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- ItemUnraveling the Light-Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis(Weinheim : Wiley-VCH, 2019) Zedler, Linda; Mengele, Alexander Klaus; Ziems, Karl Michael; Zhang, Ying; Wächtler, Maria; Gr-fe, Stefanie; Pascher, Torbjörn; Rau, Sven; Kupfer, Stephan; Dietzek, BenjaminUnderstanding photodriven multielectron reaction pathways requires the identification and spectroscopic characterization of intermediates and their excited-state dynamics, which is very challenging due to their short lifetimes. To the best of our knowledge, this manuscript reports for the first time on in situ spectroelectrochemistry as an alternative approach to study the excited-state properties of reactive intermediates of photocatalytic cycles. UV/Vis, resonance-Raman, and transient-absorption spectroscopy have been employed to characterize the catalytically competent intermediate [(tbbpy)2RuII(tpphz)RhICp*] of [(tbbpy)2Ru(tpphz)Rh(Cp*)Cl]Cl(PF6)2 (Ru(tpphz)RhCp*), a photocatalyst for the hydrogenation of nicotinamide (NAD-analogue) and proton reduction, generated by electrochemical and chemical reduction. Electronic transitions shifting electron density from the activated catalytic center to the bridging tpphz ligand significantly reduce the catalytic activity upon visible-light irradiation. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemStress-Induced 3D Chiral Fractal Metasurface for Enhanced and Stabilized Broadband Near-Field Optical Chirality(Weinheim : Wiley-VCH Verlag, 2019) Tseng M.L.; Lin Z.-H.; Kuo H.Y.; Huang T.-T.; Huang Y.-T.; Chung T.L.; Chu C.H.; Huang J.-S.; Tsai D.P.Metasurfaces comprising 3D chiral structures have shown great potential in chiroptical applications such as chiral optical components and sensing. So far, the main challenges lie in the nanofabrication and the limited operational bandwidth. Homogeneous and localized broadband near-field optical chirality enhancement has not been achieved. Here, an effective nanofabrication method to create a 3D chiral metasurface with far- and near-field broadband chiroptical properties is demonstrated. A focused ion beam is used to cut and stretch nanowires into 3D Archimedean spirals from stacked films. The 3D Archimedean spiral is a self-similar chiral fractal structure sensitive to the chirality of light. The spiral exhibits far- and near-field broadband chiroptical responses from 2 to 8 µm. With circularly polarized light (CPL), the spiral shows superior far-field transmission dissymmetry and handedness-dependent near-field localization. With linearly polarized excitation, homogeneous and highly enhanced broadband near-field optical chirality is generated at a stably localized position inside the spiral. The effective yet straightforward fabrication strategy allows easy fabrication of 3D chiral structures with superior broadband far-field chiroptical response as well as strongly enhanced and stably localized broadband near-field optical chirality. The reported method and chiral metasurface may find applications in broadband chiral optics and chiral sensing. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemRadiofrequency Hyperthermia of Cancer Cells Enhanced by Silicic Acid Ions Released during the Biodegradation of Porous Silicon Nanowires(Washington, DC : ACS Publications, 2019) Gongalsky, Maxim; Gvindzhiliia, Georgii; Tamarov, Konstantin; Shalygina, Olga; Pavlikov, Alexander; Solovyev, Valery; Kudryavtsev, Andrey; Sivakov, Vladimir; Osminkina, Liubov A.The radiofrequency (RF) mild hyperthermia effect sensitized by biodegradable nanoparticles is a promising approach for therapy and diagnostics of numerous human diseases including cancer. Herein, we report the significant enhancement of local destruction of cancer cells induced by RF hyperthermia in the presence of degraded low-toxic porous silicon (PSi) nanowires (NWs). Proper selection of RF irradiation time (10 min), intensity, concentration of PSi NWs, and incubation time (24 h) decreased cell viability to 10%, which can be potentially used for cancer treatment. The incubation for 24 h is critical for degradation of PSi NWs and the formation of silicic acid ions H+ and H3SiO4- in abundance. The ions drastically change the solution conductivity in the vicinity of PSi NWs, which enhances the absorption of RF radiation and increases the hyperthermia effect. The high biodegradability and efficient photoluminescence of PSi NWs were governed by their mesoporous structure. The average size of pores was 10 nm, and the sizes of silicon nanocrystals (quantum dots) were 3-5 nm. Degradation of PSi NWs was observed as a significant decrease of optical absorbance, photoluminescence, and Raman signals of PSi NW suspensions after 24 h of incubation. Localization of PSi NWs at cell membranes revealed by confocal microscopy suggested that thermal poration of membranes could cause cell death. Thus, efficient photoluminescence in combination with RF-induced cell membrane breakdown indicates promising opportunities for theranostic applications of PSi NWs. © 2019 American Chemical Society.
- ItemHigh-throughput screening Raman microspectroscopy for assessment of drug-induced changes in diatom cells(Cambridge : Royal Society of Chemistry, 2019) Rüger J.; Mondol A.S.; Schie I.W.; Popp J.; Krafft C.High-throughput screening Raman spectroscopy (HTS-RS) with automated localization algorithms offers unsurpassed speed and sensitivity to investigate the effect of dithiothreitol on the diatom Phaedactylum tricornutum. The HTS-RS capability that was demonstrated for this model system can be transferred to unmet analytical applications such as kinetic in vivo studies of microalgal assemblages. © 2019 The Royal Society of Chemistry.
- ItemEnergy-Dependent RBS Channelling Analysis of Epitaxial ZnO Layers Grown on ZnO by RF-Magnetron Sputtering(Basel : MDPI, 2019) Wittkämper, Florian; Bikowski, André; Ellmer, Klaus; Gärtner, Konrad; Wendler, ElkeThe transparent conducting oxides ZnO and ZnO:Al are interesting materials for a wide range of applications. Several of these applications need a large area, single crystalline, and specially doped thin layers. A common technique for the fabrication of those layers is RF (radio frequency) -magnetron sputtering. The investigation of the crystal quality of such layers requires methods of analysis that are destruction free and that are able to obtain information about the concentration and type of defects versus depth. One such option is the Rutherford backscattering spectroscopy (RBS) in channelling mode. In this work, we exploit the channelling effect and its energy dependence, which are sensitive to the type of defects. By using appropriate software and measuring RBS channelling spectra with different beam energies, we were able to determine the depth distribution of point defects and dislocation loops. The presence of dislocation loops was proven using other previously applied analysis methods. The main advantage of RBS in channelling mode is the quantification of point defects, which can be important for defining the electrical and optical properties of such layers. The technique demonstrated is applicable to other defective crystals or thin crystalline layers. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemPolymeric Photoacids Based on Naphthols—Design Criteria, Photostability, and Light-Mediated Release(Weinheim : Wiley-VCH, 2019) Wendler, Felix; Sittig, Maria; Tom, Jessica C.; Dietzek, Benjamin; Schacher, Felix H.The implementation of photoswitches within polymers offers an exciting toolbox in the design of light-responsive materials as irradiation can be controlled both spatially and temporally. Herein, we introduce a range of water-soluble copolymers featuring naphthol-based chromophores as photoacids in the side chain. With that, the resulting materials experience a drastic increase in acidity upon stimulation with UV light and we systematically studied how structure and distance of the photoacid from the copolymer backbone determines polymerizability, photo-response, and photostability. Briefly, we used RAFT (reversible addition–fragmentation chain transfer) polymerization to prepare copolymers consisting of nona(ethylene glycol) methyl ether methacrylate (MEO9MA) as water-soluble comonomer in combination with six different 1-naphthol-based (“N”) monomers. Thereby, we distinguish between methacrylates (NMA, NOeMA), methacrylamides (NMAm, NOeMAm), vinyl naphthol (VN), and post-polymerization modification based on [(1-hydroxynaphthalen-2-amido)ethyl]amine (NOeMAm, NAmeMAm). These P(MEO9MAx-co-“N”y) copolymers typically feature a 4:1 MEO9MA to “N” ratio and molar masses in the range of 10 kg mol−1. After synthesis and characterization by using NMR spectroscopy and size exclusion chromatography (SEC), we investigated how potential photo-cleavage or photo-degradation during irradiation depends on the type and distance of the linker to the copolymeric backbone and whether reversible excited state proton transfer (ESPT) occurs under these conditions. In our opinion, such materials will be strong assets as light-mediated proton sources in nanostructured environments, for example, for the site-specific creation of proton gradients. We therefore exemplarily incorporated NMA into an amphiphilic block copolymer and could demonstrate the light-mediated release of Nile red from micelles formed in water as selective solvent. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemA Machine Learning-Based Raman Spectroscopic Assay for the Identification of Burkholderia mallei and Related Species(Basel : MDPI, 2019) Silge, Anja; Moawad, Amira A.; Bocklitz, Thomas; Fischer, Katja; Rösch, Petra; Roesler, Uwe; Elschner, Mandy C.; Popp, Jürgen; Neubauer, HeinrichBurkholderia (B.) mallei, the causative agent of glanders, and B. pseudomallei, the causative agent of melioidosis in humans and animals, are genetically closely related. The high infectious potential of both organisms, their serological cross-reactivity, and similar clinical symptoms in human and animals make the differentiation from each other and other Burkholderia species challenging. The increased resistance against many antibiotics implies the need for fast and robust identification methods. The use of Raman microspectroscopy in microbial diagnostic has the potential for rapid and reliable identification. Single bacterial cells are directly probed and a broad range of phenotypic information is recorded, which is subsequently analyzed by machine learning methods. Burkholderia were handled under biosafety level 1 (BSL 1) conditions after heat inactivation. The clusters of the spectral phenotypes and the diagnostic relevance of the Burkholderia spp. were considered for an advanced hierarchical machine learning approach. The strain panel for training involved 12 B. mallei, 13 B. pseudomallei and 11 other Burkholderia spp. type strains. The combination of top- and sub-level classifier identified the mallei-complex with high sensitivities (>95%). The reliable identification of unknown B. mallei and B. pseudomallei strains highlighted the robustness of the machine learning-based Raman spectroscopic assay. © 2019 by the authors
- ItemA stimulated Stokes Raman scattering-based approach for continuous wave supercontinuum generation in optical fibers(Philadelphia, Pa. : IOP Publ., 2019) Arshad, Muhammad Assad; Hartung, Alexander; Jäger, MatthiasWe report on a new and simple approach for continuous wave supercontinuum generation in optical fibers. Our new approach uses the effect of stimulated Stokes Raman scattering in a low loss fiber ring laser. By continuously pumping this ring laser with up to 19 W optical power we excited up to six Stokes orders and covered a wavelength range of 500 nm. Due to the feedback mechanism of the ring layout additional nonlinear effects occurred next to the plain generation of individual Stokes peaks. Eventually, these effects broaden and merge the separated Stokes peaks and create a single, connected continuous supercontinuum. By using the effect of stimulated Stokes Raman scattering, we do not rely on anomalous dispersion and modulation instability as typically required for continuous wave supercontinuum generation. © 2019 Astro Ltd.
- ItemIntra-cavity measurement concept of dispersion properties with a tunable fiber-integrated laser(Philadelphia, Pa. : IOP Publ., 2019) Tiess, Tobias; Hartung, Alexander; Becker, Martin; Chojetzki, Christoph; Rothhardt, Manfred; Bartelt, Hartmut; Jäger, MatthiasThe dispersion properties of fibers depict a key characteristic to model the propagation of ultra-short pulses in waveguides. In the following, a new method is presented to directly measure the dispersion properties of fibers and optical components in the time domain. The analysis is based on pulse shape variations along the tuning range of a theta cavity fiber laser (TCFL) depending on the adjusted repetition rate. The automated measurement procedure, evaluating pulse symmetry, achieves a temporal sensitivity below 5 ps surpassing the resolution of the acquisition electronics. Exemplarily, two samples of Nufern PM980-XP fiber are investigated with an Yb-doped tunable TCFL retrieving the mean dispersion parameter D? by comparative measurements. The obtained results are compared to a reference method based on spectral interferometry. With deviations in D? between either approach of 0.3% and 1.3%, respectively, the results agree well within the measurement errors of the TCFL, verifying the presented concept. Due to the pulse formation process extending over multiple round trips, this approach achieves an enhanced sensitivity compared to competing direct temporal methods. Together with an alignment free operation, the fiber-integrated TCFL depicts a simple and robust concept showing potential in specific measurement scenarios such as in quality management. © 2019 Astro Ltd.
- ItemMagnetooptical response of permalloy multilayer structures on different substrate in the IR-VIS-UV spectral range(Bristol : IOP Publ., 2019) Patra, Rajkumar; Mattheis, Roland; Stöcker, Hartmut; Monecke, Manuel; Salvan, Georgeta; Schäfer, Rudolf; Schmidt, Oliver G.; Schmidt, HeidemarieThe magnetooptical (MO) response of Ru/Py/Ta thin film stacks with 4, 8, and 17 nm thick Ni81Fe19 permalloy (Py) films on a SiO2/Si and a ZnO substrate was measured by vector magnetooptical generalized ellipsometry. The MO response from VMOGE was modelled using a 4 × 4 Mueller matrix algorithm. The wavelength-dependent, substrate-independent and thickness-independent complex MO coupling constant (Q) of Py in the Ru/Py/Ta thin film stacks was extracted by fitting Mueller matrix difference spectra in the spectral range from 300 nm to 1000 nm. Although the composition-dependent saturation magnetization of NixFe1−x alloys (x = 0.0...1.0), e.g. of Ni81Fe19, is predictable from the two saturation magnetization end points, the MO coupling constant of NixFe1−x is not predictable from the two Q end points. However, in a small alloy range (0.0 < x < 0.2 and 0.8 < x < 1.0) the composition-dependent Q of NixFe1−x can be interpolated from a sufficiently high number of analyzed NixFe1−x alloys. The available complex MO coupling constants of six different NixFe1−x (x = 1.0 to 0.0) alloys were used to interpolate MO response of binary NixFe1−x alloys in the range from x = 0.0 to x = 1.0.
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