Often, fluoride based electrolyte was applied to synthesize highly ordered titanium dioxide nanotubes. However, in the present work, bundled titanium dioxide nanotubes were fabricated in chloride based electrolyte through electrochemical method. Structural and morphological investigations were carried out on the nanotubes synthesized under different anodization parameters. The growth mechanism of such nanotubes was elucidated and illustrated. The estimated diameter of the as-anodized nanotube was less than 150 nm while the length varied from hundreds of nanometer to microns. X-ray diffraction patterns and Raman spectra have showed anatase and rutile phases of titanium dioxide within the thermally treated samples.
The anti-corrosion performances of single(TEOS) and hybrid (APTES-TEOS) sol-gel coatings on Al alloy samples exposed to 3.5 wt% NaCl were evaluated employing electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The data acquired using the three corrosion analysis techniques were in accordance with each other where hybrid sol-gel coating offered the lowest corrosion rate and current density in comparison to the single precursor silanol coating. Tafel curves suggested that the hybrid silane coatings mitigate both the anodic and cathodic reactions simultaneously (mixed type inhibitor). These techniques justified that incorporation of hybrid sol-gel improved the Al corrosion protection performance considerably.
Laccase enzyme, a commonly used enzyme for the construction of biosensors for phenolic compounds was used for the first time to develop a new biosensor for the determination of the azo-dye tartrazine. The electrochemical biosensor was based on the immobilization of laccase on functionalized methacrylate-acrylate microspheres. The biosensor membrane is a composite of the laccase conjugated microspheres and gold nanoparticles (AuNPs) coated on a carbon-paste screen-printed electrode. The reaction involving tartrazine can be catalyzed by laccase enzyme, where the current change was measured by differential pulse voltammetry (DPV) at 1.1 V. The anodic peak current was linear within the tartrazine concentration range of 0.2 to 14 μM (R² = 0.979) and the detection limit was 0.04 μM. Common food ingredients or additives such as glucose, sucrose, ascorbic acid, phenol and sunset yellow did not interfere with the biosensor response. Furthermore, the biosensor response was stable up to 30 days of storage period at 4 °C. Foods and beverage were used as real samples for the biosensor validation. The biosensor response to tartrazine showed no significant difference with a standard HPLC method for tartrazine analysis.
In purine metabolism, the xanthine oxidoreductase enzyme converts hypoxanthine (HXN) to xanthine (XN) and XN to uric acid (UA). This leads to the deposition of UA crystals in several parts of the body and the serum UA level might be associated with various multifunctional disorders. The dietary intake of caffeine (CF) and ascorbic acid (AA) decreases the UA level in the serum, which leads to cellular damage. Hence, it is highly needed to monitor the UA level in the presence of AA, XN, HXN, and CF and vice versa. Considering this sequence of complications, the present paper reports the fabrication of an electrochemical sensor using low-cost N-doped carbon dots (CDs) for the selective and simultaneous determination of UA in the presence of AA, XN, HXN, and CF at the physiological pH. The colloidal solution of CDs was prepared by the pyrolysis of asparagine and fabricated on a GC electrode by cycling the potential from -0.20 to +1.2 V in a solution containing CDs and 0.01 M H2SO4. Here, the surface -NH2 functionalities of CDs were used to make a thin film of CDs on the GC electrode. FT-IR spectroscopy confirmed the involvement of the -NH2 group in the formation of the CD film. HR-TEM analysis depicts that the formed CDs showed spherical particles with a size of 1.67 nm and SEM analysis exhibits the 89 nm CD film on the GC electrode surface. The fabricated CD film was successfully used for the sensitive and selective determination of UA. The determination of UA was achieved selectively in a mixture consisting of AA, XN, HXN, and CF with 50-fold high concentration. The CDs-film fabricated electrode has several benefits over the bare electrode: (i) well-resolved oxidation peaks for five analytes, (ii) boosted sensitivity, (iii) shifted oxidation as well as on-set potentials toward less positive potentials, and (iv) high stability. The practical utility of the present sensor was tested by simultaneously determining the multifactorial disorders-causing agents in human fluids. The electrocatalyst developed in the present study is sustainable and can be used for multiple analyses; besides, the electrochemical method used for the fabrication of the CD film is environmentally benign.
A new electric-field driven extraction approach based on the integration of a bubbleless electrode into the electromembrane extraction (EME) across hollow polymer inclusion membranes (HPIMs) was demonstrated for the first time. The bubbleless electrode was prepared based on an in-situ synthesised polyacrylamide within a fused silica capillary. The electrode functions as a salt bridge, which conducts the electrical current between the acceptor phase in the lumen of the HPIM and the acceptor solution in the reservoir connected to a high voltage supply through a platinum electrode. Two types of HPIMs were employed, which consisted of desired proportions of cellulose acetate as base polymer, tris(2-ethylhexyl)phosphate as plasticizer, and di-(2-ethylhexyl)phosphoric acid as anionic carrier or Aliquat 336 as cationic carrier, respectively. The EME strategy was evaluated for the simultaneous determination of cationic quaternary ammonium and anionic chlorophenoxy acetic acid herbicides present in the river water, respectively. The analysis was carried out using capillary electrophoresis coupled with UV and contactless conductivity detection. Under the optimised conditions, enrichment factors in the range of 152-185-fold were obtained from 4mL of river water sample with a 20min extraction time and an applied voltage of 3000V. The proposed method provided good linearity with correlation coefficients ranging from 0.9982 to 0.9997 over a concentration range of 1-1000μg/L. The detection limits of the method for the herbicides were in the range of 0.3-0.4μg/L, with relative standard deviations of between 4.8% and 8.5%. The relative recoveries obtained when analysing the spiked river water ranged from 99.1% to 100%. A comparison was also made between the newly developed approach with the conventional EME setup by placing the platinum electrode directly in the lumen of the HPIMs.
In this work, a novel electrochemical sensor was fabricated for determination of amoxicillin in bovine milk samples by decoration of carboxylated multi-walled carbon nanotubes (MWCNTs) with gold nanoparticles (AuNPs) using ethylenediamine (en) as a cross linker (AuNPs/en-MWCNTs). The constructed nanocomposite was homogenized in dimethylformamide and drop casted on screen printed electrode. Field emission scanning electron microscopy (FESEM), energy dispersive X-Ray (EDX), X-Ray diffraction (XRD) and cyclic voltammetry were used to characterize the synthesized nanocomposites. The results show that the synthesized nanocomposites induced a remarkable synergetic effect for the oxidation of amoxicillin. Effect of some parameters, including pH, buffer, scan rate, accumulation potential, accumulation time and amount of casted nanocomposites, on the sensitivity of fabricated sensor were optimized. Under the optimum conditions, there was two linear calibration ranges from 0.2-10 µM and 10-30 µM with equations of Ipa (µA) = 2.88C (µM) + 1.2017; r = 0.9939 and Ipa (µA) = 0.88C (µM) + 22.97; r = 0.9973, respectively. The limit of detection (LOD) and limit of quantitation (LOQ) were calculated as 0.015 µM and 0.149 µM, respectively. The fabricated electrochemical sensor was successfully applied for determination of Amoxicillin in bovine milk samples and all results compared with high performance liquid chromatography (HPLC) standard method.
Nowadays, several neurological disorders and neurocrine tumours are associated with dopamine (DA) concentrations in various biological fluids. Highly accurate and ultrasensitive detection of DA levels in different biological samples in real-time can change and improve the quality of a patient's life in addition to reducing the treatment cost. Therefore, the design and development of diagnostic tool for in vivo and in vitro monitoring of DA is of considerable clinical and pharmacological importance. In recent decades, a large number of techniques have been established for DA detection, including chromatography coupled to mass spectrometry, spectroscopic approaches, and electrochemical (EC) methods. These methods are effective, but most of them still have some drawbacks such as consuming time, effort, and money. Added to that, sometimes they need complex procedures to obtain good sensitivity and suffer from low selectivity due to interference from other biological species such as uric acid (UA) and ascorbic acid (AA). Advanced materials can offer remarkable opportunities to overcome drawbacks in conventional DA sensors. This review aims to explain challenges related to DA detection using different techniques, and to summarize and highlight recent advancements in materials used and approaches applied for several sensor surface modification for the monitoring of DA. Also, it focuses on the analytical features of the EC and optical-based sensing techniques available.
In this study, a sonochemical approach was utilised for the development of graphene-gold (G-Au) nanocomposite. Through the sonochemical method, simultaneous exfoliation of graphite and the reduction of gold chloride occurs to produce highly crystalline G-Au nanocomposite. The in situ growth of gold nanoparticles (AuNPs) took place on the surface of exfoliated few-layer graphene sheets. The G-Au nanocomposite was characterised by UV-vis, XRD, FTIR, TEM, XPS and Raman spectroscopy techniques. This G-Au nanocomposite was used to modify glassy carbon electrode (GCE) to fabricate an electrochemical sensor for the selective detection of nitric oxide (NO), a critical cancer biomarker. G-Au modified GCE exhibited an enhanced electrocatalytic response towards the oxidation of NO as compared to other control electrodes. The electrochemical detection of NO was investigated by linear sweep voltammetry analysis, utilising the G-Au modified GCE in a linear range of 10-5000μM which exhibited a limit of detection of 0.04μM (S/N=3). Furthermore, this enzyme-free G-Au/GCE exhibited an excellent selectivity towards NO in the presence of interferences. The synergistic effect of graphene and AuNPs, which facilitated exceptional electron-transfer processes between the electrolyte and the GCE thereby improving the sensing performance of the fabricated G-Au modified electrode with stable and reproducible responses. This G-Au nanocomposite introduces a new electrode material in the sensitive and selective detection of NO, a prominent biomarker of cancer.
An electrochemical aptasensor is described for determination of the phytohormone of zearalenone (ZEA). The gold electrode was modified with ZEA via covalent attachment using cysteamine-hydrochloride and 1,4-phenylene diisocyanate linker. A truncated ZEA aptamer with a dissociation constant of 13.4 ± 2.1 nM was used in an aptasensor. The electrochemical property was investigated using square wave voltammetry for monitoring the change in the electron transfer using the ferro/ferricyanide system as redox probe. Under optimal experimental conditions, the response was best measured at a potential of 0.20 V (vs. Ag/AgCl). The signals depended on the competitive mechanism between the immobilised ZEA and free ZEA for the aptamer binding site. The aptasensor works in the range 0.01 to 1000 ng·mL-1 ZEA concentration, with a detection limit of 0.017 ng·mL-1. High degree of cross-reactivity with the other analogues of ZEA was observed, whereas none towards other mycotoxins. The aptasensor was further applied for the determination of ZEA in the extract of maize grain and showed good recovery percentages between 87 and 110%. Graphical abstract Schematic representation of the electrochemical determination of zearalenone based on indirect competitive assay. Step a Immobilisation of ZEA on the surface of gold electrode via covalent attachment, b competition for the ZEA aptamer binding site between immobilised and free ZEA, and c current signal of the binding event based on SWV technique.
This paper reports a rapid and in-situ electrochemical polymerization method for the fabrication of polypyrrole nanoparticles incorporated reduced graphene oxide (rGO@PPy) nanocomposites on a ITO conducting glass and its application as a counter electrode for platinum-free dye-sensitized solar cell (DSSC). The scanning electron microscopic images show the uniform distribution of PPy nanoparticles with diameter ranges between 20 and 30 nm on the rGO sheets. The electrochemical studies reveal that the rGO@PPy has smaller charge transfer resistance and similar electrocatalytic activity as that of the standard Pt counter electrode for the I₃(-)/I(-) redox reaction. The overall solar to electrical energy conversion efficiency of the DSSC with the rGO@PPy counter electrode is 2.21%, which is merely equal to the efficiency of DSSC with sputtered Pt counter electrode (2.19%). The excellent photovoltaic performance, rapid and simple fabrication method and low-cost of the rGO@PPy can be potentially exploited as a alternative counter electrode to the expensive Pt in DSSCs.
We present an investigation on a coupled system consists of gold nanoparticles and silicon nanocrystals. Gold nanoparticles (AuNPs) embedded into porous silicon (PSi) were prepared using the electrochemical deposition method. Scanning electron microscope images and energy-dispersive X-ray results indicated that the growth of AuNPs on PSi varies with current density. X-ray diffraction analysis showed the presence of cubic gold phases with crystallite sizes around 40 to 58 nm. Size dependence on the plasmon absorption was studied from nanoparticles with various sizes. Comparison with the reference sample, PSi without AuNP deposition, showed a significant blueshift with decreasing AuNP size which was explained in terms of optical coupling between PSi and AuNPs within the pores featuring localized plasmon resonances.
In this work, an electrochemical method for detection of trace amount of aluminium (Al3+), a heavy metal ion, based on a bare gold electrode (AuE) was developed. Current responses of the AuE under various type of electrolytes, redox indicators, pH, scan rate and accumulation time were investigated using cyclic voltammetry (CV) method to obtain the optimum conditions for Al3+ detection. The sensing properties of the AuE towards the target ion with different concentrations were investigated using differential pulse voltammetry (DPV) method. From the CV results, the optimal conditions for the detection of Al3+ were Tris-HCl buffer (0.1 M, pH 2) supported by 5 mM Prussian blue with scan rate and accumulation time respectively of 100 mVs−1 and 15 s. Under the optimum conditions, the DPV method was detected with different concentrations of aluminium ion ranging from 0.2 to 1.0 ppm resulted in a good linear regression r² = 0.9806. This result suggests that the optimisation of the basic parameters in electrochemical detection using AuE is crucial before further modification of the Au-electrode to improve the sensitivity and selectivity especially for the low concentration of ion detection. The developed method has a great potential for rapid detection of heavy metal ion (Al3+) in drinking water samples.
Polyoctopamine (POct), an amine-functionalised non-conducting polymer, as the transducer layer in an electrochemical biosensor, is presented. This polymer offers versatile covalent coupling either through thiol linker conjugation, carboxyl or aldehyde functional groups without the requirement of pre- or post-surface activation. The colorectal cancer biomarker carcinoembryonic antigen (CEA) was selected as the target analyte, whilst an antibody and a synthetic binding protein, an Affimer, were used as distinct bioreceptors to demonstrate the versatility of polyoctopamine as a transducer polymer layer for oriented immobilisation of the bioreceptors. The electrodeposited polymer layer was characterised using cyclic voltammetry, electrochemical impedance spectroscopy, and on-sensor chemiluminescent blotting. The performance of optimised POct-based biosensors were tested in spiked human serum. Results showed that the electropolymerisation of octopamine on screen printed gold electrode generates a thin polymer film with low resistance. Close proximity of the immobilised bioreceptors to the transducer layer greatly enhanced the sensitivity detection. The sensitivity of the smaller monomeric bioreceptor (Affimer, 12.6 kDa) to detect CEA was comparable to the dimeric antibody (150 kDa) with limit of detection at 11.76 fM which is significantly lower than the basal clinical levels of 25 pM. However, the Affimer-based sensor had a narrower dynamic range compared to the immunosensor (1-100 fM vs. 1 fM - 100 nM, respectively). All electrochemical measurements were done in less than 5 min with small sample volumes (10 μl). Hence, polyoctopamine features a simple fabrication of impedimetric biosensors using amine-functionalisation technique, provides rapid response time with enhanced sensitivity and label-free detection.
Paracetamol (PAR) is an effective antipyretic and analgesic drug utilized worldwide, safer at therapeutic levels but over-dosing and the chronic usage of PAR results in accumulation of toxic metabolites, which leads to kidney and liver damages. Hence, a simple, rapid, cost-effective, and sensitive analytical technique is needed for the accurate determination of PAR in pharmaceutical and biological samples. Though numerous techniques have been reported for PAR detection, electrochemical methods are being receiving more interest due to their advantages. Moreover, in the past few decades, room temperature ionic liquids (RTILs) have been utilized in electrochemical sensors due to their attractive properties. In this present review, authors gathered research findings available for the determination of PAR using RTIL-based electrochemical sensors and discussed. The advantages and limitations in these systems as well as the future research directions are summarized.
Microbial electrochemical systems (MESs) are an attracting technology for the disposal of wastewater treatment and simultaneous energy production. In MESs, at the anode microorganisms through the catalytic activity generates electrons that can be converted into electricity or other valuable chemical compounds. Microorganisms those having ability to donate and accept electrons to and from anode and cathode electrodes, respectively are recognized as 'exoelectrogens'. In the MESs, it renders an important function for its performance. In the present mini-review, we have discussed the role of microbiome including pure culture, enriched culture and mixed culture in different BESs application. The effects of operational and biological factors on microbiome development have been discussed. Further discussion about the molecular techniques for the evaluation of microbial community analysis is addressed. In addition different electrochemical techniques for extracellular electron transfer (EET) mechanism of electroactive biofilms have been discussed. This review highlights the importance of microbiome in the development of MESs, effective operational factors for exo-electrogens activities as well their key challenges and future technological aspects are also briefly discussed.
Detection and quantification of DNA is critical to many areas of life sciences and health care, from
disease diagnosis to drug screening. The transduction of DNA through electrochemical methods have a fast response rate and with a conductometric device like the silicon nanowire which can be fabricated to have a similar diameter of the DNA molecule being targeted, detection is real-time. Critical to this is the interfacing of a current-source and an amplifier capable of achieving a maximum of 10 pico ampere input bias. In this project, we fabricated a silicon nanowire using the top down approach and built a circuit that can mimic the output signal as low as 12 nA and achieved a gain of 1 million to be interfaced with the nanowire for real-time DNA detection.
More than 200 different cultivars of durian exist worldwide but Durio zibethinus or Musang King (MK) is the most premium and prized durian fruit among the recommended varieties. Early identification of this premium variety is critical to protect from non-authentic MK durian cultivars. However, the MK variety's morphological traits are nearly identical to other varieties. Currently, the identification of durian varieties is mostly performed via evaluation of leaf shape, fruit shape, aroma, taste and seed shape and this requires trained personnel for the morphology observation. To enable the rapid identification of the MK variety, PCR amplification of ten durian varieties using six gene candidates from the chloroplast genome was first performed to obtain DNA probes that were specific to the MK durian variety. PCR amplification of ten durian varieties using primers designed confirmed that the nadhA gene sequence showed an obvious difference in the MK variety from other durian varieties. The unique sequence of MK was used as a DNA probe to develop an electrochemical biosensor for the direct identification of the MK durian variety. The electrochemical biosensor was based on the hybridization response of the immobilized DNA probe with the target DNA from the MK variety and was monitored via differential pulse voltammetry technique. Under optimal conditions, the DNA electrochemical biosensor showed a low detection limit at 10% of MK genomic DNA concentration with a wide linear calibration range of 0.05-1.5 µM (R2 = 0.9891) and RSD value of 3.77% (n = 3). The results of the developed DNA biosensor provide high promise for the development of portable sensors employed in the determination of MK variety in the field.
Nitrite (NO2-) is widely used as an additive to extend the shelf life of food products. Excessive nitrite intake not only causes blood-related diseases but also has the potential risk of causing cancers. A disposable screen-printed electrode was modified with nano‑palladium decorated bismuth sulfide microspheres (nanoPd@Bi2S3MS/SPE), and integrated with a smartphone-interfaced potentiostat to develop a portable, electrochemical nitrite sensor. NanoPd@Bi2S3MS was prepared by the hydrothermal reduction of a Bi2S3MS and Pd2+ dispersion and drop cast on the SPE. The nanoPd@Bi2S3MS/SPE was coupled with a smartphone-controlled portable potentiostat and applied to determine nitrite in food samples. The linear range of the sensor was 0.01-500 μM and the limit of detection was 0.0033 μM. The proposed system showed good repeatability, reproducibility, catalytic stability, and immunity to interferences. The proposed electrode material and a smartphone-based small potentiostat created a simple, portable, fast electrochemical sensing system that accurately measured nitrite in food samples.
The behaviour of protonated ractopamine (RacH(+)) at an array of micro-interfaces between two immiscible electrolyte solutions (micro-ITIES) was investigated via cyclic voltammetry (CV) and linear sweep stripping voltammetry (LSSV). The micro-ITIES array was formed at silicon membranes containing 30 pores of radius 11.09±0.12 µm and pore centre-to-centre separation of 18.4±2.1 times the pore radius. CV shows that RacH(+) transferred across the water |1,6-dichlorohexane µITIES array at a very positive applied potential, close to the upper limit of the potential window. Nevertheless, CV was used in the estimation of some of the drug's thermodynamic parameters, such as the formal transfer potential and the Gibbs transfer energy. LSSV was implemented by pre-concentration of the drug, into the organic phase, followed by voltammetric detection, based on the back-transfer of RacH(+) from the organic to aqueous phase. Under optimised pre-concentration and detection conditions, a limit of detection of 0.1 µM was achieved. In addition, the impact of substances such as sugar, ascorbic acid, metal ions, amino acid and urea on RacH(+) detection was assessed. The detection of RacH(+) in artificial serum indicated that the presence of serum protein interferes in the detection signal, so that sample deproteinisation is required for feasible bioanalytical applications.
Para-arsanilic acid (p-ASA) has been widely used in the poultry industry to promote growth and prevent dysentery. It is excreted unchanged in the manure and released into non-target sites causing organoarsenic pollution risk to the environment and living system. Therefore, simple and effective analytical strategies are demanded for determining the samples that contain p-ASA. However, direct determination of both p-ASA and ortho-arsanilic acid (o-ASA) using differential pulse cathodic stripping voltammetry (DPCSV) gives the similar voltammograms that directly hamper the analysis used by the DPCSV technique. In this study, a method to determine and differentiate p-ASA from o-ASA via diazotization and coupling reaction of the amine groups followed by the direct DPCSV determination of diazo compounds is presented. The diazotization reaction carried out at pH 1.5 and 0 ± 1°C for 10 min showed two reduction peaks in DPCSV at-70 mV and -440 mV vs. Ag/AgCl (KCl 3 M). However, when the diazotization reaction was performed at pH 12.5 and 0 ± 1°C for 40 min, a coloured azo compound was produced and the DPCSV showed only one reduction peak that appeared at -600 mV vs. Ag/AgCl (3 M of KCl). The results of this study show that only p-ASA compound gave a reduction peak, whereas o-ASA compound did not give any peak. The detection limit of p-ASA was found to be 4 × 10(-8 )M. As a result, the proposed electro-analytical technique might be a good candidate to determine and differentiate the p-ASA present in the poultry and environmental samples.