Practice oriented point-of-care diagnostics require easy-to-handle, miniaturized, and low-cost analytical tools. In a novel approach, screen printed carbon electrodes (SPEs), which were functionalized with nanomaterials, are employed for selective measurements of bilirubin, which is an important biomarker for jaundice. Multi-walled carbon nanotubes (MWCNT) and graphene separately deposited on SPEs provide the core of an electrochemical sensor for bilirubin. The electrocatalytic activity towards bilirubin oxidation (bilirubin to biliverdin) was observed at +0.25 V. In addition, a further peak corresponding to the electrochemical conversion of biliverdin into purpurin appeared at +0.48 V. When compared to MWCNT, the graphene type shows a 3-fold lower detection limit (0.3 ± 0.022 nM and 0.1 ± 0.018 nM, respectively), moreover, the graphene type exhibits a larger linear range (0.1–600 µM) than MWCNT (0.5–500 µM) with a two-fold better sensitivity, i.e., 30 nA µM−1 cm−2, and 15 nA µM−1 cm−2, respectively. The viability is validated through measurements of bilirubin in blood serum samples and the selectivity is ensured by inhibiting common interfering biological substrates using an ionic nafion membrane. The presented approach enables the design and implementation of low cost and miniaturized electrochemical sensors.
C-reactive protein (CRP) is one of the most expressed proteins in blood during acute phase inflammation, and its minute level increase has also been recognized for the clinical diagnosis of cardio vascular diseases. Unfortunately, the available commercial immunoassays are labour intensive, require large sample volumes, and have practical limitations, such as low stability and high production costs. Hence, we have developed a simple, cost effective, and label-free electrochemical immunoassay for the measurement of CRP in a drop of serum sample using an immunosensor strip made up of a screen printed carbon electrode (SPE) modified with anti-CRP functionalized gold nanoparticles (AuNPs). The measurement relies on the decrease of the oxidation current of the redox indicator Fe3+/Fe2+, resulting from the immunoreaction between CRP and anti-CRP. Under optimal conditions, the present immunoassay measures CRP in a linear range from 0.4–200 nM (0.047–23.6 µg mL−1), with a detection limit of 0.15 nM (17 ng mL−1, S/N = 3) and sensitivity of 90.7 nA nM−1, in addition to a good reproducibility and storage stability. The analytical applicability of the presented immunoassay is verified by CRP measurements in human blood serum samples. This work provides the basis for a low-priced, safe, and easy-to-use point-of-care immunosensor assay to measure CRP at clinically relevant concentrations.
Silver (Ag) nanostructures and thin films are advantageous plasmonic materials as they have significantly lower losses than gold (Au). Unfortunately, Ag nanostructures suffer from poor chemical and thermal stability, which limit their applications. Here, the mechanisms leading to the deterioration of Ag nanostructures are clarified. It is first shown that oxygen alone cannot oxidize Ag nanostructures. Then, experiments using X‐ray photoelectron spectroscopy reveal that the amount of sulfur in ambient air is too low for efficient tarnishing of the Ag surface. Finally, water is found to be the most critical factor for the degradation of Ag nanostructures and thin films. At high relative humidity, adsorbed water forms a thin film enabling the migration of Ag ions at the Ag/air interface, which deteriorates the Ag nanostructures. A dehydration treatment is developed which alters the morphology of the deposited silver, leading to an improved chemical and thermal stability of the Ag nanostructures and films, which then remain stable for more than 14 weeks under ambient laboratory conditions. In addition, dehydration also improves significantly the root‐mean‐square roughness for Ag thin films deposited on a glass substrate.
After providing a detailed overview of nanofabrication techniques for plasmonics, we discuss in detail two different approaches for the fabrication of metallic nanostructures based on e-beam lithography. The first approach relies on a negative e-beam resist, followed by ion beam milling, while the second uses a positive e-beam resist and lift-off. Overall, ion beam etching provides smaller and more regular features including tiny gaps between sub-parts, that can be controlled down to about 10 nm. In the lift-off process, the metal atoms are deposited within the resist mask and can diffuse on the substrate, giving rise to the formation of nanoclusters that render the nanostructure outline slightly fuzzy. Scattering cross sections computed for both approaches highlight some spectral differences, which are especially visible for structures that support complex resonances, such as Fano resonances. Both techniques can produce useful nanostructures and the results reported therein should guide the researcher to choose the best suited approach for a given application, depending on the available technology.
Reactive oxygen species play a key role in cell signalling and oxidative stress mechanisms, therefore, sensing their production by living organisms is of fundamental interest. Here we describe a novel biosensing method for extracellular detection of endogenous hydrogen peroxide (H2O2). The method is based on the enhancement of the optical absorption spectrum of the hemoprotein cytochrome c when loaded into a highly scattering random medium. Such a configuration enables, in contrast to existing techniques, non-invasive and dynamic detection of the oxidation of cyt c in the presence of H2O2 with unprecedented sensitivity. Dynamic information on the modification of the cell oxidative status of Chlamydomonas reinhardtii, an aquatic green algae, was obtained under oxidative stress conditions induced by the presence of trace concentrations of Cd(II). Furthermore, the dynamics of H2O2 production was investigated under different lighting conditions confirming the impact of Cd(II) on the photosynthetic activity of those phytoplanktonic cells.