@article{WunderlichHauslerMaerkletal., author = {Wunderlich, Lukas and Hausler, Peter and Maerkl, Susanne and Bierl, Rudolf and Hirsch, Thomas}, title = {Nanoparticle Determination in Water by LED-Excited Surface Plasmon Resonance Imaging}, series = {Chemosensors}, volume = {9}, journal = {Chemosensors}, number = {7}, publisher = {MDPI}, issn = {2227-9040}, doi = {10.3390/chemosensors9070175}, pages = {1 -- 9}, abstract = {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.}, language = {en} } @article{JobstRecumEcijaArenasetal.2023, author = {Jobst, Simon and Recum, Patrick and {\´E}cija-Arenas, {\´A}ngela and Moser, Elisabeth and Bierl, Rudolf and Hirsch, Thomas}, title = {Semi-Selective Array for the Classification of Purines with Surface Plasmon Resonance Imaging and Deep Learning Data Analysis}, series = {ACS sensors}, volume = {8}, journal = {ACS sensors}, number = {9}, publisher = {American Chemical Society}, doi = {10.1021/acssensors.3c01114}, pages = {3530 -- 3537}, year = {2023}, abstract = {In process analytics or environmental monitoring, the real-time recording of the composition of complex samples over a long period of time presents a great challenge. Promising solutions are label-free techniques such as surface plasmon resonance (SPR) spectroscopy. They are, however, often limited due to poor reversibility of analyte binding. In this work, we introduce how SPR imaging in combination with a semi-selective functional surface and smart data analysis can identify small and chemically similar molecules. Our sensor uses individual functional spots made from different ratios of graphene oxide and reduced graphene oxide, which generate a unique signal pattern depending on the analyte due to different binding affinities. These patterns allow four purine bases to be distinguished after classification using a convolutional neural network (CNN) at concentrations as low as 50 μM. The validation and test set classification accuracies were constant across multiple measurements on multiple sensors using a standard CNN, which promises to serve as a future method for developing online sensors in complex mixtures.}, language = {en} } @article{GensleinHauslerKirchneretal., author = {Genslein, Christa and Hausler, Peter and Kirchner, Eva-Maria and Bierl, Rudolf and Baeumner, Antje J. and Hirsch, Thomas}, title = {Graphene-enhanced plasmonic nanohole arrays for environmental sensing in aqueous samples}, series = {Beilstein Journal of Nanotechnology}, journal = {Beilstein Journal of Nanotechnology}, number = {7}, doi = {10.3762/bjnano.7.150}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:355-epub-398623}, pages = {1564 -- 1573}, abstract = {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.}, language = {en} }