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151.
Afshin Nabiyan Johannes Bernhard Max Dr. Christof Neumann Magdalena Heiland Prof. Dr. Andrey Turchanin Prof. Dr. Carsten Streb Prof. Dr. Felix Helmut Schacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):16924-16929
An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core–shell hybrid materials based on a TiO2 core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO2). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO2 core. This resulted in high visible-light-driven H2 generation. The enhanced light-driven catalytic activity is attributed to the unique core–shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO2 was possible by introducing [Mo3S13]2− cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species. 相似文献
152.
Dr. Zhijia Wang Mikhail Ivanov Dr. Yuting Gao Laura Bussotti Prof. Paolo Foggi Huimin Zhang Prof. Nino Russo Prof. Bernhard Dick Prof. Jianzhang Zhao Prof. Mariangela Di Donato Dr. Gloria Mazzone Prof. Liang Luo Prof. Matvey Fedin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(5):1091-1102
Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield ΦT=60 %) was observed, with a triplet state lifetime (τT=436 μs) much longer than that accessed with the conventional heavy atom effect (τT=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the 1CT/3LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC50=75 nm ), with a negligible dark toxicity (EC50=78.1 μm ) compared with the conventional heavy atom PSs (dark toxicity, EC50=6.0 μm, light toxicity, EC50=4.0 nm ). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents. 相似文献
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154.
Prof. Dr. Bernhard Kräutler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15438-15445
The recently delineated structure- and reactivity-based concept of antivitamins B12 has begun to bear fruit by the generation, and study, of a range of such B12-dummies, either vitamin B12-derived, or transition metal analogues that also represent potential antivitamins B12 or specific B12-antimetabolites. As reviewed here, this has opened up new research avenues in organometallic B12-chemistry and bioinorganic coordination chemistry. Exploratory studies with antivitamins B12 have, furthermore, revealed some of their potential, as pharmacologically interesting compounds, for inducing B12-deficiency in a range of organisms, from hospital resistant bacteria to laboratory mice. The derived capacity of antivitamins B12 to induce functional B12-deficiency in mammalian cells and organs also suggest their valuable potential as growth inhibitors of cancerous human and animal cells. 相似文献
155.
Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post‐Synthetic Modification of a UiO‐66‐Type Metal–Organic Framework 下载免费PDF全文
Alexander Kronast Sebastian Eckstein Dr. Peter T. Altenbuchner Dr. Konrad Hindelang Dr. Sergei I. Vagin Prof. Dr. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12800-12807
The highly porous and stable metal–organic framework (MOF) UiO‐66 was altered using post‐synthetic modifications (PSMs). Prefunctionalization allowed the introduction of carbon double bonds into the framework through a four‐step synthesis from 2‐bromo‐1,4‐benzenedicarboxylic acid; the organic linker 2‐allyl‐1,4‐benzenedicarboxylic acid was obtained. The corresponding functionalized MOF (UiO‐66‐allyl) served as a platform for further PSMs. From UiO‐66‐allyl, epoxy, dibromide, thioether, diamine, and amino alcohol functionalities were synthesized. The abilities of these compounds to adsorb CO2 and N2 were compared, which revealed the structure–selectivity correlations. All synthesized MOFs showed profound thermal stability together with an increased ability for selective CO2 uptake and molecular gate functionalities at low temperatures. 相似文献
156.
157.
Baldur Föhlisch Bernhard Czauderna 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):167-171
Abstract 3-Thietanone (3a) reacts rapidly with methanolic sodium hydrogen sulfide to form a mixture of products wherein 2,4-dimethylthiophene-3-thiol (9), the corresponding disulfide (10) and 3,6-dimethyl-7-oxa-2,5-dithiabicyclc [2.2.1]-heptane (7) could be detected. These products are explained to be derived from the unstable 1-mercapto-2-propanone (5) formed by reductive cleavage of the thietanone ring. The cleavage is postulated to occur by attack of hydrogensulfide ion at the ring sulfur. 3-Thietanone can be synthesized from 3-thietanol by oxidation with dimethyl sulfoxide/benzoic acid anhydride. 3-Thietanon (3a) reagiert rasch mit methanolischem Natriumhydrogensulfid zu einem Produktgemisch, in dem 2,4-Dimethylthiophen-3-thiol (9), das entsprechende Disulfid (10) und 3,6-Dimethyl-7-oxa-2,5-dithiabicyclo [2.2.1]-heptan (7) nachgewiesen werden konnten. Diese Produkte lassen sich aus dem instabilen 1-Mercapto-2-propanon (5) ableiten, welches durch reduktive Spaltung des Thietanon-Ringes gebildet wird. Für die Spaltung wird ein Angriff des Hydrogensulfidions am Ringschwefel postuliert. 3-Thietanon kann aus 3-Thietanol durch Oxidation mit Dimethyl-sulfoxid/Benzoesäureanhydrid synthetisiert werden. 相似文献
158.
Bernhard Beckermann Daniel Bessis Luca Perotti Daniel Vrinceanu 《Numerical Algorithms》2012,61(2):189-208
We describe a new method of computing matrix Padé approximants of series with integer data in an efficient and fraction-free way, by controlling the growth of the size of intermediate coefficients. This algorithm is applied to compute high precision Padé approximants of matrix-valued generating functions of time series. As an illustration we show that we can successfully recover from noisy equidistant sampling data a joint damped signal of four antenna, even in the presence of background signals. 相似文献
159.
160.
Low-energy ion scattering with monolayer sensitivity was applied to investigate ultrathin films of zinc on Pd(1?1?1). Uptake curves taken at 150?K indicate the simultaneous growth of multilayers with negligible interlayer transport. Annealing experiments for two-monolayer films reveal a rapid decrease in the zinc content on the surface layer at temperatures above 300?K, forming a metastable state with a Pd:Zn surface ratio of approx. 1:1 in the temperature region between 400 and 550?K. This state is most easily explained as a slightly buckled p(2?×?1)-PdZn surface alloy, with Zn atoms located approx. 0.25?? above their Pd counterparts. 相似文献