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eveloping hydroxycoumarin derivatives as an antioxidant or as an electron transporting agent in biochemical processes. In addition, this information will be helpful for understanding the mechanism of removing pollutant dyes by advanced oxidation processes.Owing to the high theoretical specific capacity and energy density, lithium-sulfur (Li-S) batteries are considered an ideal candidate for next-generation rechargeable batteries. Whereas, the shuttle effect of polysulfides limits the utilization of active materials, reducing the electrochemical performance of lithium-sulfur batteries. Herein, by directly using waste newspapers as a substrate, a waste newspaper/multi-walled carbon nanotube/TiO2 (NMT) interlayer has been prepared for stable Li-S batteries. In the composite interlayer, the newspaper functions as the basic frame for loading materials. Carbon materials absorbed by the newspaper provide both a conductive pathway and physical adsorption of lithium polysulfides (LiPS). Meanwhile, TiO2 inhibits the dissolution of LiPS in the electrolyte by strong chemical bonding. The morphology and spectra prove that the newspaper plays a key frame role in the functional composite interlayer. The electrochemical analyses demonstrate that the as-fabricated interlayer can obviously improve the cycling performance of Li-S battery. At a 0.5 C (1.0 C = 1675 mA h g-1) charge-discharge current density, after 500 cycles, the Li-S battery with NMT interlayer still exhibits a discharge capacity of 463.7 mA h g-1 with a low capacity decay per cycle of 0.071%.Peptides that self-assemble into β-sheet rich aggregates are known to form a large variety of supramolecular shapes, such as ribbons, tubes or sheets. However, the underlying thermodynamic driving forces for such different structures are still not fully understood, limiting their potential applications. In the AnK peptide system (A = alanine, K = lysine), a structural transition from tubes to ribbons has been shown to occur upon an increase of the peptide length, n, from 6 to 8. In this work we analyze this transition by means of a simple thermodynamic model. We consider three energy contributions to the total free energy an interfacial tension, a penalty for deviating from the optimal β-sheet twist angle, and a hydrogen bond deformation when the β-sheets adopt a specific self-assembled structure. Whilst the first two contributions merely provide similar constant energy offsets, the hydrogen bond deformations differ depending on the studied structure. Consequently, the tube structure is thermodynamically favored for shorter AnK peptides, with a crossover at n≈ 13. This qualitative agreement of the model with the experimental observations shows, that we have achieved a good understanding of the underlying thermodynamic features within the self-assembling AnK system.A detailed analysis of the ECL interaction between luminol and tris(2,2'-bipyridyl)dichlororuthenium(ii) (Ru(bpy)32+) is required before using them in ECL systems for multianalyte detection purposes. Spectro-electrochemiluminescence demonstrates that not only must the emission properties be considered, but also their additional optical characteristics are involved in the explanation of the interaction mechanism between these luminophores.Flavins are key compounds in many photochemical and photophysical processes used by nature, because their optical properties strongly depend on the (de-)protonation site and solvation. Herein, we present the vibronic optical spectrum of protonated lumiflavin (H+LF), the parent molecule of the flavin family, obtained by visible photodissociation (VISPD) spectroscopy in a cryogenic ion trap. By comparison to time-dependent density functional theory (TD-DFT) calculations at the PBE0/cc-pVDZ level coupled to multidimensional Franck-Condon simulations, the spectrum recorded in the 420-500 nm range is assigned to vibronic bands of the optically bright S1← S0(ππ*) transition of the two most stable H+LF tautomers protonated at the O2+ and N1 position. https://www.selleckchem.com/products/ZM-447439.html While the most stable O2+ protomer has been identified previously by infrared spectroscopy, the N1 protomer is identified here for the first time. The S1 band origins of H+LF(O2+) and H+LF(N1) at 23 128 and 23 202 cm-1 are shifted by 1617 and 1691 cm-1 to the blue of that of bare LF measured in He droplets, indicating that the proton affinity of both tautomers is slightly reduced upon S1 excitation. This view is consistent with the molecular orbitals involved in the assigned ππ* transition. The spectrum of both protomers is rich in vibrational structure indicating substantial geometry changes by ππ* excitation. Interestingly, while the O2+ protomer is planar in both electronic states, the N1 protomer is slightly nonplanar giving rise to large vibrational activity of low-frequency out-of-plane modes. Comparison with protonated lumichrome and metalated lumiflavin reveals the impact of functional groups and the type of the attached cation (proton or alkali ion) on the geometric and electronic structure of flavins.Soft, low-friction particles in silos show peculiar features during their discharge. The outflow velocity and the clogging probability both depend upon the momentary silo fill height, in sharp contrast to silos filled with hard particles. The reason is the fill-height dependence of the pressure at the orifice. We study the statistics of silo discharge of soft hydrogel spheres. The outflow is found to become increasingly fluctuating and even intermittent with decreasing orifice size, and with decreasing fill height. In orifices narrower than two particle diameters, outflow can stop completely, but in contrast to clogs formed by rigid particles, these congestions may dissolve spontaneously. We analyze such non-permanent congestions and attribute them to slow reorganization processes in the container, caused by viscoelasticity of the material.Porphyrin based metal organic frameworks (MOFs) have provided a broad platform through which a wide variety of light harvesting applications have been developed. Of particular interest within light harvesting MOFs containing porphyrin chromophores is the extent to which the both environment of the porphyrin and the porphyrin conformation modulate the photophysical properties. With this in mind, a new MOF (RWLAA-1) has been synthesized based on zinc cations linked by zinc(ii) tetra(4-pyridyl)porphyrin (ZnTPyP) and benzene tricarboxylate (H3BTC) linkers in which the porphyrin exhibits significant conformational distortions that have a profound effect on the photophysics of the material including bathochromic shifts in both the optical (Soret and visible bands) and emission bands, reduction in the energy separation between the Q(0,0) and Q(0,1) emission bands and shorter singlet and triplet state lifetimes. These effects are consistent with the porphyrin deformation resulting in changes in the porphyrin electronic structure and excited state conformational dynamics that alter the vibronic coupling between the excited states (S1 and T1) and the S0 ground state.
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