ABSTRACT
Electrochemical sensors that can determine single/multiple analytes remain a key challenge in miniaturized analytical systems and devices. In this study, we present in situ synthesis and modification of gold nanodendrite electrodes to create an electrochemical system for the analysis of hydrogen peroxide. The sensor system consisted of the reference and counter electrodes as well as the working electrode. Electrochemical reduction of graphene oxide, ErGO, on the thin-film gold and gold nanodendrite working electrodes was used to achieve an efficient sensor interface for the adsorption of a biomimetic electrocatalytic sensor material, Mn(III) meso-tetra(N-methyl-4-pyridyl) porphyrin complex, with as high as 10-10 mol cm-2 surface coverage. The sensor system demonstrated a detection limit of 0.3 µM H2O2 in the presence of oxygen. Electrochemical determination of hydrogen peroxide in plant material in the concentration range from 0.09 to 0.4 µmol (gFW)-1 using the electrochemical sensor system was shown as well as in vivo real-time monitoring of the hydrogen peroxide dynamics as a sign of abiotic stress (intense sunlight). Results of the electrochemical determination were in good agreement with the results of biochemical analysis with the spectrophotometric detection. We anticipate that this method can be extended for the synthesis and integration of multisensor arrays in analytical microsystems and devices for the quantification and real-time in vivo monitoring of other analytes and biomarkers.
ABSTRACT
Porphyrin macrocycles and their supramolecular nanoassemblies are being widely explored in energy harvesting, sensor development, catalysis, and medicine because of a good tunability of their light-induced charge separation and electron/energy transfer properties. In the present work, we prepared and studied photoresponsive porphyrin nanotubes formed by the self-assembly of meso-tetrakis(4-sulfonatophenyl)porphyrin and Sn(IV) meso-tetra(4-pyridyl)porphyrin. Scanning electron microscopy and transmission electron microscopy showed that these tubular nanostructures were hollow with open ends and their length was 0.4-0.8 µm, the inner diameter was 7-15 nm, and the outer diameter was 30-70 nm. Porphyrin tectons, H4 TPPS 4 2 - : Sn(IV)TPyP4+, self-assemble into the nanotubes in a ratio of 2:1, respectively, as determined by the elemental analysis. The photoconductivity of the porphyrin nanotubes was determined to be as high as 3.1 × 10-4 S m-1, and the dependence of the photoconductance on distance and temperature was investigated. Excitation of the Q-band region with a Q-band of SnTPyP4+ (550-552 nm) and the band at 714 nm, which is associated with J-aggregation, was responsible for about 34 % of the photoconductive activity of the H4 TPPS 4 2 - -Sn(IV)TPyP4+ porphyrin nanotubes. The sensor properties of the H4 TPPS 4 2 - - Sn(IV)TPyP4+ nanotubes in the presence of iodine vapor and salicylate anions down to millimolar range were examined in a chemiresistor sensing mode. We have shown that the porphyrin nanotubes advantageously combine the characteristics of a sensor and a transducer, thus demonstrating their great potential as efficient functional layers for sensing devices and biomimetic nanoarchitectures.
ABSTRACT
The development of electrochemical multisensor systems is driven by the need for fast, miniature, inexpensive, analytical devices, and advanced interdisciplinary based on both chemometric and (nano)material approaches. A multicomponent analysis of complex mixtures in environmental and technological monitoring, biological samples, and cell culture requires chip-based multisensor systems with high-stability sensors. In this paper, we describe the development, characterization, and applications of chip-based nanoelectrochemical sensor arrays prepared by the directed electrochemical nanowire assembly (DENA) of noble metals and metal alloys to analyze aqueous solutions. A synergic action of the electrode transducer function and electrocatalytic activity of the nanostructured surface toward analytes is achieved in the assembled metal nanowire (NW) sensors. Various sensor nanomaterials (Pd, Ni, Au, and their multicomponent compositions) can be electrochemically assembled on a single chip without employing multiple cycles of photolithography process to realize multi-analyte sensing applications as well as spatial resolution of sensor analysis by this single-chip multisensor system. For multi-analyte electrochemical sensing, individual amperometric signals of two or more nanowires can be acquired, making use of the specific electrocatalytic surface properties of the individual nanowire sensors of the array toward analytes. To demonstrate the application of a new electrochemical multisensor platform, Pd-Au, Pd-Ni, Pd, and Au NW electrode arrays on a single chip were employed for the non-enzymatic analysis of hydrogen peroxide, glucose, and ethanol. The analytes are determined at low absolute values of the detection potentials with linear concentration ranges of 1.0 × 10-6 - 1.0 × 10-3 M (H2O2), 1.5 × 10-7 - 2.0 × 10-3 M (glucose), and 0.7 × 10-3 - 3.0 × 10-2 M (ethanol), detection limits of 2 × 10-7 M (H2O2), 4 × 10-8 M (glucose), and 5.2 × 10-4 M (ethanol), and sensitivities of 18 µA M-1 (H2O2), 178 µA M-1 (glucose), and 28 µA M-1 (ethanol), respectively. The sensors demonstrate a high level of stability due to the non-enzymatic detection mode. Based on the DENA-assembled nanowire electrodes of a compositional diversity, we propose a novel single-chip electrochemical multisensor platform, which is promising for acquiring complex analytical signals for advanced data processing with chemometric techniques aimed at the development of electronic tongue-type multisensor systems for flexible multi-analyte monitoring and healthcare applications.
