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1.
《Analytical letters》2012,45(18):3417-3429
Abstract

A flow‐injection spectrophotometric procedure was developed for determining N‐acetylcysteine in pharmaceutical formulations. The sample was dissolved in deionized water and 400 µl of the solution was injected into a carrier stream of 1.0×10?2 mol l?1 sodium borate solution. The sample flowed through a column (70 mm length×2.0 mm i.d.) packed with Zn3(PO4)2 immobilized in a polymeric matrix of polyester resin and Zn(II) ions were released from the solid‐phase reactor because of the formation of the Zn(II) (N‐acetylcysteine)2 complex. The mixture merged with a stream of borate buffer solution (pH 9.0) containing 5.0×10?4 mol l?1 Alizarin red S and the Zn(II)Alizarin red complex formed was measured spectrophotometrically at 540 nm. The analytical curve was linear in the N‐acetylcysteine concentration range from 3.0×10?5 to 1.5×10?4 mol l?1 (4.9 to 24.5 µg ml?1) with a detections limit of 8.0×10?6 mol l?1 (1.3 µg ml?1). The relative standard deviations (RSDs) were smaller than 0.5% (n=10) for solutions containing 5.0×10?5 mol l?1 (8.0 µg ml?1) and 8.0×10?5 mol l?1 (13.0 µg ml?1) of N‐acetylcysteine, and the analytical frequency was 60 determinations per hour. A paired t‐test showed that all results obtained for N‐acetylcysteine in commercial formulations using the proposed flow‐injection procedure and a comparative procedure agreed at the 95% confidence level.  相似文献   

2.
A newly-developed method of complete separation and sensitive determination of o-, m-, and p-aminobenzoic acid isomers was achieved by combining open-tubular columns for capillary electrochromatography (OT-CEC) and online sample stacking. In this study, spherical gold nanoparticles were modified by a covalent attachment of mono-6-thio-β-cyclodextrin, and OT-CEC was formed by immobilizing cyclodextrin-modified gold nanoparticles (CD-AuNP) on prederivatized 3-mercaptopropyl-trimethoxysilane fused-silica capillaries. Based on the theory of moving chemical reaction boundary, effects of several important factors such as the pH and concentration of running buffer and the conditions of stacking analytes were optimized. The optimized separations were carried out in 58 mmol/L HAc buffer at pH 3.0 using a capillary coated with CD-AuNP, while the optimized concentration was carried out in 50 mmol/L disodium hydrogen phosphate (pH 9.5). The linear ranges for m-, p-, and o-aminobenzoic acid were from 5.0 × 10?4–0.1, 5.0 × 10?4–0.1 and 1.0 × 10?4–0.1 mmol/L, respectively. And the detection limits (S/N = 3) were as low as 8.22 × 10?5, 8.21 × 10?5, and 3.76 × 10?5 mmol/L for m-, p-, and o-aminobenzoic acid, respectively. The run-to-run, day-to-day, and column-to-column reproducibilities of migration time were satisfactory with relative standard deviation values of less than 4.5 % in all cases. This method was successfully used in determining procaine hydrochloride injection sample with recoveries in the range of 96.1–106.6 % and relative standard deviations less than 5.0 %.  相似文献   

3.
《Analytical letters》2012,45(15):2861-2875
Abstract

A method based on capillary electrophoresis with electrochemical detection (CE‐ED) has been developed for the first time for the separation and determination of isovanillic acid, vanillic acid, quercetin, rosmarinic acid, caffeic acid, and protocatechuic acid in Origanum vulgare L. and its medicinal preparations. The effects of working electrode potential, pH level, concentration of running buffer, separation voltage, and injection time on CE‐ED were investigated. Under the optimum conditions, the analytes could be separated in a 50 mmol L?1 borate buffer (pH 8.7) within 21 min. A 300‐µm diameter carbon disk electrode has a good response at +0.95 V (vs. SCE) for all analytes. The response was linear over three orders of magnitude with detection limits (S/N=3) ranging from 4×10?8 g mL?1 to 2×10?7 g mL?1 for the analytes. The method has been successfully applied to the analysis of real sample, with satisfactory results.  相似文献   

4.
《Analytical letters》2012,45(8):1375-1386
Abstract

A novel chemiluminescence method for the quantitative assay of the organophosphorus pesticide chlorpyrifos in vegetable samples is presented. The determination is based on the reaction of chlorpyrifos with luminol-H2O2 in alkaline medium with sodium chloride being enhancer. Under the optimum conditions, the increased CL intensity was proportional with the concentration of chlorpyrifos in the range of 1.0 × 10?8 g · ml?1 ? 1.0 × 10?6 g · ml?1 and the detection limit was 3.5 × 10?9 g · ml?1 (3σ). The relative standard is less than 3.9% for 5.0 × 10?7g · ml?1 chlorpyrifos (n = 7). This method has been successfully applied to the determination of chlorpyrifos residue in vegetable sample. Further study was focused on the mechanism of chlorpyrifos and the possible mechanism was proposed.  相似文献   

5.
《Analytical letters》2012,45(5):837-852
Abstract

A simple, rapid, sensitive, and reproducible procedure for assaying norfloxacin (NOR), ciprofloxacin (CIP), and ofloxacin (OFL) was investigated. The procedure is based on the reaction of selected drugs with Sudan II (I), Congo red (II), and Gentian violet (III) in universal buffer to give soluble ion‐pair complexes. The effects of various parameters have been studied. Beer's law plots were obeyed in the concentration ranges 0.5–11 µg ml?1, whereas Ringbom optimum ranges were 0.7–9.5 µg ml?1. The apparent molar absorptivity (6.4×104 L mol?1 cm?1), Sandell sensitivity (4.99 ng cm?2), detection (0.13 µg ml?1), and quantification (0.44 µg ml?1) limits were calculated. The relative standard deviation for ten determinations, for samples containing 4.0 µg ml?1, was found to be 1.40%. The influence of commonly employed excipients in the determination of the studied drugs was examined. There was no interference from degradate product results from thermal and hydrolytic treatments. The results obtained by the proposed procedure were statistically validated. The developed procedure was successfully applied to the determination of the studied drugs in dosage forms and biological fluids.  相似文献   

6.
《Analytical letters》2012,45(18):3405-3416
Abstract

A post‐chemiluminescence (PCL) was observed when loperamide hydrochloride solution was injected into the reaction mixture after the finish of CL reaction of alkaline N‐Chlorosuccinimide (NCS) and dichlorofluorescein. Based on this phenomenon, a simple, sensitive and fast flow injection PCL method was established for the determination of loperamide hydrochloride. The possible mechanism for the PCL reaction was discussed via the investigation of the CL kinetic characteristics, the CL spectra, the fluorescence spectra. The PCL intensity responded linearly to the concentration of loperamide hydrochloride in the range 8.0×10?10 to 6.0×10?7 g · ml?1 with a linear correlation of 0.9995. The detection limit was 4×10?10 g · ml?1. The relative standard deviation was 2.4% for 4.0×10?8 g · ml?1 loperamide hydrochloride (n=11). This method has been applied to the determination of loperamide hydrochloride in human plasma and pharmaceutical samples with satisfactory results.  相似文献   

7.
R Knob  V Maier  J Petr  V Ranc  J Sevčík 《Electrophoresis》2012,33(14):2159-2166
Separation of major environmental pollutants as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) by capillary electrophoresis is reported for the first time. It is not possible to resolve the solutes in an aqueous media. However, the use of methanol and acetonitrile as the background electrolyte (BGE) solvents allowed their rapid separation in an uncoated capillary. A major effort was put into BGE optimization in respect to both separation efficiency and detection for further on‐line preconcentration. 5 mmol.L?1 naphthalene‐1‐sulfonic acid and 10 mmol.L?1 triethylamine dissolved in ACN/MeOH (50:50 v/v) provided best separation and detection conditions. Next, the large‐volume sample stacking and the field‐amplified sample injection were applied and compared. Large‐volume sample stacking improved limits of detection (LODs) with regard to the standard injection by 69 times for PFOA and 143 times for PFOS with LODs of 280 and 230 nmol.L?1, respectively. Field‐amplified sample injection improved LODs 624 times for PFOAand 806 times for PFOS with LODs 31 and 40 nmol.L?1, respectively. Both preconcentration methods showed repeatabilities of migration times less than 1.2% RSD intraday and 6.6% RSD interday. The method was applied on PFOA and PFOS analysis in a sample of river water treated with solid‐phase extraction, which further improved LOD toward 5.6 × 10?10 mol.L?1 for PFOS and 6.4 × 10?10 mol.L?1 for PFOA and allows the method to be used for river water contamination screening or decomposition studies.  相似文献   

8.
《Analytical letters》2012,45(4):823-833
Abstract

A simple, sensitive, and specific spectrophotometric method for the measurement of nitrite in water has been developed and optimum reaction conditions along with other analytical parameters have been evaluated. The azo dye, 4‐(1‐methyl‐1‐mesitylcylobutane‐3‐yl)‐2‐(p‐N,N‐dimethylazobenzene)‐1,3‐thiazole was synthesized with the reaction of 4‐(1‐methyl‐1‐mesitylcylobutane‐3‐yl)‐2‐aminothiazole and N,N‐dimethyl aniline in acidic medium. Obtained azo dye has been characterized by infrared (IR), 1H nuclear magnetic resonance (NMR), and microanalysis methods. The dye shows an absorption maximum at 482 nm. The method is optimized for acid concentration, pH, amount of reagents required, time, and interfering species. All the determinations were carried out at this wavelength throughout the work. At an analytical wavelength of 482 nm, Beer's law is obeyed over the concentration range 0.05 to 2.00 µg nitrite per mL analyte. The molar absorptivity, Sandell's sensitivity, and relative standard deviation are 2.03×104 L mol?1 cm?1±251.3 (95%), 2.28×10?3 µg cm?2, and 2.74% (n=10), respectively. The detection limit of the method is 0.012 µg ml?1 of nitrite ion. The method was succesfully applied to the determination of nitrite in tap water and lake water.  相似文献   

9.
A microchip electrophoresis method with laser induced fluorescence detection was developed for the detection of agmatine (Agm) and octopamine (Oct). The fluorescent derivatization reagent, fluorescein isothiocyanate was used for precolumn derivatization of Agm and Oct. The sodium dodecyl sulfate (SDS) micelles was employed as pseudostationary phase for the separation of Agm and Oct with other endogenous compounds exist in biological samples. Some parameters including buffer concentration, buffer pH, SDS concentration and separation voltage were investigated in detail. Under the optimum conditions, the separation and determination of Agm and Oct was performed within 40 s. The calibration curves were linear for both Agm and Oct over the concentration range of 1.0 × 10?7 to 4.0 × 10?5 M and 1.5 × 10?7 to 4.5 × 10?5 M, respectively. The detection limits of Agm and Oct (S/N = 3) are 5.0 × 10?8 and 8.0 × 10?8 M, respectively. These values make the method very suitable for the determination of Agm and Oct in rat brain tissue and human plasma as demonstrated in this paper.  相似文献   

10.
Sun  Wenhua  Dong  Yalei  Cui  Hong  Zhao  Hong  He  Yujian  Ding  Yongsheng  Li  Xiangjun  Yuan  Zhuobin 《Chromatographia》2014,77(11):821-828

A newly-developed method of complete separation and sensitive determination of o-, m-, and p-aminobenzoic acid isomers was achieved by combining open-tubular columns for capillary electrochromatography (OT-CEC) and online sample stacking. In this study, spherical gold nanoparticles were modified by a covalent attachment of mono-6-thio-β-cyclodextrin, and OT-CEC was formed by immobilizing cyclodextrin-modified gold nanoparticles (CD-AuNP) on prederivatized 3-mercaptopropyl-trimethoxysilane fused-silica capillaries. Based on the theory of moving chemical reaction boundary, effects of several important factors such as the pH and concentration of running buffer and the conditions of stacking analytes were optimized. The optimized separations were carried out in 58 mmol/L HAc buffer at pH 3.0 using a capillary coated with CD-AuNP, while the optimized concentration was carried out in 50 mmol/L disodium hydrogen phosphate (pH 9.5). The linear ranges for m-, p-, and o-aminobenzoic acid were from 5.0 × 10−4–0.1, 5.0 × 10−4–0.1 and 1.0 × 10−4–0.1 mmol/L, respectively. And the detection limits (S/N = 3) were as low as 8.22 × 10−5, 8.21 × 10−5, and 3.76 × 10−5 mmol/L for m-, p-, and o-aminobenzoic acid, respectively. The run-to-run, day-to-day, and column-to-column reproducibilities of migration time were satisfactory with relative standard deviation values of less than 4.5 % in all cases. This method was successfully used in determining procaine hydrochloride injection sample with recoveries in the range of 96.1–106.6 % and relative standard deviations less than 5.0 %.

  相似文献   

11.
Carboxymethyl cellulose-silver nanoparticle (AgNp)-silica hybrids have been synthesized in a modified Stöber process. The hybrid synthesis was optimized to obtain an efficient immobilization matrix for diastase alpha amylase, a multimeric enzyme of high technological significance. The synthesized hybrids were characterized using FTIR, XRD, SEM, TGA and BET studies. The enzyme immobilization was done by adsorption and using the immobilized enzyme, the hydrolysis of soluble starch has been optimized in comparison to free enzyme. The optimum usable pH for the immobilized enzyme ranged from pH 4 to 5, while pH 5 was optimum pH for the free enzyme activity. The kinetic parameters for the immobilized, (K M = 3.4610 mg ml?1; V max = 6.3540 mg ml?1 min?1) and free enzyme (K M = 4.1664 mg ml?1; V max = 4.291 mg ml?1 min?1) hydrolysis indicated that the immobilization at the nanohybrid has significantly improved the catalytic property of the enzyme. In the immobilized state, the enzyme remained usable for many repeated cycles like our previous material, gum acacia-gelatin-AgNp-silica. Storage experiments indicated that the immobilization has increased the stability of the enzyme and also that AgNps play a role in stabilizing the immobilized enzyme.  相似文献   

12.
High performance liquid chromatography coupled with resonance light scattering detection was developed for separation and determination of heparin in plasma. A good chromatographic separation was achieved using an aminex HPX-87H column (300 mm × 7.8 mm, 9 μm) and a mobile phase of 5.0 mmol L?1 H2SO4 at the flow rate of 0.5 mL min?1. The enhanced resonance light scattering signals were derived from a large aggregate formation between heparin and cetyltrimethylammonium bromide used as the molecular recognition probe. The parameters of the post-column reaction (pH, concentration and flow rate of the reagent, length of the reaction coil, and temperature) were optimized. The limit of detection for heparin in plasma was 0.2 mg L?1. The method has been applied to the determination of heparin in dialysis patient plasmas.  相似文献   

13.
《Analytical letters》2012,45(13):2207-2216
Abstract

A simple and selective spectrophotometric method has been developed for the determination of trace amounts of arsenic using azure B as a chromogenic reagent. The proposed method is based on the reaction of arsenic(III) with potassium iodate in acid medium to liberate iodine. The liberated iodine bleaches the violet color of azure B and is measured at 644 nm. This decrease in absorbance is directly proportional to the As(III) concentration, and Beer's law is obeyed in the range 0.2–10 µg ml?1 of As(III). The molar absorptivity, Sandell's sensitivity, detection limit, and quantitation limit of the method were found to be 1.12×104 l mol?1cm?1, 6.71×10?3 µg cm?2, 0.02 µg ml?1 and 0.08 µg ml?1, respectively. The optimum reaction conditions and other analytical parameters were evaluated. The proposed method has been successfully applied for the determination of arsenic in various environmental and biological samples.  相似文献   

14.
《Analytical letters》2012,45(7):1128-1143
Abstract

The spectrophotometric behavior of uranium (VI) with L-3-(3, 4-dihydroxy phenyl) alanine (LDOPA) reagent revealed that the uranium can form a ML2 complex with LDOPA in solution. Thus a highly sensitive adsorptive stripping voltammetric protocol for measuring of trace uranium, in which the preconcentration was achieved by adsorption of the uranium-LDOPA complex at hanging mercury drop electrode (HMDE), is described. Optimal conditions were found to be a 0.02 M ammonium buffer (pH 9.5) containing 2.0 × 10?5 M (LDOPA), an accumulation potential of ? 0.1 V (versus Ag/AgCl) and an accumulation time of 120 sec.

The peak current and concentration of uranium accorded with linear relationship in the range of 0.5–300 ng ml?1. The relative standard deviation (at 10 ng ml?1) is 3.6% and the detection limit is 0.27 ng ml?1. The interference of some common ions was studied. Applicability to different real samples is illustrated. The attractive behavior of this reagent holds great promise for routine environmental and industrial monitoring of uranium.  相似文献   

15.
Potential possibilities of long‐chain ionic liquids based on imidazole (1‐dodecyl‐3‐methylimidazolium chloride and 1‐cetyl‐3‐methylimidazolium chloride) for online sample concentration techniques (field‐amplified sample stacking, head‐column field‐amplified sample stacking, and sweeping) of catecholamines were studied in both capillary zone electrophoresis and micellar electrokinetic chromatography. The use of a high‐conductivity sample matrix in sweeping was found to significantly increase the separation efficiency of analyte up to 2 × 106 theoretical plates per meter and remarkably reduce limits of detection for catecholamines up to 50 ng/mL. This approach was shown to be suitable for the determination of trace amounts of catecholamines in biological fluids.  相似文献   

16.
《Analytical letters》2012,45(14):2234-2245
A novel chemiluminescence (CL) method is developed for determination of ofloxacin and levofloxacin with Ag(III) complex in H2SO4 solution medium. The CL intensity is proportional to drug concentration in a wider range with a correlation coefficient of 0.999. The limit of detection (s/n = 3) for ofloxacin and levofloxacin was 5.3 × 10?9 g ml?1 and 8.3 × 10?9 g ml?1, respectively, and their recoveries from urine and serum samples were in the range of 90.1–112% with the RSDs of 1.0–2.8%. The proposed method was applied for analysis of real samples with satisfactory result. The possible CL mechanism was discussed.  相似文献   

17.
The adsorption processes of alizarin onto hydrophilic carbon nanoparticles (Emperor 2000?) are investigated. The significant increase in voltammetric responses for pre-adsorbed alizarin compared with those for solution confirms high affinity of alizarin to carbon nanoparticles (possibly due to π–π stacking interaction between aromatic rings of alizarin and surface-sulfonated carbon nanoparticles). To obtain the optimum of adsorption conditions, the effects of pH, agitation rate, and adsorption time are investigated. Under square wave voltammetry conditions, the peak current for the reduction of alizarin shows a linear relationship with concentration in the range from 2.0 to 10.0 nM. The limit of detection is estimated 5.8?×?10?9 mol L?1. Next, alizarin is applied as a receptor for sensing of trace vanadium in acetate buffer pH 5. Linear calibration curves are obtained for vanadium in the range of 1.0?×?10?6 to 1.0?×?10?4 mol L?1 and the limit of detection is estimated 9.6?×?10?8 mol L?1. Determination of vanadium in real samples such as sea and tap water is demonstrated.  相似文献   

18.
《Analytical letters》2012,45(12):1913-1931
Abstract

A voltammetric study of the oxidation of fexofenadine HCl (FEXO) has been carried out at the glassy carbon electrode. The electrochemical oxidation of FEXO was investigated by cyclic, linear sweep, differential pulse (DPV), and square wave (SWV) voltammetry using glassy carbon electrode. The oxidation of FEXO was irreversible and exhibited diffusion‐controlled process depending on pH. The dependence of intensities of currents and potentials on pH, concentration, scan rate, nature of the buffer was investigated. Different parameters were tested to optimize the conditions for the determination of FEXO. For analytical purposes, a very well resolved diffusion‐controlled voltammetric peak was obtained in Britton‐Robinson buffer at pH 7.0 with 20% constant amount of methanol for DPV and SWV techniques. The linear response was obtained in supporting electrolyte in the ranges of 1.0×10?6–2.0×10?4 M with a detection limit of 6.6×10?9 M and 5.76×10?8 M and in serum samples in the ranges of 2.0×10?6–1.0×10?4 M with a detection limit of 8.08×10?8 M and 4.97×10?8 M for differential pulse and square wave voltammetric techniques, respectively. Only square wave voltammetric technique can be applied to the urine samples, and the linearity was obtained in the ranges of 2.0×10?6–1.0×10?4 M with a detection limit of 2.00×10?7 M. Based on this study, simple, rapid, selective and sensitive two voltammetric methods were developed for the determination of FEXO in dosage forms and biological fluids. For the precision and accuracy of the developed methods, recovery studies were used. The standard addition method was used for the recovery studies. No electroactive interferences were found in biological fluids from the endogenous substances and additives present in tablets.  相似文献   

19.
《Analytical letters》2012,45(12):2387-2403
Abstract

A detailed study of voltammetric behavior of ethiofencarb (ETF) is reported using glassy carbon electrode (GCE) and hanging mercury drop electrode (HMDE). With GCE, it is possible to verify that the oxidative mechanism is irreversible, independent of pH, and the maximum intensity current was observed at +1.20 V vs. AgCl/Ag at pH 1.9. A linear calibration line was obtained from 1.0×10?4 to 8.0×10?4 mol L?1 with SWV method. To complete the electrochemical knowledge of ETF pesticide, the reduction was also explored with HMDE. A well‐defined peak was observed at –1.00 V vs. AgCl/Ag in a large range of pH with higher signal at pH 7.0. Linearity was obtained in 4.2×10?6 and 9.4×10?6 mol L?1 ETF concentration range.

An immediate alkaline hydrolysis of ETF was executed, producing a phenolic compound (2‐ethylthiomethylphenol) (EMP), and the electrochemical activity of the product was examined. It was deduced that it is oxidized on GCE at +0.75 V vs. AgCl/Ag with a maximum peak intensity current at pH 3.2, but the compound had no reduction activity on HMDE.

Using the decrease of potential peak, a flow injection analysis (FIA) system was developed connected to an amperometric detector, enabling the determination of EMP over concentration range of 1.0×10?7 and 1.0×10?5 mol L?1 at a sampling rate of 60 h?1. The results provided by FIA methodology were performed by comparison with results from high‐performance liquid chromatography (HPLC) technique and demonstrated good agreement with relative deviations lower than 4%. Recovery trials were performed and the obtained values were between 98 and 104%.  相似文献   

20.
A new type of graphene-Co3O4 functionalized porphyrin was synthesized and used for selective and sensitive detection of methyl parathion (MP). Co3O4 nanoparticles were firstly modified onto graphene oxide sheets and the porphyrin/Co3O4/graphene nanocomposites were then synthesized by self-assembly decoration of anion porphyrin on Co3O4-modified graphene sheets by π–π stacking. By dexterously controlling the electrochemical reduction variables and optimizing the electrode preparation parameters, with the satisfactory conductivity, strong adsorption toward MP, the developed novel sensor fabricated with the as-synthesized nano-assembly for determination of MP shows some satisfactory properties such as a wide linear concentration range (from 4.0?×?10?7 M to 2.0?×?10?5 M), low detection limit (1.1?×?10?8 M), favorable repeatability, long-time storage stability, and satisfactory anti-interference ability. It also had high precision for the real sample analysis, which indicated the good perspective for field application.  相似文献   

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