Two different strategies for the fluorimetric determination of piroxicam in serum

Two different spectrofluorimetric methods for the determination of piroxicam (PX) in serum are presented and discussed. One of them is based on the use of three-way fluorescence data and multivariate calibration performed with parallel factor analysis (PARAFAC) and self-weighted alternating trilinear decomposition (SWATLD). This methodology exploits the so-called second-order advantage of the three-way data, allowing to obtain the concentration of the studied analyte in the presence of any number of uncalibrated (serum) components. The method was developed following two different procedures: internal standard addition and external calibration with standard solutions, which were compared and discussed. The second approach investigated is based on the combination of solid-phase extraction (SPE) and room temperature fluorimetry. Both methods here presented yield satisfactory results. The concentration range in which PX could be determined in serum was 1–10 μg ml⁻¹. The limits of quantification for the experimental solutions using the chemometric approach were 0.09 μg ml⁻¹ for the standard addition mode and 0.12 μg ml⁻¹ using external calibration (both for PARAFAC and SWATLD algorithms). In the solid-surface fluorimetric method, the calibration graph was linear up to 0.22 μg ml⁻¹ and the limit of quantification was 0.02 μg ml⁻¹.     

Spectrofluorimetric method for the determination of piroxicam and pyridoxine

A simple and highly selective method for the determination of piroxicam and pyridoxine (vitamin B6) in pharmaceutical formulations is presented. The approach is based on the combination of solid-phase extraction (SPE) and room-temperature fluorimetry (RTF). SPE under optimum pH conditions provides the separation between piroxicam and pyridoxine. The selectivity of analysis, the analytical figures of merit, and the accuracy of the method are demonstrated with the determination of piroxicam and pyridoxine in several pharmaceutical preparations.     

Vibrational Spectrum of a Platinum Complex of Piroxicam

The infrared and Raman spectra of a platinum complex of the antiinflammatory drug piroxicam (Pir) and dimethylsulfoxide (DMSO) of composition [PtCl₂Pir(DMSO)] were recorded and briefly discussed on the basis of its structural characteristics. The metal-to-ligand vibrations are analyzed in detail.     

Sensitive Quantification of Fe(III) in Food Samples at Screen Printed Carbon Electrode Modified with Graphene and Piroxicam by Catalytic Adsorptive Voltammetry

A new disposable sensitive voltammetric sensor for the determination of Fe(III) based on a graphene (G) and piroxicam (Pir) modified screen printed carbon electrode (Pir/G/SPCE) has been developed. The developed method is based on accumulation of Fe(III) on the surface of the prepared sensor strip, formation a complex with Pir and subsequent reduction the adsorbed chelated Fe(III) at ?0.03 V (vs. Ag/AgCl) coupled with the catalytic enhancement of bromate. Characterizations of the modified electrode surface were performed by field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray spectroscopy (EDX) and electrochemical impedance spectroscopy (EIS). Electrochemical behavior of the modified SPCEs was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimum conditions, the catalytic voltammetric method exhibited linear calibration plot in the concentration ranges of 1–100 ng mL^?1 and 100–3500 ng mL^?1 Fe(III) with a limit of detection of 0.3 ng mL^?1. The sensor strip displayed good reproducibility with 1.7 % relative standard deviation (RSD%). The developed method was successfully applied for the determination of iron in food samples such as vegetables, fruit, and cereal.     

甲酚红褪色分光光度法测定吡罗昔康

用褪色分光光度法(测定药物制剂和生物样品中吡罗昔康含量。)在pH8.75的tris-HCl缓冲溶液中,甲酚红与吡罗昔康反应形成离子缔合物,使甲酚红溶液褪色,最大褪色波长位于570nm,吡罗昔康浓度在0.06628～11.60μg/mL范围内遵循比尔定律,回归方程为ΔA=0.1404c+0.0067,相关系数为r=0.9996,表观摩尔吸光系数为4.703×104L·mol-1.cm-1。据此建立了方法,样品测定平均回收率为97.51%～101.4%。     

Spectroscopic studies of microenvironment dictated structural forms of piroxicam and meloxicam

Long acting non-steroidal anti-inflammatory drugs (NSAIDs) belonging to the oxicam group have attracted special interest because of their diverse biological functions. In this study we present the influence of microenvironment on the spectral properties of two oxicam drugs viz. piroxicam and meloxicam. For the two drugs, a high energy shift of the UV absorption maxima was observed with increasing drug concentrations both in protic solvent like ethanol and aprotic solvent like dimethyl sulfoxide (DMSO). Studies involving variation of percentage volume of water as well as pH, using absorption and steady state fluorescence spectroscopy, allow us to identify the principal species present at different concentrations of the drugs. It is found that even trace quantity of water present in the solvent becomes significant at low concentration of the drug making the water/drug ratio sufficiently large to support the formation of anion. As the concentration of the drug increases, the number of water molecules available per drug molecule decreases and most of the drug molecules face a relatively apolar environment in which zwitterionic/neutral species become predominant. This results in a concentration-dependent high-energy shift of the absorption maximum. This study demonstrates how microenvironments of these drugs guide the nature of the predominant form present in solution.     

吡罗昔康在纳米Fe_3O_4-石墨烯复合修饰玻碳电极上的电化学行为及电分析研究

采用纳米Fe3O4粒子(nano-Fe3O4)和石墨烯(Reduced Graphene Oxide,RGO)制备了nano-Fe3O4-RGO复合材料修饰玻碳电极(nano-Fe3O4-RGO/GCE),采用循环伏安法(cyclic voltammetry,CV),方波伏安法(square wave voltammetry,SWV),计时电流法(chronoamperometry,CA),计时库仑法(chronocoulometry,CC)研究了吡罗昔康(Piroxicam,PC)在此复合修饰电极上的电化学行为及电化学动力学性质。实验结果表明,与GCE相比,nano-Fe3O4-RGO/GCE对PC的电化学氧化作用有显著的促进作用,其氧化峰电流显著增加;对各种实验条件进行了优化,测得峰电流Ipa与PC浓度在2.0×10-6~2.0×10-4mol·L-1范围内呈良好的线性关系,检出限(S/N=3)为5.3×10-7mol·L-1,加标回收率为100.0%~104.0%。该方法快速,灵敏,并将nano-Fe3O4-RGO/GCE用于市售吡罗昔康片剂的测定,结果符合定量测定要求。     

吡洛昔康的极谱测定

在0.06mol/LHAc NaAc(pH4.5±0.1)缓冲溶液中,吡洛昔康于-1.23V(vs.SCE)处产生一灵敏的极谱催化氢波,其二阶导数峰电流与吡洛昔康浓度在2.0×10-8～5.6×10-6mol/L范围内呈线性关系(r=0.9990,n=8),检出限为1.0×10-8mol/L。该方法可用于药剂中吡洛昔康的测定。     

Spectrophotometric Determination of Piroxicam via Chelation with Fe(III) in Commercial Dosage Forms

The objective of this work is to develop and validate spectrophotometric method for the determination of piroxicam in commercial dosage forms. The method is based on the chelation of the drug with Fe(III) to form pink coloured metal chelate at room temperature which absorbs maximally at 504 nm. Beer's law is obeyed over the concentration range of 8–160 μg mL^?1 (A = 1.07 × 10^?3 + 7.75 × 10^?3 C). Under the optimized experimental conditions, proposed method is validated as per the International Conference on Harmonisation guidelines. The limits of detection and quantitation for the proposed method are 0.775 and 2.348 μg mL^?1, respectively. The proposed method has been successfully applied to the determination of piroxicam in commercial dosage forms. The results are compared with the reference El‐Ries et al. spectrophotometric method.     

Subsecond FFT‐adsorptive Voltammetric Technique as a Novel Method for Subnano Level Monitoring of Piroxicam in its Tablets and Bulk Form at Au Microelectrode in Flowing Solutions

Abstract

In this work a novel method for the determination of piroxicam in flow‐injection systems has been developed. A system using fast Fourier transform continuous cyclic voltammetry (FFTCV), at a gold microelectrode in flowing solution, was used for determining piroxicam in its pharmaceutical formulations. The developed technique is very simple, precise, accurate, time saving, and economical, compared to all of the previously reported methods. The effects of various parameters on the sensitivity of the method were investigated. The best performance was obtained with a pH value of 2, scan rate value of 40 V/s, accumulation potential of (400) mV, and accumulation time of 0.4 s. The proposed method has some advantages over other reported methods, such as, no need for the removal of oxygen from the test solution, a picomolar detection limit, and finally that the method is fast enough for the determination of any such compound, in a wide variety of chromatographic methods. To obtain a sensitive determination, the integration range of currents was set for all the potential scan ranges, including oxidation and reduction of the Au surface electrode, while performing the measurements. The potential waveform, consisting of the potential steps for cleaning, accumulation, and potential ramp of analyte, was applied on an Au disk microelectrode (with a 12.5 µm in radius) in a continuous way. The method was linear over the concentration range of 1.5–364000 pg/ml (r=0.998) with a limit of detection and quantitation of 0.33 and 1.5 pg/ml, respectively. The method has the requisite accuracy, sensitivity, precision, and selectivity to assay piroxicam in tablets.