Acid Phosphatase Assay with a Wireless Magnetoelastic Biosensor

Abstract

A wireless remote‐query disposable magnetoelastic biosensor is developed for the assay of acid phosphatase (ACP). The sensor was fabricated by applying a layer of pH‐sensitive polymer to a magnetoelastic ribbon and, on top of it, a sensing film containing bovine serum albumin and adenosine‐5′‐monophosphate (5′‐AMP), the substrate of ACP. In response to an externally applied time‐varying magnetic field, the magnetoelastic sensor mechanically vibrates at a characteristic frequency that is inversely dependent on the mass of the attached film. Because the magnetoelastic sensor is magnetostrictive, the mechanical vibrations of the sensor launch magnetic flux that can be detected remotely from the sensor using a pick‐up coil. The ACP‐catalyzed hydrolysis of 5′‐AMP decreases the solution pH, resulting in the polymer shrinking and, consequently, the resonance frequency of the magnetoelastic sensor increasing. The experimental condition was optimized to be 37°C, in 2.5 mM sodium citrate buffer solution (pH 6.5). Using citrate as buffer can enhance the ACP activity, partly offsetting the effect of the buffer capacity on the sensitivity. The kinetic parameter were measured to be: 1.64×10^–3 M (Michaelis constant) and 130 Hz/min (maximum initial rate). This work provides a remote enzymatic assay of ACP. The relative standard deviation in the measurements of six sensors in parallel is 3.4%. The proposed sensor can determine 0.2～1.2 U/ml of ACP.     

Measurement of Glucose Concentration in Blood Plasma Based on a Wireless Magnetoelastic Biosensor

Abstract

A wireless magnetoelastic glucose biosensor in blood plasma is described, based on using a mass sensitive magnetoelastic sensor as transducer. The glucose biosensor was fabricated by coating the ribbon‐like, magnetoelastic sensor with a pH sensitive polymer and a biolayer of glucose oxidase (GOx) and catalase. The pH response polymer swells or shrinks, thereby changing sensor mass loading, respectively, in response to increase or decrease of pH values. The GOx–catalyzed oxidation of the glucose in blood plasma produces gluconic acid, resulting in the pH sensitive polymer shrinking, which in turn decreases the sensor mass loading. The results show that the proposed magnetoelastic glucose biosensor can be successfully applied to determine the concentration of glucose in blood plasma. At glucose concentration range of 2.5–20.0 mmol/l, the biosensor responses are reversible and linear, with a detection limit of 1.2 mmol/l. Since no physical connections between the sensor and the monitoring instruments are required, this proposed biosensor can potentially be applied to in vivo and in situ measurement of glucose concentration in physiological fluids.     

Synthesis of Poly[2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylenevinylene] as a Light Emitting Material

In this study, a new electroluminescent poly(2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylene‐vinylene) (designated as DBP‐PPV) with no tolane‐bis–benzyl (TBB) structure defect was prepared by dehydrohalogenation of 1,4‐bisbromomethyl‐2‐decyloxy‐5‐(4′‐tert‐butyl‐phenyl) benzene (as monomer). The monomer bearing decyloxy and 4′‐tert‐butylphenyl substituents was synthesized via alkylation, bromination and Suzuki coupling reactions. The two asymmetric substituents of the monomer can suppress the formation of TBB defect during polymerization process and make the resultant polymer be soluble in common organic solvents. The structure and properties of DBP‐PPV were examined by ¹H‐NMR, FT‐IR, UV/Vis, TGA and photoluminescence (PL) analyses. Moreover, with the DBP‐PPV acting as a light‐emitting polymer, a device with sequential lamination of ITO/PEDOT/DBP‐PPV/Ca/Ag was fabricated. The electroluminescence (EL) spectrum of the device showed a maximum emission at around 546 nm, corresponding to a yellowish‐green light. The device showed a turn‐on voltage of about 8.4 V and a maximum luminescence efficiency of 0.11 cd/A at an applied voltage of 12 V.     

Sensitive Determination of Clomipramine at Poly‐ABSA/Pt Nano‐Clusters Modified Glassy Carbon Electrode

Abstract

Clomipramine, an important tricylic antidepressant drug with low redox activity, was effectively electrocatalyzed on poly‐aminobenzene sulfonic acid/Pt nano‐clusters modified glassy carbon electrode (i.e., poly‐ABSA/Pt/GCE) and generated a sensitive anodic peak at about 0.80 V in pH 8.1 PBS. ABSA was electropolymerized on the surface of GCE modified with Pt nano‐clusters. Pt nanoparticles provide a 3 D and conductive structure for the polymer immobilization. The resulting sensor exhibited a considerable enhancement in voltammetric response characteristics: extending the linear range and lowering the detection limit. The anodic peak current of clomipramine was linear with its concentration over two concentration intervals, viz., 1.0×10^?7～4.0×10^?6 M and 4.0×10^?6～4.0×10^?5 M, with the detection limit of 1.0×10^?9 M (S/N=3). This method was successfully applied to the determination of clomipramine in drug tablets and proved to be reliable compared with UV.     

Design of a Novel Gadolinium Optical Sensor Based on Immobilization of (Z)-N′-((Pyridine-2-yl) Methylene) Thiophene-2-carbohydrazide on a Triacetylcellulose Membrane and Its Application to the Urine Samples

Abstract

In this work, for the first time we report a highly selective and sensitive Gd(III) optical sensor based on immobilization of (Z)-N′-((pyridine-2-yl) methylene) thiophene-2-carbohydrazide (PMTC) on a triacetylcellulose membrane. This optode exhibits a linear range 5.0 × 10^?8 to 2.0 × 10^?5 M of Gd(III) ion concentration with a detection limit of 1.1 × 10^?8 M. The response time of the newly designed optode was within 1–2 min, depending on the Gd(III) ion concentration. The response of the sensor is independent of the pH solution in the range of 2.0–9.0. It manifests advantages of low detection limit, fast response time, and most significant, very good selectivity with respect to a number of lanthanide ions (La, Ce, Sm, and Eu ions). The proposed sensor could be successfully regenerated with a thiourea solution. Its response was reversible and reproducible (RSD less than 1.3%). This optode was applied to the determination of Gd(III) in synthetic and real samples.     

Molecular Imprinting-Chemiluminescence Sensor for the Determination of Amoxicillin

The amoxicillin-imprinted polymer was synthesized with methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross-linker. The binding characteristic of the imprinted polymer to amoxicillin was evaluated by equilibrium binding experiments. Using the imprinted polymer as recognition material, 3-(3′-nitrophenyl)-5(2′-sulfonylphenylazo)-rhodanine (4NRASP) was synthesized by the authors and was used as chemiluminescence (CL) reagent. A novel chemiluminescence (CL) sensor for the determination of amoxicillin was developed based on the CL reaction of amoxicillin with potassium permanganate in an acidic medium. The sensor displayed excellent selectivity and high sensitivity. The linear response range of the sensor was from 5.0 × 10^?9 to 1.0 × 10^?6 g · mL^?1 (r = 0.9985) and the detection limit was 1.3 × 10^?9 g · mL^?1. The relative standard deviation for the determination of 1.0 × 10^?7 g · mL^?1 amoxicillin solution was 1.7% (n = 11). The sensor was applied to the determination of amoxicillin in urine samples with satisfactory results.     

PPb Level Monitoring of Dy(III) Ions by a Highly Sensitive and Selective Dy(III) Sensor Based on a New Asymmetrical Schiff's Base

Abstract

A Dy(III) ion‐selective membrane sensor has been fabricated from polyvinyl chloride (PVC) matrix membrane containing a new asymmetrical Schiff's base [(E)‐N‐(2‐hydroxybenzylidene)benzohydraide] or BBH as a neutral carrier, sodium tetraphenyl borate (NaTPB) as an anionic excluder and nitrobenzene (NB) as a plasticizing solvent mediator. The membrane sensor displays linear potential response in the concentration range of 1.0×10^?2–1.0×10^?6 M of Dy(III). The electrode exhibits a nice Nernstian slope of 20.1±0.8 mV/decade in the pH range of 3.0–8.0. The sensor has a relatively short response time in whole concentration ranges (<20 s). The detection limit of the proposed sensor is 8.0×10^?7 M (～128 ng/mL), and it can be used over a period of six weeks. The selectivity of the proposed sensor with respect to other cations, (alkali, alkaline earth, transition and heavy metal ions) and especially lanthanid ions, is excellent. The practical utility of the sensor has been demonstrated by using it as an indicator electrode in the potentiometric titration of Dy(III) with EDTA.     

A rapid selective colorimetric and ‘On–Off’ fluorimetric sensor for detecting Cu2+ ions in aqueous media based on a simple bis-schiff-base derivative

A simple colorimetric and fluorimetric ‘On–Off’ sensor L (3,3′-dimethyl -[1,1′-biphenyl]-4,4′-diyl)bis(azanylylidene)bis(methanylylidene)bis(naphthalen-2-ol) for Cu²⁺ ions bearing o-tolidine substituents has been designed and synthesised, and exhibits significant fluorimetric and colorimetric response for Cu²⁺ in DMSO/H₂O (8:2, v/v) HEPES buffer (pH 7.2) solution. The detection limit of the sensor towards Cu²⁺ is 7.25 × 10^? 8 M and the association constant K_a of 9.86 × 10⁴ M^? 1 was determined. Furthermore, other anions, including Fe³⁺, Hg²⁺, Ag⁺, Ca²⁺, Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Cr³⁺ and Mg²⁺ have almost no influence on the probe's behaviour. Test strips based on the sensor L were fabricated, which could act as convenient and efficient Cu²⁺ test kits.     

Fabrication of Potentiometric Sensors for the Selective Determination of Ketoconazole

Abstract

The fabrication and analytical applications of two types of potentiometric sensors for the determination of ketoconazole (KET) are described. The sensors are based on the use of KET-molybdophosphoric acid (MPA) ion pair as electroactive material. The fabricated sensors include both polymer membrane and carbon paste electrodes. Both sensors showed a linear, stable and near Nernstian slope of 57.8 mV/decade and 55.2 mV/decade for PVC membrane and carbon paste sensors respectively over a relatively wide range of KET concentration (1 × 10^?2 ? 5 × 10^?5and 1 × 10^?2 ? 1 × 10^?6). The sensors showed a fast response time of < 30 sec and < 45 sec. A useful pH range of 3–6 was obtained for both types of sensors. A detection limit of 2.96 × 10^?5M was obtained for PVC membrane sensor and 6.91 × 10^?6 M was obtained for carbon paste sensor. The proposed sensors proved to have a good selectivity for KET with respect to a large number of ions. The proposed sensors were successfully applied for the determination of KET in pharmaceutical formulations. The results obtained are in good agreement with the values obtained by the standard method.     

A Novel Holmium(III) Membrane Sensor Based on N‐(1‐Thien‐2‐Ylmethylene)‐1,3‐Benzothiazol‐2‐Amine

Abstract

A novel plasticized membrane sensor for Ho(III) ions based on N‐(1‐thien‐2‐ylmethylene)‐1,3‐benzothiazol‐2‐amine (TBA) as a neutral carrier was prepared. The best performance was obtained with a membrane composition of 31% PVC, 61% benzyle acetate, 2% sodium tetra phenyl borate and 6% carrier. The electrode exhibits a Nernstian response for Ho(III) ions over a particular concentration range (1.0×10^?5?1.0×10^?2 M) with a slope of 19.7±0.2 mV decade^?1. The limit of the detection is 7.0×10^?6 M. The sensor has a response time of <15 s and a useful working pH range of 4.0–9.5. The proposed sensor discriminates relatively well towards Ho(III) ions with regard to common alkali, alkaline earth, and specially lanthanide ions. It was successfully applied as an indicator electrode in a potentiometric titration of Ho(III) ions with EDTA. It was also applied in determination of fluoride ions in a mouth wash preparation. The proposed sensor was applied for the determination of Ho(III) ion concentration in binary mixtures.     

Lanthanide Recognition: Development of an Asymetric Gadolinium Microsensor Based on N-(2-pyridyl)-N′-(4-nitrophenyl)thiourea

Abstract

The first asymmetric potentiometric Gd(III) microsensor is reported here. N-(2-Pyridyl)-N′-(4-nitrophenyl)thiourea (PyTu₄NO₂) was found to have a very selective and sensitive behavior toward Gd(III) ions, in comparison to other lanthanide ions as well as inner transition and representative metal ions and hence was used as a sensing material in the construction of a Gd(III) microelectrode. The Gd(III) sensor exhibits a Nernstian slope of 17.46 ± 0.3 mV per decade over the concentration range of 1.0 × 10^?8 to 1.0 × 10^?3 M and a detection limit of 3.0 × 10^?9 M of Gd(III) ions. The potentiometric response of the sensor is independent of the solution pH in the range of 4.0–9.0. It manifests advantages of low detection limit and fast response time (10–15 s).     

Metallomicellar Catalysis: Hydrolysis of Phosphodiester with Cu(II) and Zn(II) Complexes in Micellar Solution

Abstract

The effects of two metal complexes of 2,2′‐dipyridylamine (bpya) ligand, [(bpya)Cu]Cl₂ and [(bpya)Zn]Cl₂, in promoting the hydrolysis of bis(4‐nitrophenyl) phosphate (BNPP) have been kinetically investigated in Brij35 micellar solution and at 298 K, pH ranging from 6.41 to 8.6. In neutral micellar solution at 298 K, pH 7.02, the rate constants for the catalytic hydrolysis of BNPP by [(bpya)Cu]Cl₂ and [(bpya)Zn]Cl₂ are 1.2 × 10⁶ times and 1.5 × 10⁵ times higher than those for the spontaneous hydrolysis, respectively. Kinetic studies show that the active species in the catalytic hydrolysis of BNPP is the aquo‐hydroxy form, and the relative kinetic and thermodynamic parameters indicate that the mechanism of the reaction involves intramolecular nucleophilic attack on the metal center‐bound diester.     

Depyrimidination of synthetic poly(uridylic acid) analogue

A poly(uridylic acid) analogue, poly{[1′‐(β‐uracil‐1‐yl)‐5′‐deoxy‐D‐erythro‐pent‐4′‐enofuranose]‐alt‐[maleic acid]} (3), was synthesized by the alternating copolymerization of nucleoside derivative 1 and maleic anhydride and subsequent hydrolysis. N‐glycosidic bonds of the polymer were hydrolyzed spontaneously to liberate uracil from the polymer backbone in a buffer solution (pH 7.4) at room temperature. The depyrimidination rate constant of the polymer at pH 7.4 at 80 °C was 8.2 × 10⁻⁵ s⁻¹, which was 10⁴ times higher than that of the depyrimidination of DNA (1.2 × 10⁻⁹ s⁻¹) under the same condition. The activation energy for the depyrimidination was 16 kcal/mol, which was about half of that for the relevant nucleoside reactions. The increase in the depyrimidination rate was attributable to the high potential energy of the polymer caused by the crowded environment around the bases, so that the polymer was more susceptible to the hydrolysis. Because natural nucleic acids often have compact structures with a crowded environment around the bases by an intricate chain folding, the pyrimidination also may have been accelerated in a similar manner in the biological system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 423–429, 2000     

Fe(III) Ion‐Selective Membrane Electrode Based on 4‐Amino‐6‐methyl‐3‐methylmercapto‐1,2,4‐triazin‐5‐one

Abstract

An original highly selective and sensitive PVC membrane sensor, working as a Fe(III) ion selective electrode and using 4‐amino‐6‐methyl‐3‐methylmercapto‐1,2,4‐triazin‐5‐one (AMMTO) as an ionophore, has been developed. This cetain sensor demonstrated the following performance; a linear dynamic range between 1.0×10^?6 and 1.0×10^?1 M with a near Nernstian slope of 19.4±0.5 mV per decade; a detection limit of 6.8×10^?7 M; characteristically, the best performance was obtained with a membrane composition of 30% poly(vinyl chloride), 65.5% nitrophenyl octyl ether, 2% sodium tetraphenyl borate and 2.5% AMMTO. Furthermore, the potentiometric response of the developed electrode is independent of the solution pH in the range of 2.2–4.8. The sensor possesses the advantages of short conditioning time, fast response time (<15 s) and, especially, great selectivity towards transition and heavy metal ions and some mono, di‐ and trivalent cations. The electrode can be used for at least 9 weeks without any considerable potential divergence. It was effectively used as an indicator electrode in the potentiometric titration of Fe(III) ions with EDTA and the direct determination of Fe³⁺ in different water samples.     

Novel Potentiometric Sensor Based on Molecular Imprinted Polyacrylamide for the Determination of Shikimic Acid in Herbal Medicine

ABSTRACT

A novel potentiometric sensor based on a molecular imprinted polymer was developed for the determination of shikimic acid in herbal medicine. The imprinted polymer was synthesized via bulk polymerization of the functional monomer in the presence of trimethylolpropane triacrylate as the cross-linker with 2,2′-azo-bisisobutyronitrile as the initiator and shikimic acid as the template. The sensing membrane was constructed by the inclusion of imprinted polymer in the polyvinyl chloride matrix. The effect of the identity of the imprinted polymer on the potentiometric response was observed. The optimal imprinted polyacrylamide was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The performance of the imprinted membrane based sensor, including the effects of pH, response time and selectivity coefficient, was investigated. The imprinted sensor exhibited a fast near-Nernstian response in the concentration range of 1?×?10^?5 to 1?×?10^?1?mol/L with a detection limit of 9?×?10^?6?mol/L. The analytical performance of the sensor supported the direct determination of shikimic acid in herbs, and the obtained results were validated by ultraviolet-visible absorption spectrophotometry. Advantages of the potentiometric sensor include enhanced sensitivity, high selectivity, long-term stability and low-cost fabrication, suggesting the device offers promise for the analysis of Chinese herbal medicine.     

Flow Injection Chemiluminescence Sensor with Novel Rhodanine Ramification for Determination of Fenfluramine Based on Molecularly Imprinted Polymer

Abstract

Flow injection chemiluminescence (FI-CL) with molecularly imprinted polymer (MIP) was applied to determine fenfluramine. The fenfluramine-imprinted polymer was prepared with acrylamide (AM) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Methyl and sulfonic group were introduced to rhodanine matrix, and a novel rhodanine ramification 3MORASP was synthesized by the author, and it was used as chemiluminescence reagent. 3-(3′-Methoxyphenyl)-5(2′-sulfonylphenylazo)-rhodanine (3MORASP), first synthesized by the authors, was used as chemiluminescence (CL) reagent. The novel flow path of FI-CL was designed, which made three merged streams of reactants injected into MIP column move through different pathways simultaneously. Fenfluramine was detected based on the reaction of fenfluramine, 3MORASP, and potassium permanganate in an acidic medium. The CL intensity was correlated linearly with the concentration of fenfluramine over the range of 1.0 × 10^?7 to 5.0 × 10^?6 g · mL^?1, and the detection limit was 9.48 × 10^?9 g · mL^?1. The relative standard deviation (RSD) was 2.4% for determination of 1.0 × 10^?6 g · mL^?1 fenfluramine (n = 11). This method was successfully applied to the determination of fenfluramine in weight-reducing tonic.     

Removal of Lead (II) Ions by Poly(2‐octadecyl butanedioic acid): Isothermal and Kinetic Studies

Poly(2‐octadecyl‐butanedioic acid), prepared from polyanhydride PA‐18, possesses novel heavy metal adsorption characteristics. The adsorption capacity of this water insoluble polymer for lead (II) was substantially higher than other heterogeneous adsorbants and is equivalent to those obtained with homogeneous sorbants. The polymer exhibited pseudo‐second‐order kinetics and nearly complete adsorption of lead occurred in 15 min with initial lead (II) concentrations greater than 100 mg · L^?1. Adsorptive behavior was accurately predicted by the Dubinin‐Radushkevich isotherm model. The mean free energy of adsorption of lead (II) onto poly(2‐octadecyl‐butanedioic acid) was determined to be 31.6 kJ · mol^?1, suggesting an ion exchange component to the adsorption mechanism. Gibb's free energy values for this process indicate that it is spontaneous. Adsorption was relatively independent of pH in the range of 3–5, due to the utilization of the sodium carboxylate form of the chelating groups, and was not influenced by high Na⁺ concentration and moderate concentrations (up to 200 mg · L^?1) of Ca⁺². Lead (II) solutions containing 2000 mg · L^?1 Ca⁺² did reduce the adsorption of 2000 mg · L^?1 lead (II) by 28%.     

Determination of Pseudoephedrine Hydrochloride in Some Pharmaceutical Drugs by Potentiometric Membrane Sensor Based on Pseudoephedrine–Phosphotungstate Ion Pair

Abstract

An ion-selective electrode (ISE) was developed for the rapid determination of pseudoephedrine hydrochloride (PSEHCl) in pharmaceutical preparations. The electrode incorporates a PVC membrane with a pseudoephedrine–phosphotungstate ion pair complex. The influences of membrane composition, temperature, pH of the test solution, and the interfering ions on the electrode performance were investigated. The sensor exhibits a Nernstian response for pseudoephedrine hydrochloride ions over a relatively wide concentration range (1.0 × 10^?1 to 1.0 × 10^?5 mol L^?1) with a slope of 56.2 ± 0.5 mV per decade at 25°C. It can be used in the pH range 4.0–10.5. The isothermal temperature coefficient of this electrode amounted to 0.0009 V/°C. The membrane sensor was successfully applied to determination of PSEHCl in its tablets and syrup.     

Aptamer Immobilized Magnetoelastic Sensor for the Determination of Staphylococcus aureus

An aptamer-based magnetoelastic sensor for the determination of Staphylococcus aureus is reported. Aptamers specific to S. aureus were used to ensure specific and selective binding of bacteria on the sensor surface. The sensors were exposed to S. aureus concentrations of 1 × 10¹–1 × 10¹¹ colony forming units per milliliter, and the changes in resonance frequency were monitored. The sensitivity was higher for sensors with smaller physical dimensions. The biosensor with dimensions of 2 × 5 × 0.028 millimeters provided a linear dynamic range of 10¹–10¹¹ colony forming units per milliliter and a detection limit of 5 colony forming units per milliliter. The results also demonstrated that the magnetoelastic sensors determined the targeted pathogenic species with good selectivity. The method was employed to determine S. aureus in water, and the results were comparable to those obtained by plate-counting methods. The high sensitivity, selectivity, and stability of the aptamer provide a promising approach for the determination of pathogenic bacteria.     

Molecular Imprinting-Chemiluminescence Sensor for the Determination of Prulifloxacin

Abstract

A selective molecular imprinting-chemiluminescence sensor is developed for the determination of prulifloxacin by using a prulifloxacin-imprinted polymer as recognition material and the cerium(IV)/sodium thiosulfate/prulifloxacin chemiluminescence reaction as the detection system. The linear response range of the sensor is from 8.0 × 10^?8 to 7.0 × 10^?6 mol L^?1 with a detection limit of 2.0 × 10^?8 mol L^?1. The relative standard deviation for 5.0 × 10^?7 mol L^?1prulifloxacin solution is 1.3% (n = 7). This sensor has been applied to the determination of prulifloxacin in urine samples, and the results obtained are satisfactory.