@article{GrinsvenBonStrauvenetal.2012, author = {Grinsven, Bart van and Bon, Natalie vanden and Strauven, Hannelore and Grieten, Lars and Murib, Mohammed and Jim{\´e}nez Monroy, Kathia L. and Janssens, Stoffel D. and Haenen, Ken and Sch{\"o}ning, Michael Josef and Vermeeren, Veronique and Ameloot, Marcel and Michiels, Luc and Thoelen, Ronald and Ceuninck, Ward de and Wagner, Patrick}, title = {Heat-Transfer Resistance at Solid-Liquid Interfaces: A Tool for The Detection of Single Nucleotide Polymorphisms in DNA.}, series = {ACS Nano}, volume = {6}, journal = {ACS Nano}, number = {3}, publisher = {ACS Publications}, address = {Washington, DC}, issn = {1936-086X}, doi = {10.1021/nn300147e}, pages = {2712 -- 2721}, year = {2012}, abstract = {In this article, we report on the heat-transfer resistance at interfaces as a novel, denaturation-based method to detect single-nucleotide polymorphisms in DNA. We observed that a molecular brush of double-stranded DNA grafted onto synthetic diamond surfaces does not notably affect the heat-transfer resistance at the solid-to-liquid interface. In contrast to this, molecular brushes of single-stranded DNA cause, surprisingly, a substantially higher heat-transfer resistance and behave like a thermally insulating layer. This effect can be utilized to identify ds-DNA melting temperatures via the switching from low- to high heat-transfer resistance. The melting temperatures identified with this method for different DNA duplexes (29 base pairs without and with built-in mutations) correlate nicely with data calculated by modeling. The method is fast, label-free (without the need for fluorescent or radioactive markers), allows for repetitive measurements, and can also be extended toward array formats. Reference measurements by confocal fluorescence microscopy and impedance spectroscopy confirm that the switching of heat-transfer resistance upon denaturation is indeed related to the thermal on-chip denaturation of DNA.}, language = {en} } @article{RiedelKartchemnikSchoeningetal.2014, author = {Riedel, Marc and Kartchemnik, Julia and Sch{\"o}ning, Michael Josef and Lisdat, Fred}, title = {Impedimetric DNA detection - steps forward to sensorial application}, series = {Analytical chemistry}, volume = {86 (2014)}, journal = {Analytical chemistry}, number = {15}, publisher = {ACS Publications}, address = {Columbus}, issn = {1520-6882 (E-Journal); 0003-2700 (Print); 0096-4484 (Print)}, doi = {10.1021/ac501800q}, pages = {7867 -- 7874}, year = {2014}, abstract = {This study describes a label-free impedimetric sensor based on short ssDNA recognition elements for the detection of hybridization 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 hybridization of ssDNA to the sensor surface. Investigations on the impedimetric signal stability demonstrate a clear influence of the buffers used during the sensor preparation and the choice of the passivating mercaptoalcanol compound. A stable sensor system has been developed, enabling a reproducible detection of 25mer target DNA in the low nanomolar range. After hybridization, a sensor regeneration can be reached with deionized water by adjustment of effective convection conditions, ensuring a sensor reusability. By investigations 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. This is found to result in an increase in the relative Rct change. These results suggest that DNA and consequently negative charge near the electrode possess a larger impact on the impedimetric signal than DNA further away.}, language = {en} } @article{SiqueiraMolinnusBegingetal.2014, author = {Siqueira, Jose R. and Molinnus, Denise and Beging, Stefan and Sch{\"o}ning, Michael Josef}, title = {Incorporating a hybrid urease-carbon nanotubes sensitive nanofilm on capacitive field-effect sensors for urea detection}, series = {Analytical chemistry}, volume = {86}, journal = {Analytical chemistry}, number = {11}, publisher = {ACS Publications}, address = {Columbus}, issn = {1520-6882 (E-Journal); 0003-2700 (Print); 0096-4484 (Print)}, doi = {10.1021/ac500458s}, pages = {5370 -- 5375}, year = {2014}, abstract = {The ideal combination among biomolecules and nanomaterials is the key for reaching biosensing units with high sensitivity. The challenge, however, is to find out a stable and sensitive film architecture that can be incorporated on the sensor's surface. In this paper, we report on the benefits of incorporating a layer-by-layer (LbL) nanofilm of polyamidoamine (PAMAM) dendrimer and carbon nanotubes (CNTs) on capacitive electrolyte-insulator-semiconductor (EIS) field-effect sensors for detecting urea. Three sensor arrangements were studied in order to investigate the adequate film architecture, involving the LbL film with the enzyme urease: (i) urease immobilized directly onto a bare EIS [EIS-urease] sensor; (ii) urease atop the LbL film over the EIS [EIS-(PAMAM/CNT)-urease] sensor; and (iii) urease sandwiched between the LbL film and another CNT layer [EIS-(PAMAM/CNT)-urease-CNT]. The surface morphology of all three urea-based EIS biosensors was investigated by atomic force microscopy (AFM), while the biosensing abilities were studied by means of capacitance-voltage (C/V) and dynamic constant-capacitance (ConCap) measureaments at urea concentrations ranging from 0.1 mM to 100 mM. The EIS-urease and EIS-(PAMAM/CNT)-urease sensors showed similar sensitivity (∼18 mV/decade) and a nonregular signal behavior as the urea concentration increased. On the other hand, the EIS-(PAMAM/CNT)-urease-CNT sensor exhibited a superior output signal performance and higher sensitivity of about 33 mV/decade. The presence of the additional CNT layer was decisive to achieve a urea based EIS sensor with enhanced properties. Such sensitive architecture demonstrates that the incorporation of an adequate hybrid enzyme-nanofilm as sensing unit opens new prospects for biosensing applications using the field-effect sensor platform.}, language = {en} } @article{SchusserKrischerBaeckeretal.2015, author = {Schusser, Sebastian and Krischer, Maximillian and B{\"a}cker, Matthias and Poghossian, Arshak and Wagner, Patrick and Sch{\"o}ning, Michael Josef}, title = {Monitoring of the Enzymatically Catalyzed Degradation of Biodegradable Polymers by Means of Capacitive Field-Effect Sensors}, series = {Analytical Chemistry}, volume = {87}, journal = {Analytical Chemistry}, number = {13}, publisher = {ACS Publications}, address = {Washington, DC}, issn = {1520-6882}, doi = {10.1021/acs.analchem.5b00617}, pages = {6607 -- 6613}, year = {2015}, abstract = {Designing novel or optimizing existing biodegradable polymers for biomedical applications requires numerous tests on the effect of substances on the degradation process. In the present work, polymer-modified electrolyte-insulator-semiconductor (PMEIS) sensors have been applied for monitoring an enzymatically catalyzed degradation of polymers for the first time. The thin films of biodegradable polymer poly(d,l-lactic acid) and enzyme lipase were used as a model system. During degradation, the sensors were read-out by means of impedance spectroscopy. In order to interpret the data obtained from impedance measurements, an electrical equivalent circuit model was developed. In addition, morphological investigations of the polymer surface have been performed by means of in situ atomic force microscopy. The sensor signal change, which reflects the progress of degradation, indicates an accelerated degradation in the presence of the enzyme compared to hydrolysis in neutral pH buffer media. The degradation rate increases with increasing enzyme concentration. The obtained results demonstrate the potential of PMEIS sensors as a very promising tool for in situ and real-time monitoring of degradation of polymers.}, language = {en} } @article{SchollMoraisGabrieletal.2017, author = {Scholl, Fabio and Morais, Paulo and Gabriel, Rayla and Sch{\"o}ning, Michael Josef and Siqueira, Jose Roberto, Jr. and Caseli, Luciano}, title = {Carbon nanotubes arranged as smart interfaces in lipid Langmuir-Blodgett films enhancing the enzymatic properties of penicillinase for biosensing applications}, series = {Applied Materials \& Interfaces}, volume = {9}, journal = {Applied Materials \& Interfaces}, number = {36}, publisher = {ACS}, address = {Washington}, issn = {1944-8252}, doi = {10.1021/acsami.7b08095}, pages = {31054 -- 31066}, year = {2017}, abstract = {In this paper, carbon nanotubes (CNTs) were incorporated in penicillinase-phospholipid Langmuir and Langmuir-Blodgett (LB) films to enhance the enzyme catalytic properties. Adsorption of the penicillinase and CNTs at dimyristoylphosphatidic acid (DMPA) monolayers at the air-water interface was investigated by surface pressure-area isotherms, vibrational spectroscopy, and Brewster angle microscopy. The floating monolayers were transferred to solid supports through the LB technique, forming mixed DMPA-CNTs-PEN films, which were investigated by quartz crystal microbalance, vibrational spectroscopy, and atomic force microscopy. Enzyme activity was studied with UV-vis spectroscopy and the feasibility of the supramolecular device nanostructured as ultrathin films were essayed in a capacitive electrolyte-insulator-semiconductor (EIS) sensor device. The presence of CNTs in the enzyme-lipid LB film not only tuned the catalytic activity of penicillinase but also helped conserve its enzyme activity after weeks, showing increased values of activity. Viability as penicillin sensor was demonstrated with capacitance/voltage and constant capacitance measurements, exhibiting regular and distinctive output signals over all concentrations used in this work. These results may be related not only to the nanostructured system provided by the film, but also to the synergism between the compounds on the active layer, leading to a surface morphology that allowed a fast analyte diffusion because of an adequate molecular accommodation, which also preserved the penicillinase activity. This work therefore demonstrates the feasibility of employing LB films composed of lipids, CNTs, and enzymes as EIS devices for biosensing applications.}, language = {en} } @article{BronderJessingPoghossianetal.2018, author = {Bronder, Thomas and Jessing, Max P. and Poghossian, Arshak and Keusgen, Michael and Sch{\"o}ning, Michael Josef}, title = {Detection of PCR-Amplified Tuberculosis DNA Fragments with Polyelectrolyte-Modified Field-Effect Sensors}, series = {Analytical Chemistry}, volume = {90}, journal = {Analytical Chemistry}, number = {12}, publisher = {ACS Publications}, address = {Washington, DC}, issn = {0003-2700}, doi = {10.1021/acs.analchem.8b01807}, pages = {7747 -- 7753}, year = {2018}, abstract = {Field-effect-based electrolyte-insulator-semiconductor (EIS) sensors were modified with a bilayer of positively charged weak polyelectrolyte (poly(allylamine hydrochloride) (PAH)) and probe single-stranded DNA (ssDNA) and are used for the detection of complementary single-stranded target DNA (cDNA) in different test solutions. The sensing mechanism is based on the detection of the intrinsic molecular charge of target cDNA molecules after the hybridization event between cDNA and immobilized probe ssDNA. The test solutions contain synthetic cDNA oligonucleotides (with a sequence of tuberculosis mycobacteria genome) or PCR-amplified DNA (which origins from a template DNA strand that has been extracted from Mycobacterium avium paratuberculosis-spiked human sputum samples), respectively. Sensor responses up to 41 mV have been measured for the test solutions with DNA, while only small signals of ∼5 mV were detected for solutions without DNA. The lower detection limit of the EIS sensors was ∼0.3 nM, and the sensitivity was ∼7.2 mV/decade. Fluorescence experiments using SybrGreen I fluorescence dye support the electrochemical results.}, language = {en} } @article{RodriguesMoraisNordietal.2018, author = {Rodrigues, Raul T. and Morais, Paulo V. and Nordi, Cristina S. F. and Sch{\"o}ning, Michael Josef and Siqueira Jr., Jos{\´e} R. and Caseli, Luciano}, title = {Carbon Nanotubes and Algal Polysaccharides To Enhance the Enzymatic Properties of Urease in Lipid Langmuir-Blodgett Films}, series = {Langmuir}, volume = {34}, journal = {Langmuir}, number = {9}, publisher = {ACS Publications}, address = {Washington, DC}, issn = {1520-5827}, doi = {10.1021/acs.langmuir.7b04317}, pages = {3082 -- 3093}, year = {2018}, abstract = {Algal polysaccharides (extracellular polysaccharides) and carbon nanotubes (CNTs) were adsorbed on dioctadecyldimethylammonium bromide Langmuir monolayers to serve as a matrix for the incorporation of urease. The physicochemical properties of the supramolecular system as a monolayer at the air-water interface were investigated by surface pressure-area isotherms, surface potential-area isotherms, interfacial shear rheology, vibrational spectroscopy, and Brewster angle microscopy. The floating monolayers were transferred to hydrophilic solid supports, quartz, mica, or capacitive electrolyte-insulator-semiconductor (EIS) devices, through the Langmuir-Blodgett (LB) technique, forming mixed films, which were investigated by quartz crystal microbalance, fluorescence spectroscopy, and field emission gun scanning electron microscopy. The enzyme activity was studied with UV-vis spectroscopy, and the feasibility of the thin film as a urea sensor was essayed in an EIS sensor device. The presence of CNT in the enzyme-lipid LB film not only tuned the catalytic activity of urease but also helped to conserve its enzyme activity. Viability as a urease sensor was demonstrated with capacitance-voltage and constant capacitance measurements, exhibiting regular and distinctive output signals over all concentrations used in this work. These results are related to the synergism between the compounds on the active layer, leading to a surface morphology that allowed fast analyte diffusion owing to an adequate molecular accommodation, which also preserved the urease activity. This work demonstrates the feasibility of employing LB films composed of lipids, CNT, algal polysaccharides, and enzymes as EIS devices for biosensing applications.}, language = {en} } @article{MennickenPeterKaulenetal.2020, author = {Mennicken, Max and Peter, Sophia K. and Kaulen, Corinna and Simon, Ulrich and Karth{\"a}user, Silvia}, title = {Transport through Redox-Active Ru-Terpyridine Complexes Integrated in Single Nanoparticle Devices}, series = {The Journal of Physical Chemistry C}, volume = {124}, journal = {The Journal of Physical Chemistry C}, number = {8}, publisher = {ACS Publications}, address = {Washington, DC}, issn = {1932-7455}, doi = {10.1021/acs.jpcc.9b11716}, pages = {4881 -- 4889}, year = {2020}, abstract = {Transition metal complexes are electrofunctional molecules due to their high conductivity and their intrinsic switching ability involving a metal-to-ligand charge transfer. Here, a method is presented to contact reliably a few to single redox-active Ru-terpyridine complexes in a CMOS compatible nanodevice and preserve their electrical functionality. Using hybrid materials from 14 nm gold nanoparticles (AuNP) and bis-{4′-[4-(mercaptophenyl)-2,2′:6′,2″-terpyridine]}-ruthenium(II) complexes a device size of 30² nm² inclusive nanoelectrodes is achieved. Moreover, this method bears the opportunity for further downscaling. The Ru-complex AuNP devices show symmetric and asymmetric current versus voltage curves with a hysteretic characteristic in two well separated conductance ranges. By theoretical approximations based on the single-channel Landauer model, the charge transport through the formed double-barrier tunnel junction is thoroughly analyzed and its sensibility to the molecule/metal contact is revealed. It can be verified that tunneling transport through the HOMO is the main transport mechanism while decoherent hopping transport is present to a minor extent.}, language = {en} } @article{PilasSelmerKeusgenetal.2019, author = {Pilas, Johanna and Selmer, Thorsten and Keusgen, Michael and Sch{\"o}ning, Michael Josef}, title = {Screen-printed carbon electrodes modified with graphene oxide for the design of a reagent-free NAD+-dependent biosensor array}, series = {Analytical Chemistry}, volume = {91}, journal = {Analytical Chemistry}, number = {23}, publisher = {ACS Publications}, address = {Washington}, doi = {10.1021/acs.analchem.9b04481}, pages = {15293 -- 15299}, year = {2019}, language = {en} }