Potentiometric urea biosensor based on multi-walled carbon nanotubes (MWCNTs)/silica composite material

A novel potentiometric urea biosensor has been fabricated with urease (Urs) immobilized multi-walled carbon nanotubes (MWCNTs) embedded in silica matrix deposited on the surface of indium tin oxide (ITO) coated glass plate. The enzyme Urs was covalently linked with the exposed free –COOH groups of functionalized MWCNTs (F-MWCNTs), which are subsequently incorporated within the silica matrix by sol–gel method. The Urs/MWCNTs/SiO₂/ITO composite modified electrode was characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and UV–visible spectroscopy. The morphologies and electrochemical performance of the modified Urs/MWCNTs/SiO₂/ITO electrode have been investigated by scanning electron microscopy (SEM) and potentiometric method, respectively. The synergistic effect of silica matrix, F-MWCNTs and biocompatibility of Urs/MWCNTs/SiO₂ made the biosensor to have the excellent electro catalytic activity and high stability. The resulting biosensor exhibits a good response performance to urea detection with a wide linear range from 2.18 × 10^? 5 to 1.07 × 10^? 3 M urea. The biosensor shows a short response time of 10–25 s and a high sensitivity of 23 mV/decade/cm².     

Carbon nanotube/chitosan/gold nanoparticles-based glucose biosensor prepared by a layer-by-layer technique

A new amperometric glucose biosensor was constructed, based on the immobilization of glucose oxidase (GOx) with cross-linking in the matrix of chitosan on a glassy carbon electrode, which was modified by layer-by-layer assembled carbon nanotube (CNT)/chitosan (CHIT)/gold nanoparticles (GNp) multilayer films. With the increasing of CNT/CHIT/GNp layers, the response current to H₂O₂ was changed regularly and the response current reached a maximum value when the number of CNT/CHIT/GNp layers was 8. The assembling process of multilayer films was simple to operate. With GOx as an enzyme model, a new glucose biosensor was fabricated. The excellent electocatalytic activity and special structure of the enzyme electrode resulted in good characteristics. The linear range was 6 × 10^? 6 ～ 5 × 10^? 3 M, with a detection limit of 3 × 10^? 6 M estimated at a signal-to-noise ratio of 3, fast response time (less than 6 s). Moreover, it exhibited good reproducibility and stability.     

A highly-sensitive l-lactate biosensor based on sol-gel film combined with multi-walled carbon nanotubes (MWCNTs) modified electrode

A new type of amperometric l-lactate biosensor based on silica sol-gel and multi-walled carbon nanotubes (MWCNTs) organic–inorganic hybrid composite material was developed. The sol-gel film was used to immobilize l-lactate oxidase on the surface of glassy carbon electrode (GCE). MWCNTs were used to increase the current response and improve the performance of biosensor. The sol-gel film fabrication process parameters such as H₂O : TEOS and pH were optimized, Effects of some experimental variables such as applied potential, temperature, and pH on the current response of the biosensor were investigated. Analytical characteristics and dynamic parameters of the biosensors with and without MWCNTs in the hybrid film were compared, and the results showed that analytical performance of the biosensor could be improved greatly after introduction of the MWCNTs. Sensitivity, linear range, limit of detection (S / N = 3) were 2.097 μA mM^− 1, 0.3 to 1.5 mM, 0.8 × 10^− 3 mM for the biosensor without MWCNTs and 6.031 μA mM^− 1, 0.2 to 2.0 mM, 0.3 × 10^− 3 mM for the biosensor with MWCNTs, respectively. This method has been used to determine the l-lactate concentration in real human blood samples.     

Multi-walled carbon nanotubes-based glucose biosensor prepared by a layer-by-layer technique

The loading of multi-walled carbon nanotubes (MWNTs) and glucose oxidase (GOx) in the alternate layers of a glucose biosensor was first optimized based on a layer-by-layer construction on the surface of a graphite disk electrode. With the increasing of MWNTs/GOx layers, the response current to glucose was changed regularly and the response current reached a maximum value when the number of MWNTs/GOx layers was 6. Owing to a good electrical conductivity, strong adsorption and excellent bioconsistency of MWNTs, the (MWNTs/GOx)₆ films-coated glucose biosensor had an excellent electrochemical properties. The response current of the (MWNTs/GOx)₆ films-coated biosensor to 3 × 10^− 2 M glucose was 1.63 μA while the response time was only 6.7 s. The linear range and the lowest detectable concentration of this biosensor was 5 × 10^− 4∼1.5 × 10^− 2 M and 0.9 × 10^− 4 M, respectively.     

Application of graphene–pyrenebutyric acid nanocomposite as probe oligonucleotide immobilization platform in a DNA biosensor

A stable and uniform organic–inorganic nanocomposite that consists of graphene (GR) and pyrenebutyric acid (PBA) was obtained by ultrasonication, which was characterized by scanning electron microscopy (SEM) and UV–vis absorption spectra. The dispersion was dropped onto a gold electrode surface to obtain GR–PBA modified electrode (GR–PBA/Au). Electrochemical behaviors of the modified electrode were characterized by cyclic voltammetry and electrochemical impedance spectroscopy using [Fe(CN)₆]^3 ?/4 ? as the electroactive probe. A novel DNA biosensor was constructed based on the covalent coupling of amino modified oligonucleotides with the carboxylic group on PBA. By using methylene blue (MB) as a redox-active hybridization indicator, the biosensor was applied to electrochemically detect the complementary sequence, and the results suggested that the peak currents of MB showed a good linear relationship with the logarithm values of target DNA concentrations in the range from 1.0 × 10^? 15 to 5.0 × 10^? 12 M with a detection limit of 3.8 × 10^? 16 M. The selectivity experiment also showed that the biosensor can well distinguish the target DNA from the non-complementary sequences.     

Multi-walled carbon nanotube modified carbon paste electrode as an electrochemical sensor for the determination of epinephrine in the presence of ascorbic acid and uric acid

A biocompatible electrochemical sensor for selective detection of epinephrine (EP) in the presence of 1000-fold excess of ascorbic acid (AA) and uric acid (UA) was fabricated by modifying the carbon paste electrode (CPE) with multi-walled carbon nanotubes (MWCNTs) using a casting method. The electro-catalytic activity of the modified electrode for the oxidation of EP was investigated. The current sensitivity of EP was enhanced to about five times upon modification. A very minimum amount of modifier was used for modification. The voltammetric response of EP was well resolved from the responses of AA and UA. The electrochemical impedance spectroscopic (EIS) studies reveal the least charge transfer resistance for the modified electrode. The AA peak that is completely resolved from that of EP at higher concentrations of AA and the inability of the sensor to give an electrochemical response for AA below a concentration of 3.0 × 10^? 4 M makes it a unique electrochemical sensor for the detection of EP which is 100% free from the interference of AA. Two linear dynamic ranges of 1.0 × 10^? 4–1.0 × 10^? 5 and 1.0 × 10^? 5–5.0 × 10^? 7 M with a detection limit of 2.9 × 10^? 8 M were observed for EP at modified electrode. The practical utility of this modified electrode was demonstrated by detecting EP in spiked human blood serum and EP injection. The modified electrode is highly reproducible and stable with anti fouling effects.     

Ho3+ carbon paste sensor based on multi-walled carbon nanotubes: Applied for determination of holmium content in biological and environmental samples

For the first time a novel multi-walled carbon nanotubes (MWCNTs) modified Ho³⁺ carbon paste sensor is introduced. The electrode with a composition containing 20% paraffin oil, 60% graphite powder, 15% N-(1-thia-2-ylmethylene)-1,3-benzothiazole-2-amine (TBA) as an ionophore, and 5% MWCNTs, exhibits a stable potential response to Ho³⁺ ions with a nice Nernstian behavior (19.3 ± 0.3 mV decade^? 1) in a wide dynamic linear concentration range of Ho³⁺ ions (1 × 10^? 8–1.0 × 10^? 2 M). In the absence of MWCNTs, sensitivity of the Ho³⁺ sensor was relatively poor. The proposed modified Ho³⁺ sensor shows very low detection limit (7.0 × 10^? 9 M) and a fast response time (13 s). It has a long life time (more than 2 months) and its response is independent of pH in the range of 3.8–7.5. In term of selectivity, Ho³⁺ sensor has a good selectivity over all lanthanide members and common alkali and alkaline earth metal ions. The Ho³⁺ sensor was applied for the determination of Ho³⁺ ion concentration in water, holmium alloys and synthetic human serum.     

Determination of Pb2+ ions by a modified carbon paste electrode based on multi-walled carbon nanotubes (MWCNTs) and nanosilica

A novel carbon paste ion selective electrode for determination of trace amount of lead was prepared. Multi-walled carbon nanotubes (MWCNTs) and nanosilica were used for improvement of a lead carbon paste sensor response. MWCNTs have a good conductivity which helps the transduction of the signal in carbon paste electrode. The electrode composition of 20 wt% paraffin oil, 57% graphite powder, 15% ionophore (thiram), 5% MWCNTs, and 3% nanosilica showed the stable potential response to Pb²⁺ ions with the Nernstian slope of 29.8 (±0.2) mV decade^?1 over a wide linear concentration range of 10^?7–10^?2 mol L^?1. The electrode has fast response time, and long term stability (more than 2 months). The proposed electrode was used to determine the concentration of lead ions in waste water and black tea samples.     

Preparation and characterization of copper nanoparticles/zinc oxide composite modified electrode and its application to glucose sensing

We report a new method for selective detection of d(+)-glucose using a copper nanoparticles (Cu-NPs) attached zinc oxide (ZnO) film coated electrode. The ZnO and Cu-NPs were electrochemically deposited onto indium tin oxide (ITO) coated glass electrode and glassy carbon electrode (GCE) by layer-by-layer. In result, Cu-NPs/ZnO composite film topography was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. SEM and AFM confirmed the presence of nanometer sized Cu-NPs/ZnO composite particles on the electrode surface. In addition, X-ray diffraction pattern revealed that Cu-NPs and ZnO films were attached onto the electrode surface. Indeed, the Cu-NPs/ZnO composite modified electrode showed excellent electrocatalytic activity for glucose oxidation in alkaline (0.1 M NaOH) solution. Further, we utilized the Cu-NPs/ZnO composite modified electrode as an electrochemical sensor for detection of glucose. This glucose sensor showed a linear relationship in the range from 1 × 10^? 6 M to 1.53 × 10^? 3 M and the detection limit (S/N = 3) was found to be 2 × 10^? 7 M. The Cu-NPs/ZnO composite as a non-enzymatic glucose sensor presents a number of attractive features such as high sensitivity, stability, reproducibility, selectivity and fast response. The applicability of the proposed method to the determination of glucose in human urine samples was demonstrated with satisfactory results.     

Effects of poly(oxyethylene)-block structure in polyetheramines on the modified carbon nanotube/poly(lactic acid) composites

The hybrids of multi-walled carbon nanotube and poly(lactic acid) (MWCNT/PLA) were prepared by a melt-blending method. In order to enhance the compatibility between the PLA and MWCNTs, the surface of the MWCNTs was covalently modified by Jeffamine® polyetheramines by functionalizing MWCNTs with carboxylic groups. Different molecular weights and hydrophilicity of the polyethermaines were grafted onto MWCNTs with the assistance of a dehydrating agent. The results showed that low-molecular-weight Jeffamine® polyetheramine modified MWCNTs can effectively improve the thermal properties of PLA composites. On the other hand, high-molecular-weight and poly(oxyethylene)-segmented polyetheramine could render the modified MWCNTs of well dispersion in PLA, and consequently affecting the improvements of mechanical properties and conductivity of composite materials. With the addition of 3.0 wt% MWCNTs, the increment of E′ of the composite at 40 °C was 79%. For conductivity, the surface resistivity decreased from 1.27 × 10¹² Ω/sq for neat PLA to 8.30 × 10⁻³ Ω/sq for the composites.     

Highly sensitive amperometric sensor for micromolar detection of trichloroacetic acid based on multiwalled carbon nanotubes and Fe(II)–phtalocyanine modified glassy carbon electrode

A highly sensitive electrochemical sensor for the detection of trichloroacetic acid (TCA) is developed by subsequent immobilization of phthalocyanine (Pc) and Fe(II) onto multiwalled carbon nanotubes (MWCNTs) modified glassy carbon (GC) electrode. The GC/MWCNTs/Pc/Fe(II) electrode showed a pair of well-defined and nearly reversible redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) with surface-confined characteristics. The surface coverage (Γ) and heterogeneous electron transfer rate constant (k_s) of immobilized Fe(II)–Pc were calculated as 1.26 × 10^? 10 mol cm^? 2 and 28.13 s^? 1, respectively. Excellent electrocatalytic activity of the proposed GC/MWCNTs/Pc/Fe(II) system toward TCA reduction has been indicated and the three consequent irreversible peaks for electroreduction of CCl₃COOH to CH₃COOH have been clearly seen. The observed chronoamperometric currents are linearly increased with the concentration of TCA at concentration range up to 20 mM. Detection limit and sensitivity of the modified electrode were 2.0 μM and 0.10 μA μM^? 1 cm^? 2, respectively. The applicability of the sensor for TCA detection in real samples was tested. The obtained results suggest that the proposed system can serve as a promising electrochemical platform for TCA detection.     

Application of 1-ethyl-3-(2,5-dihydro-4-(3,5-dimethyl-1H-pyrazol-4-yl)-5-oxo-1H-pyrazol-3-yl)thiourea as sensing material for construction of Tm3+-PVC membrane sensor

A thulium(III) membrane sensor was made using 2% sodium tetraphenyl borate (NaTPB), 65% dibutylphthalate (DBP), 30% poly(vinyl chloride) (PVC) and 3% 1-ethyl-3-(2,5-dihydro-4-(3,5-dimethyl-1H-pyrazol-4-yl)-5-oxo-1H-pyrazol-3-yl)thiourea (ET) as an ionophore. Conductometric study shows selectivity of the Et toward Tm³⁺ ions. Nernstian response of 19.6 ± 0.4 mV per decade of thulium concentration was observed, and the electrode worked well in concentration range of 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^? 1 with a lower detection limit (LDL) of 7.2 × 10^? 7 mol L^? 1, in a pH range of 4.3–10.4. The selectivity of the sensor over alkaline, alkaline earth, transition and heavy metal ions was also found to be in a satisfactory range. To check the analytical applicability of the proposed Tm³⁺ sensor, it was successfully used as an indicator electrode in analysis of thulium in certified reference materials.     

Fabrication of a PVC membrane samarium(III) sensor based on N,N′,N″-tris(4-pyridyl)trimesic amide as a selectophore

A new ion-selective electrode for Sm^3 + ion is described based on the incorporation of N,N′,N″-tris(4-pyridyl)trimesic amide (TPTA) in a poly(vinylchloride) (PVC) matrix. The membrane sensor comprises nitrobenzene (NB) as a plasticizer, and oleic acid (OA) as an anionic additive. The sensor with the optimized composition shows a Nernstian potential response of 19.8 ± 0.5 mV decade^? 1 over a wide concentration range of 1.0 × 10^? 2 and 1 × 10^? 6 mol L^? 1, with a lower detection limit of 4.7 × 10^? 7 mol L^? 1 and satisfactor applicable pH range of 3.6–9.2. Having a short response time of less than 10 s and a very good selectivity towards the Sm^3 + over a wide variety of interfering cations (e.g. alkali, alkaline earth, transition and heavy metal ions) the sensor seemed to be a promising analytical tool for determination of the Sm^3 +. Hence, it was used as an indicator electrode in the potentiometric titration of samarium ion with EDTA. It was also applied to the direct samarium recovery in binary mixtures.     

Highly selective determination of perchlorate by a novel potentiometric sensor based on a synthesized complex of copper

In this paper, a highly selective poly (vinyl chloride) (PVC) membrane electrode based on (1, 9-dibenzyl-1, 3, 7, 9, 11, 15-hexaaza cyclohexa decane) copper(II) perchlorate; [Cu((benzyl)₂[16]aneN₆)](ClO₄)₂; as a synthesized ionophore, for perchlorate-selective electrode is reported. The influence of membrane composition, pH and possible interfering anions were investigated on the response properties of the electrode. The sensor responds to perchlorate ion in linear range from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a slope ? 59.4 ± 0.3 mV per decade. The limit of detection of the electrode was 4.0 × 10^? 7 M ClO₄^–. Selectivity coefficients indicate a good discriminating ability towards ClO₄^– ion in comparison to other anions. The proposed sensor has a fast response time of about 7 s and can be used for at least 2 months without any considerable divergence in potential. Due to importance of analysis of perchlorate in water samples, this selective electrode was applied as potentiometric sensor in determination of perchlorate ion in real samples.     

Study on electrochemical behaviors and the reaction mechanisms of dopamine and epinephrine at the pre-anodized inlaying ultrathin carbon paste electrode with nichrome as a substrate

In this paper, nichrome was adopted as a substrate, to fabricate the pre-anodized inlaying ultrathin carbon paste electrode (PAIUCPE). The electrochemical behaviors of dopamine (DA) and epinephrine (EP) at the electrode were investigated by cyclic voltammetry (CV). The reaction mechanisms of DA and EP have also been put forward. It was found that the electrode showed an excellent electrochemical behavior for electrode reaction of DA and EP. The cathodic potential difference of DA and EP was about 370 mV and the simultaneous determination of DA and EP was achieved based on it. The reduction peak current was proportional to the DA and EP concentrations in the range of 8.0 × 10^? 7–3.0 × 10^? 4 M and 2.0 × 10^? 6–1.5 × 10^? 4 M with the detection limits of 1.70 × 10^? 7 M and 3.27 × 10^? 7 M, respectively. Because the oxidation of ascorbic acid (AA) is an irreversible reaction at the PAIUCPE, the interferences of AA for determining DA and EP were eliminated. The method has been successfully applied to the determination of DA and EP in hydrochloride injection with satisfactory results.     

Fabrication of an iron(III) PVC-membrane sensor based on bis-benzilthiocarbohydrazide as a selective sensing material

The construction, performance characteristics, and application of a novel iron(III) membrane sensor based on a new bis-benzilthiocarbohydrazide (BBTC) are reported in this paper. The sensor is prepared by incorporating of BBTC, nitrobenzene (NB), and sodium tetraphenyl borate (NaTPB) into a plasticized poly(vinyl chloride) membrane. The electrode reveals a Nernstian behavior over a wide iron ion concentration range (1.0 × 10^? 2–1.0 × 10^? 7 mol L^? 1), and relatively low detection limit (8.6 × 10^? 8 mol L^? 1). The potentiometric response is independent on the pH of the solution in the range of 1.6–4.3. The electrode shows a very short response time (< 10 s). The proposed electrode can be used for at least nine weeks without any considerable divergence in potentials. It exhibits very good selectivity relative to a wide variety of alkali, alkaline earth, transition and heavy metal ions. In fact, the selectivity of the proposed sensor shows great improvements compared to the previously reported electrodes for the iron ion. Also, the sensors accuracy was investigated in two ways: (i) with the potentiometric titration of a Fe(III) solution with EDTA and (ii) with the Fe(III) monitoring in river and wastewater samples.     

Simultaneous determination of phenylhydrazine and hydrazine by a nanostructured electrochemical sensor

In the present paper, the use of a nanostructured electrochemical sensor was described for simultaneous determination of phenylhydrazine (PhH) and hydrazine (HZ). This electrochemical sensor was prepared by a simple and rapid method by modification of carbon paste electrode with a derivative of hydroquinone and TiO₂ nanoparticles. The modified electrode showed an excellent character for electrocatalytic oxidation of PhH. Using differential pulse voltammetry, a highly selective and simultaneous determination of PhH and HZ has been explored at the modified electrode. Differential pulse voltammetry peak currents of PhH and HZ increased linearly with their concentration at the ranges of 2.0 × 10^? 6 to 1.0 × 10^? 3 M and 7.5 × 10^? 5–1.0 × 10^? 3 M, respectively and the detection limits for PhH and HZ were 7.5 × 10^? 7 M and 9.0 × 10^? 6 M, respectively.     

Application of nanostructured ZnO films for electrochemical DNA biosensor

Nanostructured zinc oxide (nsZnO) films have been fabricated onto conducting indium–tin–oxide (ITO) coated glass plate, by cathodic electro-deposition to immobilize probe DNA specific to M. tuberculosis via physisorption based on strong electrostatic interactions between positively charged ZnO (isoelectric point = 9.5) and negatively charged DNA to detect its complementary target. Electrochemical studies reveal that the presence of nano-structured ZnO results in increased electro-active surface area for loading of DNA molecules. The DNA–nsZnO/ITO bioelectrode exhibits interesting characteristics such as detection range of 1 × 10^?6 ? 1 × 10^?12 M, detection limit of 1 × 10^?12 M (complementary target) and 1 × 10^?13 M (genomic DNA), reusability of about 10 times, response time of 60s and stability of up to 4 months when kept at 4°C.     

Accumulation and trace measurement of paraquat at kaolin-modified carbon paste electrode

The carbon paste electrode modified by kaolin (KCPE) has been utilized for the determination of pesticides with high sensitivity based on their redox behavior. The experiment is performed on the use of cyclic and square wave voltammetry. Experimental conditions were optimized by varying the accumulation time, kaolin loading and measuring solution pH. Square wave voltammetric response showed a linear calibration curve in the range from 3.9 × 10^? 9 to 9 × 10^? 5 mol L^? 1 with a detection limit of 2 × 10^? 10 mol L^? 1 at kaolin-modified carbon paste electrode. As a result, it was found that there was feasibility in the use of kaolin to improve the carbon paste electrode properties.     

Potentiometric detection of silver (I) ion based on carbon paste electrode modified with diazo-thiophenol-functionalized nanoporous silica gel

For the first time, triazene compound functionalized silica gel was incorporated into carbon paste electrode for the potentiometric detection of silver (I) ion. A novel diazo-thiophenol-functionalized silica gel (DTPSG) was synthesized, and the presence of DTPSG acted as not only a paste binder, but also a reactive material. The electrode with optimum composition, exhibited an excellent Nernstian response to Ag⁺ ion ranging from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a detection limit of 9.5 × 10^? 7 M and a slope of 60.4 ± 0.2 mV dec^? 1 over a wide pH range (4.0–9.0) with a fast response time (50 s) at 25 °C. The electrode also showed a long-time stability, high selectivity and reproducibility. The response mechanism of the proposed electrode was investigated by using AC impedance. Moreover, the electrode was successfully applied for the determination of silver ions in radiology films, and for potentiometric titration of the mixture solution of Cl^? and Br^? ions.