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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.
Surface Plasmon Resonance (SPR) is a well-known and established technology in bioanalysis and pharmaceutical sciences. Due to the expensive instrumentation and the need of trained people, it is mainly limited to applications in laboratories. However, there are some areas like environmental monitoring, chemical processing and civil infrastructure, which urgently need new sensor technologies. SPR has the potential to serve these fields. In order to be qualified for a use in these areas SPR has to overcome some hurdles. The instrumentation has to be robust, small in size and cheap. A device, which fits these needs, will be a micro-opto-electro-mechanical system (MOEMS) with integrated intelligent algorithms. In this book chapter, examples of miniaturized SPR devices are introduced, the limitations which have to be overcome as well as the possibilities for future applications are proposed. Due to the manifold advantages of this technology and the dropping prices for imaging sensors, Surface Plasmon Resonance imaging (SPRi) might become one of the leading technologies for SPR smart sensor systems.
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 sp<sup>2</sup>-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 (<i>D</i>/<i>P</i>) 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.
Miniaturisierte Sensoren basierend auf Oberflächenplasmonenresonanz, Chancen und Herausforderungen
(2021)
Derzeit gibt es zahlreiche Bereiche, wie Umwelt Monitoring und zivile Infrastruktur in denen geeignete Sensoren für die Überwachung der Systeme fehlen. SPR-basierte Sensoren haben das Potential diese Lücke zu schließen. Um für den Einsatz in der Umwelt tauglich zu werden, müssen die Sensoren noch robuster werden. Hier wird eine mögliche Lösung gezeigt.
Gezeigt wird die Miniaturisierung eines Messsystems für Oberflächenplasmonenresonanzspektroskopie (SPR), einer markierungs-, sowie zerstörungsfreien als auch hoch sensitiven Technologie. Aufgrund der hohen Kosten klassischer SPR-Geräte wird sie bisher jedoch vornehmlich in der Bio- und Medizintechnik eingesetzt. Das Messprinzip ermöglicht die Erfassung von Brechungsindexänderungen nahe einer Oberfläche. Der Transfer dieser Technologie von Laborgeräten hin zu einem miniaturisierten Sensorsystem senkt die Kosten, macht das System robuster und ermöglicht so ein wesentlich breiteres Anwendungsspektrum. Ein sehr vielversprechendes Merkmal des hier vorgestellten Systems ist die Möglichkeit den SPR-Effekt winkelabhängig zur Lichtquelle ohne bewegliche Bauteile zu verfolgen.
The miniaturization of Surface Plasmon Resonance (SPR) technology, which mainly finds its applications in pharmaceutical screening and biotechnology so far, is described. SPR spectroscopy is a label-free, non destructive and highly sensitive measurement principle which is capable of detecting changes in the refractive index in striking distance to a gold surface. A transfer of this technology to a miniaturized sensor will broaden the range of possible applications. A promising feature which is included in the miniaturized system is the angle-dependent recording of the SPR signals without moving parts.
The increasing popularity of nanoparticles in many applications has led to the fact that these persistent materials pollute our environment and threaten our health. An online sensor system for monitoring the presence of nanoparticles in fresh water would be highly desired. We propose a label-free sensor based on SPR imaging. The sensitivity was enhanced by a factor of about 100 by improving the detector by using a high-resolution camera. This revealed that the light source also needed to be improved by using LED excitation instead of a laser light source. As a receptor, different self-assembled monolayers have been screened. It can be seen that the nanoparticle receptor interaction is of a complex nature. The best system when taking sensitivity as well as reversibility into account is given by a dodecanethiol monolayer on the gold sensor surface. Lanthanide-doped nanoparticles, 29 nm in diameter and with a similar refractive index to the most common silica nanoparticles were detected in water down to 1.5 mu g mL(-1). The sensor can be fully regenerated within one hour without the need for any washing buffer. This sensing concept is expected to be easily adapted for the detection of nanoparticles of different size, shape, and composition, and upon miniaturization, suitable for long-term applications to monitor the quality of water.
We describe the miniaturization of the Surface Plasmon Resonance (SPR) technology which mainly finds its applications in pharmaceutical screening and biotechnology so far. SPR spectroscopy is a label-free, non-destructive and highly sensitive measurement principle detecting changes in the refractive index in striking distance to a gold surface. A transfer of this technology to a miniaturized sensor will broaden the range of possible applications. A promising feature which is included in the miniaturized system is the angle-dependent recording of the SPR signals without moving parts. Commercial SPR assays are mainly working with a small number of sensing spots. In contrast, the SPR imaging system shown here will allow to use an array of many sensing spots. In combination with chemical receptors designed as an artificial nose, the simultaneous detection of many analytes is envisioned for future applications.