ZnO is one of the most widely studied semiconductors due to its direct wide band gap and high exciton binding energy. Due to its ease of synthesis, robustness and low cost, ZnO has been applied in a wide range of devices, including nanogenerators, solar cells, and photodetectors. In this work, ZnO nanorods were synthesized in a single step using an aqueous method at temperatures below 100 °C. The nanorods were annealed in oxygen and nitrogen and a p-type polymer poly(3,4-ethylenedioxythiophene)polystyrene sulfonate (PEDOT:PSS) was spray coated onto the top of ZnO nanorods to form a p–n junction. The I–V characteristics of the device showed that the annealing atmosphere had a significant effect on the rectification ratio of the device. Further analysis using Mott–Schottky, photoluminescence, and X-ray photoelectron spectroscopy (XPS) indicated that oxygen vacancy concentration correlated well with the free electron density in ZnO as well as the rectification ratio of the p–n junction devices. Devices made with ZnO nanorods annealed in nitrogen had a better rectification ratio than oxygen, representing a simple method to improve p–n junction diode behaviour through tuning the defect properties of the nanorods via controlled annealing.
Matrix metalloproteinase-9 (MMP-9) plays an important role in both physiological and pathological processes. This enzyme is a peripheral biomarker of neuroinflammation in multiple sclerosis (MS), a chronic autoimmune disease of the central nervous system. Presently, expensive magnetic resonance imaging (MRI) studies are used to monitor subclinical disease activity in MS. An alternative to costly MRI scans could be the detection of MMP-9, using a low-cost, disposable sensor system for MMP-9 suitable for home-monitoring of inflammation. This would allow an early prediction of the failure of anti-inflammatory therapies and more timely clinical intervention to limit neuronal damage and prevent disability. Herein we present the development of a disposable sensor for fast and straightforward detection of MMP-9. Biosensors were produced by coating electrodes with oxidized dextran and subsequent cross-linking with peptides containing specific cleavage sites for MMP-9. Exposure of the films to the enzyme resulted in the degradation of the films, which was monitored using impedance measurements. Sensor response was rapid, a significant impedance change was usually observed within 5 min after the addition of MMP-9. Sensors showed a negligible response to matrix metalloproteinase-2 (MMP-2), a protease which may interfere with MMP-9 detection. The peptide sequence with the highest sensitivity and selectivity Leu-Gly-Arg-Met-Gly-Leu-Pro-Gly-Lys was selected to construct calibration curves. MMP-9 was successfully detected in a clinically relevant range from 50 to 400 ng/ml. Two different processes of hydrogel degradation were observed on electrode surfaces with different roughness, and both appeared suitable to monitor MMP-9 activity. The sensor materials are generic and can be easily adopted to respond to other proteases by selecting peptide cross-linkers with suitable cleavage sites.