@article{HeckPrinzDatheetal.2017, author = {Heck, Christian and Prinz, Julia and Dathe, Andre and Merk, Virginia and Stranik, Ondrej and Fritzsche, Wolfgang and Kneipp, Janina and Bald, Ilko}, title = {Gold Nanolenses Self-Assembled by DNA Origami}, series = {ACS Photonics}, volume = {4}, journal = {ACS Photonics}, publisher = {American Chemical Society}, address = {Washington}, issn = {2330-4022}, doi = {10.1021/acsphotonics.6b00946}, pages = {1123 -- 1130}, year = {2017}, abstract = {Nanolenses are self-similar chains of metal nanoparticles, which can theoretically provide extremely high field enhancements. Yet, the complex structure renders their synthesis challenging and has hampered closer analyses so far. Here, DNA origami is used to self-assemble 10, 20, and 60 nm gold nanoparticles as plasmonic gold nanolenses (AuNLs) in solution and in billions of copies. Three different geometrical arrangements are assembled, and for each of the three designs, surface-enhanced Raman scattering (SERS) capabilities of single AuNLs are assessed. For the design which shows the best properties, SERS signals from the two different internal gaps are compared by selectively placing probe dyes. The highest Raman enhancement is found for the gap between the small and medium nanoparticle, which is indicative of a cascaded field enhancement.}, language = {en} } @article{HeckKanehiraKneippetal.2018, author = {Heck, Christian and Kanehira, Yuya and Kneipp, Janina and Bald, Ilko}, title = {Placement of Single Proteins within the SERS Hot Spots of Self-Assembled Silver Nanolenses}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {57}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {25}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201801748}, pages = {7444 -- 7447}, year = {2018}, abstract = {This study demonstrates the bottom-up synthesis of silver nanolenses. A robust coating protocol enabled the functionalization of differently sized silver nanoparticles with DNA single strands of orthogonal sequence. Coated particles 10nm, 20nm, and 60nm in diameter were self-assembled by DNA origami scaffolds to form silver nanolenses. Single molecules of the protein streptavidin were selectively placed in the gap of highest electric field enhancement. Streptavidin labelled with alkyne groups served as model analyte in surface-enhanced Raman scattering (SERS) experiments. By correlated Raman mapping and atomic force microscopy, SERS signals of the alkyne labels of a single streptavidin molecule, from a single silver nanolens, were detected. The discrete, self-similar aggregates of solid silver nanoparticles are promising for plasmonic applications.}, language = {en} } @article{VogelEbelSchuermannetal.2019, author = {Vogel, Stefanie and Ebel, Kenny and Sch{\"u}rmann, Robin Mathis and Heck, Christian and Meiling, Till and Milosavljevic, Aleksandar R. and Giuliani, Alexandre and Bald, Ilko}, title = {Vacuum-UV and Low-Energy Electron-Induced DNA Strand Breaks}, series = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, volume = {20}, journal = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, number = {6}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1439-4235}, doi = {10.1002/cphc.201801152}, pages = {823 -- 830}, year = {2019}, abstract = {DNA is effectively damaged by radiation, which can on the one hand lead to cancer and is on the other hand directly exploited in the treatment of tumor tissue. DNA strand breaks are already induced by photons having an energy below the ionization energy of DNA. At high photon energies, most of the DNA strand breaks are induced by low-energy secondary electrons. In the present study we quantified photon and electron induced DNA strand breaks in four different 12mer oligonucleotides. They are irradiated directly with 8.44 eV vacuum ultraviolet (VUV) photons and 8.8 eV low energy electrons (LEE). By using Si instead of VUV transparent CaF2 as a substrate the VUV exposure leads to an additional release of LEEs, which have a maximum energy of 3.6 eV and can significantly enhance strand break cross sections. Atomic force microscopy is used to visualize strand breaks on DNA origami platforms and to determine absolute values for the strand break cross sections. Upon irradiation with 8.44 eV photons all the investigated sequences show very similar strand break cross sections in the range of 1.7-2.3x10(-16) cm(2). The strand break cross sections for LEE irradiation at 8.8 eV are one to two orders of magnitude larger than the ones for VUV photons, and a slight sequence dependence is observed. The sequence dependence is even more pronounced for LEEs with energies <3.6 eV. The present results help to assess DNA damage by photons and electrons close to the ionization threshold.}, language = {en} } @article{HeckKanehiraKneippetal.2019, author = {Heck, Christian and Kanehira, Yuya and Kneipp, Janina and Bald, Ilko}, title = {Amorphous Carbon Generation as a Photocatalytic Reaction on DNA-Assembled Gold and Silver Nanostructures}, series = {Molecules}, volume = {24}, journal = {Molecules}, number = {12}, publisher = {MDPI}, address = {Basel}, issn = {1420-3049}, doi = {10.3390/molecules24122324}, pages = {10}, year = {2019}, abstract = {Background signals from in situ-formed amorphous carbon, despite not being fully understood, are known to be a common issue in few-molecule surface-enhanced Raman scattering (SERS). Here, discrete gold and silver nanoparticle aggregates assembled by DNA origami were used to study the conditions for the formation of amorphous carbon during SERS measurements. Gold and silver dimers were exposed to laser light of varied power densities and wavelengths. Amorphous carbon prevalently formed on silver aggregates and at high power densities. Time-resolved measurements enabled us to follow the formation of amorphous carbon. Silver nanolenses consisting of three differently-sized silver nanoparticles were used to follow the generation of amorphous carbon at the single-nanostructure level. This allowed observation of the many sharp peaks that constitute the broad amorphous carbon signal found in ensemble measurements. In conclusion, we highlight strategies to prevent amorphous carbon formation, especially for DNA-assembled SERS substrates.}, language = {en} }