Ayman H. Kamel

Man-tailored biomimetic sensor of molecularly imprinted materials for the potentiometric measurement of oxytetracycline

A novel biomimetic sensor for the potentiometric transduction of oxytetracycline is presented. The artificial host was imprinted in methacrylic acid and/or acrylamide based polymers. Different amounts of molecularly imprinted and non-imprinted polymers were dispersed in different plasticizing solvents and entrapped in a poly(vinyl chloride) matrix. Only molecularly imprinted based sensors allowed a potentiometric transduction, suggesting the existence of host-guest interactions. These sensors exhibited a near-Nernstian response in steady state evaluations; slopes and detection limits ranged 42-63 mV/decade and 2.5-31.3 μg/mL, respectively. Sensors were independent from the pH of test solutions within 2-5. Good selectivity was observed towards glycine, ciprofloxacin, creatinine, acid nalidixic, sulfadiazine, cysteine, hydroxylamine and lactose. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (65 mV/decade), wide linear range (5.0×10(-5) to 1.0×10(-2) mol/L), low detection limit (19.8 μg/mL), and a stable baseline for a 5×10(-3) M citrate buffer (pH 2.5) carrier. The sensors were successfully applied to the analysis of drugs and urine. This work confirms the possibility of using molecularly imprinted polymers as ionophores for organic ion recognition in potentiometric transduction.

Electrochemical determination of antioxidant capacities in flavored waters by guanine and adenine biosensors.

The immobilization and electro-oxidation of guanine and adenine as DNA bases on glassy carbon electrode are evaluated by square wave voltammetric analysis. The influence of electrochemical pretreatments, nature of supporting electrolyte, pH, accumulation time and composition of DNA nucleotides on the immobilization effect and the electrochemical mechanism are discussed. Trace levels of either guanine or adenine can be readily detected following short accumulation time with detection limits of 35 and 40 ngmL(-1) for guanine and adenine, respectively. The biosensors of guanine and adenine were employed for the voltammetric detection of antioxidant capacity in flavored water samples. The method relies on monitoring the changes of the intrinsic anodic response of the surface-confined guanine and adenine species, resulting from its interaction with free radicals from Fenton-type reaction in absence and presence of antioxidant. Ascorbic acid was used as standard to evaluate antioxidant capacities of samples. Analytical data was compared with that of FRAP method.

A simple-potentiometric method for determination of acid and alkaline phosphatase enzymes in biological fluids and dairy products using a nitrophenylphosphate plastic membrane sensor

A novel poly(vinyl chloride) matrix membrane sensor responsive to 4-nitrophenylphosphate (4-NPP) substrate is described, characterized and used for the potentiometric assay of acid (ACP) and alkaline (ALP) phosphatase enzymes. The sensor is based on the use of the ion-association complex of 4-NPP anion with nickel(II)-bathophenanthroline cation as an electroactive material and nitrophenyloctyl ether (NPOE) as a solvent mediator. The sensor displays good selectivity and stability and demonstrates a near-Nernstian response for 4-NPP over the concentration range 9.6x10(-6) to 1.0x10(-2) M with an anionic slope of 28.6+/-0.3 mV decade(-1) and a detection limit of 6.3x10(-6) M over the pH range 4.5-10. The sensor is used to measure the decrease of a fixed concentration of 4-NPP substrate as a function of acid and alkaline phosphatase enzyme activities at optimized conditions of pH and temperature. A linear relationship between the initial rate of 4-NPP substrate hydrolysis and enzyme activity holds over 0.05-3.0 and 0.03-3.4 IU L(-1) of ACP and ALP enzymes, respectively. Validation of the method by measuring the lower detection limit, range, accuracy, precision, within-day repeatability and between-day-variability reveals good performance characteristics of the proposed sensor. The sensor is used for the determination of acid and alkaline phosphatase enzyme activities in biological fluids of some patients suffering from alcoholic cirrhosis, acute myelocytic leukemia, pre-eclampsia and prostatic cancer. The sensor is also utilized for assessment of alkaline phosphatase enzyme in milk and dairy products. The results obtained agree fairly well with data obtained by the standard spectrophotometric methods.

New potentiometric sensors based on selective recognition sites for determination of ephedrine in some pharmaceuticals and biological fluids

New cost-effective potentiometric membrane sensors with cylindrical configuration responsive to ephedrine are described. The sensors setup is, based on the use of triacetyl-β-cyclodextrin [(triacetyl-β-CD)] as a neutral ionophore embedded in a plasticized poly (vinyl chloride) (PVC) matrix (sensor I) and carboxylated poly(vinyl chloride) [(PVC-COOH)] as a simultaneous plastic matrix and ion exchanger (sensor II). Both sensors showed significant enhancement of response towards ephedrinium cation (EPD(+)) over a concentration range of 3.0 × 10(-5)-8.0 × 10(-3) mol L(-1) at pH 4-9 and 3-8 with low detection limits of 5.7 × 10(-6) and 6.2 × 10(-6) mol L(-1) for sensors (I) and (II), respectively. The sensors displayed near-Nernstian cationic slope of 57.0 and 55.6 mV decade(-1) for EPD(+) and the effects of lipophilic salts and various foreign common ions were examined. The sensors were also satisfactorily used as tubular detectors in a double channel flow injection system. The intrinsic characteristics of the detectors in a low dispersion manifold under hydrodynamic mode of operation were determined and compared with data obtained under batch mode of operation. Validation of the method revealed good performance characteristics including long life span, good selectivity for EPD(+) over a wide variety of other organic compounds, long term stability, high reproducibility, fast response, low detection limit, wide measurement range, acceptable accuracy and precision. Applications of the sensors to the determination of EPD(+) in pharmaceutical formulations and spiked biological fluid samples were carried out and compared with standard techniques. Notably, the sensors introduced offer several advantages over many of those previously described that are amenable to quality control/quality assurance assessment of the homogeneity, stability and purity of ephedrine drug tablets.

Biomimetic ciprofloxacin sensors made of molecularly imprinted network receptors for potential measurements

A molecularly imprinted polymer (MIP), with special molecule recognition properties of ciprofloxacin CIP), was prepared by thermal polymerization in which ciprofloxacin acted as the template molecule, methacrylic acid (MAA), acrylonitrile (AN) and 2-vinylpyridine (2-VP) acted as the functional monomer and ethylene glycol dimethacrylate (EGDMA) acted as the crosslinker. A biomimetic potentiometric field monitoring device was developed for the assessment of cirofloxacin (CIP) antibiotics based on these newly synthezised imprinted polymers. The sensing elements were fabricated by the inclusion of CIP imprinted polymers in polyvinyl chloride (PVC) matrix. The sensors showed a high selectivity and a sensitive response to the template in an aqueous system. Electrochemical evaluation of these sensors revealed near-Nernstian response with slopes of 29.9 ± 0.7, 27.9 ± 0.5, and 30.3 ± 0.8 mV decade−1 with a detection limit 41.3, 46.3, and 32 μg mL−1CIP with MIP/MAA, MIP/2-VP and MIP/AN membrane based sensors plasticized with DOP, respectively. The effects of lipophilic salts and various foreign common ions were tested. The sensors were easily used in a single channel flow injection system and compared with a tubular detector. The intrinsic characteristics of the detectors in a low dispersion manifold were determined and compared with data obtained under a hydrodynamic mode of operation. Significantly improved accuracy, precision, response time, stability, selectivity and sensitivity were offered by these simple and cost-effective potentiometric sensors compared with other standard techniques. The method had the requisite accuracy, sensitivity and precision to assay CIP in pharmaceutical formulations and biological fluids.

Batch and hydrodynamic monitoring of vitamin C using novel periodate selective sensors based on a newly synthesized Ni(II)-Schiff bases complexes as a neutral receptors

A highly selective membrane electrodes based on a two newly synthesized nickel (II) Schiff bases, [NiL(1)] and [NiL(2)] where L(1) and L(2) are 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)) were used as a neutral carrier ionophores for static and hydrodynamic potentiometric mode of operations for the determination of periodate. Under static mode of operation, the sensors displayed a near-Nernstian slope of -66.1+/-0.8 and -59.9+/-1.1mV decade(-1) of activity and detection limits to 5.2x10(-6) and 7.3x10(-6)molL(-1) for the sensors based on [NiL(1)] and [NiL(2)], respectively. Under hydrodynamic mode of operation (FIA), the slope of the calibration plot, limit of detection, and working linear range were -71.1mV decade(-1) of activity, 7.3x10(-6) and 1.0x10(-5) to 1.0x10(-3)molL(-1), respectively. The response time of the sensors in whole concentration ranges was very short (<10s). The response of the sensors was independent on the pH range of 3-8. A tubular version was further developed and coupled to a flow injection system for ascorbic acid (AA) determination in beverages and pharmaceutical preparations. This approach was achieved by selecting a 50-cm reactor and an overall flow of 3mLmin(-1), and injecting volume 100microL of AA standards in a 1.0x10(-4)molL(-1) IO(4)(-) solution. Under these conditions, a linearity range of 2-13microgmL(-1), with a slope of 4.97mV (mg/L)(-1) (r(2)=0.9995), detection limit 0.9mgL(-1) and a reproducibility of +/-1.1mV (n=5) was recorded. This simple and inexpensive flow injection analysis manifold, with a good potentiometric detector, enabled the analysis of approximately 50 samples h(-1) without requiring pretreatment procedures. An average recovery of 98.8% and a mean standard deviation of 1.3% were obtained.

New biomimetic sensors for the determination of tetracycline in biological samples: Batch and flow mode operations

New potentiometric membrane sensors with cylindrical configuration for tetracycline (TC) are described based on the use of a newly designed molecularly imprinted polymer (MIP) material consisting of 2-vinylpyridine as a functional monomer in a plasticized PVC membrane. The sensor exhibited significantly enhanced response towards TC over the concentration range 1.59 × 10−5–1.0 × 10−3 mol L−1 at pH 3–5 with a lower detection limit of 1.29 × 10−5 mol L−1. The response was near-Nernstian, with average slopes of 63.9 mV decade−1. The effect of lipophilic salts and various foreign common ions were tested and were found to be negligible. The possibility of applying the proposed sensor to TC determination in spiked biological fluid samples was demonstrated.

Molecularly-Imprinted Materials for Potentiometric Transduction: Application to the Antibiotic Enrofloxacin

Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mV/Δlog([ENR]/M) varied within 48–63. The detection limits ranged from 0.28 to 1.01 µg mL−1. Sensors were independent from the pH of test solutions within 4–7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ± 0.7%), fast response, good sensitivity (47 mV/Δlog([ENR]/M), wide linear range (1.0 × 10−5–1.0 × 10−3 M), low detection limit (0.9 µg mL−1), and a stable baseline for a 5 × 10−2 M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.

New potentiometric transducer based on a Mn(II) [2-formylquinoline thiosemicarbazone] complex for static and hydrodynamic assessment of azides.

A new potentiometric transducer for selective recognition of azide is characterized and developed. The PVC plasticized based sensor incorporates Mn(II) [2-formylquinoline thiosemicarbazone] complex in the presence of tri dodecyl methyl ammonium chloride (TDMAC) as a lipophilic cationic additive. The sensor displayed a near-Nernstian response for azide over 1.0×10(-2)-1.0×10(-5) mol L(-1), with an anionic slope of -55.8±0.6 mV decade(-1) and lower limit of detection 0.34 µg mL(-1). The sensor was pH independent in the range 5.5-9 and presented good selectivity features towards several inorganic anions, and it is easily used in a flow injection system and compared with a tubular detector. The intrinsic characteristics of the detector in a low dispersion manifold were determined and compared with data obtained under a hydrodynamic mode of operation. This simple and inexpensive automation, with a good potentiometric detector, enabled the analysis of ~33 samples h(-1) without requiring pre-treatment procedures. The proposed method is also applied to the analysis of trace levels of azide in primer mixtures. Significantly improved accuracy, precision, response time, stability and selectivity were offered by these simple and cost-effective potentiometric sensor compared with other standard techniques. The method has the requisite accuracy, sensitivity and precision to determine azide ions.

Fabrication of novel sensors based on a synthesized acyclic pyridine derivative ionophore for potentiometric monitoring of copper

Two synthesized acyclic di-peptide pyridine derivatives were used as an effective neutral ionophore, and potassium p,chloro tetraphenylborate (KpClTPB) as anionic excluder for copper-selective poly(vinyl) chloride (PVC) membrane sensors. The sensors exhibited fast and stable near-Nernstian response over a concentration range of 8.0 × 10−6 mol L−1 to 1.0 × 10−2 mol L−1 Cu2+ with a cationic slope of 26.2–23.3 mV per decade at a pH range 3.5–5.5 with a lower detection limit of 0.32–0.57 μg mL−1. Effects of plasticizers, lipophilic salts and various foreign common ions were also tested. The validation of the method revealed good performance characteristics, including long life span, good selectivity for Cu2+ over a wide variety of other alkalis, alkali earth and transition metal ions (e.g. Na+, K+, Ag+, Hg2+, Ca2+, Zn2+, Cd2+, Co2+, Pb2+, Ni2+, Fe2+, Mg2+, Fe3+), long term stability, high reproducibility, fast response, low detection limit, wide measurement range, acceptable accuracy and precision. The sensors were successfully applied to direct determination of copper(II) in water and waste water samples. The results agreed fairly well with data obtained using atomic absorption spectrometry.