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The spectral luminescent properties of dipyrromethenates halogenated with bromine on both ends of the long axis and coordinated using boron fluoride, zinc, or cadmium in neutral ethanol and acidified with hydrochloric acid solutions were studied. The constants of the acid–base equilibrium of the complexes in the proton-donor solvents in the ground and excited states was determined. The mechanisms of complex protonation were discussed, depending on the structure of the compounds. The electronic structures of the neutral and protonated compounds were modeled and analyzed based on the quantum-chemical method. The structures and spectral-luminescence properties were calculated using the SMD model of ethanol solvent using the TD-DFT theory with the B3LYP functional and the composite def2-SVP/def2-TZVP/def2-TZVPP_ECP basis sets, depending on the atomic number of the elements. 相似文献
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Isaiah Adelabu Patrick TomHon Mohammad S. H. Kabir Shiraz Nantogma Mustapha Abdulmojeed Iuliia Mandzhieva Dr. Jessica Ettedgui Dr. Rolf E. Swenson Dr. Murali C. Krishna Prof. Thomas Theis Prof. Boyd M. Goodson Prof. Eduard Y. Chekmenev 《Chemphyschem》2022,23(2):e202100839
Signal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE-SHEATH) is investigated to achieve rapid hyperpolarization of 13C1 spins of [1-13C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co-ligation of DMSO and H2O. Order-unity 13C (>50 %) polarization of catalyst-bound [1-13C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1-13C]pyruvate at lower temperatures. On the catalyst bound pyruvate, 39 % polarization is measured using a 1.4 T NMR spectrometer, and extrapolated to >50 % at the end of build-up in situ. The highest measured polarization of a 30-mM pyruvate sample, including free and bound pyruvate is 13 % when using 20 mM DMSO and 0.5 M water in CD3OD. Efficient 13C polarization is also enabled by favorable relaxation dynamics in sub-microtesla magnetic fields, as indicated by fast polarization buildup rates compared to the T1 spin-relaxation rates (e. g., ∼0.2 s−1 versus ∼0.1 s−1, respectively, for a 6 mM catalyst-[1-13C]pyruvate sample). Finally, the catalyst-bound hyperpolarized [1-13C]pyruvate can be released rapidly by cycling the temperature and/or by optimizing the amount of water, paving the way to future biomedical applications of hyperpolarized [1-13C]pyruvate produced via comparatively fast and simple SABRE-SHEATH-based approaches. 相似文献
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Avinash Chettri Jan-Hendrik Kruse Keshav Kumar Jha Lara Dröge Dr. Iuliia Romanenko Dr. Christof Neumann Dr. Stephan Kupfer Prof. Dr. Andrey Turchanin Prof. Dr. Sven Rau Prof. Dr. Felix H. Schacher Prof. Dr. Benjamin Dietzek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17049-17058
Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold. 相似文献
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External electric field effect on electronic properties and charge transfer in CoI2/NiI2 spinterface
Iuliia Melchakova Evgenia A. Kovaleva Natalia S. Mikhaleva Felix N. Tomilin Sergey G. Ovchinnikov Alexander A. Kuzubov Paul Avramov 《International journal of quantum chemistry》2020,120(3):e26092
Electronic structure and spin-related properties of CoI2/NiI2 heterostructure were studied by means of density functional theory. It was shown that the electronic structure at the Fermi level can be characterized by a band gap. The effect of the external electric field on charge transfer and electronic properties of the CoI2/NiI2 interface was investigated, and it was found that band gap width depends on the strength of the applied electric field, switching its nature from semiconducting to a half-metallic one. An easy control of the electronic properties and promising spin-polarized nature of the CoI2/NiI2 spinterface allows the heterostructure to be used in spin-related applications. 相似文献
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The effect of UV/visible/NIR light (380/450/530/650/808/1064 nm) on ROS generation, mitochondrial activity and viability is experimentally compared in human neuroblastoma cancer cells. The absorption of photons by mitochondrial photoacceptors in Complexes I, III and IV is in detail investigated by sequential blocking with selective pharmaceutical blockers. Complex I absorbs UV/blue light by heme P450, resulting in a very high rate (14 times) of ROS generation leading to cell death. Complex III absorbs green light, by cytochromes b, c1 and c, and possesses less ability for ROS production (seven times), so that only irradiation lower than 10 mW cm−2 causes an increase in cell viability. Complex IV is well-known as the primary photoacceptor for red/NIR light. Light of 650/808 nm at 10–100 mW cm−2 generates a physiological ROS level about 20% of a basal concentration, which enhance mitochondrial activity and cell survival, while 1064 nm light does not show any distinguished effects. Further, ROS generation induced by low-intensity red/NIR light is compared in neurons, immune and cancer cells. Red light seems to more rapidly stimulate ROS production, mitochondrial activity and cell survival than 808 nm. At the same time, different cell lines demonstrate slightly various rates of ROS generation, peculiar to their cellular physiology. 相似文献
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Back Cover: Polynuclear SmIII Polyamidoamine‐Based Dendrimer: A Single Probe for Combined Visible and Near‐Infrared Live‐Cell Imaging (Angew. Chem. Int. Ed. 11/2014)
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Edyta Paradowska Mirosawa Studziska Agnieszka Jaboska Valeri Lozovski Natalia Rusinchuk Iuliia Mukha Nadiia Vitiuk Zbigniew J. Lenikowski 《Molecules (Basel, Switzerland)》2021,26(19)
The antiviral activity of nonfunctionalized gold nanoparticles (AuNPs) against herpes simplex virus type-1 (HSV-1) in vitro was revealed in this study. We found that AuNPs are capable of reducing the cytopathic effect (CPE) of HSV-1 in Vero cells in a dose- and time-dependent manner when used in pretreatment mode. The demonstrated antiviral activity was within the nontoxic concentration range of AuNPs. Interestingly, we noted that nanoparticles with smaller sizes reduced the CPE of HSV-1 more effectively than larger ones. The observed phenomenon can be tentatively explained by the near-field action of nanoparticles at the virus envelope. These results show that AuNPs can be considered as potential candidates for the treatment of HSV-1 infections. 相似文献
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Convenient Access to Fluorescent Probes by Chemoselective Acylation of Hydrazinopeptides: Application to the Synthesis of the First Far‐Red Ligand for Apelin Receptor Imaging
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Dr. Jean‐François Margathe Dr. Xavier Iturrioz Pierre Regenass Iuliia A. Karpenko Dr. Nicolas Humbert Dr. Hugues de Rocquigny Prof. Marcel Hibert Dr. Catherine Llorens‐Cortes Dr. Dominique Bonnet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1399-1405
Herein, we develop a convenient method to facilitate the solution‐phase fluorescent labelling of peptides based on the chemoselective acylation of α‐hydrazinopeptides. This approach combines the advantages of using commercially available amine‐reactive dyes and very mild conditions, which are fully compatible with the chemical sensitivity of the dyes. The usefulness of this approach was demonstrated by the labelling of apelin‐13 peptide. Various fluorescent probes were readily synthesized, enabling the rapid optimization of their affinities for the apelin receptor. Thus, the first far‐red fluorescent ligand with sub‐nanomolar affinity for the apelin receptor was characterized and shown to track the receptor efficiently in living cells by fluorescence confocal microscopy. 相似文献