RESUMO
The Stokes-Einstein relation, which relates the diffusion coefficient of a molecule to its hydrodynamic radius, is commonly used to determine molecular sizes in chemical analysis methods. Here, we combine the size sensitivity of such diffusion-based methods with the structure sensitivity of Raman spectroscopy by performing Raman diffusion-ordered spectroscopy (Raman-DOSY). The core of the Raman-DOSY setup is a flow cell with a Y-shaped channel containing two inlets: one for the sample solution and one for the pure solvent. The two liquids are injected at the same flow rate, giving rise to two parallel laminar flows in the channel. After the flow stops, the solute molecules diffuse from the solution-filled half of the channel into the solvent-filled half at a rate determined by their hydrodynamic radius. The arrival of the solute molecules in the solvent-filled half of the channel is recorded in a spectrally resolved manner by Raman microspectroscopy. From the time series of Raman spectra, a two-dimensional Raman-DOSY spectrum is obtained, which has the Raman frequency on one axis and the diffusion coefficient (or equivalently, hydrodynamic radius) on the other. In this way, Raman-DOSY spectrally resolves overlapping Raman peaks arising from molecules of different sizes. We demonstrate Raman-DOSY on samples containing up to three compounds and derive the diffusion coefficients of small molecules, proteins, and supramolecules (micelles), illustrating the versatility of Raman-DOSY. Raman-DOSY is label-free and does not require deuterated solvents and can thus be applied to samples and matrices that might be difficult to investigate with other diffusion-based spectroscopy methods.
RESUMO
We show that the surface of ice is scratch healing: micrometer-deep scratches in the ice surface spontaneously disappear by thermal relaxation on the time scale of roughly an hour. Following the dynamics and comparing it to different mass transfer mechanisms, we find that sublimation from and condensation onto the ice surface is the dominant scratch-healing mechanism. The scratch-healing kinetics shows a strong temperature dependence, following an Arrhenius behavior with an activation energy of ΔE = 58.6 ± 4.6 kJ/mol, agreeing with the proposed sublimation mechanism and at odds with surface diffusion or fluid flow or evaporation-condensation from a quasi-liquid layer.
RESUMO
We show that macroscopic crystals of NaCl that form from evaporating drops of aqueous salt solutions can spontaneously lift themselves up and away from a hydrophobic surface. At the end of the evaporation process, tiny crystals of NaCl grow onto larger ones and form "legs" that push the large crystals away from the surface. The temperature dependence of the lifting speed is found to exhibit Arrhenius behavior with an activation energy similar to that of crystals growing in solution: the crystal growth itself determines the lifting speed that can be up to half a centimeter per minute. We show that surface hydrophobicity is a necessary but not a sufficient condition to obtain this "self-lifting" behavior.
RESUMO
Inorganic perovskites display an enticing foreground for their wide range of optoelectronic applications. Recently, supercrystals (SCs) of inorganic perovskite nanocrystals (NCs) have been reported to possess highly ordered structure as well as novel collective optical properties, opening new opportunities for efficient films. Here, we report the large-scale assembly control of spherical, cubic, and hexagonal SCs of inorganic perovskite NCs through templating by oil-in-oil emulsions. We show that an interplay between the roundness of the cubic NCs and the tension of the confining droplet surface sets the superstructure morphology, and we exploit this interplay to design dense hyperlattices of SCs. The SC films show strongly enhanced stability for at least two months without obvious structural degradation and minor optical changes. Our results on the controlled large-scale assembly of perovskite NC superstructures provide new prospects for the bottom-up production of optoelectronic devices based on the microfluidic production of mesoscopic building blocks.
