Development of an aptamer-based SPR-biosensor for the determination of kanamycin residues in foods.

A biosensor in which an affinity reaction occurs in the sensitive microzone through the use of specific aptamers to determine kanamycin residues in agri-food samples has been developed. It is an irreversible and continuous flow aptameric biosensor (aptasensor) in which the signal variations are monitored by surface plasmon resonance (SPR) measurements based on the specific interaction of the aptamer with the antibiotic. The signal variation is proportional to the analyte concentration. Graphene is known for efficient binding of molecules with its π-electron system, so a monolayer of graphene prepared from chemical vapor deposition (CVD) has been compared to a multilayer of graphene made from reduced graphene oxide (rGO) for immobilization of the aptamer on the gold surface of the physicochemical transducer. The best results have been obtained with CVD graphene. The dynamic range was between 1 and 100 µmol L-1 of kanamycin concentration (r2 = 0.9981, n = 7, r = 4), with a limit of detection of 285 nmol L-1 and a sampling frequency of 6 h-1. The precision, expressed as relative standard deviation (RSD%), was established in the range of 1.49 and 3.89%, calculated for 1, 10, and 50 µmol L-1. The selectivity was studied applying the described method to determine other antibiotics, obtaining no significant difference in the analytical signal. The method was applied to determine kanamycin residues in milk samples with recovery values ranging between 90 and 96%.

Recent developments in carbon-based two-dimensional materials: synthesis and modification aspects for electrochemical sensors.

This review (162 references) focuses on two-dimensional carbon materials, which include graphene as well as its allotropes varying in size, number of layers, and defects, for their application in electrochemical sensors. Many preparation methods are known to yield two-dimensional carbon materials which are often simply addressed as graphene, but which show huge variations in their physical and chemical properties and therefore on their sensing performance. The first section briefly reviews the most promising as well as the latest achievements in graphene synthesis based on growth and delamination techniques, such as chemical vapor deposition, liquid phase exfoliation via sonication or mechanical forces, as well as oxidative procedures ranging from chemical to electrochemical exfoliation. Two-dimensional carbon materials are highly attractive to be integrated in a wide field of sensing applications. Here, graphene is examined as recognition layer in electrochemical sensors like field-effect transistors, chemiresistors, impedance-based devices as well as voltammetric and amperometric sensors. The sensor performance is evaluated from the material's perspective of view and revealed the impact of structure and defects of the 2D carbon materials in different transducing technologies. It is concluded that the performance of 2D carbon-based sensors is strongly related to the preparation method in combination with the electrical transduction technique. Future perspectives address challenges to transfer 2D carbon-based sensors from the lab to the market. Graphical abstract Schematic overview from synthesis and modification of two-dimensional carbon materials to sensor application.

Graphene-enhanced plasmonic nanohole arrays for environmental sensing in aqueous samples.

The label-free nature of surface plasmon resonance techniques (SPR) enables a fast, specific, and sensitive analysis of molecular interactions. However, detection of highly diluted concentrations and small molecules is still challenging. It is shown here that in contrast to continuous gold films, gold nanohole arrays can significantly improve the performance of SPR devices in angle-dependent measurement mode, as a signal amplification arises from localized surface plasmons at the nanostructures. This leads consequently to an increased sensing capability of molecules bound to the nanohole array surface. Furthermore, a reduced graphene oxide (rGO) sensor surface was layered over the nanohole array. Reduced graphene oxide is a 2D nanomaterial consisting of sp2-hybridized carbon atoms and is an attractive receptor surface for SPR as it omits any bulk phase and therefore allows fast response times. In fact, it was found that nanohole arrays demonstrated a higher shift in the resonance angle of 250-380% compared to a continuous gold film. At the same time the nanohole array structure as characterized by its diameter-to-periodicity ratio had minimal influence on the binding capacity of the sensor surface. As a simple and environmentally highly relevant model, binding of the plasticizer diethyl phthalate (DEP) via π-stacking was monitored on the rGO gold nanohole array realizing a limit of detection of as low as 20 nM. The concentration-dependent signal change was studied with the best performing rGO-modified nanohole arrays. Compared to continuous gold films a diameter-to-periodicity ratio (D/P) of 0.43 lead to a 12-fold signal enhancement. Finally, the effect of environmental waters on the sensor was evaluated using samples from sea, lake and river waters spiked with analytically relevant amounts of DEP during which significant changes in the SPR signal are observed. It is expected that this concept can be successfully transferred to enhance the sensitivity in SPR sensors.