Green and cost-effective voltammetric assay for spiramycin based on activated glassy carbon electrode and its applications to urine and milk samples.

A simple, cost-effective, and efficient differential pulse voltammetric (DPV) assay for monitoring spiramycin adipate (SPA) in its dosage forms, urine, and milk samples at an activated glassy carbon electrode (GCE) was developed. GCE was electrochemically activated by anodization at a high positive voltage (2.5 V). The activated glassy carbon electrode (AGCE) was surface characterized, optimized, and utilized for the electrochemical assay of SPA. The electrochemical behavior of the AGCEs was investigated using cyclic voltammetry (CV) which shows a remarkable increase in the anodic peak of SPA in comparison with GCE. This behavior reflects a remarkable increase in the electrocatalytic oxidation of SPA at AGCE. The impacts of various parameters such as scan rate, accumulation time, and pH were investigated. The analytical performance of the activated glassy carbon electrodes was studied utilizing DPV. Under optimum conditions, the oxidation peak current exhibited two linear ranges of 80 nm to 0.8 µM and 0.85-300 µM with a lower limit of detection (LOD) of 20 nM. The developed assay exhibited high sensitivity, excellent repeatability, and good selectivity. Additionally, the developed SPA-sensitive modified GCE was successfully applied for SPA assay in its pharmaceutical dosage form and diluted biological fluids as well, with satisfactory recovery results which correlated well with the results obtained using spectrophotometry.

Evaluation of mesoporous borosilicate glass-ceramic composites as frits in reference electrodes.

The development of new mesoporous frits for reference electrodes to overcome the limitations of cross-contamination and screening effect is essential for many electrochemical measurements. Available frit-based reference electrodes (e.g., mesoporous, microporous) still suffer from cross-contamination and/or errors in electrochemical measurements. In this work, a mesoporous glass-ceramic composite is prepared to mitigate such limitations. Mesoporous glass-ceramic frits were prepared from low-cost materials (i.e., borosilicate and kaolin) at relatively low temperatures (750-850 °C). The prepared glass-ceramic frits were characterized using scanning electron microscopy (SEM), impedance measurements, and nitrogen sorption isotherms. The developed mesoporous glass-ceramic composites are characterized by a high chemical resistance against corrosive materials and a low thermal expansion. Reference electrodes constructed with the developed mesoporous glass-ceramic frits exhibited a low flow rate of 0.002 ± 0.001 to 0.41 ± 0.06 µL h-1 and high potential stability as well as very small potential drift of -2.4 ± 0.2 to -4.9 ± 0.2 µV h-1. Mesoporous glass-ceramic based reference electrodes exhibited average potential variations of 13 ± 3 mV over the concentration range of 1 mM to 0.1 M KCl. This indicates that mesoporous glass-ceramic frit-based reference electrodes exhibited a much lower flow rate compared to available microporous frit-based reference electrodes. Moreover, the developed mesoporous ceramic-based reference electrodes exhibited a 4-15-fold improvement in potential variations and a large improvement in potential stability in comparison with the reported mesoporous-frit-based reference electrodes.

Activated Glassy Carbon Electrode as an Electrochemical Sensing Platform for the Determination of 4-Nitrophenol and Dopamine in Real Samples.

Glassy carbon electrode (GCE) was electrochemically activated using a repetitive cyclic voltammetric technique to develop an activated glassy carbon electrode (AGCE). The developed AGCE was optimized and utilized for the electrochemical assay of 4-nitrophenol (4-NP) and dopamine (DA). Cyclic voltammetry (CV) was employed to investigate the electrochemical behavior of the AGCE. Compared to the bare GCE, the developed AGCE exhibits a significant increase in redox peak currents of 4-NP and DA, which indicates that the AGCE significantly improves the electrocatalytic reduction of 4-NP and oxidation of DA. The electrochemical signature of the activation process could be directly associated with the formation of oxygen-containing surface functional groups (OxSFGs), which are the main reason for the improved electron transfer ability and the enhancement of the electrocatalytic activity of the AGCE. The effects of various parameters on the voltammetric responses of the AGCE toward 4-NP and DA were studied and optimized, including the pH, scan rate, and accumulation time. Differential pulse voltammetry (DPV) was also utilized to investigate the analytical performance of the AGCE sensing platform. The optimized AGCE exhibited linear responses over the concentration ranges of 0.04-65 µM and 65-370 µM toward 4-NP with a lower limit of detection (LOD) of 0.02 µM (S/N = 3). Additionally, the AGCE exhibited a linear responses over the concentration ranges of 0.02-1.0 and 1.0-100 µM toward DA with a lower limit of detection (LOD) of 0.01 µM (S/N = 3). Moreover, the developed AGCE-based 4-NP and DA sensors are distinguished by their high sensitivity, excellent selectivity, and repeatability. The developed sensors were successfully applied for the determination of 4-NP and DA in real samples with satisfactory recovery results.

Glassy Carbon Electrode Electromodification in the Presence of Organic Monomers: Electropolymerization versus Activation.

Several reports in the literature deal with the modification of glassy carbon electrode (GCE) surface via electropolymerization of some organic monomers, particularly p-aminobenzenesulfonic acid (p-ABSA) and l-cysteine using intensive oxidative conditions, and attributed the improved electrocatalytic activities toward various analytes to the formation of the electropolymerized layer. What is the real cause for this improvement in electrocatalytic activity? Is it because of the electrochemical activation process of GCE or electropolymerization? Combining a set of surface and electrochemical characterization techniques, we first showed that the electrochemical peaks previously assigned in many reports to electropolymerization processes at the surface of GCE correspond to electrochemical activation of the GCE surface. We further demonstrated that the anodization of GCE at high voltage causes activation of its surface and the formation of surface functional groups (SFGs). In fact, those SFGs are found to be the main reason for the enhancement in electrocatalytic activity of the activated GCE (AGCE). The surface features of the modified electrodes were characterized by Raman spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The electrochemical behavior was investigated using cyclic voltammetry (CV). The analytical performance of AGCE toward dopamine (DA) was assessed using differential pulse voltammetry (DPV). As compared to the previously reported dopamine electrochemical sensors assuming such electropolymerization processes, the AGCE showed analytical performance practically similar to that of these sensors. This further confirms that the enhancement in electrocatalytic activity is due to the electrochemical activation of the GCE surface.

Simple spectrofluorimetric methods for determination of veterinary antibiotic drug (apramycin sulfate) in pharmaceutical preparations and milk samples.

This work describes the development of highly sensitive as well as simple two spectrofluorimetric methods for the determination of apramycin sulfate. The first method depends on measuring the inherent native fluorescence of the aqueous neutral solution of the drug at 388 nm (λex 335 nm). While the second method mainly based on enhancing the native fluorescence intensity of the drug using sodium dodecyl sulfate (SDS) micellar media by about 4 fold enhancement. The fluorescence intensity - concentration relationship for the two methods was found rectilinear over the concentration range 1.0-100.0 and 0.1-20.0 µg/mL for the first and second method respectively. The limit of detection for method I and II were 0.05 and 0.02 µg/mL respectively. The proposed methods can be effectively connected for the assurance of the medication without impedances from common normal excipients. Furthermore, the two methods were high sensitive enough for the assurance of the drug in spiked milk samples with high percentage recoveries.

Correlating the potentiometric selectivity of cyclosporin-based electrodes with binding patterns obtained from electrospray ionization-mass spectrometry.

Electrospray ionization mass spectrometry ESI-MS is a powerful technique for the characterization of macromolecules and their noncovalent binding with guest ions. We herein evaluate the feasibility of using ESI-MS as a screening tool for predicting potentiometric selectivities of ionophores. Ion-selective electrodes based on the cyclic peptide, cyclosporin A, were developed, and their potentiometric selectivity pattern was evaluated. Optimized electrodes demonstrated near-Nernstian slopes with micromolar detection limits toward calcium. ESI-MS and ESI-MS/MS were employed to determine the relative association strengths of cyclosporin A with various cations. The observed MS intensities of ion-ionophore complexes correlate favorably with the potentiometric selectivity pattern that was demonstrated by cyclosporin-based electrodes. This correlation was found to hold true for other established ionophores, such as valinomycin and benzo-18-crown-6. Taken together, these experiments demonstrate that mass spectrometry could be used to predict the selectivity patterns of new ionophores for potentiometric and optical ion sensors. Further, this approach could be useful in screening mixtures or libraries of newly-synthesized compounds to identify selective ionophores.

Enhancing biocompatibility of some cation selective electrodes using heparin modified bacterial cellulose.

Bacterial cellulose (BC) and heparin-modified bacterial cellulose (HBC) were utilized to enhance the biocompatibility of highly thrombogenic PVC-based potassium and calcium membrane electrodes. Three types of membrane electrodes were prepared: (1) conventional PVC electrode (control), (2) PVC-based electrode sandwiched with bacterial cellulose membrane (BC-PVC), and (3) PVC-based electrode sandwiched with heparin-modified bacterial cellulose membrane (HBC-PVC). The potentiometric response characteristics of the modified potassium and calcium membrane electrodes (BC-PVC and HBC-PVC) were compared with those of the control PVC-based potassium and calcium selective electrode, respectively. Response characteristics of the modified membrane electrodes were comparable to the control PVC membrane electrode. The platelet adhesion investigations indicated that (BC) and (HBC) layers are less thrombogenic compared to PVC. Therefore, use of BC or HBC would enable the enhancement of the biocompatibility of PVC-based membrane electrodes for potassium and calcium while practically maintaining the overall electrochemical performance of the PVC sensing film.

Cyanex based uranyl sensitive polymeric membrane electrodes.

Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO2(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO2(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods.

Reduction of thrombogenicity of PVC-based sodium selective membrane electrodes using heparin-modified chitosan.

Heparin-modified chitosan (H-chitosan) membrane was utilized to enhance biocompatibility of sodium selective membrane electrode based on the highly thrombogenic polyvinyl chloride (PVC). Sodium ion sensing film was prepared using PVC, sodium ionophore-X, potassium tetrakis(chlorophenyl)-borate, and o-nitrophenyloctylether. The PVC-based sensing film was sandwiched to chitosan or H-chitosan to prevent platelet adhesion on the surface of PVC. Potentiometric response characteristics of PVC-chitosan and PVC-H-chitosan membrane electrodes were found to be comparable to that of a control PVC based sodium-selective electrode. This indicates that chitosan and H-chitosan layers do not alter the response behaviour of the PVC-based sensing film. Biocompatibility of H-chitosan was confirmed by in vitro platelet adhesion study. The platelet adhesion investigations indicated that H-chitosan film is less thrombogenic compared to PVC, which could result in enhancement of biocompatibility of sodium selective membrane electrodes based on PVC, while maintaining the overall electrochemical performance of the PVC-based sensing film.

Synthesis, spectroscopic, photoluminescence properties and biological evaluation of novel Zn(II) and Al(III) complexes of NOON tetradentate Schiff bases.

Novel mononuclear Zn(II) and Al(III) complexes were synthesized from the reactions of Zn(OAc)(2).2H(2)O and anhydrous AlCl(3) with neutral N2O2 donor tetradentate Schiff bases; N,N'bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H(2)L(1)) and N,N'bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H(2)L(2)). The new complexes were fully characterized by using micro analyses (CHN), FT-IR, (1)H NMR, UV-Vis spectra and thermal analysis. The analytical data have been showed that, the stoichiometry of the complexes is 1:1. Spectroscopic data suggested tetrahedral and square pyramidal geometries for Zn(II) and Al(III) complexes, respectively. The synthesized Zn(II), and Al(III) complexes exhibited intense fluorescence emission in the visible region upon UV-excitation in methylene chloride solution at ambient temperature. This high fluorescence emission was assigned to the strong coordination of the ligands to the small and the highly charged Zn(II) and Al(III) ions. Such strong coordination seems to extend the π-conjugation of the complexes. Thermal analysis measurements indicated that the complexes have good thermal stability. As a potential application the biological activity (e.g., antimicrobial action) of the prepared ligands and complexes was assessed by in-vitro testing of their effect on the growth of various strains of bacteria and fungi.

A novel poly(vinyl chloride) matrix membrane sensor for batch and flow-injection determinations of thiocyanate, cyanide and some metal ions.

A poly(vinyl chloride) matrix membrane sensor for the selective determination of thiocyanate has been developed based on the use of copper(II)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex (Cu-PADAP) as a novel charged carrier, and o-nitrophenyloctyl ether (o-NPOE) as a solvent mediator. The sensor displays a significantly enhanced response towards SCN(-) ions over the concentration range 7.0 x 10(-6) to 1.0 x 10(-2) mol L(-1) with a detection limit of 5.6 x 10(-6) mol L(-1) and a calibration slope of -57.5 +/- 0.5 mV decade(-1). The sensor exhibits a long life-span, long-term stability, high reproducibility, and a fast response time. The selectivity coefficients of some anions were calculated using the separate solutions method, and found to be in the following order: SCN(-) > ClO(4)(-) > I(-) > Sal(-) > NO(2)(-) > Br(-) > NO(3)(-) = CH(3)COO(-) > Cl(-) > SO(4)(2-) = PO(4)(3-). The effects of the pH and ionic membrane additives (e.g. tridodecylmethylammonium chloride, TDMAC and potassium tetrakis[bis(3,5-trifluoromethyl)phenyl] borate, KTFPB) were examined. The sensor was used for the determination of SCN(-) ions in saliva and urine samples collected from some smoker and non-smoker donors. The developed sensor was also applied to determine the cyanide content in electroplating waste water samples after its conversion into thiocyanate. The application of the sensor to monitor the potentiometric titration of Ag(+) and Hg(2+) using SCN(-) resulted in sharp inflection breaks at the equivalent points. The data obtained using the proposed sensor correlate very well with results collected using the standard methods of thiocyanate, cyanide and metal analysis.

Potentiometric anion selectivity of polymer-membrane electrodes based on cobalt, chromium, and aluminum salens.

Metallo-salens of cobalt(II) (Co-Sal), chromium(III) (Cr-Sal), and aluminum(III) (Al-Sal) are used as the active ionophores within plasticized poly(vinyl chloride) membranes. It is shown that central metal-ion plays a critical role in directing the ionophore selectivity. Polymer-membrane electrodes based on Co-Sal, Cr-Sal, and Al-Sal are demonstrated to exhibit enhanced responses and selectivity toward nitrite/thiocyanate, thiocyanate, and fluoride anions, respectively. The improved anion selectivity of the three ionophore systems is shown to deviate significantly from the classical Hofmeister pattern that is based only on ion lipophilicity. For example, optimized membrane electrodes for nitrite ion based on Co-Sal exhibit logK(Nitrite,Anion)(pot) values of -5.22, -4.66, -4.48, -2.5 towards bromide, perchlorate, nitrate, and iodide anions, respectively. Optimized membrane electrodes based on Co-Sal and Cr-Sal show near-Nernstian responses towards nitrite (-57.9+/-0.9 mV/decade) and thiocyanate (-56.9+/-0.8 mV/decade), respectively, with fast response and recovery times. In contrast, Al-Sal based membrane electrodes respond to fluoride ion in a super-Nernstian (-70+/-3 mV/decade) and nearly an irreversible mode. The operative response mechanism of Co-Sal, Cr-Sal, and Al-Sal membrane electrodes is examined using the effect of added ionic sites on the potentiometric response characteristics. It is demonstrated that addition of lipophilic anionic sites to membrane electrodes based on the utilized metallo-salens enhances the selectivity towards the primary ion, while addition of cationic sites resulted in Hofmeister selectivity patterns suggesting that the operative response mechanism is of the charged carrier type. Electron spin resonance (ESR) data indicates that Co(II) metal-ion center of Co-Sal ionophore undergoes oxidation to Co(III). This process leads to formation of a charged anion-carrier that is consistent with the response behavior obtained for Co-Sal based membrane electrodes.

Fluoride-selective optical sensor based on aluminum(III)-octaethylporphyrin in thin polymeric film: further characterization and practical application.

More detailed analytical studies of a new fluoride-selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4',5'-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-visible spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band lambda(max) of the porphyrin and a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 microM-1.6 mM. Optical selectivity coefficients of <10(-6) for common anions (e.g., sulfate, chloride, nitrate, etc.) and <10(-4) for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3-based fluoride ion-selective electrode method.

Highly selective optical fluoride ion sensor with submicromolar detection limit based on aluminum(III) octaethylporphyrin in thin polymeric film.

A highly selective, sensitive, and reversible fluoride optical sensing film based on aluminum(III)octaethylporphyrin as a fluoride ionophore and a lipophilic pH indicator as the optical transducer is described. The fluoride optical sensing films exhibit a submicromolar detection limit and high discrimination for fluoride over several lipophilic anions such as nitrate, perchlorate, and thiocyanate.

Response behavior of sodium-selective electrodes modified by surface attachment of the anticoagulant polysaccharides heparin and chondroitin sulfate.

Two different polysaccharides with anticoagulant activities, heparin and chondroitin sulfate, were used to modify the surface of sodium-selective electrodes based on asymmetric cellulose triacetate (CTA) membranes. The membranes were formulated with sodium ionophore X, anionic additive, and o-nitrophenyl octyl ether. The response behavior of the surface-modified sodium electrodes was compared with that of control CTA, as well as poly(vinyl chloride) (PVC)-based sodium-selective electrodes. It was found that the selectivity coefficients obtained with the surface modified CTA membrane electrodes were slightly higher than those of the control, but in the case of heparin-modified electrodes they still met the requirements for analysis of sodium in physiological fluids within an error of <1%; the corresponding error for chondroitin sulfate-modified electrodes was also <1% except for the case of potassium ion in which the error was 1.3%. Likewise, it was found that other response characteristics, such as detection limit, linear range, slope of the response plot, selectivity pattern, and response time were comparable in both the control and the polysaccharide-modified electrodes. Therefore, the surface modification does not significantly alter the response behavior of the sensors.

Fluorescent ion-selective optode membranes incorporated onto a centrifugal microfluidics platform.

The development of an integrated analysis system for small ions based on ion-selective optodes and centrifugal microfluidics is reported. The performance of this system was evaluated through five-point calibration plots for two types of optode membranes, one being cation-selective and the other anion-selective, which were incorporated into a microfluidics platform on which fluid motion is induced via angular rotation. Additionally, the application of the microfluidic platform to ion analysis is studied via a two-point calibration protocol used to quantify an unknown sample. Calibrant solutions are delivered from reservoirs fabricated onto the platform to a measuring area that contains the optode membrane, with a change in membrane fluorescence being monitored. This work demonstrates the first instance of a microfluidic-based analysis system with detection based on ion-selective optode membranes monitored with fluorescence transduction. Furthermore, in addition to employing a standard excitation source where a fiber-optic probe is coupled to a tungsten-halogen lamp, laser diodes such as those employed in portable CD/DVD players were studied as excitation sources to enhance the observed fluorescence signals.

Improving the blood compatibility of ion-selective electrodes by employing poly(MPC-co-BMA), a copolymer containing phosphorylcholine, as a membrane coating.

The hydrogelpoly(2-methacryloyloxyethylphosphorylcholine-co-butyl methacrylate), or poly(MPC-co-BMA), was used as a coating for polyurethane- and poly(vinyl chloride)-based membranes to develop ion-selective electrodes (ISEs) with enhanced blood compatibility. Adverse interactions of poly(MPC-co-BMA) with blood were diminished due to the phosphorylcholine functionalities of the hydrogel, which mimic the phospholipid polar groups present on the surface of many cell membranes. As demonstrated by immunostaining, hydrogel-coated PVC membranes soaked in platelet-rich plasma showed less adhesion and activation of platelets than uncoated PVC membranes, indicating an improvement in biocompatibility owing to the hydrogel. Furthermore, little differences in the potentiometric response characteristics, e.g., slope, detection limit, and selectivity, of ISEs employing uncoated and coated membranes were observed.