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111.
Lenard Hanf Jonas Henschel Marcel Diehl Martin Winter Sascha Nowak 《Electrophoresis》2020,41(9):697-704
A new CE method with ultraviolet–visible detection was developed in this study to investigate manganese dissolution in lithium ion battery electrolytes. The aqueous running buffer based on diphosphate showed excellent stabilization of labile Mn3+, even under electrophoretic conditions. The method was optimized regarding the concentration of diphosphate and modifier to obtain suitable signals for quantification. Additionally, the finally obtained method was applied on carbonate-based electrolytes samples. Dissolution experiments of the cathode material LiNi0.5Mn1.5O4 (lithium nickel manganese oxide [LNMO]) in aqueous diphosphate buffer at defined pH were performed to investigate the effect of a transition metal-ion-scavenger on the oxidation state of dissolved manganese. Quantification of both Mn species revealed the formation of mainly Mn3+, which can be attributed to a comproportionation reaction of dissolved and complexed Mn2+ with Mn4+ at the surface of the LNMO structure. It was also shown that the formation of Mn3+ increased with lower pH. In contrast, dissolution experiments of LNMO in carbonate-based electrolytes containing LIPF6 showed only dissolution of Mn2+. 相似文献
112.
Marcel Aebli Bogdan M. Benin Kyle M. McCall Viktoriia Morad Debora Thöny Hansjörg Grützmacher Maksym V. Kovalenko 《Helvetica chimica acta》2020,103(7):e2000080
Inorganic lead halide perovskites have gained immense scientific interest for optoelectronic applications. In this work, we present a one-dimensional polymorph of cesium lead bromide (δ-CsPbBr3) synthesized through a simple anion-exchange reaction, wherein distorted edge-sharing PbBr6 octahedra form 1D chains isolated by Cs ions. δ-CsPbBr3 was characterized by Raman spectroscopy, X-ray diffraction, 207Pb and 133Cs solid-state NMR, and by optical emission and absorption spectroscopies. This non-perovskite material irreversibly transforms into the well-known three-dimensional perovskite phase (γ-CsPbBr3) upon heating to above 151 °C. The indirect bandgap was determined by absorption measurements and calculation to be 2.9 eV. δ-CsPbBr3 exhibits broadband yellow photoluminescence with a quantum yield of 3.2 %±0.2 % at room temperature and 95 %±5 % at 77 K, and this emission is attributed to the recombination of self-trapped excitons. This study emphasizes that the metastable δ-CsPbBr3 may be a persistent, concomitant phase in Cs−Pb-Br-containing materials systems, such as those used in solar cells and LEDs, and it showcases the characterization tools used for its detection. 相似文献
113.
Karwal Saurabh Verheijen Marcel A. Arts Karsten Faraz Tahsin Kessels Wilhelmus M. M. Creatore Mariadriana 《Plasma Chemistry and Plasma Processing》2020,40(3):697-712
Plasma Chemistry and Plasma Processing - In this work, we report on the atomic layer deposition (ALD) of HfNx thin films by employing CpHf(NMe2)3 as the Hf(IV) precursor and Ar–H2 plasma in... 相似文献
114.
Alexander Vogel Mathias Bosse Marcel Gauglitz Sarah Wistuba Peter Schmidt Anette Kaiser Vsevolod V. Gurevich Annette G. Beck-Sickinger Peter W. Hildebrand Daniel Huster 《Molecules (Basel, Switzerland)》2020,25(23)
We report data on the structural dynamics of the neuropeptide Y (NPY) G-protein-coupled receptor (GPCR) type 1 (Y1R), a typical representative of class A peptide ligand GPCRs, using a combination of solid-state NMR and molecular dynamics (MD) simulation. First, the equilibrium dynamics of Y1R were studied using 15N-NMR and quantitative determination of 1H-13C order parameters through the measurement of dipolar couplings in separated-local-field NMR experiments. Order parameters reporting the amplitudes of the molecular motions of the C-H bond vectors of Y1R in DMPC membranes are 0.57 for the Cα sites and lower in the side chains (0.37 for the CH2 and 0.18 for the CH3 groups). Different NMR excitation schemes identify relatively rigid and also dynamic segments of the molecule. In monounsaturated membranes composed of longer lipid chains, Y1R is more rigid, attributed to a higher hydrophobic thickness of the lipid membrane. The presence of an antagonist or NPY has little influence on the amplitude of motions, whereas the addition of agonist and arrestin led to a pronounced rigidization. To investigate Y1R dynamics with site resolution, we conducted extensive all-atom MD simulations of the apo and antagonist-bound state. In each state, three replicas with a length of 20 μs (with one exception, where the trajectory length was 10 μs) were conducted. In these simulations, order parameters of each residue were determined and showed high values in the transmembrane helices, whereas the loops and termini exhibit much lower order. The extracellular helix segments undergo larger amplitude motions than their intracellular counterparts, whereas the opposite is observed for the loops, Helix 8, and termini. Only minor differences in order were observed between the apo and antagonist-bound state, whereas the time scale of the motions is shorter for the apo state. Although these relatively fast motions occurring with correlation times of ns up to a few µs have no direct relevance for receptor activation, it is believed that they represent the prerequisite for larger conformational transitions in proteins. 相似文献
115.
Dr. Diego Carnevale Marcel Hollenstein Prof. Geoffrey Bodenhausen 《Chemphyschem》2020,21(10):1044-1051
The isotopic enrichment of nucleic acids with nitrogen-15 is often carried out by solid-phase synthesis of oligonucleotides using phosphoramidite precursors that are synthetically demanding and expensive. These synthetic challenges, combined with the overlap of chemical shifts, explain the lag of nitrogen-15 NMR studies of nucleic acids behind those of proteins. For the structural characterization of DNA and RNA-related systems, new NMR methods that exploit the naturally occurring 99.9 % abundant nitrogen-14 isotope are therefore highly desirable. In this study, we have investigated nitrogen-14 spectra of self-assembled quartets based on the nucleobase guanine in the solid state by means of magic-angle spinning NMR spectroscopy. The network of dipolar proton–nitrogen couplings between neighboring stacked purine units is probed by 2D spectra based on 1H→14N→1H double cross-polarization. Interplane dipolar contacts are identified between the stacked G quartets. The assignment is supported by density functional theory (DFT) calculations of the anisotropic chemical shifts and quadrupolar parameters. The experimental spectra are fully consistent with internuclear distances obtained in silico. Averaging of chemical shifts due to internal motions can be interpreted by semiempirical calculations. This method can easily be extended to synthetic G quartets based on nucleobase or nucleoside analogs and potentially to oligonucleotides. 相似文献
116.
Reem A. Kamel Ahmed S. Abdel-Razek Abdelaaty Hamed Reham R. Ibrahim Hans Georg Stammler Marcel Frese 《Natural product research》2020,34(8):1080-1090
AbstractIsoshamixanthone (1), a new stereoisomeric pyrano xanthone together with the previously known fungal metabolites, epiisoshamixanthone (2), sterigmatocystin (3), arugosin C (4), norlichexanthone (5), diorcinol (6), ergosterol and methyllinoleate, were obtained from the endophytic fungal strain Aspergillus sp. ASCLA isolated from leaf tissues of the medicinal plant Callistemon subulatus. The chemical structure of the new xanthone (1) was elucidated by extensive 1D, 2D NMR, and ESI HR mass measurements, and by comparison with literature data. The constitutions and absolute configurations of 1 and epiisoshamixanthone (2) were additionally confirmed by X-ray crystallography. Compounds 1,2 were evaluated for their potential anticancer activity using the human cervix carcinoma cell line (KB-3-1). The antimicrobial activities of the fungal extract and compounds 1,2 were studied using a panel of pathogenic microorganisms as well. 相似文献
117.
118.
Celest Samyn Goedele Claes Marcel van Beylen Anneleen De Wachter Andre Persoons 《Macromolecular Symposia》1996,102(1):145-158
The synthesis and second harmonic coefficients, d3,1 and d3,3 as well as the related susceptibilities χ(2)zzz of five series of (NLO-dye methacrylate)-(methyl methacrylate) copolymers were investigated. The NLO-chromophores bound covalently to the polymer backbone were 5-(2,2-dicyanovinyl)-or 4-(2-cyano-2-methoxycarbonyl)vinyl-1-piperidino-2-thiophene (P1 and P2), 4-nitro-4′-alkoxy-stilbene (P3), 4-nitro-3′-methoxy-4′-alkoxystilbene (P4) and 4-nitro-4′-alkoxy-α-cyano stilbene (P5). The second order nonlinear optical properties of corona-poled aligned thin polymer films, using a needle electrode in order to induce noncentrosymmetry, were evaluated. Nonlinear susceptibilities, χ(2)zzz, of the films were derived from the analysis of full-angle Maker fringe patterns at 1064 nm, χ(2)zzz values as high as 1.98×10−7 esu for P2 copolymers and of 1.19×10−7 esu for P3 copolymers could be achieved. 相似文献
119.
A time-resolved fluorescence spectrometer with laser excitation and picosecond time-correlated single photon counting detection is described. The parameter recovery from experimental data is discussed in detail. Correction methods for errors in the time-correlated single photon counting technique are indicated. Applications of this photophysical tool to polymer research are given. 相似文献