Choline-based electrolytes have been proposed as environmentally friendly and low-cost alternatives for secondary zinc air batteries. Choline acetate [Ch]+[OAc]− in protic (D2O) and aprotic (DMSO-d6) solvents has been studied by means of concentration-dependent 1H NMR, viscosity, and density measurements. The viscosities have been calculated on the basis of the Jones-Dole equation and showed that the dominant contribution originates from short-range ion-solvent interactions. Site-specific association affinities were assigned from NMR chemical shift titrations. In DMSO-d6, the hydroxyl group of choline was found to have the smallest dissociation constant followed by the methyl group of acetate. The corresponding Gibbs energies at low concentration were found to be in agreement with a solvent-separated ion pair (2SIP) configuration, whereas at concentrations above 300 mM, a solvent-shared ion pair (SIP) configuration was assigned. For [Ch]+[OAc]− in D2O, association effects were found to be weaker, attributed to the high dielectric constant of the solvent. On time scales on the order of 100 ms, NMR linewidth perturbations indicated a change in the local rotational dynamics of the ions, attributed to short-range cation-solvent interactions and not to solvent viscosity. At 184 mM, 40 % of the cations in DMSO-d6 and 10 % in D2O were found to exhibit short-range interactions, as indicated by the linewidth perturbations. It was found that at about 300 mM, the ions in DMSO-d6 exhibit a transition from free to collective translational dynamics on time scales on the order of 400 ms. In DMSO-d6, both ions were found to be almost equally solvated, whereas in D2O solvation of acetate was stronger, as indicated by the obtained effective hydrodynamic radii. For [Ch]+[OAc]− in DMSO-d6, the results suggest a solvent-shared ion association with weak H-bonding interactions for concentrations between 0.3–1 M. Overall, the extent of ion association in solvents such as DMSO is not expected to significantly limit charge transport and hinder the performance of choline-based electrolytes. 相似文献
We construct highly edge-connected -regular graphs of even order which do not contain pairwise disjoint perfect matchings. When is a multiple of 4, the result solves a problem of Thomassen [4]. 相似文献
A stable cyclic (alkyl)(amino)carbene (CAAC) 1 inserts into the para‐CF bond of pentafluoropyridine, and after fluoride abstraction, the iminium‐pyridyl adduct [ 3 ]+ was isolated. A cyclic voltammetry study shows a reversible three‐state redox system involving [ 3 ]+, [ 3 ] ? , and [ 3 ] ? . The CAAC‐pyridyl radical [ 3 ] ? , obtained by reduction of [ 3 ]+ with magnesium, has been spectroscopically and crystallographically characterized. In contrast to the lack of π communication between the CAAC and the pyridine units in cation [ 3 ]+, the unpaired electron of [ 3 ] ? is delocalized over an extended π system involving both heterocycles. 相似文献
9,10‐(Bpin)2‐anthracene ( 3 , HBpin=pinacolborane) was synthesized from 9,10‐dibromoanthracene in a stepwise lithiation/borylation sequence. The reaction of 3 with highly activated magnesium furnished the diborylated magnesium anthracene 4 , which was quenched in situ with ethereal HCl to yield cis‐9,10‐(Bpin)2‐DHA (cis‐ 5 , DHA=9,10‐dihydroanthracene). Compound cis‐ 5 , in turn, can be reduced with Li[AlH4] in THF to give its diborate Li2[cis‐9,10‐(BH3)2‐DHA] (Li2[cis‐ 6 ]). In the crystal lattice, the THF solvate Li2[cis‐ 6 ] ? 3 THF establishes a dimeric structure with Li‐(μ‐H)‐B coordination modes. Hydride abstraction from Li2[cis‐ 6 ] with Me3SiCl yields the B?H?B‐bridged DHA Li[ 7 ]. This product can also be viewed as a unique cyclic B2H7? derivative with a hydrocarbon backbone. Treatment of Li2[cis‐ 6 ] with the stronger hydride abstracting agent Me3SiOTf (HOTf=trifluoromethanesulfonic acid) in THF affords the THF diadduct of cis‐9,10‐(BH(OTf))2‐DHA. 相似文献
Charge heterogeneity profiling is important for the quality control (QC) of biopharmaceuticals. Because of the increasing complexity of these therapeutic entities [1], the development of alternative analytical techniques is needed. In this work, flow‐through partial‐filling affinity capillary electrophoresis (FTPFACE) has been established as a method for the analysis of a mixture of two similar monoclonal antibodies (mAbs). The addition of a specific ligand results in the complexation of one mAb in the co‐formulation, thus changing its migration time in the electric field. This allows the characterization of the charged variants of the non‐shifted mAb without interferences. Adsorption of proteins to the inner capillary wall has been circumvented by rinsing with guanidine hydrochloride before each injection. The presented FTPFACE approach requires only very small amounts of ligands and provides complete comparability with a standard CZE of a single mAb. 相似文献
Multiphase flow in porous media is strongly influenced by the pore-scale arrangement of fluids. Reservoir-scale constitutive relationships capture these effects in a phenomenological way, relying only on fluid saturation to characterize the macroscopic behavior. Working toward a more rigorous framework, we make use of the fact that the momentary state of such a system is uniquely characterized by the geometry of the pore-scale fluid distribution. We consider how fluids evolve as they undergo topological changes induced by pore-scale displacement events. Changes to the topology of an object are fundamentally discrete events. We describe how discontinuities arise, characterize the possible topological transformations and analyze the associated source terms based on geometric evolution equations. Geometric evolution is shown to be hierarchical in nature, with a topological source term that constrains how a structure can evolve with time. The challenge associated with predicting topological changes is addressed by constructing a universal geometric state function that predicts the possible states based on a non-dimensional relationship with two degrees of freedom. The approach is validated using fluid configurations from both capillary and viscous regimes in ten different porous media with porosity between 0.10 and 0.38. We show that the non-dimensional relationship is independent of both the material type and flow regime. We demonstrate that the state function can be used to predict history-dependent behavior associated with the evolution of the Euler characteristic during two-fluid flow.
The stannides RE2Au3Sn6 (RE = La, Ce, Pr, Nd, Sm) were synthesized from the elements by arc-melting. Small single crystals were grown by annealing samples in sealed tantalum tubes in an induction furnace with a special annealing sequence. The polycrystalline phases were characterized through their X-ray powder diffraction pattern. The structures of Ce2Au3Sn6, Pr2Au3Sn6, and Nd2Au3Sn6 were refined from single-crystal X-ray diffractometer data. The RE2Au3Sn6 stannides crystallize with the orthorhombic La2Zn3Ge6 type, space group Cmcm. The basic structural building units are Au1@Sn4 tetrahedra and Au2@Sn5 square pyramids. These units are condensed to layers and the structure can be described by a simple stacking of tetrahedral and pyramidal layers with the rare earth cations in between. Temperature dependent susceptibility studies indicate that all rare earth atoms are in the trivalent oxidation state, as their effective magnetic moments match the expected values of the free RE3+ ions. Pr2Au3Sn6 and Nd2Au3Sn6 exhibit antiferromagnetic ordering at TN = 6.3(1) and 6.7(1) K. Investigations of the electrical resistivity of La2Au3Sn6 and Ce2Au3Sn6 confirmed that these compounds are metallic, for La2Au3Sn6 a lower resistivity was observed, in line with the absence of screening unpaired electrons. 119Sn Mössbauer spectra for La2Au3Sn6, Ce2Au3Sn6, Pr2Au3Sn6 and Nd2Au3Sn6 show a complex superposition of three sub-spectra which can be differentiated through their distinctly different quadrupole splitting parameters. The isomer shifts (1.87 to 2.22 mm · s–1) indicate significant s electron density at the tin nuclei. 相似文献