Potentiometric determination of antihistaminic diphenhydramine hydrochloride in pharmaceutical preparations and biological fluids using screen-printed electrode

The performance characteristic of sensitive screen-printed (SPE) and carbon paste (CPE) electrodes was investigated for the determination of diphenhydramine hydrochloride (DPH) drug in pure, pharmaceutical preparations and biological fluids. Different experimental conditions namely types of materials used to prepare the working electrode (plasticizer), titrant, pH, temperature and life time were studied. Under these conditions, the SPE shows the best performance than CPE with respect to total potential change and potential break at the end point. The SPE and CPE exhibit suitable response to DPH in a concentration range of 1.0.10^{− 2} to 1.0.10^{− 6} mol/L with a limit of detection 9.70.10^{− 7} and 9.80.10^{− 7} mol/L, respectively. The slope of the system was 55.2 ± 1.0 and 54.7 ± 1.0 mV/decade over pH range 3.0–8.0 and 3–7 for SPE and CPE, respectively. Selectivity coefficients for DPH relative to a numbers of potential interfering substances were investigated. The SPE and CPE show a fast response time of 10 and 16 s and were used over a period of 2 months with a good reproducibility. The sensors were applied successfully to determine DPH in pharmaceutical preparations and biological fluids. The results are compared with the official method.     

Association interaction and voltammetric determination of 1-aminopyrene and 1-hydroxypyrene at cyclodextrin and DNA based electrochemical sensors

The aim of this work was voltammetric determination of 1-aminopyrene and 1-hydroxypyrene using carbon paste electrodes modified with cyclodextrin derivatives and double stranded deoxyribonucleic acid (dsDNA). The detection schemes based on a preconcentration and differential pulse voltammetric (DPV) determination at beta-cyclodextrin and gamma-cyclodextrin modified carbon paste electrode (beta-CD/CPE, gamma-CD/CPE), neutral beta-cyclodextrin polymer and carboxymethyl-beta-cyclodextrin polymer modified screen-printed electrode (beta-CDP/SPE, beta-CDPA/SPE) and dsDNA modified screen-printed electrode (DNA/SPE) are proposed for the trace determination of studied analytes within the concentration range from 2 x 10(-8) to 4 x 10(-7) mol dm(-3) and from 2 x 10(-7) to 4 x 10(-6) mol dm(-3) with the limits of quantification down to 10(-8) mol dm(-3). Depending on pH, 1-aminopyrene interacts with both surface attached CD and DNA by electrostatic bonds and supramolecular complexation while 1-hydroxypyrene associates with the CD hosts via complexation. The 1-aminopyrene interaction with dsDNA was confirmed by fluorimetric measurements in the solution phase using a competing DNA-TO-PRO-3 dye complex. In addition, the effect of temperature on this association was investigated using an electrically heated DNA-modified carbon paste electrode (DNA/CPE).     

MnO2-GOx碳糊电极对葡萄糖的电位响应

研制一种新型二氧化锰-酶修饰碳糊电极.应用直接电位法分别研究了磷酸盐底液的pH值、不同种类的粘合剂、二氧化锰修饰含量以及温度等各因素对该修饰电极测定H2O2和葡萄糖电位响应的影响.在优化实验条件(35℃,磷酸缓冲底液pH=7)下,葡萄糖检测的线性范围为2.0×10-5~5.2×10-3mol.L-1,灵敏度:36.12~34.62 mV/pG lucose,检测限:3.3×10-6mol.L-1.该电极具有良好的选择性、灵敏度、稳定性和重复性,大多数常见阴阳离子、甘露醇、丙三醇和脲不干扰测定.     

Septonex-tetraphenylborate screen-printed ion selective electrode for the potentiometric determination of Septonex in pharmaceutical preparations

A screen-printed electrode (SPE) was fabricated for the determination of 1-(ethoxycarbonyl)pentadecyltrimethylammonium bromide (Septonex) based on the use of Septonex-tetraphenylborate as the electroactive substance, and o-nitrophenyloctylether (o-NPOE) as the plasticizing agent. The electrode passes a near-Nernstian cationic slope of 59.33 ± 0.85 mV from activity between pH values of 2 to 9 with a lower detection limit of 9×10(-7) M and response time of about 5 s and exhibits an adequate shelf-life of 6 months. The method was applied for the determination of Septonex in pharmaceutical preparations. A percentage recovery of 99.88% was obtained with RSD=1.24%. The electrode was successfully applied in the determination of Septonex in laboratory-prepared samples by direct potentiometric, calibration curve and standard addition methods. Potentiometric titration of Septonex with sodium tetraphenylborate and phosphotungstic acid as a titrant was monitored with the modified screen-printed electrode as an end-point indicator electrode. Selectivity coefficients for Septonex relative to a number of potential interfering substances were determined. The sensor was highly selective for Septonex over a large number of compounds. Selectivity coefficient data for some common ions show negligible interference; however, cetyltrimethylammonium bromide and iodide ions interfere significantly. The analytical usefulness of the proposed electrode was evaluated by its application in the determination of Septonex in laboratory-prepared pharmaceutical samples with satisfactory results. The results obtained with the fabricated sensor are comparable with those obtained by the British Pharmacopeia method.     

Flow injection potentiometric determination of pancuronium bromide in pharmaceutical preparation and urine samples using modified carbon paste electrodes

Carbon paste electrodes for pancuronium bromide was prepared based on ion association complexes of pancuronium bromide with sodium tetraphenylborate (NaTPB) or ammonium reineckate using dibutyl phthalate as solvent mediator and tetradodecylammonium tetrakis-(4-chlorophenyl)borate (ETH 500) as lipophilic additive. The sensors showed a near-Nernstian slope of 28.1 mV concentration decade(-1) at 25°C within the concentration range 6.31×10(-6)-1.00×10(-2) M in case of pancuronium-tetraphenylborate electrode and 26.6 mV concentration decade(-1) in the concentration range 5.66×10(-5)-1.00×10(-2) M in case of pancuronium-reineckate electrode. The sensors were successfully applied for the potentiometric determination of pancuronium bromide in pharmaceutical preparation and biological fluids in batch and flow injection conditions.     

Ionic Liquids Modify the Performance of Carbon Based Potentiometric Sensors

A new type of potentiometric sensor based on a recently constructed carbon ionic liquid electrode (CILE) is described. Two kinds of ionic liquids, i.e., N‐octylpyridinium hexafluorophosphate (OPFP) and 1‐butyl‐3‐methylimidazoluim hexafluorophosphate (BMFP) were tested as binder for construction of the carbon composite electrode. The characteristics of these electrodes as potentiometric sensors were evaluated and compared with those of the traditional carbon paste electrode (CPE). The results indicate that potentiometric sensors constructed with ionic liquid show an increase in performance in terms of Nernstian slope, selectivity, response time, and response stability compared to CPE.     

石墨烯/十二烷基硫酸钠复合物修饰碳糊电极测定氯霉素

以液体石蜡和硅油为混合粘合剂,与石墨粉混合制备了碳糊电极基底电极,将石墨烯/十二烷基硫酸钠复合物修饰在基底碳糊电极上,得到了基于石墨烯复合物的新型修饰碳糊电极。应用扫描电镜和循环伏安法分别研究了该电极的表面特性和电化学性质,结果表明,石墨烯和十二烷基硫酸钠修饰的碳糊电极增大了比表面积,有利于电子传递。在pH 3.0的HAc-NaAc缓冲溶液中,该修饰碳糊电极对氯霉素具有良好的电化学响应,氧化峰电位为0.194 V,氧化峰电流是基底碳糊电极的10倍。在最优实验条件下,该氧化峰电流与氯霉素的浓度在1.0×10~(-8)~5.0×10~(-4)mol/L范围内呈良好的线性关系,检出限为5.0×10~(-9)mol/L。该方法简便,重现性及选择性好,用于测定氯霉素滴眼液和虾中氯霉素残留,结果满意。     

基于表面活性剂增敏有序介孔SiO2修饰碳糊电极测定L-色氨酸

利用水热法合成得到有序介孔二氧化硅( OMS),采用X射线衍射、N2吸附-脱附、透射电镜等技术对其进行了表征。制备OMS修饰碳糊电极( OMS/CPE),采用循环伏安和交流阻抗技术考察了修饰电极的电化学性能,发现与裸碳糊电极(CPE)相比,OMS/CPE具有更大的电活性面积和更快的电子传导速率。研究了L-色氨酸(L-Trp)在表面活性剂十二烷基磺酸钠(SDS)存在下,在OMS/CPE上的电化学行为和动力学性质,结果表明,OMS和SDS具有良好的协同作用,能明显增加L-Trp的响应信号; SDS存在下,L-Trp在修饰电极上的电化学氧化是2电子和2质子参加的不可逆过程,电极过程受吸附控制。优化了表面活性剂浓度、富集时间、富集电位、介质 pH 值等测定参数,在最优条件下, L-Trp 氧化峰电流与其浓度在8.0×10-8~4.0×10-6 mol/L范围内呈良好线性关系,检出限为7.0×10-8 mol/L(S/N=3)。本方法用于氨基酸口服液样品的加标回收检测,回收率为99.6％~102.6％。     

Preparation and characterization of in situ carbon paste and screen-printed potentiometric sensors for determination of econazole nitrate: surface analysis using SEM and EDX

The construction and performance characteristics of new sensitive and selective in situ carbon paste (ICPE) and screen-printed (ISPE) potentiometric sensors modified with ion-pairing agents such as phosphotungstic acid, sodium tetraphenylborate, phosphomolybdic acid and ammonium reineckate for determination of econazole nitrate (ECN) have been developed. The reaction mechanism between ECN and ion-pairing agents at the electrode surface was studied through scanning electron microscope and energy-dispersive X-ray analysis. The electrodes under investigation showed potentiometric response for ECN in the concentration range from 1.0 × 10^?6 to 5.0 × 10^?3 mol L^?1 and from 1.0 × 10^?6 to 1.0 × 10^?2 mol L^?1 for ISPE (electrode I) and ICPE (electrode II) potentiometric sensors, respectively, at 25 °C. The electrode response was pH independent in the range 2.5–7.5 and 2.5–6.5 for electrodes I and II, respectively. These sensors have Nernstian slope values of 59.4 ± 0.2 and 59.10 ± 0.2 mV decade^?1 with detection limit of 1.0 × 10^?6 mol L^?1 for electrodes I and II, respectively. The electrodes showed fast response time of 4 and 9 s for electrodes I and II, respectively. The ISPE (electrode I) showed lifetime of 28 days, and this was considered as advantage over ICPE (electrode II). Selectivity for ECN with respect to a number of interfering materials was also investigated. The proposed electrodes were applied for determination of ECN in pure and pharmaceutical formulation using calibration, potentiometric titration and standard addition methods. The results showed good agreement with those obtained using official method. The t and F values indicated no significant difference between the suggested and reported methods. Method validation parameters were optimized according to ICH recommendations.     

Comparative study between two fabricated potentiometric sensors to enhance selectivity towards ferrous ions

Electroanalytical methods are highly selective for measuring electrical quantities including the charge, potential and current with their relation to chemical parameters. They are widely applied in various fields such as biochemical analysis, industrial quality control and environmental monitoring. They have many advantages over other techniques in that they are not time consuming and are specific for certain oxidation states of certain elements which give these techniques high selectivity and sensitivity features. This paper is based on two parts: the first part describes the fabrication of screen‐printed electrodes (SPEs) modified with methyl red as electroactive material, while second part describes the preparation and characterization of Fe(II)–methyl red complex using various spectroscopic tools, the complex being used for the construction of carbon paste electrodes (CPEs). The two proposed electrodes were successfully applied for the determination of Fe(II) in water and pharmaceutical (pharovit) samples. The electrodes under investigation show potentiometric response for Fe(II) in the concentration range 8.0 × 10^?7–1.0 × 10^?2 and 5.0 × 10^?7–1.0 × 10^?2 M at 25°C for SPE and CPE, respectively, and the electrode response is independent of pH in the range 1.5–7.0. These sensors show Nernstian slopes of 29.1 ± 0.2 and 29.7 ± 0.16 mV decade^?1 with detection limit values of 8.0 × 10^?7 and 5.0 × 10^?7 M for SPE and CPE, respectively. These electrodes show fast response time of 6 and 4 s and exhibit a lifetime of 100 and 30 days for SPE and CPE, respectively. The mechanism of chemical reaction between modifier and Fe(II) on the SPE surface was studied using infrared spectra, scanning electron microscopy and energy‐dispersive X‐ray analysis. The proposed potentiometric method was validated according to the IUPAC recommendations. The results obtained using the proposed sensors were comparable with those obtained with inductively coupled plasma analysis.     

Potentiometric determination of cetylpyridinium chloride using a new type of screen-printed ion selective electrodes

A new type of screen-printed ion-selective electrode for the determination of cetylpyridinium chloride (CPC) is presented. These new electrodes involve in situ, modified and unmodified screen-printed ion-selective electrodes for the determination of CPC. The screen-printed electrodes (SPEs) show a stable, near-Nernstian response for 1 × 10⁻² to 1 × 10⁻⁶ M CPC at 25 °C over the pH range 2-8 with cationic slope 60.66 ± 1.10. The lower detection limit is found to be 8 × 10⁻⁷ M and response time of about 3 s and exhibit adequate shelf-life (6 months). The fabricated electrodes can be also successfully used in the potentiometric titration of CPC with sodium tetraphenylborate (NaTPB). The analytical performances of the SPEs are compared with those for carbon paste electrode (CPE) and polyvinyl chloride (PVC) electrodes. The method is applied for pharmaceutical preparations with a percentage recovery of 99.60% and R.S.D. = 0.53. The frequently used CPC of analytical and technical grade as well as different water samples has been successfully titrated and the results obtained agreed with those obtained with commercial electrode and standard two-phase titration method. The sensitivity of the proposed method is comparable with the official method and ability of field measurements.     

Preparation of tetraheptylammonium iodide-iodine graphite-multiwall carbon nanotube paste electrode: electrocatalytic determination of ascorbic acid in pharmaceuticals and foods

The present work describes the construction of a new modified graphite-multiwall carbon nanotube paste electrode by casting the appropriate mixture of tetraheptylammonium iodide-iodine as a new modifier. The modified paste electrode was used for the determination of ascorbic acid (AA) in a phosphate buffer solution (pH 2.0). When compared to activated carbon, a graphite and multiwall carbon nanotube paste electrode containing a new modifier, the proposed modified paste electrode not only shifted the oxidation potential of AA towards a less-positive potential but also enhanced its oxidation peak current. Further, the oxidation of AA was highly stable at the modified paste electrode. The optimum analytical conditions were sought. The current response of AA increases linearly while increasing its concentration from 5.6 × 10(-5) to 1.2 × 10(-2) M with a correlation coefficient of 0.9991; the detection limit (3σ) was found to be of 3.6 × 10(-5) M. The present modified paste electrode was also successfully used for the determination of AA in the presence of common interference compounds. The present modified electrode was successfully demonstrated towards the determination of AA in pharmaceutical and food samples.     

碳糊电极阳极吸附伏安法测定卡托普利

在0.40 mol/L的HAc-NaAc(pH=4.8)缓冲溶液中,卡托普利(Captopril,CPT)在碳糊电极(CPE)上有一灵敏的吸附氧化峰,峰电位为0.23 V(vs.SCE)。该氧化峰的二阶导数峰电流与卡托普利的浓度在2.0×10-8～1.0×10-6mol/L(富集90 s)范围内呈良好的线性关系,相关系数为0.9966,检出限为8.0×10-9mol/L,并成功应用于卡托普利片含量的测定。探讨了卡托普利在碳糊电极上的伏安性质和电极反应机理。     

Development of new potentiometric sensors for the determination of proguanil hydrochloride in serum and urine

Potentiometric electrodes were developed for the rapid determination of proguanil hydrochloride in pure samples, pharmaceutical preparations and spiked serum and urine samples using PVC membrane,screen printed(SPE), coated wired(CWE), carbon paste(CPE) and modified carbon paste(MCPE)electrodes based on the ion-exchanger of proguanil with phosphotungestic acid(Pr-PT) as a chemical modifier. The prepared electrodes showed Nernestian slopes of 59.7, 58.1, 58.5, 58.5 and 57.0 for the PVC,SPE, CWE, CPE and MCPE for the proguanil ions in a wide concentration range of 1.0 * 10~(-5)–1.0 * 10~(-2)mol L~(-1) at 25°C with detection limits of 7.94 * 10~(-6), 1.0 * 10~(-5), 1.0 * 10~(-6), 7.07 * 10~(-6) and 2.5 * 10~(-6) mol L~(-1), respectively. The prepared electrodes exhibited high proguanil selectivity in relation to several inorganic ions and sugars and they could be successfully utilized for its determination in pure solutions, pharmaceutical preparations and serum and urine samples using the direct potentiometry and standard addition methods with very good recovery values.     

Direct electrocatalvtic reduction of p-nitrophenol at room temperature ionic 1iquid modified electrode

Direct electrochemical reduction of p-nitrophenol(PNP)was investigated on a room temperature ionic liquid N-butylpyridinium hexafluorophosphate(BPPF6)modified carbon paste electrode(CILE).The cathodic peak potential was positively shifted and the peak currents were increased compared to that obtained on traditional carbon paste electrode(CPE).The results indicated that the presence of ionic liquid BPPF6 on the electrode surface showed excellent catalytic ability to the electrochemical reduction of PNP.The electrochemical behaviors of PNP on the CILE were investigated by cyclic voltammetry and the conditions such as the scan rate,the buffer pH,the substrate concentration were optimized.The electrochemical parameters were further calculated with the results of the electron transfer number(n),the charge-transfer coefficient(α)and the surface concentration(ΓΥ)as 1.76,0.37 and 2.47×10-9 mol/cm2,respectively,for the selected reducfive peak.The results indicated that PNP showed all irreversible adsorption-controlled electrode process on the CILE.     

Potentiometric Determination of Ciprofloxacin in Physiological Fluids Using Carbon Paste and Nano‐Composite Carbon Paste Electrodes

Nano‐composite carbon paste and simple carbon paste based potentiometric sensors were constructed and used for determination of ciprofloxacin at different pH values. Sensors were formulated utilizing graphite, suitable plasticizer, cirprofloxacinium‐phosphotungstate, as well as a highly lipophilic cation‐exchanger, sodium tetrakis(trifluoromethyl)phenyl borate. Effect of the incorporation of multi‐walled carbon nanotubes (MWCNTs) on the response characteristics of the prepared sensors was investigated. Results obtained were compared to that of a PVC‐sensor contains only the cation‐exchanger. In addition, the effect of solutions pH on the response characteristics was also studied; at pH 4.1, the slopes of bare carbon paste and MWCNTs‐based sensors were 55.7 and 66.6 mV/conc.decade in a concentration range of 10⁻²‐10⁻⁵ M with detection limits of 1.0x10⁻⁵ and 7.9x10⁻⁶ M, respectively. Although both sensors exhibited super‐Nernstian slopes at pH 2.0, the selectivity was improved compared to that measured at pH 4.1. Optimized sensors were successfully applied for the determination of ciprofloxacin in its pure form, pharmaceutical preparations, as well as spiked urine and serum samples, with high recovery.     

Potentiometric carbon paste sensors for lead(II) based on dithiodibenzoic and mercaptobenzoic acids.

Dithiodibenzoic (DTB) acid and mercaptobenzoic (MB) acid were studied to characterize their abilities as modifier agents for lead(II) sensors. For both sensors, the best results were obtained with modified carbon paste electrodes with 24.1% of ligand. The pH influence on the potentiometric response was studied. The selectivity coefficients for both modified electrodes were tabulated. A potentiometric sensor based on DTB acid exhibited a more sensitive and selective response to lead ions than an MB electrode. The limits of detection for the DTB and MB electrodes were very similar, 5.01 x 10(-8) M and 3.98 x 10(-8) M, respectively, for lead(II) activity. The DTB sensor was applied to lead(II) ion determination in real samples and as an indicator electrode in potentiometric titrations. Natural and commercial humic acids were titrated using the DTB electrode to estimate the stability constant between these organic compounds and the lead(II) ions with successful results.     

硫化物在乙酰二茂铁修饰碳糊电极上的电化学行为及电分析

研究了S2-在乙酰二茂铁(AFc)修饰碳糊电极(AFc/CPE)上的电催化氧化行为及其电化学分析方法。实验结果表明,AFc/CPE对S2-的电化学氧化具有良好的催化作用。用计时电流法(CA)测定了S2-在AFc/CPE上的电催化氧化反应速率常数k为(2.60±0.05)×105 L.mol-1.s-1。用方波伏安法(SWV)测得催化氧化峰电流与S2-的浓度在5.0×10-5～1.0×10-3 mol.L-1范围内呈良好线性关系,检出限(S/N=3)为1.3×10-7 mol.L-1,同时运用SWV法对造纸废水水样中S2-的含量进行了电化学定量测定。     

Sensitive voltammetric determination of tryptophan using an acetylene black paste electrode modified with a Schiff's base derivative of chitosan

Chitosan was modified by salicylaldehyde via Schiff's base reaction and the resulting product was modified on the surface of an acetylene black paste electrode (ABPE) by the drop-coating method. In 0.5 mol L(-1) acetate buffer (pH 4.2), a substantial increase in the anodic stripping peak current of tryptophan (Trp) (compared to conventional bare carbon paste electrode (CPE) and bare ABPE) is observed at the Schiff's base chitosan-modified electrode. The parameters influencing voltammetric determination of Trp have been optimized. Under the selected conditions, the linearity between the anodic peak currents and concentrations of Trp demonstrated a wide range of 6.0 × 10(-8) mol L(-1) to 2.0 × 10(-6) mol L(-1), 2.0 × 10(-6) mol L(-1) to 4.0 × 10(-5) mol L(-1) and 4.0 × 10(-5) mol L(-1) to 1.0 × 10(-4) mol L(-1), a low detection limit of 2.0 × 10(-9) mol L(-1) was obtained after a 60 s accumulation. In addition, the developed electrochemical sensor has been successfully applied for the determination of Trp in pharmaceutical and biological samples with satisfactory assay results.     

Chemical Modified Carbon Paste Electrode for Potentiometric Determination of Mo(VI) and its Application in Food Analysis and Agriculture Fertilizers

Since to the best of our knowledge, there is no potentiometric sensors based on carbon paste electrodes were proposed for the potentiometric determination of molybdenum(VI) ion. In this study, 2,2′-(propane-1,3-diylbis(oxy))dibenzoic acid (PBODBA) was synthesized and used as modifier in the fabrication of carbon paste electrode (CPE) for the quantification of molybdenum(VI). The developed electrodes I and II showed hexavalent Nernstian response of 9.80±0.05 and 9.90±0.08 mV decade⁻¹ over the concentration ranges of 1.0×10⁻⁷–1.0×10⁻³ and 1.0×10⁻⁸–1.0×10⁻³ mol L⁻¹, respectively. The electrodes showed good selectivity for Mo(VI). The modified electrodes were applied for the determination of Mo(VI) concentration in masscuaje agricultural fertilizer and spiked juice extractions containing several metals.