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- ItemExcited-state relaxation of hydrated thymine and thymidine measured by liquid-jet photoelectron spectroscopy: experiment and simulation(Washington, DC : ACS Publications, 2015) Buchner, Franziska; Nakayama, Akira; Yamazaki, Shohei; Ritze, Hans-Hermann; Lübcke, AndreaTime-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys.2013, 139, 214304). The temporal evolution of ionization energies for the excited ππ* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the ππ* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the nπ* state is possible at the given photon energies, but we have not found any experimental indication for signal from the nπ* state. In contrast to currently accepted relaxation mechanisms, we suggest that the nπ* state is not involved in the relaxation process of thymine in aqueous solution.
- ItemReduced Faradaic Contributions and Fast Charging of Nanoporous Carbon Electrodes in a Concentrated Sodium Nitrate Aqueous Electrolyte for Supercapacitors(Weinheim [u.a.] : Wiley-VCH, 2019) Abbas, Qamar; Gollas, Bernhard; Presser, VolkerThe Faradaic processes related to electrochemical water reduction at the nanoporous carbon electrode under negative polarization are reduced when the concentration of aqueous sodium nitrate (NaNO3) is increased or the temperature is decreased. This effect enhances the relative contribution of ion electrosorption to the total charge storage process. Hydrogen chemisorption is reduced in aqueous 8.0 m NaNO3 due to the low degree of hydration of the Na+ cation; consequently, less free water is available for redox contributions, driving the system to exhibit electrical double-layer capacitive characteristics. Hydrogen adsorption/desorption is facilitated in 1.0 m NaNO3 due to the high molar ratio. The excess of water shifts the local pH in carbon nanopores to neutral values, giving rise to a high overpotential for dihydrogen evolution in the latter. The dilution effect on local pH shift in 1.0 m NaNO3 can be reduced by decreasing the temperature. A symmetric activated carbon cell assembled with 8.0 m NaNO3 exhibits a high capacitance and coulombic efficiency, a larger contribution of ion electrosorption to the overall charge storage process, and a stable capacitance performance at 1.6 V. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemDetermination of interfacial parameters of a soluble particle in a nonideal solution from measured deliquescence and efflorescence humidities(München : European Geopyhsical Union, 2015) Hellmuth, O.; Shchekin, A.K.In order to study the growth/shrinking of a hygroscopic nanoparticle during hydration/dehydration in an atmosphere of water vapour, we have employed a thermodynamic approach proposed by Shchekin et al. (2008). This approach uses the mechanic and thermodynamic concept of disjoining pressure of thin films and allows, among others, the prediction of the humidity growth factor of both (i) a homogeneous solution droplet with completely dissolved residual core and (ii) a heterogeneous solution droplet with partially dissolved residual core as a function of the ambient relative humidity. For application to a nanometric sodium chloride particle we have extended the original approach by (i) considering the nonideality of the solution through the dependence of molecular volumes of the solvent and solute molecules and the solute and solvent activities on the solution concentration, (ii) deriving an equation for the estimation of the efflorescence properties of a homogeneous solution droplet, and (iii) combining the empirical power law fittings for the size dependence of the deliquescence and efflorescence relative humidity values by Biskos et al. (2006a). It was demonstrated how the solution/solute interface energy and the correlation length of a thin solution film can be determined from a combination of experimentally determinable efflorescence and deliquescence humidities with the present calculus. The solution/solute interface energy was found to be in close agreement with some previous values reported in the literature, while it strongly differs from data of some other sources. The calculated deliquescence humidity shows a low sensitivity to the choice of the numerical value for the film correlation length. The estimated film correlation length of 1 nm for a nanometric sodium chloride particle with dry particle radius of 5 nm was found to be reconcilable with available a priori estimates of the correlation length from the literature when the measurement uncertainty of the deliquescence humidity is considered. Considering the combination of an extensive calculus, a comprehensive set of thermophysical constraints, and independent measurements of the deliquescence and efflorescence humidities as functions of dry particle radius, the obtained values of the solution/solute interface energy and the correlation length are in close agreement with previous estimations. The humidification of sodium chloride particles in the initial hydration stages was found to be very sensitive to the specification of the disjoining pressure. The enhancement of the wettability of the particle surface leads to an earlier onset of hygroscopic growth.
- ItemScreening Libraries of Amphiphilic Janus Dendrimers Based on Natural Phenolic Acids to Discover Monodisperse Unilamellar Dendrimersomes(Columbus, Ohio : American Chemical Society, 2019) Buzzacchera, Irene; Xiao, Qi; Han, Hong; Rahimi, Khosrow; Li, Shangda; Kostina, Nina Yu; Toebes, B. Jelle; Wilner, Samantha E.; Möller, Martin; Rodriguez-Emmenegger, Cesar; Baumgart, Tobias; Wilson, Daniela A.; Wilson, Christopher J.; Klein, Michael L.; Percec, VirgilNatural, including plant, and synthetic phenolic acids are employed as building blocks for the synthesis of constitutional isomeric libraries of self-assembling dendrons and dendrimers that are the simplest examples of programmed synthetic macromolecules. Amphiphilic Janus dendrimers are synthesized from a diversity of building blocks including natural phenolic acids. They self-assemble in water or buffer into vesicular dendrimersomes employed as biological membrane mimics, hybrid and synthetic cells. These dendrimersomes are predominantly uni- or multilamellar vesicles with size and polydispersity that is predicted by their primary structure. However, in numerous cases, unilamellar dendrimersomes completely free of multilamellar assemblies are desirable. Here, we report the synthesis and structural analysis of a library containing 13 amphiphilic Janus dendrimers containing linear and branched alkyl chains on their hydrophobic part. They were prepared by an optimized iterative modular synthesis starting from natural phenolic acids. Monodisperse dendrimersomes were prepared by injection and giant polydisperse by hydration. Both were structurally characterized to select the molecular design principles that provide unilamellar dendrimersomes in higher yields and shorter reaction times than under previously used reaction conditions. These dendrimersomes are expected to provide important tools for synthetic cell biology, encapsulation, and delivery.