TY - JOUR A1 - Genslein, Christa A1 - Hausler, Peter A1 - Kirchner, Eva-Maria A1 - Bierl, Rudolf A1 - Baeumner, Antje J. A1 - Hirsch, Thomas T1 - Graphene-enhanced plasmonic nanohole arrays for environmental sensing in aqueous samples JF - Beilstein Journal of Nanotechnology N2 - 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. KW - diethyl phthalate KW - environmental sensing KW - nanohole array KW - nanosphere lithography KW - surface plasmon resonance Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:355-epub-398623 IS - 7 SP - 1564 EP - 1573 ER - TY - JOUR A1 - Genslein, Christa A1 - Hausler, Peter A1 - Kirchner, Eva-Maria A1 - Bierl, Rudolf A1 - Baeumner, Antje J. A1 - Hirsch, Thomas T1 - Graphene-enhanced plasmonic nanohole arrays for environmental sensing in aqueous samples JF - Beilstein Journal of Nanotechnology N2 - 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. Y1 - 2016 U6 - https://doi.org/10.3762/bjnano.7.150 VL - 7 SP - 1564 EP - 1573 PB - Beilstein-Institut ER - TY - CHAP A1 - Genslein, Christa A1 - Hauser, Peter A1 - Kirchner, Eva-Maria A1 - Bierl, Rudolf A1 - Baeumner, Antje J. A1 - Hirsch, Thomas T1 - Detection of small molecules with surface plasmon resonance by synergistic plasmonic effects of nanostructured surfaces and graphene T2 - SPIE Proceedings, Plasmonics in Biology and Medicine XIV, 2017, San Francisco, California N2 - Surface plasmon resonance depends on the dielectric medium at the vicinity and makes it a quasi-universal detector. Therefore, and due to the label-free nature, SPR is a widely used sensing tool for real‐time monitoring molecular interactions of various analytes. However, detection of highly diluted analytes and small molecules (< 400 Da) is still challenging. Gold nanohole arrays provide plasmonic hotspots with improved surface sensitivity and 2D carbon nanomaterials enable binding near the surface. Both effects together are promising in the development of SPR sensors for the efficient determination of small molecules. Graphene is known for efficient binding of molecules with delocalized aromatic π-systems. Additionally, the electromagnetic field is locally enhanced and modulated by the interaction of graphene photonics with the plasmonics of metal nanostructures. The advantages of chemical vapor deposition (CVD) graphene over reduced graphene oxide (rGO) is illustrated by a proof of concept study. In comparison to substrates consisting of a continuous film the surface sensitivity is enhanced for a nanohole arrays and further improved for CVD graphene functionalization in contrast to rGO. The feasibility of the sensor was demonstrated for the detection of adenine down to a concentration of 0.9 μM. Y1 - 2017 U6 - https://doi.org/10.1117/12.2252256 VL - 10080 IS - 1008001F ER -