TY - JOUR A1 - Riedel, Marc A1 - Höfs, Soraya A1 - Ruff, Adrian A1 - Schuhmann, Wolfgang A1 - Lisdat, Fred T1 - A Tandem Solar Biofuel Cell: Harnessing Energy from Light and Biofuels JF - Angewandte Chemie International Edition N2 - We report on a photobioelectrochemical fuel cell consisting of a glucose‐oxidase‐modified BiFeO3 photobiocathode and a quantum‐dot‐sensitized inverse opal TiO2 photobioanode linked to FAD glucose dehydrogenase via a redox polymer. Both photobioelectrodes are driven by enzymatic glucose conversion. Whereas the photobioanode can collect electrons from sugar oxidation at rather low potential, the photobiocathode shows reduction currents at rather high potential. The electrodes can be arranged in a sandwich‐like manner due to the semi‐transparent nature of BiFeO3, which also guarantees a simultaneous excitation of the photobioanode when illuminated via the cathode side. This tandem cell can generate electricity under illumination and in the presence of glucose and provides an exceptionally high OCV of about 1 V. The developed semi‐artificial system has significant implications for the integration of biocatalysts in photoactive entities for bioenergetic purposes, and it opens up a new path toward generation of electricity from sunlight and (bio)fuels. Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:526-opus4-13680 SN - 1521-3773 VL - 60 IS - 4 SP - 2078 EP - 2083 PB - Wiley ER - TY - JOUR A1 - Zhao, Shuang A1 - Riedel, Marc A1 - Patarroyo, Javier A1 - Bastús, Neus G. A1 - Puntes, Victor A1 - Zhao, Yue A1 - Lisdat, Fred A1 - Parak, Wolfgang J. T1 - Tailoring of the photocatalytic activity of CeO₂ nanoparticles by the presence of plasmonic Ag nanoparticles JF - Nanoscale N2 - The present study investigates basic features of a photoelectrochemical system based on CeO2 nanoparticles fixed on gold electrodes. Since photocurrent generation is limited to the absorption range of the CeO2 in the UV range, the combination with metal nanoparticles has been studied. It can be shown that the combination of silver nanoparticles with the CeO2 can shift the excitation range into the visible light wavelength range. Here a close contact between both components has been found to be essential and thus, hybrid CeO2@Ag nanoparticles have been prepared and analyzed. We have collected arguments that electron transfer occurs between both compositional elements of the hybrid nanoparticles.The photocurrent generation can be rationalized on the basis of an energy diagram underlying the necessity of surface plasmon excitation in the metal nanoparticles, which is also supported by wavelength-dependent photocurrent measurements. However, electrochemical reactions seem to occur at the CeO2 surface and consequently, the catalytic properties of this material can be exploited as exemplified with the photoelectrochemical reduction of hydrogen peroxide. It can be further demonstrated that the layer-by layer technique can be exploited to create a multilayer system on top of a gold electrode which allows the adjustment of the sensitivity of the photoelectrochemical system. Thus, with a 5-layer electrode with hybrid CeO2@Ag nanoparticles submicromolar hydrogen peroxide concentrations can be detected. Y1 - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:526-opus4-16361 VL - 14 SP - 12048 EP - 12059 PB - Royal Society of Chemistry (RSC) ER - TY - GEN A1 - Riedel, Marc A1 - Kartchemnik, Julia A1 - Schöning, Michael J. A1 - Lisdat, Fred T1 - Impedimetrischer DNA Nachweis - Schritte in Richtung sensorischer Anwendung T2 - Wissenschaftliche Beiträge 2015 N2 - Diese Studie beschreibt einen labelfreien impedimetrischen Sensor auf der Grundlage von kurzen einzelsträngigen DNA-Erkennungselementen für den Nachweis von Hybridisierungsereignissen. Der Fokus der Arbeit liegt auf der Aufklärung des Einflusses der Ziel-DNA-Länge und der Erkennungssequenzposition auf die sensorische Leistungsfähigkeit. Die impedimetrischen Messungen werden in Anwesenheit des Redoxsystems Kaliumhexacyanoferrat (II/III) durchgeführt und zeigen einen Anstieg des Durchtrittswiderstandes nach der Hybridisierung mit komplementärer Ziel-DNA mit einer Nachweisgrenze im unteren nanomolaren Bereich. Nach der Hybridisierung kann die Regeneration des Sensors mit deionisiertem Wasser durch die Einstellung effektiver Konvektionsbedingungen erreicht werden und ermöglicht somit eine Wiederverwendbarkeit des Sensors. Untersuchungen zu längeren Ziel-DNA-Strängen mit einem zur Lösung exponierten Überhang demonstrieren die Anwendbarkeit des impedimetrischen Nachweises für längere Sequenzen. Allerdings resultiert eine zunehmende Überhanglänge in einer verringerten Durchtrittswiderstandsänderung. Um die Impedanzänderung für längere Ziel-DNA zu erhöhen, wird die Erkennungssequenzposition verändert, sodass ein kleiner Überhang zur Elektrode ausgerichtet ist. Die Ergebnisse legen nahe, dass DNA in direkter Nähe zur Elektrode einen größeren Einfluss auf das impedimetrische Signal besitzt als weiter entfernte DNA. N2 - This study describes a label-free impedimetric sensor based on short ssDNA recognition elements for the detection of hybridisation events. We concentrate on the elucidation of the influence of target length and recognition sequence position on the sensorial performance. The impedimetric measurements are performed in the presence of the redox system ferri-/ferrocyanide and show an increase in charge transfer resistance upon hybridisation of complementary ssDNA in the nanomolar range. After hybridisation, a sensor regeneration can be achieved with deionised water by adjustment of effective convection conditions, ensuring sensor reusability. By investigation of longer targets with overhangs exposed to the solution, we can demonstrate applicability of the impedimetric detection for longer ssDNA. However, a decreasing charge transfer resistance change (ΔRct) is found by extending the overhang. As a strategy to increase the impedance change for longer target strands, the position of the recognition sequence can be designed in a way that a small overhang is exposed to the electrode surface. These results suggest that DNA near the electrode possesses a larger impact on the impedimetric signal than DNA further away. Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:526-opus4-3538 SN - 0949-8214 VL - 19 SP - 21 EP - 28 ER - TY - GEN A1 - Riedel, Marc A1 - Schäfer, Daniel A1 - Parak, Wolfgang J. A1 - Ruff, Adrian A1 - Schuhmann, Wolfgang A1 - Lisdat, Fred T1 - Quantum Dot-modifizierte TiO2-Strukturen für die Licht-gesteuerte Bioelektrokatalyse T2 - Wissenschaftliche Beiträge 2019 N2 - Die funktionale Kopplung von photoaktiven Nanostrukturen mit Enzymen stellt eine neue Strategie zum Aufbau lichtgesteuerter biohybrider Systeme dar. Hier sind Untersuchungen zusammengefasst, welche die effiziente Kontaktierung der FAD-abhängigen Glukosedehydrogenase (FAD-GDH) mit Hilfe eines Osmium-Redoxpolymers (P Os ) an PbS-Quantum Dots (PbS QDs) zeigen, welche direkt auf dreidimensionalen TiO 2 -Elektrodenstrukturen synthetisiert wurden. Diese biohybriden Strukturen erlauben die Licht-induzierte Oxidation von Glukose. Dazu wird zunächst ein Verfahren vorgestellt, bei welchem durch den Aufbau invers-opaler TiO 2 (IO-TiO 2 ) Strukturen hohe Bindungskapazitäten für die Integration von QDs, Redoxpolymer und Enzym erreicht werden. In Folge wird gezeigt wie elektrochemische Signalketten durch Licht gesteuert werden können, indem Ladungsträger in den QDs unter Beleuchtung erzeugt werden. Diese Aktivierung ermöglicht dann die Ausbildung einer Elektrontransferkaskade vom Enzym über das Redoxpolymer zu den QDs und final zur IO-TiO 2 -Elektrode. Die resultierenden anodischen Photoströme können durch das Potential, die Lichtintensität und die Glukosekonzentration moduliert werden. So können in Anwesenheit von Glukose Photoströme von bis zu 207 μA/cm2 und erste Oxidationssignale bereits bei einem Potential von -540 mV vs Ag/AgCl, 1 M KCl erhalten werden. Dies entspricht einem Potentialgewinn von über 500 mV im Vergleich zu nicht lichtsensitiven Elektroden. Das vorgestellte biohybride System kombiniert Vorteile einer großen Oberfläche (durch IO-TiO 2 -Struktur), die effiziente Ladungsträgergenerierung und -trennung an der QD/TiO 2 -Schnittstelle sowie die effiziente Kontaktierung von FAD-GDH mit den QDs mit Hilfe eines Redoxpolymers. Die Ergebnisse verdeutlichen das Potential dieser leistungsfähigen Photobioanode für die Sensorik und die Erzeugung von Energie aus Licht und Glukose. N2 - The combination of photoactive nanostructures with enzymes represents a new strategy for the construction of light-directed biohybrid systems. The study demonstrates the efficient linkage of FAD-dependent glucose dehydrogenase (FAD-GDH) to PbS quantum dot (QD)-sensitized inverse opal TiO 2 (IO-TiO 2 ) electrodes using an osmium redox polymer (P Os ). How these biohybrid structures can oxidize glucose in a light-directed fashion is highlighted in detail. For this purpose, firstly a method for the construction of IO-TiO 2 electrodes is presented, which gives rise to high binding capacities for the integration of QDs, redox polymer and enzyme. It can be shown how electrochemical signal chains can be controlled with light, resulting in a generation of charge carriers within the QDs. The activation of the electron transfer cascade then allows for an electron transfer from the enzyme via the redox polymer to the QDs and finally to the IO-TiO 2 electrode. The resulting anodic photocurrents can be modulated by potential, light intensity and glucose concentration. In the presence of glucose, photocurrents of up to 207 μA/cm 2 can be generated and first electron withdrawal from the biocatalytic sugar oxidation already proceeds at a potential of -540 mV vs Ag/AgCl (1 M KCl). This corresponds to a potential gain of over 500 mV compared to light-insensitive electrodes. The proposed biohybrid system combines the advantages of a large surface area (IO-TiO 2 ), efficient charge carrier generation (PbS QDs) and separation at the TiO 2 /QDs interface and the efficient linkage of FAD-GDH to the QDs using a redox polymer. This illustrates the potential of this powerful photobioanode for sensing and power supply. Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:526-opus4-10773 SN - 0949-8214 VL - 23 SP - 11 EP - 17 ER - TY - CHAP A1 - Riedel, Marc A1 - Göbel, Gero A1 - Parak, Wolfgang J. A1 - Lisdat, Fred T1 - Light-addressable amperometric electrodes for enzyme sensors based on direct quantum dot-electrode contacts N2 - Quantum dots allow the generation of charge carriers upon illumination. When these particles are attached to an electrode a photocurrent can be generated. This allows their use as a light-switchable layer on the surface. The QDs can not only exchange electronics with the electrode, but can also interact with donor or acceptor compounds in solution providing access to the construction of signal chains starting from an analytic molecule. The magnitude and the direction of the photocurrent depend on several factors such as electrode polarization, solution pH and composition. These defined dependencies have been evaluated with respect to the combination of QD-electrodes with enzyme reactions for sensorial purpose. CdSe/ZnS-QD-modified electrodes can be used to follow enzymatic reactions in solution based on the oxygen sensitivity. In order to develop a photoelectrochemical biosensor, e.g. glucose oxidase is immobilized on the CdSe/ZnS-electrode. One immobilization strategy applies the layer-by-layer-technique of GOD and a polyelectrolyte. Photocurrent measurements of such a sensor show a clear concentration dependent behavior. The principle of combing QD oxidase. The sensitivity of quantum dot electrodes can be influenced by additional nanoparticles, but also by multiple layers of the QDs. In another direction of research it can be influenced by additional nanoparticles, but also by multiple layers of the QDs. In another direction of research it can be demonstrated that direct electron transfer from excited quantum dots can be achieved with the redox protein cytochrome c. This allows the detection of the protein, but also interaction partners such as a enzymes or superoxide. KW - quantum dot electrode KW - enzyme sensor KW - signal chain KW - photobioelectrochemistry KW - light adressability Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:526-opus4-15266 SP - 195 EP - 200 PB - Society of Photo-Optical Instrumentation Engineers (SPIE) ER -