The ionic Soret effect induced by temperature gradients is investigated in organic electrolytes (tetramethylammonium and tetrabutylammonium hydroxides) dispersed in water using a holographic grating experiment. We report the influences of temperature and salt concentrations on the Soret, diffusion, and thermal diffusion coefficients. Experimental results to the thermal diffusion coefficient are compared with a theoretical description for thermodiffusion of Brownian particles in liquids based in the thermal expansion of the liquid solution. It is observed that the obtained thermal diffusion coefficients for the organic electrolytes present a similar temperature dependence as the theoretical prediction. Comparing the experimental results for the organic and common inorganic salts it is proposed an additional physical mechanism as the cause to the different thermal diffusion coefficients in both types of salt. We propose that the temperature dependence of hydration free energy gives rise to a force term that also leads to ion migration in a temperature gradient. We describe the thermal diffusion results as a competition between thermal expansion and hydration effects. The specific structure each type of ion cause in water molecules is considered in the heat of transport theory to describe thermal diffusion of electrolytes. A qualitative agreement is seen between our results and the classical heat of transport theory.
The temperature dependence of the Soret coefficient S(T)(T) in electrostatically charged magnetic colloids is investigated. Two different ferrofluids, with different particles' mean dimensions, are studied. In both cases we obtain a thermophilic behavior of the Soret effect. The temperature dependence of the Soret coefficient is described assuming that the nanoparticles migrate along the ionic thermoelectric field created by the thermal gradient. A model based on the contributions from the thermoelectrophoresis and variation of the double-layer energy, without fitting parameters, is used to describe the experimental results of the colloid with the bigger particles. To do so, independent measurements of the ζ potential, mass diffusion coefficient, and Seebeck coefficient are performed. The agreement of the theory and the experimental results is rather good. In the case of the ferrofluid with smaller particles, it is not possible to get experimentally reliable values of the ζ potential and the model described is used to evaluate this parameter and its temperature dependence.
Ultrasmall gold nanoparticles with a metallic core diameter of 2 nm were surface-conjugated with peptides that selectively target epitopes on the surface of the WW domain of the model protein hPin1 (hPin1-WW). The binding to the gold surface was accomplished via the thiol group of a terminal cysteine. The particles were analyzed by NMR spectroscopy, highresolution transmission electron microscopy, and differential centrifugal sedimentation. The surface loading was determined by conjugating a FAMlabeled peptide, followed by UV−vis spectroscopy, and by quantitative 1 H NMR spectroscopy, showing about 150 peptide molecules conjugated to each nanoparticle. The interaction between the peptide-decorated nanoparticles with hPin1-WW was probed by 1 H− 15 N-HSQC NMR titration, fluorescence polarization spectroscopy (FP), and isothermal titration calorimetry (ITC). The particles showed a similar binding (K D = 10−20 μM) compared to the dissolved peptides (K D = 10−30 μM). Small-angle Xray scattering (SAXS) showed that the particles were well dispersed and did not agglomerate after the addition of hPin1-WW (no cross-linking by the protein). Each nanoparticle was able to bind about 20 hPin1-WW protein molecules. An unspecific interaction with hPin1 was excluded by the attachment of a nonbinding peptide to the nanoparticle surface. The uptake by cells was studied by confocal laser scanning microscopy. The peptide-functionalized nanoparticles penetrated the cell membrane and were located in the cytosol. In contrast, the dissolved peptide did not cross the cell membrane. Peptide-functionalized nanoparticles are promising agents to target proteins inside cells.
Colloidal particles, including ferrofluidic nanoparticles (NP), move in a temperature gradient due to thermodiffusion. Organic salts, which are often added to disperse the NP in aqueous solution, also move in the temperature gradient. This can have a strong influence on the behavior of the NP, which not only respond to the temperature gradient but also to the concentration gradient of the dispersive salt, an effect termed diffusiophoresis. In this work we present experimental results on thermodiffusion of iron oxide nanoparticles dispersed in aqueous solutions of organic hydroxides, which illustrate the possibility to manipulate the thermodiffusion of NP through the addition of organic salts. Our experiments investigate the temperature dependence of the particles' Soret coefficient, a recurring question on thermodiffusion of water-dispersed particles. Existing theoretical approaches are compared and we relate the Soret coefficient of the NP with two main physical parameters ruling particle motion: the NP's electrostatic potential and the Soret coefficient of the dispersing ions. These parameters are also experimentally determined. At the order of magnitude of the NP's Soret coefficient good agreement between experiments and theory is achieved by including the experimental data on the Soret coefficient of the dispersing ions and therefore the NP's displacement due to the ion concentration gradient. Taking into account the temperature dependence of such previously unknown parameters is a relevant step to describe the temperature dependence of the NP's Soret coefficient.
The Soret coefficient (ST) of positively charged magnetic colloids was measured as a function of the nanoparticles' diameter. The Z-scan technique and the generalization of the thermal lens model proved to be a reliable technique to measure ST. We show that ST is negative and increases with the particle's diameter, being best described by a functional dependence of the type ST∝d0. Potentiometric and conductometric experiments show that the particle's surface charge decreases as the temperature increases, changing the electrostatic interaction between the nanoparticles. The temperature gradient imposed in the ferrofluid by the Gaussian laser beam leads to the formation of the particle's concentration gradient. The origin of this phenomenon is discussed in terms of the decrease of the particle's surface charge in the hottest region of the sample and the thermoelectric field due to the inhomogeneous distribution of hydrogenous ions present in the colloidal suspension.
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