 nm,HSA溶液的最大激发波长为290 nm。分别向溶液中加入PTB后,原有的最大发射波长处的强度明显减弱。说明PTB对BSA和HAS有荧光猝灭作用。PTB与BSA,HSA有中等强度的结合。测得15 ℃时PTB与BSA,HSA的结合常数分别为3.66×103和3.83×103,结合位点数n分别为1.02和1.16;37 ℃时PTB与BSA,HSA的结合常数分别为3.58×103和3.35×103,结合位点数分别为0.95和0.87。根据热力学常数确定了PTB与BSA,HSA之间的主要作用力类型均为静电作用力。通过Fster偶级-偶级非辐射能量转移原理,得到BSA,HSA与PTB结合的位置距色氨酸残基的距离分别为7.5和7.9 nm。根据白蛋白的结构,可以推测BSA,HSA与PTB结合的位点在ⅡA亚结构域,靠近Try214的区域。     

Magnetically assisted solid phase extraction using Fe3O4 nanoparticles combined with enhanced spectrofluorimetric detection for aflatoxin M1 determination in milk samples

A novel, facile and inexpensive solid phase extraction (SPE) method using ethylene glycol bis-mercaptoacetate modified 3-(trimethoxysilyl)-1-propanethiol grafted Fe₃O₄ nanoparticles coupled with spectrofluorimetric detection was proposed for determination of aflatoxin M1 (AFM1) in liquid milk samples. The method uses the advantage fluorescence enhancement by β-cyclodexterin complexation of AFM1 in 12% (v/v) acetonitrile–water and the remarkable properties of Fe₃O₄ nanoparticles namely high surface area and strong magnetization were utilized to achieve high enrichment factor (57) and satisfactory extraction recoveries (91–102%) using only 100 mg of magnetic adsorbent. Furthermore, fast separation time of about 15 min avoids many time-consuming column-passing procedures of conventional SPE. The main factors affecting extraction efficiency including pH value, desorption conditions, extraction/desorption time, sample volume, and adsorbent amount were evaluated and optimized. Under the optimal conditions, a wide linear range of 0.04–8 ng mL⁻¹ with a low detection limit of 0.015 ng mL⁻¹ was obtained. The developed method was applied for extraction and preconcentration of AFM1 in three commercially available milk samples and the results were compared with the official AOAC method.     

A novel magnetic poly(aniline-naphthylamine)-based nanocomposite for micro solid phase extraction of rhodamine B

A novel Fe₃O₄–poly(aniline-naphthylamine)-based nanocomposite was synthesized by chemical oxidative polymerization process as a magnetic sorbent for micro solid phase extraction. The scanning electron microscopy images of the synthesized nanocomposite revealed that the copolymer posses a porous structure with diameters less than 50 nm. The extraction efficiency of this sorbent was examined by isolation of rhodamine B, a mutagenic and carcinogenic dye, from aquatic media in dispersion mode. Among different synthesized polymers, Fe₃O₄/poly(aniline-naphthylamine) nanocomposite showed a prominent efficiency. Parameters including the desorption solvent, amount of sorbent, desorption time, sample pH, ionic strength, extraction time and stirring rate were optimized. Under the optimum condition, a linear spiked calibration curve in the range of 0.35–5.00 μg L⁻¹ with R² = 0.9991 was obtained. The limits of detection (3S_b) and limits of quantification (10S_b) of the method were 0.10 μg L⁻¹ and 0.35 μg L⁻¹ (n = 3), respectively. The relative standard deviation for water sample with 0.5 μg L⁻¹ of RhB was 4.2% (n = 5) and the absolute recovery was 92%. The method was applied for the determination of rhodamine B in dishwashing foam, dishwashing liquid, shampoo, pencil, matches tips and eye shadows samples and the relative recovery percentage were in the range of 94–99%.     

荧光法测定维生素K3

维生素K3（Vitamin K3,VK3）是一种油溶性化舍物,不发荧光。L-半胱氨酸（L-cysteine,L-Cys）可将VK3还原为有荧光的甲萘酚,据此建立了一种测定药物制剂中VK3含量的新的荧光分光光度法。甲萘酚的激发波长和发射波长分别为389nm和520nm,荧光强度与VK3的浓度在3.2×10^-7－1.6×10^-5mol／L范围内呈良好的线性关系,相关系数为0.9994,检出限为1.2×10^-9mol／L,平均回收率为98.2％。方法用于VK3注射液的测定,结果令人满意。     

Kinetic Spectrophotometric Analysis and Spectrofluorimetric Analysis of Ciprofloxacin Hydrochloride and Norfloxacin in Pharmaceutical Preparations Using 4‐Chloro‐7‐Nitrobenzo‐2‐Oxa‐1,3‐Diazole (NBD‐Cl)

Simple, reliable, sensitive and accurate kinetic spectrophotometric and spectrofluorimetric methods were proposed for the determination of ciprofloxacin hydrochloride (CPX) and norfloxacin (NRX) in pure form and in pharmaceuticals. The methods are based on coupling the studied drugs with 4‐chloro‐7‐nitrobenzo‐2‐oxa‐1,3‐diazole (NBD‐Cl) in the presence of alkaline borate buffer. Spectrophotometric measurement was achieved by recording the absorbance at 477 nm after a fixed time of 20 and 15 min on a water bath adjusted at 70 ± 1 °C for CPX and NRX, respectively. The same product exhibited emission peaks at 540 nm. The different experimental parameters affecting the development and stability of the color were carefully studied and optimized. The absorbance concentration plots were linear over the ranges 3‐18 and 2.5‐15.0 μg/mL for CPX and NRX, respectively, while the fluorescence concentration plots were linear over the ranges 0.06‐0.36 and 0.05‐0.30 μg/mL for CPX and NRX, respectively. The limit of detection of the kinetic method was about 0.2 μg/mL for both drugs while the fluorescence measurement enabled their detection at a concentration of about 0.012 μg/mL. The proposed methods were successfully applied for the assay of the two drugs in their commercial products. The results obtained were statistically compared with those obtained by reference HPLC and spectrophotometric methods. The stoichiometry of the reaction was determined and the reaction pathway was postulated.     

Determination of the oxidation stability of biodiesel and oils by spectrofluorimetry and multivariate calibration

Oxidation stability is an important quality parameter for biodiesel. In general, the methods used to evaluate the oxidation stability of oils and biodiesels are time-consuming. This work reports the use of spectrofluorimetry, a fast analytical technique, associated with multivariate data analysis as a powerful analytical tool to prediction of the oxidation stability. The prediction of the oxidation stability showed a good agreement with the results obtained by the EN14112 reference method Rancimat. The models presented high correlation (0.99276 and 0.97951) between real and predicted values. The R² values of 0.98557 and 0.95943 indicated the accuracy of the models to predict the oxidation stability of soy oil and soy biodiesel, respectively. The residual distribution does not follow a trend with respect to the predicted variables indicating the good quality of the fits.     

Detection of Human Serum Albumin by a Photoinduced Fluorogenic Reaction

ABSTRACT

9,10-anthraquinone (AQ), a photochemically reactive substrate, has been conjugated together with human serum albumin (HSA), and the photoinduced fluorogenic reaction of the HSA-AQ conjugate was studied. This conjugate shows a greatly enhanced photochemical fluorimetric activity compared with that of free AQ. The spectral characteristics of the photoreduction product of the HSA-AQ conjugate was investigated and large blue shifts in both the excitation and emission bands, compared with those of free AQ, were observed. The kinetic behavior of the photoinduced fluorogenic reaction and the effects of some experimental conditions were also investigated. The enhancement in the photoinduced fluorogenic reactivity of HSA-AQ was utilized in the sensitive detection of HSA by a simple in-situ photoinduced kinetic fluorimetric method. The calibration graph was linear over the range 0-1.0x10^?6 mol/L HSA. The detection limit was 6.5x10^?10 mol/L HSA and the relative standard deviation was 2.7% for 6.0x10^?8 mol/L HSA (n=6).     

Determination of Biacetyl by Sensitized Photochemical Kinetic Fluorimetry

Abstract

A new in-situ photochemical kinetic fluorimetric method was proposed for the determination of biacetyl (BI). It is based on the sensitization of BI on the photochemical reaction of amaranth (AM). AM, a nonfluorescent compound was converted into an intensively fluorescent compound in a slightly alkaline medium by the sensitized photochemical reaction, and BI was indirectly determined by monitoring the change of the fluorescence intensity. The determination can be carried out by fixed-time method or tangent method. The kinetic behavior of the reaction and the effects of some experimental conditions were investigated and discussed. The calibration graph was rectilinear from 1.0 μg ml^?1 to 10.0 μg ml^?1 of BI (r = 0.999), the limit of detection was 1.0 ng ml^?1, and the coefficient of variation was 0.44% for 0.90 μg ml^?1 of BI (n = 6). The mechanism for the sensitization of BI was examined and the triplet-triplet energy transfer, in which BI acted as the energy donor and AM as the energy acceptor, was suggested to be the main cause. Its application to real samples has been tested.