Field-flow fractionation in microfluidic channels of low aspect ratio

The shape of the steady-state three-dimensional flow velocity profile established in carrier liquid flowing inside the rectangular cross-sectional channel for field-flow fractionation should be taken into account to optimize the separation. The central parts of this profile in the planes parallel to the main channel walls are flat with almost identical flow velocities which drop down to zero at the side walls. The separated species transported by the flow in the close-to-side walls regions move with lower average velocities compared to the species transported in the central part of the channel and are undesirably broadened. The hydrodynamic splitting of the carrier liquid at the entry of the channel where the sample is injected only into the central part of the channel eliminates the excessive zone broadening. The aspect ratio of the breadth to the thickness of the channel ratio can thus be reduced. The effect of various aspect ratios on the shape of the flow velocity profile is calculated and the results are used to optimize the aspect ratio of microfluidic channels. The experiments carried out by microthermal field-flow fractionation confirmed that the aspect ratio cannot be reduced to a value of 1, proposed by other authors.     

Structure of Zinc and Nickel Histidine Complexes in Solution Revealed by Molecular Dynamics and Raman Optical Activity

The histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis₂ complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis₂ is more similar to the octahedral structure found by X-ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems.     

Solvation and Ion-Pairing Effects of Choline Acetate Electrolyte in Protic and Aprotic Solvents Studied by NMR Titrations

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.     

Hexagonal Si−Ge Class of Semiconducting Alloys Prepared by Using Pressure and Temperature

Multi-anvil and laser-heated diamond anvil methods have been used to subject Ge and Si mixtures to pressures and temperatures of between 12 and 17 GPa and 1500–1800 K, respectively. Synchrotron angle dispersive X-ray diffraction, precession electron diffraction and chemical analysis using electron microscopy, reveal recovery at ambient pressure of hexagonal Ge−Si solid solutions (P6₃/mmc). Taken together, the multi-anvil and diamond anvil results reveal that hexagonal solid solutions can be prepared for all Ge−Si compositions. This hexagonal class of solid solutions constitutes a significant expansion of the bulk Ge−Si solid solution family, and is of interest for optoelectronic applications.     

Proton-Transfer Dynamics of Photoacidic Merocyanines in Aqueous Solution

Photoacids attract increasing scientific attention, as they are valuable tools to spatiotemporally control proton-release reactions and pH values of solutions. We present the first time-resolved spectroscopic study of the excited state and proton-release dynamics of prominent merocyanine representatives. Femtosecond transient absorption measurements of a pyridine merocyanine with two distinct protonation sites revealed dissimilar proton-release mechanisms: one site acts as a photoacid generator as its pK_a value is modulated in the ground state after photoisomerization, while the other functions as an excited state photoacid which releases its proton within 1.1 ps. With a pK_a drop of 8.7 units to −5.5 upon excitation, the latter phenolic site is regarded a super-photoacid. The 6-nitro derivative exhibits only a phenolic site with similar, yet slightly less photoacidic characteristics and both compounds transfer their proton to methanol and ethanol. In contrast, for the related 6,8-dinitro compound an intramolecular proton transfer to the ortho-nitro group is suggested that is involved in a rapid relaxation into the ground state.     

Capillary electrophoretic study of interactions of metal ions with crown ethers,a sulfated beta-cyclodextrin,and zwitterionic buffers present as additives in the background electrolyte

Stability constants of K, Na, Ca, and Ba with 18-crown-6, K, Na, Li with sulfated beta-cyclodextrin and K, Li, Ca, Mg, Sr, and Ba ions with ([2-hydroxy-1,1-bis(hydroxymethyl) ethyl]-amino)-1-propanesulfonic acid (TAPS) were determined by capillary electrophoresis and computed using a general least squares minimizing program CELET. The results for 18-crown-6 agreed well with those evaluated by graphical methods or reported in the literature. Previously unknown stability constants of sulfated beta-cyclodextrins and TAPS determined for alkali and alkaline earth metals show that sulfated beta-cyclodextrin interacts with monovalent metals allowing to manipulate their effective mobility. It interacts stronger with divalent metal cations. TAPS, as zwitterionic buffer widely used in various analytical, biochemical and other applications, forms complexes with alkali and alkaline earth cations, and although the stability constants are rather low, the equilibria should be taken into account when TAPS is used and metal cations are present in solution at the same time.     

The Chiral Trimer and a Metastable Chiral Dimer of Achiral Hexafluoroisopropanol: A Multi‐Messenger Study

1,1,1,3,3,3‐hexafluoro‐propan‐2‐ol aggregates preferentially into an achiral dimer of achiral monomers, but the trimer is found to prefer three metastable chiral monomer units arranged into a strained OH???O hydrogen‐bonded ring, which is reinforced by secondary CH???FC interactions. This is shown by a combination of infrared, microwave, and Raman spectroscopy in supersonic jet expansions and supported by high‐level quantum chemical calculations. It involves an activation of the monomers by >15 kJ mol^?1, clearly driven by the much stronger hydrogen‐bond interaction available to the gauche and even more to the cis monomer units.