Enhanced electrochemical performance at screen-printed carbon electrodes by a new pretreating procedure

A new method for the pretreatment of screen-printed carbon electrodes (SPCEs) by two successive steps was proposed. In step one, fresh SPCEs were soaked into NaOH with high concentration (e.g. 3 M) for tens to hundreds of minutes, and the resulted electrodes were called as SPCE-I. In step two, SPCE-I were pre-anodized in low concentration of NaOH, which were designated as SPCE-II. The pretreated electrodes showed remarkable enhancement in heterogeneous electron transfer rate constant (k⁰) increased from 1.6 × 10⁻⁴ cm s⁻¹ at the fresh SPCE to 1.1 × 10⁻² cm s⁻¹ at SPCE-I for Fe(CN)₆^3−/4− couple. The peak to peak separation (ΔE_p) in cyclic voltammetry was reduced from ca. 480 to 84 mV, indicating that the electrochemical reversibility was greatly promoted, possibly due to the removing of polymers/oil binder from the electrode surfaces. The electroactive area (A_ea) of the electrode was increased by a factor of 17 after pretreatment in step one. Further analysis by the electrochemical impedance method showed that the electron transfer resistance (R_ct) decreased from ca. 2100 to 1.4 Ω. These pretreated electrodes, especially SPCE-II, exhibited excellent electrocatalytic behavior for the redox of dopamine (DA). Interference from ascorbic acid (AA) in the detection of DA at SPCE-II could be effectively eliminated due to the anodic peak separation (190 mV) between DA and AA, which resulted from the functionalization of the electrode surface in the pretreatment of step two. Under optimum conditions, current responses to DA were linearly changed in two concentration intervals, one was from 3.0 × 10⁻⁷ to 9.8 × 10⁻⁶ M, and the other was from 9.8 × 10⁻⁶ to 3.3 × 10⁻⁴ M. The detection limit for DA was down to 1.0 × 10⁻⁷ M.     

Enantioselective, potentiometric membrane electrodes based on cyclodextrins: application for the determination of R-baclofen in its pharmaceutical formulation

Two enantioselective, potentiometric membrane electrodes based on α- and γ-cyclodextrins were proposed for the assay of R-baclofen. The slopes of the electrodes were 59.50 and 51.00 mV/pR-baclofen for α- and γ-cyclodextrin-based electrodes, respectively. The detection limits of the proposed electrodes were 7 × 10⁻⁹ mol l⁻¹ for α-cyclodextrin-based electrode and 1.44 × 10⁻¹⁰ mol l⁻¹ for γ-cyclodextrin-based electrode. The enantioselectivity was determined over S-baclofen. The proposed electrodes can be employed for the assay of R-baclofen raw materials and its pharmaceutical formulation, Norton-Baclofen^® tablets. The surfaces of the electrodes are stable and easily renewable by polishing on alumina paper.     

A validated stripping voltammetric procedure for quantification of the anti-hypertensive and benign prostatic hyperplasia drug terazosin in tablets and human serum

The electrochemical behavior of terazosin at the hanging mercury drop electrode was studied in Britton-Robinson buffer (pH 2-11), acetate buffer (4.5-5.5), and in 0.1 M solution of each of sodium sulfate, sodium nitrate, sodium perchlorate and potassium chloride as supporting electrolytes. The square-wave adsorptive cathodic stripping voltammogram of terazosin exhibited a single well-defined two-electron irreversible cathodic peak which may be attributed to the reduction of CO double bond of the drug molecule. A fully validated, simple, high sensitive, precise and inexpensive square-wave adsorptive cathodic stripping voltammetric procedure was described for determination of terazosin in bulk form, tablets and human serum. A mean recovery for 1×10⁻⁸ M terazosin in bulk form, following preconcentration onto the hanging mercury drop electrode for 60 s at a −1.0 V (versus Ag/AgCl/KCl_s), of 99±0.7% (n=5) was obtained. Limits of detection (LOD) and quantitation (LOQ) of 1.5×10⁻¹¹ and 5×10⁻¹¹ M bulk terazosin were achieved, respectively. The proposed procedure was successfully applied to determination of the drug in its Itrin^® tablets and human serum samples. The achieved LOD and LOQ of the drug in human serum samples were 5.3×10⁻¹¹ and 1.8×10⁻¹⁰ M THD, respectively. The pharmacokinetic parameters of the drug in human plasma were estimated as: C_max=77.5 ng ml⁻¹, t_max=1.75 h, AUC_0-t=602.3 ng h ml⁻¹, K_e=0.088 h⁻¹ and t_1/2=11.32 h) which are favorably compared with those reported in literature.     

Schiff bases as cadmium(II) selective ionophores in polymeric membrane electrodes

The construction and performance characteristics of polymeric membrane electrodes based on two neutral ionophores, N,N′-[bis(pyridin-2-yl)formylidene]butane-1,4-diamine (S₁) and N-(2-pyridinylmethylene)-1,2-benzenediamine (S₂) for quantification of cadmium ions, are described. The influences of membrane compositions on the potentiometric response of the electrodes have been found to substantially improve the performance characteristics. The best performance was obtained with the electrode having a membrane composition (w/w) of (S₁) (2.15%):PVC (32.2%):o-NPOE (64.5%):KTpClPB (1.07%). The proposed electrode exhibits Nernstian response in the concentration range of 7.9 × 10⁻⁸ to 1.0 × 10⁻¹ M Cd²⁺ with limit of detection 5.0 × 10⁻⁸ M, performs satisfactorily over wide pH range (2.0-8.0) with a fast response time (10 s). The sensor has been found to work satisfactorily in partially non-aqueous media up to 30% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 2 months. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of cadmium in real samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants.     

A new ion-selective electrode for anionic surfactants

The new ligand 7-methyl-7,13-di-octyl-1,4,10-trioxa-13-aza-7-azonia-cyclopentadecane (L¹) has been designed, synthesised and used as ionophore in the development ion-selective electrodes for anionic surfactants. Different PVC-membrane anionic-surfactants-selective electrodes were prepared by using L¹ as ionophore and bis(2-ethylhexyl)sebacate (BEHS), dibutyl phthalate (DBP) and nitrophenyl octyl ether (NPOE) as plasticizers. The PVC-membrane electrode containing L¹ and NPOE (electrode E1) showed a Nernstian response to lauryl sulfate with a slope of −59.5 mV per decade in a range of concentrations from 1.3 × 10⁻⁶ to 6.8 × 10⁻³ M and a detection limit of 6.0 × 10⁻⁷ M. The electrode E1 also showed a reasonable response to other alkyl sulfates and alkylbenzene sulfonates, whereas it does not respond to carboxylates and to cationic and non-ionic surfactants. A similar electrode to E1 but additionally containing the cationic additive n-octylammonium bromide was also prepared (electrode E2) and compared with the response of E1. Selectivity coefficients for different anions with respect to lauryl sulfate were determined by means of the fixed interference method considering lauryl sulfate as the principal anion and using a concentration of 1.0 × 10⁻² mol dm⁻³ for the corresponding interfering anion. The selectivity sequence found for the electrode E1 was: LS⁻ > SCN⁻ > ClO₄⁻ > CH₃COO⁻ > I⁻ > HCO₃⁻ > Br⁻ > NO₃⁻ > NO₂⁻ > Cl⁻ > IO₃⁻ > phosphate > SO₃²⁻ > C₂O₄²⁻ > SO₄²⁻. Electrode E1 showed remarkably better selectivity coefficients than electrode E2.     

Electrochemical determination of L-phenylalanine at polyaniline modified carbon electrode based on β-cyclodextrin incorporated carbon nanotube composite material and imprinted sol-gel film

A sensitive and selective electrochemical sensor based on a polyaniline modified carbon electrode for the determination of l-phenylalanine has been proposed by utilizing β-cyclodextrin (β-CD) incorporated multi-walled carbon nanotube (MWNT) and imprinted sol-gel film. The electrochemical behavior of the sensor towards l-phenylalanine was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric i-t curve. The surface morphologies of layer-by-layer assembly electrodes were displayed by scanning electron microscope (SEM). The response mechanism of the imprinted sensor for l-phenylalanine was based on the inclusion interaction of β-CD and molecular recognition capacity of the imprinted film for l-phenylalanine. A linear calibration plot was obtained covering the concentration range from 5.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 1.0 × 10⁻⁹ mol L⁻¹. With excellent sensitivity, selectivity, stability, reproducibility and recovery, the electrochemical imprinted sensor was used to detect l-phenylalanine in blood plasma samples successfully.     

Construction of novel simple phosphate screen-printed and carbon paste ion-selective electrodes

The construction and performance characteristics of different phosphate ion-selective electrodes are described. Three types of electrodes are demonstrated, namely screen-printed, carbon paste and the conventional PVC membrane electrodes. The cited electrodes are based on bisthiourea ionophores and show a considerable selectivity towards hydrogenphosphate with Nernstian slopes depending on the type of the electrode and the ionophore used. Matrix compositions of each electrode are optimised on the basis of effects of type and concentration of the ionophore as well as influence of the selected plasticizers. The screen-printed electrodes work satisfactorily in the concentration range 10⁻⁵ to 10⁻² mol L⁻¹ with anionic Nernstian compliance (32.8 mV/decade activity) and detection limit 4.0 × 10⁻⁶ mol L⁻¹. The screen-printed electrodes show fast response time of about 2.2 s and exhibit adequate shelf-life (4 months). The fabricated electrodes can be also successfully used in the potentiometric titration of HPO₄²⁻ with Ba²⁺.     

Copper nanoparticles entrapped in SWCNT-PPy nanocomposite on Pt electrode as NOx electrochemical sensor

A highly sensitive NO_x sensor was designed and developed by electrochemical incorporation of copper nanoparticles (CuNP) on single-walled carbon nanotubes (SWCNT)-polypyrrole (PPy) nanocomposite modified Pt electrode. The modified electrodes were characterized by scanning electron microscopy and energy dispersive X-ray analysis. Further, the electrochemical behavior of the CuNP-SWCNT-PPy-Pt electrode was investigated by cyclic voltammetry. It exhibited the characteristic CuNP reversible redox peaks at −0.15 V and −0.3 V vs. Ag/AgCl respectively. The electrocatalytic activity of the CuNP-SWCNT-PPy-Pt electrode towards NO_x is four-fold than the CuNP-PPy-Pt electrode. These results clearly revealed that the SWCNT-PPy nanocomposite facilitated the electron transfer from CuNP to Pt electrode and provided an electrochemical approach for the determination of NO_x. A linear dependence (r² = 0.9946) on the NO_x concentrations ranging from 0.7 to 2000 μM, with a sensitivity of 0.22 ± 0.002 μA μM⁻¹ cm⁻² and detection limit of 0.7 μM was observed for the CuNP-SWCNT-PPy-Pt electrode. In addition, the sensor exhibited good reproducibility and retained stability over a period of one month.     

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni²⁺ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni²⁺ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni²⁺ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)₂ complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 × 10⁻⁹ to 1.0 × 10⁻⁶ mol L⁻¹ with detection limit of 2.0 × 10⁻⁹ mol L⁻¹. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 μmol L⁻¹ Ni²⁺ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni²⁺ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni²⁺ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step.     

Electrical detection of deoxyribonucleic acid hybridization based on carbon-nanotubes/nano zirconium dioxide/chitosan-modified electrodes

A novel and sensitive electrochemical DNA biosensor based on nanoparticles ZrO₂ and multi-walled carbon nanotubes (MWNTs) for DNA immobilization and enhanced hybridization detection is described. The MWNTs/nano ZrO₂/chitosan-modified glassy carbon electrode (GCE) was fabricated and oligonucleotides were immobilized to the GCE. The hybridization reaction on the electrode was monitored by differential pulse voltammetry (DPV) analysis using electroactive daunomycin as an indicator. Compared with previous DNA sensors with oligonucleotides directly incorporated on carbon electrodes, this carbon nanotube-based assay with its large surface area and good charge-transport characteristics increased DNA attachment quantity and complementary DNA detection sensitivity. The response signal increases linearly with the increase of the logarithm of the target DNA concentration in the range of 1.49 × 10⁻¹⁰ to 9.32 × 10⁻⁸ mol L⁻¹ with the detection limit of 7.5 × 10⁻¹¹ mol L⁻¹ (S/N = 3). The linear regression equation is I = 32.62 + 3.037 log C_DNA (mol L⁻¹) with a correlation coefficient value of 0.9842. This is the first application of carbon nanotubes combined with nano ZrO₂ to the fabrication of an electrochemical DNA biosensor with a favorable performance for the rapid detection of specific hybridization.     

A reagentless DNA biosensor based on cathodic electrochemiluminescence at a C/CxO1−x electrode

A reagentless signal-on electrochemiluminescence (ECL) biosensor for DNA hybridization detection was developed based on the quenching effect of ferrocene (Fc) on intrinsic cathodic ECL at thin oxide covered glassy carbon (C/C_xO_1−x) electrodes. To construct the DNA biosensor, molecular beacon (MB) modified with ferrocene (3′-Fc) was attached to a C/C_xO_1−x electrode via the covalent bound between labeled amino (5′-NH₂) and surface functional groups. It was found that the immobilization of the probe on the electrode surface mainly depended on the fraction of surface carbonyl moiety. When a complementary target DNA (cDNA) was present, the stem-loop of MB on the electrode was converted into a linear double-helix configuration due to hybridization, resulting in the moving away of Fc from the electrode surface, and the restoring of the cathodic ECL signal. The restoration of the ECL intensity was linearly changed with the logarithm of cDNA concentration in the range of 1.0 × 10⁻¹¹ to 7.0 × 10⁻⁸ M, and the detection limit was ca. 5.0 pM (S/N = 3). Additionally, single-base mismatched DNA can be effectively discriminated from the cDNA. The great advantage of the biosensor lies in its simplicity and cost-effective with ECL generated from the electrode itself, and no adscititious luminophore is required.     

Electrosorption of Os(III)-complex at single-wall carbon nanotubes immobilized on a glassy carbon electrode: application to nanomolar detection of bromate, periodate and iodate

A simple procedure was developed to prepare a glassy carbon electrode modified with single-wall carbon nanotubes (SWCNTs) and Os(III)-complex. The glassy carbon (GC) electrode modified with CNTs was immersed into Os(III)-complex solution (direct deposition) for a short period of time (60 s). 1,4,8,12-Tetraazacyclotetradecane osmium(III) chloride, (Os(III)LCl₂)·ClO₄, irreversibly and strongly adsorbed on SWCNTs immobilized on the surface of GC electrode. Cyclic voltammograms of the Os(III)-complex-incorporated-SWCNTs indicate a pair of well defined and nearly reversible redox couple with surface confined characteristic at wide pH range (1-8). The surface coverage (Γ) and charge transfer rate constant (k_s) of the immobilized Os-complex on SWCNTs were 3.07 × 10⁻⁹ mol cm⁻², 5.5 (±0.2) s⁻¹, 2.94 × 10⁻⁹ mol cm⁻², 7.3 (±0.3) s⁻¹ at buffer solution with pH 2 and 7, respectively, indicate high loading ability of SWCNTs for Os(III) complex and great facilitation of the electron transfer between electroactive redox center and carbon nanotubes immobilized on the electrode surface. Modified electrodes showed higher electrocatalytic activity toward reduction of BrO₃⁻, IO₃⁻ and IO₄⁻ in acidic solutions. The catalytic rate constants for catalytic reduction bromate, periodate and iodate were 3.79 (±0.2) × 10³, 7.32 (±0.2) × 10³ and 1.75 (±0.2) × 10³ M⁻¹ s ⁻¹, respectively. The hydrodynamic amperometry of rotating modified electrode at constant potential (0.3 V) was used for nanomolar detection of selected analytes. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantage of this sensor.     

Coated wire linear alkylbenzenesulfonate sensor based on polypyrrole and improvement of the selectivity behavior

The potentiometric behavior of coated wire electrodes based on dodecylbenzenesulfonate-doped polypyrrole (PPy-DBS) and hyamine as ion exchanger was investigated. The PPy-DBS was prepared electrochemically by anodic polymerization of pyrrole in the presence of DBS⁻ ions in aqueous solution and used as ionophore for construction of the sensor. Two types of coated wire electrodes made of PVC-PPy-DBS and PVC-Hyamine-DBS, plasticized with ortho-nitrophenyloctylether (o-NPOE) showed the Nernstian behavior (with respective calibration slopes of about 58 and 60 mV per decade) over the DBS⁻ concentration range of 3.0×10⁻⁶ to 1.1×10⁻³ M and 5.0×10⁻⁶ to 1.3×10⁻³ M, respectively. The influence of membrane composition, type of plasticizer, and pH of test solution on the potentiometric responses of the two electrodes was investigated. The potentiometric response was independent of the pH of test solution in the range 3-10. The response time of electrodes was fast (10 s for both types of electrode), and they can be used for at least 3 months without any significant change in potential. The proposed electrodes revealed very good selectivity for DBS⁻ ion over diverse inorganic and organic anions. The potentiometric selectivity coefficients for the PPy-DBS based electrode revealed a significant improvement as compared to the electrode made by conventional Hyamine-DBS (Hya-DBS) anion exchanger. The proposed electrode was used for determination of DBS⁻ ion in some commercial detergents. The results of the potentiometric determinations were in satisfactory agreement with those obtained by a standard method (two-phase titration).     

Electrocatalytic oxidation of phytohormone salicylic acid at copper nanoparticles-modified gold electrode and its detection in oilseed rape infected with fungal pathogen Sclerotinia sclerotiorum

Salicylic acid (SA) is a biological substance that acts as a phytohormone and plays an important role in signal transduction in plants. It is important to accurately and sensitively detect SA levels. A gold electrode modified with copper nanoparticles was used to assay the electrocatalytic oxidation of salicylic acid. It was found that the electrochemical behavior of salicylic acid was greatly improved at copper nanoparticles, indicating that anodic oxidation could be catalyzed at copper nanoparticles. And the pH had remarkable effect on the electrochemical process, a very well-defined oxidation peak appeared at pH 13.3 (0.2 M NaOH). The kinetics parameters of this process were calculated and the heterogeneous electron transfer rate constant (k) was determined to be 1.34 × 10⁻³ cm s⁻¹, and (1 − α)n_α was 1.22. The gold electrode modified with copper nanoparticles could detect SA at a higher sensitivity than common electrodes. The electrode was used to detect the SA levels in oilseed rape infected with the fungal pathogen Sclerotinia sclerotiorum. The results showed that the SA concentration reached a maximum during the 10th-25th hours after infection. This result was very similar to that determined by HPLC, indicating that the gold electrodes modified with copper nanoparticles could be used as salicylic acid sensors.     

Molecularly imprinted TiO(2) thin film using stable ground-state complex as template as applied to selective electrochemical determination of mercury

Molecular recognition sites for mercury ions were imprinted in TiO₂ film using stable ground-state complex of 1-amino-8-naphtol-3,6-disodium sulfonate (ANDS) and mercury ions as template. The complex ratio between mercury ions and ANDS was estimated to be 2:1. Compared with the controlled and pure TiO₂ electrodes, the imprinted electrode revealed selectivity towards the imprinted ions. Linear calibration plots for mercury ions were obtained and the regression equation was I_p (μA) = 4.29 × 10⁻⁷ + 19.40 [Hg²⁺] with a detection limit of 3.06 × 10⁻⁹ mol/l. The imprinted electrode could be used for more than 1 month. Recoveries were calculated at both high and low concentrations, with a mean recovery of 99.6%.     

Myoglobin/arylhydroxylamine film modified electrode: Direct electrochemistry and electrochemical catalysis

The adsorption processes and electrochemical behavior of 4-nitroaniline (4-NA) adsorbed onto glassy carbon electrodes (GCE) have been investigated in aqueous 0.1 M nitric acid (HNO₃) electrolyte solutions using cyclic voltammetry (CV). 4-NA adsorbs onto GCE surfaces, and upon potential cycling past −0.2 V, is transformed into the arylhydroxylamine (ArHA) derivative which exhibits a well-behaved pH dependent redox couple centered at 0.32 V at pH 1.5. It is noted as arylhydroxylamine modified glassy carbon electrodes (HAGCE). This modified electrode can be readily used as an immobilization matrix to entrap proteins and enzymes. In our studies, myoglobin (Mb) was used as a model protein for investigation. A pair of well-defined reversible redox peaks of Mb (Fe(III)-Fe(II)) was obtained at the Mb/arylhydroxylamine modified glassy carbon electrode (Mb/HAGC) by direct electron transfer between the protein and the GCE. The formal potential (E^0′), the apparent coverage (Γ^*) and the electron-transfer rate constant (k_s) were calculated as −0.317 V, 8.26 × 10⁻¹² mol/cm² and 51 ± 5 s⁻¹, respectively. Dramatically enhanced biocatalytic activity was exemplified at the Mb/HAGC electrode by the reduction of hydrogen peroxide (H₂O₂), trichloroacetic acid (TCA) and oxygen (O₂). The Mb/arylhydroxylamine film was also characterized by UV-visible spectroscopy (UV-vis), scanning electron microscope (SEM) indicating excellent stability and good biocompatibility of the protein in the arylhydroxylamine modified electrode. This new Mb/HAGC electrode exhibited rapid electrochemical response (2 s) for H₂O₂ and had good stability in physiological condition, showing the potential applicability of the films in the preparation of third generation biosensors or bioreactors based on direct electrochemistry of the proteins.     

Calorimetric investigation of the effect of hydroxyanthraquinones in Rheum officinale Baill on Staphylococcus aureus growth

The inhibitory effects of five hydroxyanthraquinones (HAQs) from root and rhizoma of Rheum officinale Baill, a traditional Chinese medicinal (TCM) herb, on Staphylococcus aureus growth were investigated by calorimetry. The power-time curves of S.aureus with and without HAQ were acquired and the extent and duration of inhibitory effects on the metabolism evaluated by growth rate constants (k₁, k₂), half inhibitory ratio (IC₅₀), maximum heat output (P_max) and peak time (t_p). The value of k₁ and k₂ of S. aureus in the presence of the five HAQs decreased with the increasing concentrations of HAQs. Moreover, P_max was reduced and the value of t_p increased with increasing concentrations of the five drugs. The inhibitory activity varied for different drugs. IC₅₀ of the five HAQs was 4 μg ml⁻¹ for emodin, 3.5 μg ml⁻¹ for rhein, 10 μg ml⁻¹ for aloe-emodin, 1000 μg ml⁻¹ for chrysophanol, 1600 μg ml⁻¹ for physcion. The sequence of antimicrobial activity of the five HAQs: rhein > emodin > aloe-emodin > chrysophanol > physicion.     

Langmuir-Blodgett film of p-tert-butylthiacalix[4]arene modified glassy carbon electrode as voltammetric sensor for the determination of Hg(II)

The π-A isotherms and UV-vis spectra of the transferred films suggested that the monolayer of p-tert-butylthiacalix[4]arene can coordinate with Hg²⁺ at the air-water surface. From these observations, a glassy carbon electrode coated with Langmuir-Blodgett film of p-tert-butylthiacalix[4] arene as a new voltammetric sensor is designed for the determination of trace amounts of Hg²⁺. Compared with bare glassy carbon electrode and modified glassy carbon electrode using direct coating method, the Langmuir-Blodgett film-modified electrode can greatly improve the measuring sensitivity of Hg²⁺. Under the selected conditions, the Langmuir-Blodgett film-modified electrode in 0.1 mol L⁻¹ H₂SO₄ + 0.01 mol L⁻¹ KCl solution shows a linear voltammetric response for Hg²⁺ in the range of 5.0 × 10⁻¹⁰ to 1.5 × 10⁻⁷ mol L⁻¹, with a detection limit of 2.0 × 10⁻¹⁰ mol L⁻¹. The proposed method was also applied to determine Hg²⁺ in water samples (tap, lake and river water). In addition, the fabricated electrode exhibited a distinct advantage of simple preparation, non-toxicity, good reproducibility and good stability.     

Determination of l-carnitine using enantioselective, potentiometric membrane electrodes based on macrocyclic antibiotics

In order to determine the enantiopurity of l-carnitine three enantioselective, potentiometric membrane electrodes were proposed for the assay of l-carnitine. The electrodes were designed using macrocyclic glycopeptide antibiotics—vancomycin and teicoplanin. Acetonitrile was added to the teicoplanine to design a modified teicoplanine based electrode. The linear concentration ranges for the proposed enantioselective membrane electrodes were 10⁻⁴ to 10⁻² mol l⁻¹ for electrodes based on vancomycin and teicoplanin and 10⁻⁵ to 10⁻² mol l⁻¹ for electrode based on teicoplanin modified with acetonitrile. The slopes of the electrodes were 56.5 mV per pl-carnitine; 54.5 mV per pl-carnitine and 58.3 mV per pl-carnitine for vancomycin-, teicoplanin- and teicoplanin modified with acetonitrile-based electrodes, respectively. The enantioselectivity was determined over d-carnitine. The proposed electrodes could be employed reliably for the assay of l-carnitine raw material and its pharmaceutical formulation, Carnilean^® capsules. The surfaces of the electrodes are stable and easily renewable by polishing on alumina paper.     

Determination of cerium ion by polymeric membrane and coated graphite electrode based on novel pendant armed macrocycle

Plasticized membranes using 2,3,4:12,13,14-dipyridine-1,3,5,8,11,13,15,18-octaazacycloicosa-2,12-diene (L₁) and 2,3,4:12,13,14-dipyridine-1,5,8,11,15,18-hexamethylacrylate-1,3,5,8,11,13,15,18-octaazacycloicosa-2,12-diene (L₂) have been prepared and explored as Ce(III) selective sensors. Effect of various plasticizers viz. dibutylphthalate (DBP), tri-n-butylphthalate (TBP), o-nitrophenyloctylether (o-NPOE), dioctylphthalate (DOP), benzylacetate (BA) and anion excluders, sodium tetraphenylborate (NaTPB) and potassium tetrakis p-(chlorophenyl) borate was studied in detail and improved performance was observed. Optimum performance was observed for the membrane sensor having a composition of L₂:PVC:o-NPOE:KTpClPB in the ratio of 6:34:58:2 (w/w, mg). The performance of the membrane based on L₂ was compared with polymeric membrane electrode (PME) as well as with coated graphite electrode (CGE). The electrodes exhibit Nernstian slope for Ce(III) ions with limits of detection of 8.3 × 10⁻⁸ mol L⁻¹ for PME and 7.7 × 10⁻⁹ mol L⁻¹ for CGE. The response time for PME and CGE was found to be 12 s and 10 s respectively. The potentiometric responses are independent of the pH of the test solution in the pH range 3.5-7.5 for PME and 2.5-8.5 for CGE. The CGE could be used for a period of 5 months. The practical utility of the CGE has been demonstrated by its usage as an indicator electrode in potentiometric titration of oxalate and fluoride ions with Ce(III) solution. The proposed electrode was also successfully applied to the determination of fluoride ions in mouthwash solution and oxalate ions in real samples.