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- ItemPhotoswitching of DNA Hybridization Using a Molecular Motor(Washington, DC : ACS Publications, 2018) Lubbe, Anouk S.; Liu, Qing; Smith, Sanne J.; de Vries, Jan Willem; Kistemaker, Jos C. M.; de Vries, Alex H.; Faustino, Ignacio; Meng, Zhuojun; Szymanski, Wiktor; Herrmann, Andreas; Feringa, Ben L.Reversible control over the functionality of biological systems via external triggers may be used in future medicine to reduce the need for invasive procedures. Additionally, externally regulated biomacromolecules are now considered as particularly attractive tools in nanoscience and the design of smart materials, due to their highly programmable nature and complex functionality. Incorporation of photoswitches into biomolecules, such as peptides, antibiotics, and nucleic acids, has generated exciting results in the past few years. Molecular motors offer the potential for new and more precise methods of photoregulation, due to their multistate switching cycle, unidirectionality of rotation, and helicity inversion during the rotational steps. Aided by computational studies, we designed and synthesized a photoswitchable DNA hairpin, in which a molecular motor serves as the bridgehead unit. After it was determined that motor function was not affected by the rigid arms of the linker, solid-phase synthesis was employed to incorporate the motor into an 8-base-pair self-complementary DNA strand. With the photoswitchable bridgehead in place, hairpin formation was unimpaired, while the motor part of this advanced biohybrid system retains excellent photochemical properties. Rotation of the motor generates large changes in structure, and as a consequence the duplex stability of the oligonucleotide could be regulated by UV light irradiation. Additionally, Molecular Dynamics computations were employed to rationalize the observed behavior of the motor–DNA hybrid. The results presented herein establish molecular motors as powerful multistate switches for application in biological environments.
- ItemMitochondria Targeted Protein-Ruthenium Photosensitizer for Efficient Photodynamic Applications(Washington, DC : ACS Publications, 2017) Chakrabortty, Sabyasachi; Agrawalla, Bikram Keshari; Stumper, Anne; Vegi, Naidu M.; Fischer, Stephan; Reichardt, Christian; Kögler, Michael; Dietzek, Benjamin; Feuring-Buske, Michaela; Buske, Christian; Rau, Sven; Weil, TanjaOrganelle-targeted photosensitization represents a promising approach in photodynamic therapy where the design of the active photosensitizer (PS) is very crucial. In this work, we developed a macromolecular PS with multiple copies of mitochondria-targeting groups and ruthenium complexes that displays highest phototoxicity toward several cancerous cell lines. In particular, enhanced anticancer activity was demonstrated in acute myeloid leukemia cell lines, where significant impairment of proliferation and clonogenicity occurs. Finally, attractive two-photon absorbing properties further underlined the great significance of this PS for mitochondria targeted PDT applications in deep tissue cancer therapy.
- ItemTailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation(Cambridge : RSC Publ., 2021) Mendes, Rafael G.; Ta, Huy Q.; Yang, Xiaoqin; Bachmatiuk, Alicja; Praus, Petr; Mamakhel, Aref; Iversen, Bo B.; Su, Ren; Gemming, Thomas; Rümmeli, Mark H.Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C–N–C, [double bond, length as m-dash]NH or –NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4.
- ItemStructural defects in Fe-Pd-based ferromagnetic shape memory alloys: Tuning transformation properties by ion irradiation and severe plastic deformation(Bristol : IOP, 2012) Mayr, S.G.; Arabi-Hashemi, A.Fe-Pd-based ferromagnetic shape memory alloys constitute an exciting class of magnetically switchable smart materials that reveal excellent mechanical properties and biocompatibility. However, their application is severely hampered by a lack of understanding of the physics at the atomic scale. A many-body potential is presented that matched ab inito calculations and can account for the energetics of martensite ↔ austenite transition along the Bain path and relative phase stabilities in the ordered and disordered phases of Fe-Pd. Employed in massively parallel classical molecular dynamics simulations, the impact of order/disorder, point defects and severe plastic deformation in the presence of single- and polycrystalline microstructures are explored as a function of temperature. The model predictions are in agreement with experiments on phase changes induced by ion irradiation, cold rolling and hammering, which are also presented.
- ItemEvaluation of electron induced crosslinking of masticated natural rubber at different temperatures(Basel : MDPI, 2019) Huang, Ying; Gohs, Uwe; Müller, Michael Thomas; Zschech, Carsten; Wießner, SvenIn this work, natural rubber (NR) was masticated using an internal mixer to fit the requirements of reactive blending with polylactide and characterized by size exclusion chromatography (SEC), Fourier-transform infrared (FT-IR) spectroscopy and dynamic rheology measurements. Subsequently, the effect of elevated temperatures (25 °C, 80 °C, and 170 °C) on the electron beam (EB) induced crosslinking and degradation of masticated natural rubber (mNR) in a nitrogen atmosphere without adding crosslinking agents has been investigated. The sol gel investigation showed that the gel dose of mNR slightly increased with increasing irradiation temperature, which is also confirmed by the swelling test. The chain scission to crosslinking ratio (Gs/Gx) was found to be less than 1 for irradiated mNR at 25 °C and 80 °C, suggesting a dominating crosslinking behavior of mNR. However, a significant increase of Gs/Gx ratio (~1.12) was observed for mNR irradiated at 170 °C due to the enhanced thermal degradation behavior at high temperature. A remarkably improved elasticity (higher complex viscosity, higher storage modulus, and longer relaxation time) for EB modified mNR was demonstrated by dynamic rheological analysis. Particularly, the samples modified at higher temperatures represented more pronounced elasticity behavior which resulted from the higher number of branches and/or the longer branched chains.
- ItemModulating the luminance of organic light-emitting diodes: Via optical stimulation of a photochromic molecular monolayer at transparent oxide electrode(Cambridge : RSC Publ., 2020) Ligorio, Giovanni; Cotella, Giovanni F.; Bonasera, Aurelio; Zorn Morales, Nicolas; Carnicella, Giuseppe; Kobin, Björn; Wang, Qiankun; Koch, Norbert; Hecht, Stefan; List-Kratochvil, Emil J.W.; Cacialli, FrancoSelf-assembled monolayers (SAMs) deposited on bottom electrodes are commonly used to tune charge carrier injection or blocking in optoelectronic devices. Beside the enhancement of device performance, the fabrication of multifunctional devices in which the output can be modulated by multiple external stimuli remains a challenging target. In this work, we report the functionalization of an indium tin oxide (ITO) electrode with a SAM of a diarylethene derivative designed for optically control the electronic properties. Following the demonstration of dense SAM formation and its photochromic activity, as a proof-of-principle, an organic light-emitting diode (OLED) embedding the light-responsive SAM-covered electrode was fabricated and characterized. Optically addressing the two-terminal device by irradiation with ultraviolet light doubles the electroluminescence. The original value can be restored reversibly by irradiation with visible light. This expanded functionality is based on the photoinduced modulation of the electronic structure of the diarylethene isomers, which impact the charge carriers' confinement within the emissive layer. This approach could be successfully exploited in the field of opto-communication technology, for example to fabricate opto-electronic logic circuits. © 2020 The Royal Society of Chemistry.
- ItemAn electron beam profile instrument based on FBGs(Basel : MDPI AG, 2014) Sporea, D.; Stǎncǎlie, A.; Becherescu, N.; Becker, M.; Rothhardt, M.Along with the dose rate and the total irradiation dose measurements, the knowledge of the beam localization and the beam profile/energy distribution in the beam are parameters of interest for charged particle accelerator installations when they are used in scientific investigations, industrial applications or medical treatments. The transverse profile of the beam, its position, its centroid location, and its focus or flatness depend on the instrument operating conditions or on the beam exit setup. Proof-of-concept of a new type of charged particle beam diagnostics based on fiber Bragg gratings (FBGs) was demonstrated. Its operating principle relies on the measurement of the peak wavelength changes for an array of FBG sensors as function of the temperature following the exposure to an electron beam. Periodically, the sensor irradiation is stopped and the FBG are force cooled to a reference temperature with which the temperature influencing each sensor during beam exposure is compared. Commercially available FBGs, and FBGs written in radiation resistant optical fibers, were tested under electron beam irradiation in order to study their possible use in this application.