Flow-Injection Analysis Based on Extraction and Spectrophotometric Determination of Penicillins with Thiazine Dyes

Abstract

A new method for flow-injection analysis (FIA) for the determination of penicillins based on the extraction and spectrophotometric determination of ion associates with selected thiazine dyes (methylene blue, azure A, and azure B) is proposed. The reaction conditions (c_dye = 2 × 10^?4 mol l^?1, c_KCl = 1 mol l^?1, pH ? 6, λ = 635 nm) were found. The factorial design has been carried out to determine the optimum flow conditions. A wide linear dynamic range of calibration curves (5.1–700 µg ml^?1 for penicillin V with all dyes, R = 0.9985) and good repeatability (e.g., relative standard deviation [RSD] = 4.6–0.6% in this concentration range for the reaction with azure B) were found. The detection limit for penicillin V is 1.5 µg ml^?1, and the determination limit is 5.1 µg ml^?1. The maximum analysis rate is 35 samples per h. The practical samples of pharmaceutics were tested. There are no interferences from the additives in pharmaceutics.     

Spectrophotometric Determination of Some Fluoroquinolone Derivatives in Dosage Forms and Biological Fluids Using Ion‐Pair Complex Formation

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.     

Novel Method for Selective Spectrophotometric Determination of Titanium(IV) with Water Extract of Slippery Elm Leaf as a New Reagent

Abstract

A novel spectrophotometric method for the determination of titanium(IV) by using a new reagent, water extract of slippery elm leaf is developed. In 0.05 M hydrochloric acid, titanium(IV) reacts with this reagent to form a yellow product. The formed product shows maximum absorbance at 415 nm with a molar absorptivity value of 0.68×10⁴ l mol^–1 cm^–1 and the method was linear in the 0.2–6 µg ml^?1 concentration range. The detection limit value was found to be 0.0131 µg ml^?1. The proposed method was simple, low cost, selective, and sensitive. It was applied to the analytic samples with satisfactory results.     

Chemiluminescence Determination of Organophosphorus Pesticides Chlorpyrifos in Vegetable

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.     

A Novel Enhanced Chemiluminescence System with Ag(III) Complex for the Determination of Ofloxacin and Levofloxacin in Pharmaceutical Preparation and Biological Fluid

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.     

Post‐chemiluminescence Method of the Determination of Loperamide Hydrochloride in Human Plasma and Pharmaceutical by Using Dichlorofluorescein as Chemiluminescence Reagent

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.     

Nonextractive Trace Level Simultaneous Determination of Mercury(II) and Zinc(II) in Environmental Samples with 2‐(5‐Bromo‐2‐pyridylazo)‐5‐diethylaminophenol and Cetylpyridinium Chloride

Abstract

A simple, rapid, selective, and sensitive method for the derivative spectrophotometric determination of Hg(II) and its simultaneous determination in the presence of Zn(II) using 2‐(5‐bromo‐2‐pyridylazo)‐5‐diethylaminophenol in the presence of cetylpyridinium chloride, a cationic surfactant, has been developed. The molar absorption coefficient and analytical sensitivity of the 1∶1 Hg(II) complex at 558 nm (λ_max) are 5.78×10⁴ L mol^?1 cm^?1 and 0.67 ng mL^?1, respectively. The detection limit of Hg(II) is 1.40×10^?2 ng mL^?1, and Beer's law is valid in the concentration range 0.05–2.40 µg mL^?1. Overlapping spectral profiles of Hg(II) and Zn(II) complexes in zero‐order mode interfere in their simultaneous determination. However, 0.10–2.00 µg mL^?1 of Hg(II) and 0.065–0.650 µg mL^?1 of Zn(II), when present together, can be simultaneously determined at zero cross point of the derivative spectrum, without any prior separation. The relative standard deviation for six replicate measurements of solutions containing 0.134 µg mL^?1 of Hg(II) and 0.620 µg mL^?1 of Zn(II) is 1.72 and 1.47%, respectively. The proposed method has successfully been evaluated for trace level simultaneous determination of Hg(II) and Zn(II) in environmental samples.     

Adsorptive Stripping Voltammetric Determination of Antimony by Using Alizarin Red S

Abstract

A sensitive and selective voltammetric method for determination of antimony(III) using Alizarin Red S (ARS) as complexing agent is described. The method is based on the monitoring the oxidation peak of antimony(III)-ARS complex at ?520 mV in ammonium-ammonia buffer (pH = 7.5). The peak current was measured by scanning the potential from ?700 mV versus Ag/AgClto more positive potentials without accumulation in the presence of 1 × 10^?6 mol L^?1 of ARS. The limit of detection (3 s) and limit of quantification (10 s) of the method were calculated from calibration curve as 1.45 µg L^? and 4.8 µg L^? respectively. The calibration plot for antimony(III) was linear in the range of 4.8–30 µg L^?. The interference of various ions was examined. Serious interference from Al(III), Fe(III), Cu(II), Pb(II), and Zn(II) was eliminated by addition of EDTA to the solution. The method was applied to drinking water samples. The recoveries were in the range 94% – 105%. The results obtained from the developed method were compared with those from the differential-pulse anodic-stripping method and no statistically significant difference was found.     

Rapid and selective determination of osmium(IV) by UV-visible spectrophotometry using o-methylphenyl thiourea as a chromogenic chelating ligand: sequential separation of osmium(IV), rhodium(III) and platinum(IV)

The objective of this research work was to develop a simple, highly sensitive and precise method for spectrophotometric determination of osmium(IV). O-Methylphenyl thiourea (OMPT) coordinates with osmium(IV) as a 1:1 (osmium(IV)–OMPT) complex in hydrochloric acid media (0.8 mol l^?1). The novelty of the investigated method is instant complex formation at room temperature with no need of heating or standing. The complex is stable for more than 8 days. The method is applicable over a wide linearity range (up to 110 µg ml^?1). A low reagent concentration is required (2 ml, 0.009 mol l^?1 in ethanol). The complex exhibits maximum absorption in the range of wavelength 510–522 nm and 514 nm was selected for further study. The molar absorptivity was 1.864 × 10³ l mol^?1 cm^?1, Sandell’s sensitivity was 0.102 µg of osmium(IV) cm^?2. Proposed method was successfully applied for separation and determination of osmium(IV) from binary and ternary synthetic mixtures containing associated metal ions. A scheme for mutual separation of osmium(IV), rhodium(III) and platinum(IV) is developed.     

Flow‐Injection Spectrophotometric Determination of N‐acetylcysteine in Pharmaceutical Formulations with On‐Line Solid‐Phase Reactor Containing Zn(II) Phosphate Immobilized in a Polyester Resin

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.     

A Novel Method for the Determination of Streptomycin Using Sodium Nitroprusside as a Chromogenic Reagent by Spectrophotometry

Abstract

A rapid and simple spectrophotometric method for the determination of streptomycin has been developed and validated. The method was based on the reaction of streptomycin with sodium nitroprusside in the alkaline medium forming a red product measured at the maximum absorption of 495 nm. The stoichiometric ratio of the product is 1:1. Beer's law is obeyed in a range of 1.87 µg mL^?1 ～ 279.8 µg mL^?1 of streptomycin and ?₄₉₅ is 6.0 × 10³ L·mol^?1 cm^?1.Under the optimum condition, the equation of linear regression is A = 0.00742 + 0.05683 C (× 10⁵ mol·L^?1), with a linear correlation coefficient of 0.9990. The detection limit (3σ/k) is 0.96 µg mL^?1, the relative standard deviation (RSD) is 2.40%, and the average recovery rate is 98.3%–102.7%. Every parameter has been optimized, and the reaction mechanism has been studied. The proposed method has been successfully applied to the determination of streptomycin for injections and tablets of pharmaceutical preparation. Analytical results obtained by this new method were very gratifying.     

A New Flow‐Injection Chemiluminescence Method for the Determination of Acyclovir and Gancyclovir

Abstract

A rapid and sensitive flow‐injection chemiluminescence (FI‐CL) method, which is based on the CL intensity that generated from the redox reaction of Ce(IV)‐rhodamine B in H₂SO₄ medium, for the determination of acyclovir and gancyclovir is described. For acyclovir, the determination range is 3×10^?8 g mL^?1–7×10^?5 g mL^?1, with 1.56×10^?8 g mL^?1 as its determination limit. During 11 repeated measurements for 1×10^?6 g mL^?1 acyclovir, the relative standard deviation was 2.08%. For gancyclovir, the determination range was 5×10^?8 g mL^?1–7×10^?5 g mL^?1, with 2.35×10^?8 g mL^?1 as its determination limit. The relative standard deviation is 2.83% with 11 repeated measurements of 1×10^?6 g mL^?1 gancyclovir. This method can be successfully used to determine the content of acyclovir and gancyclovir in injections, acyclovir in eye drops, and, maybe, also for other ciclovirs.     

Study on Chemiluminescence Assay of Surfactant PEG-400 Using Luminol–Hydrogen Peroxide System

Abstract

Based on the fact that nonionic surfactant polyethylene glycol-400 (PEG-400) catalyzed the chemiluminescence of luminol-H₂O₂ system, a novel and simple chemiluminescence method has been developed for the determination of PEG-400. Under the optimal conditions, the standard curve was Y = 198835X–2091.8, where the correlation coefficient (R) was 0.9999. The detection limit was 4 × 10^?5 g·ml^?1 PEG-400 and the linear range was 1.0 × 10^?4–4.0 × 10^?2g·ml^?1. The relative standard deviation was 3.2% at 2.0 × 10^?3 g·ml^?1 PEG-400 (n = 7). This method has been applied to the determination of PEG-400 in cosmetic samples with satisfactory results. Furthermore, the dynamics characteristic curve of PEG-400 in luminol-H₂O₂ system was compared to typical metallic ion and other surfactants. Moreover, the mechanism of the luminol-H₂O₂-PEG-400 chemiluminescence system was studied, assisted by fluorescence spectra and UV spectra.     

Abilities of Partial Least‐Squares (PLS‐2) Multivariate Calibration in the Analysis of Quaternary Mixture of Food Colors (E‐110, E‐122, E‐124, E‐131)

Abstract

Sunset Yellow (SY), Carmoisine (C), Ponceau 4R (P), and Patent Blue V (PB) are synthetic organic dyes which are under governmental regulations all over the world because of their toxicity and carcinogenicity.

In this study, a simple and fast analytical procedure was proposed for the simultaneous determination of food dyes (SY, C, P, and PB) in powder drinks by means the partial least‐square treatment of spectrophotometric absorbance between 450 –730 nm, taken at 10 nm intervals. The experimental calibration matrix was constructed with 27 samples. The concentration ranges considered were 2, 3, 4 µg · ml^?1 for SY, 7, 8, 9 µg · ml^?1 for C, 9, 10, 11 µg · ml^?1 for P, and 0.3, 0.4, 0.5 µg · ml^?1 for PB. The method was applied to the determination of dyes in different commercially available powder drinks. The results obtained by the application of the PLS‐2 method were statistically compared with those obtained by an HPLC method using the F and t tests. Very similar values were found by two methods. No time consuming pretreatment was needed and this method also provides rapid, accurate and economical analysis of these colors.     

Selective extraction and preconcentration of ultra-trace amounts of arsenic(V) ions using carbon nanotubes as a novel sorbent

In the present study, multiwalled carbon nanotubes (MWCNTs) as solid phase extraction sorbent were developed for preconcentration of arsenic(V) species prior to graphite furnace atomic absorption spectrometry (GFAAS) determination. Arsenic(V) was selectively sorbed on the packed column with MWCNTs within a pH 9.5 in the presence of 2-(5-bromo-2-pyridylazo)-5-diethyl amino phenol (5-Br-PADAP). The adsorbed species was then desorbed with 1 mL of 2.0 M HNO₃. Experimental parameters including pH, sample volume and flow rate, type, volume and concentration of eluent that influence the recovery of the arsenic(V) species were optimised. Under the optimised conditions, the calibration curve was linear in the range of 0.2–10.0 µg L^?1 with detection limit of 0.016 µg L^?1. The relative standard deviations (RSD) for seven replicate determinations at 1.0 µg L^?1 level of arsenic was 6.69%. The proposed method was successfully applied to the determination of arsenic in water samples and certified reference material (NIST RSM 1643e).     

Catalyzed Determination of Glucose with a Mimic Enzyme Constructed of Bis‐[‐6‐O‐(‐β‐ethyloic‐butanedioic Acid‐1,4‐ester‐4‐)]β‐Cyclodextrin · Fe3+

Abstract

Catalyzed determination of glucose with mimic glucose oxidase is constructed by the reaction of β‐cyclodextrin, maleic anhydride, and chloroacetic acid with iron trichloride in hydrogen peroxide. The method is simple and convenient, and sensitivity and repeatability are ideal. Beer's law is obeyed in a concentration range of 30–197 µg · ml^?1 glucose with an excellent correlation coefficient (r=0.9994), while the detection limit is 4.10 µg · ml^?1, the RSD is 0.98% (n=8). The recovery of sample is 95.8–103.1%.     

Selective determination of selenium(IV) from environmental samples by UV-visible spectrophotometry using O-methoxyphenyl thiourea as a chelating ligand

A selective extraction–spectrophotometric method has been developed for determination of selenium(IV) using O-methoxyphenyl thiourea (OMePT) as a chelating agent. The basis of the proposed method is the spectrophotometric determination of selenium(IV)–OMePT complex obtained after extraction of selenium(IV) from 3.5 M hydrochloric acid media using OMePT in chloroform solvent. The complex shows maximum absorbance at 350 nm against the reagent blank. The Beer’s law was obeyed over the concentration range 5–60 µg mL^?1 of selenium(IV). The optimum concentration range was 20–50 µg mL^?1 as evaluated from Ringbom’s plot. The molar absorptivity and Sandell’s sensitivity of the selenium(IV)–OMePT complex in chloroform were 3.312 × 10² L mol^?1cm^?1 and 0.2384 µg cm^?2, respectively. The composition of selenium(IV)–OMePT complex was 1:2 established from slope ratio method, mole ratio method and Job’s continuous variation method. The complex was stable for more than 72 h. The interfering effect of various foreign ions was studied and suitable masking agents were used wherever necessary to enhance the selectivity of the developed method. The proposed method was successfully applied for the determination of selenium(IV) from real samples, viz. pharmaceutical formulations, shampoo, vegetable sample, synthetic mixtures and environmental samples. Repetition of the method was checked by finding the relative standard deviation (RSD) for 10 determinations which was 0.35%.     

Determination of Gold(III) by Simplified Room-Temperature Ionic Liquid Extraction with Flame Atomic Absorption Spectrometry

A new simplified extraction of gold(III) using a room-temperature ionic liquid prior to determination by flame atomic absorption spectrometry has been developed. The extraction method uses 1-butyl-3-methylimidazolium hexafluorophosphate without a chelating agent. The parameters of the extraction system were investigated in detail. Under the optimized conditions, a linear range of 0.19 to 38.20 µg · mL^?1, a limit of detection of 0.072 µg · mL^?1, an enrichment factor of 10.0, and an extraction capacity of 6.6 mg · g^?1 were obtained. The extraction mechanism and the selectivity of 1-butyl-3-methylimidazolium hexafluorophosphate for gold(III) were also investigated. The method was applied for the determination of gold(III) in water samples with satisfactory results.     

Study of Spectrophotometric Determination of Amoxicillin Using Sodium 1,2‐Naphthoquinone‐4‐Sulfonate as the Chemical Derivative Chromogenic Reagent

Abstract

A simple and sensitive spectrophotometric method is described for determination of amoxicillin. The method is based on a nucleophilic substitution reaction to measure the pink compound produced by the reaction of amoxicillin with sodium 1,2‐naphthoquinone‐4‐sulfonate in pH 9.00 buffer solution. The stoichiometric ratio of the compound is 1:1, and its maximum absorption wavelength is at 468 nm, ε=3.91×10³ L · mol^?1 · cm^?1. The Beer's law is obeyed in the range of 0.8–120 µg · mL^?1 of amoxicillin. The linear regression equation is A=0.041239+0.22128 C, with 0.9994 of a linear regression correlation coefficient. The detection limit is 2.0 µg · mL^?1, and average recovery is over 98.5%. This paper further optimizes the determination of amoxcillin compared to the previous methods, and the kinetic property and reaction mechanism are studied intensively. This proposed method has been successfully applied to the determination of amoxicillin in tablets and capsules. The results obtained by this method agreed well with those by the official method high pressure liquid chromatography (HPLC).     

A Sensitive Flow Injection Fluorimetry for the Determination of Carbamazepine in Human Plasma

Abstract

A simple, sensitive, and specific flow injection fluorimetric method has been developed for the determination of carbamazepine (CBZ). The proposed method is based on use of a solid‐phase reactor containing lead dioxide for on‐line oxidization of CBZ into a strongly fluorescent compound in a medium of phosphoric acid. The product has a green‐yellow fluorescence at a maximum excitation wavelength of 355 nm and an emission wavelength of 478 nm. Under the optimum conditions, the fluorescence intensity is proportional to the concentration of CBZ ranging from 0.0005 to 4.000 µg mL^?1. The detection limit is 5.7×10^?5 µg mL^?1 (2.4×10^?10 mol L^?1) and the relative standard deviation is 1.4% at the sampling rate of 45 h^?1. The proposed method has been applied to clinical estimation of CBZ in real patients' plasma samples with the results compared with those obtained by HPLC method.