TY - JOUR A1 - Vogel, Stefanie A1 - Ebel, Kenny A1 - Schürmann, Robin Mathis A1 - Heck, Christian A1 - Meiling, Till A1 - Milosavljevic, Aleksandar R. A1 - Giuliani, Alexandre A1 - Bald, Ilko T1 - Vacuum-UV and Low-Energy Electron-Induced DNA Strand Breaks BT - Influence of the DNA Sequence and Substrate JF - ChemPhysChem : a European journal of chemical physics and physical chemistry N2 - 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. KW - DNA origami KW - DNA radiation damage KW - DNA strand breaks KW - low-energy electrons KW - vacuum-UV radiation Y1 - 2019 U6 - https://doi.org/10.1002/cphc.201801152 SN - 1439-4235 SN - 1439-7641 VL - 20 IS - 6 SP - 823 EP - 830 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Vogel, Stefanie A1 - Ebel, Kenny A1 - Heck, Christian A1 - Schürmann, Robin Mathis A1 - Milosavljevic, Aleksandar R. A1 - Giuliani, Alexandre A1 - Bald, Ilko T1 - Vacuum-UV induced DNA strand breaks BT - influence of the radiosensitizers 5-bromouracil and 8-bromoadenine JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Radiation therapy is a basic part of cancer treatment. To increase the DNA damage in carcinogenic cells and preserve healthy tissue at the same time, radiosensitizing molecules such as halogenated nucleobase analogs can be incorporated into the DNA during the cell reproduction cycle. In the present study 8.44 eV photon irradiation induced single strand breaks (SSB) in DNA sequences modified with the radiosensitizer 5-bromouracil (U-5Br) and 8-bromoadenine ((8Br)A) are investigated. U-5Br was incorporated in the 13mer oligonucleotide flanked by different nucleobases. It was demonstrated that the highest SSB cross sections were reached, when cytosine and thymine were adjacent to U-5Br, whereas guanine as a neighboring nucleobase decreases the activity of U-5Br indicating that competing reaction mechanisms are active. This was further investigated with respect to the distance of guanine to U-5Br separated by an increasing number of adenine nucleotides. It was observed that the SSB cross sections were decreasing with an increasing number of adenine spacers between guanine and U-5Br until the SSB cross sections almost reached the level of a non-modified DNA sequence, which demonstrates the high sequence dependence of the sensitizing effect of U-5Br. (8Br)A was incorporated in a 13mer oligonucleotide as well and the strand breaks were quantified upon 8.44 eV photon irradiation in direct comparison to a non-modified DNA sequence of the same composition. No clear enhancement of the SSB yield of the modified in comparison to the non-modified DNA sequence could be observed. Additionally, secondary electrons with a maximum energy of 3.6 eV were generated when using Si as a substrate giving rise to further DNA damage. A clear enhancement in the SSB yield can be ascertained, but to the same degree for both the non-modified DNA sequence and the DNA sequence modified with (8Br)A. Y1 - 2019 U6 - https://doi.org/10.1039/c8cp06813e SN - 1463-9076 SN - 1463-9084 VL - 21 IS - 4 SP - 1972 EP - 1979 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Schürmann, Robin Mathis A1 - Vogel, Stefanie A1 - Ebel, Kenny A1 - Bald, Ilko T1 - The physico-chemical basis of DNA radiosensitization BT - implications for cancer radiation therapy JF - Chemistry - a European journal N2 - High-energy radiation is used in combination with radiosensitizing therapeutics to treat cancer. The most common radiosensitizers are halogenated nucleosides and cisplatin derivatives, and recently also metal nanoparticles have been suggested as potential radiosensitizing agents. The radiosensitizing action of these compounds can at least partly be ascribed to an enhanced reactivity towards secondary low-energy electrons generated along the radiation track of the high-energy primary radiation, or to an additional emission of secondary reactive electrons close to the tumor tissue. This is referred to as physico-chemical radiosensitization. In this Concept article we present current experimental methods used to study fundamental processes of physico-chemical radiosensitization and discuss the most relevant classes of radiosensitizers. Open questions in the current discussions are identified and future directions outlined, which can lead to optimized treatment protocols or even novel therapeutic concepts. KW - cancer KW - dissociative electron attachment KW - low-energy electrons KW - radiation therapy KW - radiosensitizers Y1 - 2018 U6 - https://doi.org/10.1002/chem.201800804 SN - 0947-6539 SN - 1521-3765 VL - 24 IS - 41 SP - 10271 EP - 10279 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Meiling, Till Thomas A1 - Schürmann, Robin Mathis A1 - Vogel, Stefanie A1 - Ebel, Kenny A1 - Nicolas, Christophe A1 - Milosavljevic, Aleksandar R. A1 - Bald, Ilko T1 - Photophysics and Chemistry of Nitrogen-Doped Carbon Nanodots with High Photoluminescence Quantum Yield JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Fluorescent carbon nanodots (CNDs) are very promising nanomaterials for a broad range of applications because of their high photostability, presumed selective luminescence, and low cost at which they can be produced. In this respect, CNDs are superior to well-established semiconductor quantum dots and organic dyes. However, reported synthesis protocols for CNDs typically lead to low photoluminescence quantum yield (PLQY) and low reproducibility, resulting in a poor understanding of the CND chemistry and photophysics. Here, we report a one-step synthesis of nitrogen-doped carbon nanodots (N-CNDs) from various carboxylic acids, Tris, and ethylenediaminetetraacetic acid resulting in high PLQY of up to 90%. The reaction conditions in terms of starting materials, temperature, and reaction time are carefully optimized and their influence on the photophysical properties is characterized. We find that citric acid-derived N-CNDs can result in a very high PLQY of 90%, but they do not show selective luminescence. By contrast, acetic acid-derived N-CNDs show selective luminescence but a PLQY of 50%. The chemical composition of the surface and core of these two selected N-CND types is characterized among others by high-resolution synchrotron X-ray photoelectron spectroscopy using single isolated N-CND clusters. The results indicate that photoexcitation occurs in the N-CND core, whereas the emission properties are determined by the N-CND surface groups. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpcc.8b00748 SN - 1932-7447 VL - 122 IS - 18 SP - 10217 EP - 10230 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Vogel, Stefanie A1 - Rackwitz, Jenny A1 - Schuerman, Robin A1 - Prinz, Julia A1 - Milosavljevic, Aleksandar R. A1 - Refregiers, Matthieu A1 - Giuliani, Alexandre A1 - Bald, Ilko T1 - Using DNA origami nanostructures to determine absolute cross sections for UV photon-induced DNA strand breakage JF - The journal of physical chemistry letters N2 - We have characterized ultraviolet (UV) photon-induced DNA strand break processes by determination of absolute cross sections for photoabsorption and for sequence-specific DNA single strand breakage induced by photons in an energy range from 6.50 to 8.94 eV. These represent the lowest-energy photons able to induce DNA strand breaks. Oligonudeotide targets are immobilized on a UV transparent substrate in controlled quantities through attachment to DNA origami templates. Photon-induced dissociation of single DNA strands is visualized and quantified using atomic force microscopy. The obtained quantum yields for strand breakage vary between 0.06 and 0.5, indicating highly efficient DNA strand breakage by UV photons, which is clearly dependent on the photon energy. Above the ionization threshold strand breakage becomes clearly the dominant form of DNA radiation damage, which is then also dependent on the nucleotide sequence. Y1 - 2015 U6 - https://doi.org/10.1021/acs.jpclett.5b02238 SN - 1948-7185 VL - 6 IS - 22 SP - 4589 EP - 4593 PB - American Chemical Society CY - Washington ER -