A New Solid-State pH Sensor and Its Application in the Construction of all Solid-State Urea Biosensor

A new solid-state pH sensor is developed using neutral poly(3-cyclohexyl thiophene) assembled over a Pt disk electrode. The new sensor is developed following two different approaches; 1) the neutral poly(3-cyclohexyl thiophene) dissolved in chloroform and subsequent coating on to a Pt disk electrode; 2) the neutral polymer is incorporated into plasticized poly(vinyl chloride) matrix membrane. In both cases the polymer modified electrode is sensitive to pH and a reversible super Nernstian behavior is observed. The typical response of the pH sensor and its reversibility are reported. The polymer coated electrode is subsequently used to construct an all solid-state urea sensor. The construction of this new urea sensor involves the following two major steps; a) 20 µL of urease solution (40 mg /mL) is allowed to assemble overnight at 4 °C over neutral poly (3-cyclohexyl thiophene) modified electrode; b) an organically modified sol-gel layer is allowed to form over the urease adsorbed polymer modified electrode. The new solid-state urea sensor provides excellent reproducibility of the measurements and is stable for 3 months when stored at 4 °C under dry condition. The typical response of the solid-state urea sensor and the calibration plot of urea analysis are reported.     

Chemically modified electrode based on poly[tetra(4-aminophenyl)porphyrin] as a pH sensor

A chemically modified platinum electrode with coated poly[tetra(4-aminophenyl)porphyrin] has been used as a potentiometric pH sensor. It gives a linear response over the pH range 1.5-13.7 with a slope of 55 mV/pH (at 20 degrees ). The sensor has fair resistance to erosion of hydrofluoric acid and to interference of a coexisting redox couple. The sensor can be used for pH determination and end-point indication for potentiometric titration of hydrofluoric acid with sodium hydroxide. The a.c. impedance of the polymer membrane has also been studied.     

A deuterium-palladium electrode as a new sensor in non-aqueous solutions: potentiometric titration of weak acids in acetonitrile and benzonitrile

A deuterium-palladium electrode was employed as a new indicator electrode for the titration of weak acids in acetonitrile and benzonitrile. The investigated electrode showed a linear dynamic response for p-toluenesulfonic acid in the concentration range from 0.001 M to 0.1 M with a Nernstian slope of 48 mV in acetonitrile. Sodium methylate, potassium hydroxide and tetrabutylammonium hydroxide proved to be very suitable titrating agents for these titrations. The response time was less than 10-11 s and the lifetime of the electrode was limitless. Advantages of the electrode are: long-term stability, fast response, reproducibility, easy preparation and low cost.     

Flow Injection Potentiometric Determination of Coke Acidity and Acetic Acid Content in Vinegar Using an Antimony Electrode

Abstract

A flow injection potentiometric procedure is proposed for the determination of acidity of several samples using an antimony/ antimony oxide electrode. The ΔE/pH curve in phosphate buffer solutions in the pH range from 1.58 to 12.00 showed a linear sub-Nernstian behavior with an operational slope S =-42.1mV/pH_c and a conditional standard potential of 264.8mV. This flow potentiometric electrode responds linearly to low acidity variations of dilute acetic acid solutions from 3.16 to 100mM with a slope of 30.1mV/dec and analytical frequency of 23 results/h. Good reproducibility and an average standard deviation of ±0.5% was obtained. The application of this sensor for the determination of coke acidity and acetic acid in vinegar is reported.     

A polymeric sulfur nitride, (sn)x,electrode responsive to ph and its application to the aqueous potentiometric titration of weak acids

The characteristics of polymeric sulfur nitride, (SN)_x, electrodes for the sensing of pH in aqueous acid—base systems is reported. The application of this new pH-sensor to titrations of both strong and weak acids with strong base is described. The (SN)_x. electrode has significant advantages for titrations of weak acids (pK_a ? 9) with a strong base, compared to the classical procedure with the glass electrode. Comparative titration curves and quantitative results for hydrochloric acid, perchloric acid, trifluoroacetic acid, boric acid, p-nitrophenol, resorcinol, glycine, phenol, acetic acid, benzoic acid and propanoic acid with glass electrode and (SN)_x electrode are given.     

Development of Uric Acid Sensor Based on Molecularly Imprinted Polymer‐Modified Hanging Mercury Drop Electrode

Uric acid (UA) sensor based on molecularly imprinted polymer‐modified hanging mercury drop electrode was developed for sensitive and selective analysis in aqueous and blood serum samples. The uric acid‐imprinted polymer was prepared from melamine and chloranil and coated directly onto the surface of a hanging mercury drop electrode, under charge‐transfer interactions at +0.4 V (vs. Ag/AgCl), in model 303A electrode system connected with a polarographic analyzer/stripping voltammeter (PAR model 264A). The binding event of uric acid was detected in the imprinted polymer layer through differential pulse, cathodic stripping voltammetry (DPCSV) at optimized operational conditions [accumulation potential +0.4 V (vs. Ag/AgCl), accumulation time 120 s, pH 7.0, scan rate 10 mV s^?1, pulse amplitude 25 mV]. The limit of detection for UA was found to be 0.024 μg mL^?1 (RSD=0.64%, S/N=3). Under the optimized operational conditions, the sensor was able to differentiate between uric acid and other closely structural‐related compounds and interfering substances. Ascorbic acid (AA), a major interferent in UA estimation, was not adsorbed on the surface of sensor electrode. The present sensor is, therefore, UA‐selective at all concentrations of AA present in human blood serum samples. The précised and accurate quantification of UA have been made in the dilute as well as concentrated regions varying within limits 0.1–4.0 and 9.8–137.0 μg mL^?1, respectively.     

A Review of the Extraction of Herbicide Residues from Aged Saskatchewan Field Soils

Abstract

Polar solvents based on aqueous methanol and aqueous acetonitrile are good extractants of herbicides from Saskatchewan field soils that had received treatments of the individual chemicals 6 to 17 months previously. The addition of small amounts of acetic acid or ammonium hydroxide to aqueous acetonitrile resulted in greater recovery of most herbicides. In general, 50 ml of the extraction solvent were added to 20 g of soil and the soils were then initially extracted for 1-hr on a wrist-action shaker and then allowed to stand overnight before being shaken for a further 1-hr period.     

8-羟基喹啉-5-磺酸修饰电极pH传感器的制备及应用

制备了8-羟基喹啉-5-磺酸(HQS)修饰铂丝电极pH传感器,对其pH响应范围,斜率,线性相关系数,响应时间等进行了考察.将该电极用于表面修饰氨基纳米二氧化硅的测定,取得了满意结果.     

Ascorbate amperometric determination using conducting copolymers from aniline and N-(3-propane sulfonic acid)aniline

The sequential electrochemical polymerization of aniline and N-(3-propane sulfonic acid)aniline (PSA) is proposed to construct a sensor able to detect ascorbate at physiological conditions. Compared to poly(aniline) modified electrode, a device with improved conducting and electrochemical properties at neutral pH is obtained. The electrochemical copolymerization of the same starting materials is also carried out. For a PSA:aniline ratio of 10:90, a polymer with a similar electrochemical behavior to the one grown in the sequential mode is observed.The detection of ascorbate was tested for both configurations at pH 7.2, the modified electrode is able to determine ascorbate at 0 mV versus Ag/AgCl; an optimized sensor constructed by sequential polymerization can easily detect ascorbate concentrations with a detection limit of 2.2 μM. Uric acid and dopamine does not interfere in the ascorbate determination.     

Simple PVC–PPy electrode for pH measurement and titrations

Cobaltabis(dicarbollide) [3,3'-Co(1,2-C2B9H11)](-)-doped polypyrrole (PPy) films have been prepared galvanostatically on glassy carbon electrodes in acetonitrile solution. The potential response behavior of the film of this new material has been investigated in some common pH buffers and in acid-base titrations. The potentiometric characteristics of the resulting films are indicative of a quasi-Nernstian response (approximately 50 mV/pH unit), a linearity range from pH 12 to 3 and correlation coefficients (r2) of approximately 0.98. The electrode is suitable for pH measurements and for monoprotic titrations of strong alkalis with strong acids, and weak bases with strong acids, but the long response time hinders the use of this electrode for multiprotic titrations. The time response has been dramatically improved by reducing the film thickness by using the template effect of a non-conducting polymer (PVC) cast over the graphite surface before PPy deposition. PPy polymerization occurs in the free channels of PVC leading to the formation of PPy wires. The morphological change of PPy does not affect the slope or linearity range. The response of the PVC-PPy electrochemical sensor is rapid and the sensor is easy to prepare, at low cost, and its performance is comparable with that of commercial glass electrodes.     

Simultaneous determination of dopamine, ascorbic acid and uric acid at poly (Evans Blue) modified glassy carbon electrode

A sensitive and selective electrochemical method for the determination of dopamine using an Evans Blue polymer film modified on glassy carbon electrode was developed. The Evans blue polymer film modified electrode shows excellent electrocatalytic activity toward the oxidation of dopamine in phosphate buffer solution (pH 4.5). The linear range of 1.0 x 10(-6)-3.0 x 10(-5) M and detection limit of 2.5 x 10(-7) M were observed in pH 4.5 phosphate buffer solutions. The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of ascorbic acid and uric acid. The separation of the oxidation peak potentials for dopamine-ascorbic acid and dopamine-uric acid were about 182 mV and 180 mV, respectively. The differences are large enough to determine AA, DA and UA individually and simultaneously. This work provides a simple and easy approach to selectively detect dopamine in the presence of ascorbic acid and uric acid in physiological samples.     

An amperometric sensor for uric acid based on ordered mesoporous carbon-modified pyrolytic graphite electrode

A novel amperometric sensor for uric acid based on ordered mesoporous carbon modified pyrolytic graphite electrode was developed. Uric acid oxidation was easily catalyzed by this electrode in a phosphate buffer solution at pH 7.0, with an anodic potential decrease about 140 mV compared to bare pyrolytic graphite electrode. The uric acid level was determined by the amperometric method, at a constant potential of 0.31 mV, the catalytic current of uric acid vs. its concentration showed a good linearity in the range of 1.0 × 10⁻⁶−1.0 × 10⁻⁴ mol L⁻¹, with a correlation coefficient of 0.999. The detection limit was 4.0 × 10⁻⁷ mol L⁻¹. The proposed method could be effectively used for uric acid amperometric sensing in human urine.     

Sulfamethoxazole‐Imprinted Polymeric Receptor as Ionophore for Potentiometric Transduction

This work proposes a new biomimetic sensor material for sulfamethoxazole. It is prepared by means of radical polymerization, having ethylene glycol dimethacrylate as a cross‐linker, 2,2′‐azobisisobutyronitrile as radical initiator, methacrylic acid as a functional monomer and acetonitrile as porogenic solvent. Sulfamethoxazole sensor with 10.9 % of imprinted particles showed the best response in terms of slope (58.3 mV/decade) and detection limit (6.3×10^?8 mol L^?1). This electrode displayed also a good selectivity towards the sulfonamide antibiotics, glucose, calcium, ammonium, nickel, sodium and zinc. The sensor was not affected by pH<2.2 and pH>6. The electrode was successfully applied to the analysis of food and biological samples.     

Facile synthesis of polyacrylate directed silver nanoparticles for pH sensing through naked eye

Poly(acrylic acid) (PAA) and its salt poly(acrylate) (PA) have been synthesized through modified free radical polymerization in environmentally begin aqueous medium under ultrasound to make the process robust. The synthesized polymer is well-characterized through conventional techniques. Its salt is employed to produce highly stable and stimuli sensitive colloidal silver (Ag-PA sol) without using any additional reducing chemical reagents like sodium borohydride, ascorbic acid, hydrazine, etc or UV/Gamma radiation. A detailed mechanistic path of the polymerization and reduction of Ag⁺ on polyacrylate chains has been evaluated. Finally Ag-PA sol is used for pH sensing through naked eye to eliminate the need for sophisticated instrument for data collection. The present work focuses mainly the development of a low cost pH sensing system based on colorimetric ‘smart polymer’ having high practical utility. The unique structural and photo-physical features of nano-scaled materials open new opportunities for the applications of colorimetric pH sensor. In the present work, Ag nano-clusters capped by PA^? are employed as an effective colorimetric pH sensor for the first time, requiring no further functionalization.     

A ferrocene-modified platinum electrode as a potentiometric sensor for l-ascorbic acid

A half-oxidized platinum electrode modified with a monolayer of ferrocene is proposed as a potentiometric sensor for l-ascorbic acid in an aqueous glycine buffer pH 2.2. The ferrocene was covalently attached to the surface by a silane carbon chain. The potentials of 15 electrodes were measured and a slope of (50 ± 8.8) mV per decade change in concentration of ascorbic acid was obtained over the concentration range 10^?3-10^?6 M. Recovery experiments with pure l-ascorbic acid solutions showed a relative standard deviation of 1.9%, in the analysis of fresh orange juice, the relative standard deviation was 6.1%.     

One-pot electrosynthesis of polyglycine-like thin film on platinum electrodes as transducer for solid state pH measurements

The anodic oxidation of concentrated glycine based aqueous electrolyte on smooth platinum electrode leads to a strongly grafted polyglycine-like coating on the surface in an irreversible way. Due to the proton affinity towards amino groups of polyglycine (PG), the electrodeposited thin film was used as receptor for solid potentiometric pH sensor. In order to reach local pH measurement, we developed miniaturized microelectrodes on glass substrate thanks to photolithography process. We used silver chloride on silver as the reference electrode. The couple (silver chloride, PG based platinum electrode) of microelectrodes gives linear potentiometric response vs. pH in the range [2-12], reversibly and with a sensitivity of 52.4 mV/pH (for 1 mm electrode size). PG based pH electrode is compared to other organic polymer based pH receptor such as linear polyethylenimine (L-PEI), polyaniline (PANI) and glass membrane.     

Selective Detection of Dopamine and Its Metabolite,DOPAC, in the Presence of Ascorbic Acid Using Diamond Electrode Modified by the Polymer Film

The surface of boron‐doped diamond (BDD) electrode is modified by the polymer film for the first time. The cationic polymer film of N,N‐dimethylaniline (DMA) is electrochemically deposited on BDD electrode surface. This polymer (PDMA) film‐coated BDD electrode is used as a sensor which selectively detect dopamine (DA) in the presence of ascorbic acid (AA). This electrode also can detect both DA and its metabolite, 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the presence of AA in the range of the physiological concentrations of these species. Favorable ionic interaction (i.e., electrostatic attraction) between the PDMA film and AA or DOPAC lowers their oxidation potentials and enhances the current response for AA and DOPAC compared to that at the bare electrode. The PDMA film also shows a hydrophobic interaction with DA and DOPAC. In cyclic voltammetric measurements, the PDMA film‐coated electrode can successfully separate the oxidation potentials for AA and DA coexisting in the same solution and the separation is about 200 mV. AA oxidizes at more negative potential than DA. In square‐wave voltammetry, the sensitivity of the PDMA film‐coated BDD electrode for DA in the presence of higher concentration of AA is higher than that of the PDMA film‐coated glassy carbon electrode. The hydrodynamic amperometric experiments confirm that the oxidation of AA is not affected by the oxidized product of DA and vice versa. So, unlike the bare electrode the catalytic oxidation of AA by the oxidized DA is eliminated at the PDMA film‐coated BDD electrode. The sensitivities of the modified electrode for AA, DA and DOPAC, which are present in the same solution with their physiological concentration ratios, are calculated to be 0.070, 0.363 and 0.084 μA μM^?1, respectively. The modified electrode exhibits a stable and sensitive response to DA.     

Detection of Uric Acid in the Presence of Dopamine and High Concentration of Ascorbic Acid Using PDDA Modified Graphite Electrode

The properties of graphite electrode (Gr) modified with poly(diallyl dimethyl ammonium chloride) (PDDA) for the detection of uric acid (UA) in the presence of dopamine (DA) and high concentration of ascorbic acid (AA) have been investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The polymer modified graphite electrode was prepared by a very simple method just by immersing the graphite electrode in PDDA solution for 20 minutes. The PDDA/Gr modified electrode displayed excellent electrocatalytic activity towards the oxidation of UA, DA and AA compared to that at the bare graphite electrode. The electrochemical oxidation signals of UA, DA and AA are well resolved into three distinct peaks with peak potential separations of 220 mV, 168 mV and 387 mV between AA‐DA, DA‐UA and AA‐UA respectively in cyclic voltammetry studies and the corresponding peak potential separations are 230 mV, 130 mV and 354 mV respectively in differential pulse voltammetry. The lowest detection limits obtained for UA, DA and AA were 1×10^?7 M, 2×10^?7 M and 800×10^?9 M respectively. The PDDA/Gr electrode efficiently eliminated the interference of DA and a high concentration of AA in the determination of UA with good selectivity, sensitivity and reproducibility. The modified electrode was also successfully applied for simultaneous determination of UA, DA and AA in their ternary mixture.     

A deuterium–palladium electrode as a new sensor in non-aqueous solutions: potentiometric titration of weak acids in N,N-dimethylformamide and N-methylpyrrolidone

A deuterium–palladium electrode was employed as a new indicator electrode for the titration of weak acids in N,N-dimethylformamide and methylpyrrolidone. The investigated electrode showed a linear dynamic response for p-toluenesulfonic acid in the concentration range from 0.1 to 0.001 M, with a nernstian slope of 78.0 mV in N,N-dimethylformamide and of 64 mV per decade in N-methylpyrrolidone. Sodium methylate, potassium hydroxide, and tetrabutylammonium hydroxide proved to be very suitable titrating agents for these titrations. The potential in the course of the titration and at the titration end point was rapidly established. The response time was less than 10–11 s, and the lifetime of the electrode is long. The experimental results obtained for the proposed electrochemical sensor and a conventional glass electrode were in good agreement. The advantages of the electrode are log-term stability, fast response, reproducibility, and easy preparation.     

邻苯二胺、邻氨基酚的电化学聚合及聚合的膜性质

邻苯二胺(ODB), 邻氨基酚(OAP)在酸性水溶液中易电聚合, 可形成致密的聚合膜。聚邻苯二胺(PODB)在PH<4时具有电活性, 其氧化还原反应与电变色效应对应。聚邻苯二胺,聚邻氨基酚(POAP)膜电极电位在pH=4～10范围对pH有Nernst响应, 电极系数分别为59mV/pH和57mV/pH。响应时间小于3分钟。PODB, POAP膜能与Ni~(2+), Co~(2+)过渡金属离子形成稳定的聚合络合膜。此膜在碱性介质中具有稳定的循环伏安行为, 膜中的金属离子可被H~+交换。PODB电极的—NH_2基可再修饰引入醌/氢醌功能团。