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    Photodynamic opening of the blood-brain barrier using different photosensitizers in mice
    (Basel : MDPI, 2019) Semyachkina-Glushkovskaya, Oxana; Borisova, Ekaterina; Mantareva, Vanya; Angelov, Ivan; Eneva, Ivelina; Terskov, Andrey; Mamedova, Aysel; Shirokov, Alexander; Khorovodov, Alexander; Klimova, Maria; Agranovich, Ilana; Blokhina, Inna; Lezhnev, Nikita; Kurths, Jurgen
    In a series of previous studies, we demonstrated that the photodynamic therapy (PDT), as a widely used tool for treatment of glioblastoma multiforme (GBM), also site-specifically opens the blood-brain barrier (BBB) in PDT-dose and age-related manner via reversible disorganization of the tight junction machinery. To develop the effective protocol of PDT-opening of the BBB, here we answer the question of what kind of photosensitizer (PS) is the most effective for the BBB opening. We studied the PDT-opening of the BBB in healthy mice using commercial photosensitizers (PSs) such as 5-aminolevulenic acid (5-ALA), aluminum phthalocyanine disulfonate (AlPcS), zinc phthalocyanine (ZnPc) and new synthetized PSs such as galactose functionalized ZnPc (GalZnPc). The spectrofluorimetric assay of Evans Blue albumin complex (EBAC) leakage and 3-D confocal imaging of FITC-dextran 70 kDa (FITCD) extravasation clearly shows a revisable and dose depended PDT-opening of the BBB toEBACand FITCD associated with a decrease in presence of tight junction (TJ) in the vascular endothelium. The PDT effects on the BBB permeability, TJ expression and the fluorescent signal from the brain tissues are more pronounced in PDT-GalZnPc vs. PDT-5-ALA/AlPcS/ZnPc. These pre-clinical data are the first important informative platform for an optimization of the PDT protocol in the light of new knowledge about PDT-opening of the BBB for drug brain delivery and for the therapy of brain diseases. © 2019 by the authors.
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    Selective Earth-Abundant System for CO2 Reduction: Comparing Photo- and Electrocatalytic Processes
    (Washington, DC : American Chemical Society, 2019) Steinlechner C.; Roesel A.F.; Oberem E.; Päpcke A.; Rockstroh N.; Gloaguen F.; Lochbrunner S.; Ludwig R.; Spannenberg A.; Junge H.; Francke R.; Beller M.
    The valorization of CO2 via photo- or electrocatalytic reduction constitutes a promising approach toward the sustainable production of fuels or value-added chemicals using intermittent renewable energy sources. For this purpose, molecular catalysts are generally studied independently with respect to the photo- or the electrochemical application, although a unifying approach would be much more effective with respect to the mechanistic understanding and the catalyst optimization. In this context, we present a combined photo- and electrocatalytic study of three Mn diimine catalysts, which demonstrates the synergistic interplay between the two methods. The photochemical part of our study involves the development of a catalytic system containing a heteroleptic Cu photosensitizer and the sacrificial BIH reagent. The system shows exclusive selectivity for CO generation and renders turnover numbers which are among the highest reported thus far within the group of fully earth-abundant photocatalytic systems. The electrochemical part of our investigations complements the mechanistic understanding of the photochemical process and demonstrates that in the present case the sacrificial reagent, the photosensitizer, and the irradiation source can be replaced by the electrode and a weak Brønsted acid. © 2019 American Chemical Society.
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    Structure of Ni(OH)2 intermediates determines the efficiency of NiO-based photocathodes – a case study using novel mesoporous NiO nanostars
    (Cambridge : RSC, 2019) Wahyuono, Ruri Agung; Dellith, Andrea; Schmidt, Christa; Dellith, Jan; Ignaszak, Anna; Seyring, Martin; Rettenmayr, Markus; Fize, Jennifer; Artero, Vincent; Chavarot-Kerlidou, Murielle; Dietzek, Benjamin
    We report the wet chemical synthesis of mesoporous NiO nanostars (NS) as photocathode material for dye-sensitized solar cells (DSSCs). The growth mechanism of NiO NS as a new morphology of NiO is assessed by TEM and spectroscopic investigations. The NiO NS are obtained upon annealing of preformed β-Ni(OH)2 into pristine NiO with low defect concentrations and favorable electronic configuration for dye sensitization. The NiO NS consist of fibers self-assembled from nanoparticles yielding a specific surface area of 44.9 m2 g-1. They possess a band gap of 3.83 eV and can be sensitized by molecular photosensitizers bearing a range of anchoring groups, e.g. carboxylic acid, phosphonic acid, and pyridine. The performance of NiO NS-based photocathodes in photoelectrochemical application is compared to that of other NiO morphologies, i.e. nanoparticles and nanoflakes, under identical conditions. Sensitization of NiO NS with the benchmark organic dye P1 leads to p-DSSCs with a high photocurrent up to 3.91 mA cm-2 whilst the photoelectrochemical activity of the NiO NS photocathode in aqueous medium in the presence of an irreversible electron acceptor is reflected by generation of a photocurrent up to 23 μA cm-2 © 2019 The Royal Society of Chemistry.
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    Determination of side products in the photocatalytic generation of hydrogen with copper photosensitizers by resonance Raman spectroelectrochemistry
    (London : RSC Publishing, 2016) Zhang, Ying; Heberle, Martin; Wächtler, Maria; Karnahl, Michael; Dietzek, Benjamin
    A combination of UV-Vis and resonance Raman spectroscopy in conjunction with electrochemistry is employed to reveal the nature of a side product formed when using heteroleptic Cu(I)-photosensitizers [(P^P)Cu(N^N)]+ for photocatalytic hydrogen generation. It is shown that homoleptic [Cu(N^N)2]+ complexes are formed under oxidative conditions confirming a proposed deactivation pathway.