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    Energy-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, Elke
    The 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.
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    Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature
    (Basel : MDPI, 2021) Ben-Miled, Aziz; Nabiyan, Afshin; Wondraczek, Katrin; Schacher, Felix H.; Wondraczek, Lothar
    A quartz crystal microbalance with dissipation monitoring (QCM-D) was employed for in situ investigations of the effect of temperature and light on the conformational changes of a poly (triethylene glycol acrylate-co-spiropyran acrylate) (P (TEGA-co-SPA)) copolymer containing 12–14% of spiropyran at the silica–water interface. By monitoring shifts in resonance frequency and in acoustic dissipation as a function of temperature and illumination conditions, we investigated the evolution of viscoelastic properties of the P (TEGA-co-SPA)-rich wetting layer growing on the sensor, from which we deduced the characteristic coil-to-globule transition temperature, corresponding to the lower critical solution temperature (LCST) of the PTEGA part. We show that the coil-to-globule transition of the adsorbed copolymer being exposed to visible or UV light shifts to lower LCST as compared to the bulk solution: the transition temperature determined acoustically on the surface is 4 to 8 K lower than the cloud point temperature reported by UV/VIS spectroscopy in aqueous solution. We attribute our findings to non-equilibrium effects caused by confinement of the copolymer chains on the surface. Thermal stimuli and light can be used to manipulate the film formation process and the film’s conformational state, which affects its subsequent response behavior.
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    Shape-Dependent Catalytic Activity of Gold and Bimetallic Nanoparticles in the Reduction of Methylene Blue by Sodium Borohydride
    (Basel : MDPI, 2021) Stolle, Heike Lisa Kerstin Stephanie; Kluitmann, Jonas Jakobus; Csáki, Andrea; Köhler, Johann Michael; Fritzsche, Wolfgang
    In this study the catalytic activity of different gold and bimetallic nanoparticle solutions towards the reduction of methylene blue by sodium borohydride as a model reaction is investigated. By utilizing differently shaped gold nanoparticles, i.e., spheres, cubes, prisms and rods as well as bimetallic gold–palladium and gold–platinum core-shell nanorods, we evaluate the effect of the catalyst surface area as available gold surface area, the shape of the nanoparticles and the impact of added secondary metals in case of bimetallic nanorods. We track the reaction by UV/Vis measurements in the range of 190–850 nm every 60 s. It is assumed that the gold nanoparticles do not only act as a unit transferring electrons from sodium borohydride towards methylene blue but can promote the electron transfer upon plasmonic excitation. By testing different particle shapes, we could indeed demonstrate an effect of the particle shape by excluding the impact of surface area and/or surface ligands. All nanoparticle solutions showed a higher methylene blue turnover than their reference, whereby gold nanoprisms exhibited 100% turnover as no further methylene blue absorption peak was detected. The reaction rate constant k was also determined and revealed overall quicker reactions when gold or bimetallic nanoparticles were added as a catalyst, and again these were highest for nanoprisms. Furthermore, when comparing gold and bimetallic nanorods, it could be shown that through the addition of the catalytically active second metal platinum or palladium, the dye turnover was accelerated and degradation rate constants were higher compared to those of pure gold nanorods. The results explore the catalytic activity of nanoparticles, and assist in exploring further catalytic applications.
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    FLIm and raman spectroscopy for investigating biochemical changes of bovine pericardium upon genipin cross-linking
    (Basel : MDPI, 2020) Shaik, Tanveer Ahmed; Alfonso-Garcia, Alba; Richter, Martin; Korinth, Florian; Krafft, Christoph; Marcu, Laura; Popp, Jürgen
    Biomaterials used in tissue engineering and regenerative medicine applications benefit from longitudinal monitoring in a non-destructive manner. Label-free imaging based on fluorescence lifetime imaging (FLIm) and Raman spectroscopy were used to monitor the degree of genipin (GE) cross-linking of antigen-removed bovine pericardium (ARBP) at three incubation time points (0.5, 1.0, and 2.5 h). Fluorescence lifetime decreased and the emission spectrum redshifted compared to that of uncross-linked ARBP. The Raman signature of GE-ARBP was resonance-enhanced due to the GE cross-linker that generated new Raman bands at 1165, 1326, 1350, 1380, 1402, 1470, 1506, 1535, 1574, 1630, 1728, and 1741 cm-1. These were validated through density functional theory calculations as cross-linker-specific bands. A multivariate multiple regression model was developed to enhance the biochemical specificity of FLIm parameters fluorescence intensity ratio (R2 = 0.92) and lifetime (R2 = 0.94)) with Raman spectral results. FLIm and Raman spectroscopy detected biochemical changes occurring in the collagenous tissue during the cross-linking process that were characterized by the formation of a blue pigment which affected the tissue fluorescence and scattering properties. In conclusion, FLIm parameters and Raman spectroscopy were used to monitor the degree of cross-linking non-destructively. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
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    Investigating light-induced processes in covalent dye-catalyst assemblies for hydrogen production
    (Basel : MDPI, 2020) Bold, Sebastian; Straistari, Tatiana; Muñoz-García, Ana B.; Pavone, Michele; Artero, Vincent; Chavarot-Kerlidou, Murielle; Dietzek, Benjamin
    The light-induced processes occurring in two dye-catalyst assemblies for light-driven hydrogen production were investigated by ultrafast transient absorption spectroscopy. These dyads consist of a push-pull organic dye based on a cyclopenta[1,2-b:5,4-b’]dithiophene (CPDT) bridge, covalently linked to two different H2-evolving cobalt catalysts. Whatever the nature of the latter, photoinduced intramolecular electron transfer from the excited state of the dye to the catalytic center was never observed. Instead, and in sharp contrast to the reference dye, a fast intersystem crossing (ISC) populates a long-lived triplet excited state, which in turn non-radiatively decays to the ground state. This study thus shows how the interplay of different structures in a dye-catalyst assembly can lead to unexpected excited state behavior and might open up new possibilities in the area of organic triplet sensitizers. More importantly, a reductive quenching mechanism with an external electron donor must be considered to drive hydrogen production with these dye-catalyst assemblies. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
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    ConsensusPrime—A Bioinformatic Pipeline for Ideal Consensus Primer Design
    (Basel : MDPI, 2022) Collatz, Maximilian; Braun, Sascha D.; Monecke, Stefan; Ehricht, Ralf
    Background: High-quality oligonucleotides for molecular amplification and detection procedures of diverse target sequences depend on sequence homology. Processing input sequences and identifying homogeneous regions in alignments can be carried out by hand only if they are small and contain sequences of high similarity. Finding the best regions for large and inhomogeneous alignments needs to be automated. Results: The ConsensusPrime pipeline was developed to sort out redundant and technical interfering data in multiple sequence alignments and detect the most homologous regions from multiple sequences. It automates the prediction of optimal consensus primers for molecular analytical and sequence-based procedures/assays. Conclusion: ConsensusPrime is a fast and easy-to-use pipeline for predicting optimal consensus primers that is executable on local systems without depending on external resources and web services. An implementation in a Docker image ensures platform-independent executability and installability despite the combination of multiple programs. The source code and installation instructions are publicly available on GitHub.
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    A Review on Data Fusion of Multidimensional Medical and Biomedical Data
    (Basel : MDPI, 2022) Azam, Kazi Sultana Farhana; Ryabchykov, Oleg; Bocklitz, Thomas
    Data fusion aims to provide a more accurate description of a sample than any one source of data alone. At the same time, data fusion minimizes the uncertainty of the results by combining data from multiple sources. Both aim to improve the characterization of samples and might improve clinical diagnosis and prognosis. In this paper, we present an overview of the advances achieved over the last decades in data fusion approaches in the context of the medical and biomedical fields. We collected approaches for interpreting multiple sources of data in different combinations: image to image, image to biomarker, spectra to image, spectra to spectra, spectra to biomarker, and others. We found that the most prevalent combination is the image-to-image fusion and that most data fusion approaches were applied together with deep learning or machine learning methods.
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    A 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, Heinrich
    Burkholderia (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
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    DNA-Biofunctionalization of CTAC-Capped Gold Nanocubes
    (Basel : MDPI, 2020) Slesiona, Nicole; Thamm, Sophie; Stolle, H. Lisa K.S.; Weißenborn, Viktor; Müller, Philipp; Csáki, Andrea; Fritzsche, Wolfgang
    Clinical diagnostics and disease control are fields that strongly depend on technologies for rapid, sensitive, and selective detection of biological or chemical analytes. Nanoparticles have become an integral part in various biomedical detection devices and nanotherapeutics. An increasing focus is laid on gold nanoparticles as they express less cytotoxicity, high stability, and hold unique optical properties with the ability of signal transduction of biological recognition events with enhanced analytical performance. Strong electromagnetic field enhancements can be found in close proximity to the nanoparticle that can be exploited to enhance signals for e.g., metal-enhanced fluorescence or Raman spectroscopy. Even stronger field enhancements can be achieved with sharp-edged nanoparticles, which are synthesized with the help of facet blocking agents, such as cetyltrimethylammonium bromide/chloride (CTAB/CTAC). However, chemical modification of the nanoparticle surface is necessary to reduce the particle’s cytotoxicity, stabilize it against aggregation, and to bioconjugate it with biomolecules to increase its biocompatibility and/or specificity for analytical applications. Here, a reliable two-step protocol following a ligand exchange with bis (p-sulfonatophenyl) phenyl phosphine (BSPP) as the intermediate capping-agent is demonstrated, which results in the reliable biofunctionalization of CTAC-capped gold nanocubes with thiol-modified DNA. The functionalized nanocubes have been characterized regarding their electric potential, plasmonic properties, and stability against high concentrations of NaCl and MgCl2.
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    Time Optimization of Seed-Mediated Gold Nanotriangle Synthesis Based on Kinetic Studies
    (Basel : MDPI, 2021) Podlesnaia, Ekaterina; Csáki, Andrea; Fritzsche, Wolfgang
    The synthesis of shape-anisotropic plasmonic nanoparticles such as gold nanotriangles is of increasing interest. These particles have a high potential for applications due to their notable optical properties. A key challenge of the synthesis is usually the low reproducibility. Even the optimized seed-based methods often lack in the synthesis yield or are labor- and time-consuming. In this work, a seed-mediated synthesis with high reproducibility is replicated in order to determine the necessary reaction time for each step. Online monitoring of the reaction mixtures by UV–VIS spectroscopy is used as a powerful tool to track the evolution of the synthesis. The kinetics of the individual stages is elucidated by real-time investigations. As a consequence, the complete synthesis could be optimized and can now be realized in a single day instead of three without any loss in the resulting sample quality.