@article{FandrichBullerSchaeferetal.2015, author = {Fandrich, Artur and Buller, Jens and Sch{\"a}fer, Daniel and Wischerhoff, Erik and Laschewsky, Andr{\´e} and Lisdat, Fred}, title = {Electrochemical characterization of a responsive macromolecular interface on gold}, series = {Physica status solidi : A, Applications and materials science}, volume = {212}, journal = {Physica status solidi : A, Applications and materials science}, number = {6}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1862-6300}, doi = {10.1002/pssa.201431698}, pages = {1359 -- 1367}, year = {2015}, abstract = {This study reports on the investigation of a thermoresponsive polymer as a thin film on electrodes and the influence of coupling a peptide and an antibody to the film. The utilized polymer from the class of poly(oligoethylene glycol)-methacrylate polymers (poly(OEGMA)) with carboxy functions containing side chains was synthesized and properly characterized in aqueous solutions. The dependence of the cloud point on the pH of the surrounding media is discussed. The responsive polymer was immobilized on gold electrodes as shown by electrochemical, quartz crystal microbalance (QCM), and atomic force microscopy (AFM) techniques. The temperature dependent behavior of the polymer covalently grafted to gold substrates is investigated using cyclic voltammetry (CV) in ferro-/ferricyanide solution. Significant changes in the slope of the temperature-dependence of the voltammetric peak current and the peak separation values clearly indicate the thermally induced conformational change on the surface. Finally, a biorecognition reaction between a short FLAG peptide (N-Asp-Tyr-Lys-Asp-Asp-Asp-Asp-Lys-C) covalently immobilized on the polymer interface and the corresponding IgG antibody was performed. The study shows that the responsiveness of the electrode is retained after peptide coupling and antibody binding, although the response is diminished.}, language = {en} } @article{FlossGranucciSaalfrank2012, author = {Floss, Gereon and Granucci, Giovanni and Saalfrank, Peter}, title = {Surface hopping dynamics of direct trans -> cis photoswitching of an azobenzene derivative in constrained adsorbate geometries}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {137}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {23}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4769087}, pages = {9}, year = {2012}, abstract = {With ongoing miniaturization of electronic devices, the need for individually addressable, switchable molecules arises. An example are azobenzenes on surfaces which have been shown to be switchable between trans and cis forms. Here, we examine the "direct" (rather than substrate-mediated) channel of the trans -> cis photoisomerization after pi pi* excitation of tetra-tert-butyl-azobenzene physisorbed on surfaces mimicking Au(111) and Bi(111), respectively. In spirit of the direct channel, the electronic structure of the surface is neglected, the latter merely acting as a rigid platform which weakly interacts with the molecule via Van-der-Waals forces. Starting from thermal ensembles which represent the trans-form, sudden excitations promote the molecules to pi pi*-excited states which are non-adiabatically coupled among themselves and to a n pi*-excited and the ground state, respectively. After excitation, relaxation to the ground state by internal conversion takes place, possibly accompanied by isomerization. The process is described here by "on the fly" semiclassical surface hopping dynamics in conjunction with a semiempirical Hamiltonian (AM1) and configuration-interaction type methods. It is found that steric constraints imposed by the substrate lead to reduced but non-vanishing, trans -> cis reaction yields and longer internal conversion times than for the isolated molecule. Implications for recent experiments for azobenzenes on surfaces are discussed.}, language = {en} } @article{KruegerSchwarzeBaumannetal.2018, author = {Kr{\"u}ger, Stefanie and Schwarze, Michael and Baumann, Otto and G{\"u}nter, Christina and Bruns, Michael and K{\"u}bel, Christian and Szabo, Dorothee Vinga and Meinusch, Rafael and Bermudez, Veronica de Zea and Taubert, Andreas}, title = {Bombyx mori silk/titania/gold hybrid materials for photocatalytic water splitting}, series = {Beilstein journal of nanotechnology}, volume = {9}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {2190-4286}, doi = {10.3762/bjnano.9.21}, pages = {187 -- 204}, year = {2018}, abstract = {The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO2)/gold(Au)/Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m(2)/g. The diameter of the TiO2 nanoparticles (NPs) - mainly anatase with a minor fraction of brookite - and the Au NPs are on the order of 5 and 7-18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.}, language = {en} } @article{WuGlebeBoeker2017, author = {Wu, Lei and Glebe, Ulrich and B{\"o}ker, Alexander}, title = {Fabrication of Thermoresponsive Plasmonic Core-Satellite Nanoassemblies with a Tunable Stoichiometry via Surface-Initiated Reversible Addition-Fragmentation Chain Transfer Polymerization from Silica Nanoparticles}, series = {Advanced materials interfaces}, volume = {4}, journal = {Advanced materials interfaces}, publisher = {Wiley}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.201700092}, pages = {10}, year = {2017}, abstract = {This work presents a fabrication of thermoresponsive plasmonic core-satellite nanoassemblies. The structure has a silica nanoparticle core surrounded by gold nanoparticle satellites using thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) chains as scaffolds. The thiol-terminated PNIPAM shell is densely grafted on the silica core via surface-initiated reversible addition-fragmentation chain transfer polymerization and used to anchor numerous gold nanoparticle satellites with a tunable stoichiometry. Below and above lower critical solution temperature, the chain conformation of PNIPAM reversibly changes between swollen and shrunken state. The reversible change of the polymer size varies the refractive index of the local medium surrounding the satellites and the distance between them. The two effects together lead to the thermoresponsive plasmonic properties of the nanoassemblies. Under different satellite densities, two distinctive plasmonic features appear.}, language = {en} }