Abstract:Amperometric hydrogen peroxide enzyme inhibition biosensors based on horseradish peroxidase (HRP) immobilised on electropolymerised neutral red (NR) or directly on the surface of carbon film electrodes (CFE) have been successfully applied to the determination of toxic Cr(III) and Cr(VI). Parameters influencing the performance of the biosensor including the enzyme immobilisation method, the amount of hydrogen peroxide, applied potential and electrolyte pH were optimised. The inhibition of horseradish peroxidase… Show more
“…Measurements of trace levels of Cr(VI) as well as total chromium level in groundwater have attracted much attention for human health and environmental control. Generally, Cr(VI) is analyzed by atomic absorption spectroscopy, UV-vis spectroscopy, inductively coupled plasma-mass spectrometry, fluorescence, or electrochemical analysis [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. However, these methods often suffer from some issues such as complicated separation/pre-concentration procedures, high cost, time-consuming, or lack of portability.…”
A rapid and highly sensitive photoelectrochemical (PEC) method has been proposed for the determination of trace amounts of chromium in water samples under visible-light irradiation. Here, a unique nanostructured hybrid of formate anion incorporated graphitic carbon nitride (F-g-C3N4) is smartly integrated with a Cr(VI) ion-imprinted polymer (IIP) as a photoactive electrode (denoted as IIP@F-g-C3N4). The nanohybrid of F-g-C3N4 exhibits an enhanced charge separation with substantially improved PEC responses versus g-C3N4. The newly designed IIP@F-g-C3N4 PEC sensor exhibits high sensitivity and selectivity for the determination of Cr(VI) because it offers efficient photogenerated electron reduction toward Cr(VI). The PEC analysis is highly linear over Cr(VI) concentrations ranging from 0.01 to 100.00ppb with a detection limit of 0.006ppb (S/N=3). Our approach can be used to detect Cr(VI), Cr(III) and the total chromium level in aqueous solution through oxidation of Cr(III) to Cr(VI) and the determination of the total chromium as Cr(VI). In practical applications, this low-cost and sensitive assay has been successfully applied for speciation determination of chromium in environmental water samples.
“…Measurements of trace levels of Cr(VI) as well as total chromium level in groundwater have attracted much attention for human health and environmental control. Generally, Cr(VI) is analyzed by atomic absorption spectroscopy, UV-vis spectroscopy, inductively coupled plasma-mass spectrometry, fluorescence, or electrochemical analysis [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. However, these methods often suffer from some issues such as complicated separation/pre-concentration procedures, high cost, time-consuming, or lack of portability.…”
A rapid and highly sensitive photoelectrochemical (PEC) method has been proposed for the determination of trace amounts of chromium in water samples under visible-light irradiation. Here, a unique nanostructured hybrid of formate anion incorporated graphitic carbon nitride (F-g-C3N4) is smartly integrated with a Cr(VI) ion-imprinted polymer (IIP) as a photoactive electrode (denoted as IIP@F-g-C3N4). The nanohybrid of F-g-C3N4 exhibits an enhanced charge separation with substantially improved PEC responses versus g-C3N4. The newly designed IIP@F-g-C3N4 PEC sensor exhibits high sensitivity and selectivity for the determination of Cr(VI) because it offers efficient photogenerated electron reduction toward Cr(VI). The PEC analysis is highly linear over Cr(VI) concentrations ranging from 0.01 to 100.00ppb with a detection limit of 0.006ppb (S/N=3). Our approach can be used to detect Cr(VI), Cr(III) and the total chromium level in aqueous solution through oxidation of Cr(III) to Cr(VI) and the determination of the total chromium as Cr(VI). In practical applications, this low-cost and sensitive assay has been successfully applied for speciation determination of chromium in environmental water samples.
“…Speciation ability of Cr is reported in Attar et al (2014). Even if the biosensor is sensitive to both Cr(III) and Cr(VI), authors claim, probably on the basis of the lower sensitivity for Cr(III) (I 50 = 37 μM) in comparison to Cr(VI) (I 50 = 3.8 μM), selective determination of Cr (VI) and Cr(III) in mixtures.…”
Recent work relevant to heavy metal determination by inhibition-enzyme electrochemical biosensors and by selected biomimetic sensors based on molecularly imprinted polymers has been reviewed. General features and peculiar aspects have been evidenced. The replace of biological component by artificial receptors promises higher selectivity and stability, while biosensors keep their capability of producing an integrated response directly related to biological toxicity of the samples.
“…56 Previous heavy metal enzyme inhibition-based biosensors have reported response times, defined as the time required to reach steady-state after introduction of the inhibitor, on the order of several minutes 29,30,57 or longer 58 , but often are unreported 33 . In some cases, especially those with irreversible inhibition, the biosensor is incubated in inhibitor solution for several minutes (often 10 min+) at each step in the calibration curve.…”
An amperometric glucose biosensor based on immobilization of glucose oxidase on nitrogen-doped carbon nanotubes (N-CNTs) was successfully developed for the determination of silver ions. Upon exposure to glucose, a steady-state enzymatic turnover rate was detected through amperometric oxidation of the H2O2 byproduct, directly related to the concentration of glucose in solution. Inhibition of the steady-state enzymatic glucose oxidase reaction by heavy metals ions such as Ag(+), produced a quantitative decrease in the steady-state rate, subsequently creating an ultrasensitive metal ion biosensor through enzymatic inhibition. The Ag(+) biosensor displayed a sensitivity of 2.00 × 10(8) ± 0.06 M(-1), a limit of detection (σ = 3) of 0.19 ± 0.04 ppb, a linear range of 20-200 nM, and sample recovery at 101 ± 2%, all acquired at a low-operating potential of 0.05 V (vs Hg/Hg2SO4). Interestingly, the biosensor does not display a loss in sensitivity with continued use due to the % inhibition based detection scheme: loss of enzyme (from continued use) does not influence the % inhibition, only the overall current associated with the activity loss. The heavy metals Cu(2+) and Co(2+) were also detected using the enzyme biosensor but found to be much less inhibitory, with sensitivities of 1.45 × 10(6) ± 0.05 M(-1) and 2.69 × 10(3) ± 0.07 M(-1), respectively. The mode of GOx inhibition was examined for both Ag(+) and Cu(2+) using Dixon and Cornish-Bowden plots, where a strong correlation was observed between the inhibition constants and the biosensor sensitivity.
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