Solvent-Tuned Supramolecular Assembly of Fluorescent Catechol/Pyrene Amphiphilic Molecules.

The synthesis and structuration of a novel low-molecular-weight amphiphilic catechol compound is reported. The combination of a hydrophilic tail containing a catechol unit and a pyrene-based hydrophobic head favors solvent-tuned supramolecular assembly. Formation of hollow nanocapsules/vesicles occurs in concentrated solutions of polar protic and nonprotic organic solvents, whereas a fibril-like aggregation process is favored in water, even at low concentrations. The emission properties of the pyrene moiety allow monitoring of the self-assembly process, which could be confirmed by optical and electronic microscopy. In organic solvents and at low concentrations, this compound remains in its nonassembled monomeric form. As the concentration increases, the aggregation containing preassociated pyrene moieties becomes more evident up to a critical micellar concentration, at which vesicle-like structures are formed. In contrast, nanosized twist beltlike fibers are observed in water, even at low concentrations, whereas microplate structures appear at high concentrations. The interactions between molecules in different solvents were studied by using molecular dynamics simulations, which have confirmed different solvent-driven supramolecular interactions.

Effects of magnetic field gradients on the aggregation dynamics of colloidal magnetic nanoparticles.

We have used low-field (1)H nuclear-magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) to investigate the aggregation dynamics of magnetic particles in ionic ferrofluids (IFFs) in the presence of magnetic field gradients. At the beginning of the experiments, the measured NMR spectra were broad and asymmetric, exhibiting two features attributed to different dynamical environments of water protons, depending on the local strength of the field gradients. Hence, the spatial redistribution of the magnetic particles in the ferrofluid caused by the presence of an external magnetic field in a time scale of minutes can be monitored in real time, following the changes in the features of the NMR spectra during a period of about an hour. As previously reported [Heinrich et al., Phys. Rev. Lett., 2011, 106, 208301], in the homogeneous magnetic field of a NMR spectrometer, the aggregation of the particles of the IFF proceeds in two stages. The first stage corresponds to the gradual aggregation of monomers prior to and during the formation of chain-like structures. The second stage proceeds after the chains have reached a critical average length, favoring lateral association of the strings into hexagonal zipped-chain superstructures or bundles. In this work, we focus on the influence of a strongly inhomogeneous magnetic field on the aforementioned aggregation dynamics. The main observation is that, as the sample is immersed in a certain magnetic field gradient and kept there for a time τinh, magnetophoresis rapidly converts the ferrofluid into an aggregation state which finds its correspondence to a state on the evolution curve of the pristine sample in a homogeneous field. From the degree of aggregation reached at the time τinh, the IFF sample just evolves thereafter in the homogeneous field of the NMR spectrometer in exactly the same way as the pristine sample. The final equilibrium state always consists of a colloidal suspension of zipped-chain bundles with the chain axes aligned along the magnetic field direction.

Simple analytical model for the magnetophoretic separation of superparamagnetic dispersions in a uniform magnetic gradient.

Magnetophoresis--the motion of magnetic particles under applied magnetic gradient--is a process of great interest in novel applications of magnetic nanoparticles and colloids. In general, there are two main different types of magnetophoresis processes: cooperative magnetophoresis (a fast process enhanced by particle-particle interactions) and noncooperative magnetophoresis (driven by the motion of individual particles in magnetic fields). In the case of noncooperative magnetophoresis, we have obtained a simple analytical solution which allows the prediction of the magnetophoresis kinetics from particle characterization data (size and magnetization). Our comparison with new experimental results shows good quantitative agreement. In addition, we show the existence of a universal curve onto which all experimental results should collapse after proper rescaling. The range of applicability of the analytical solution is discussed in light of the predictions of a magnetic aggregation model [Soft Matter 7, 2336 (2011)].

Irreversible adsorption of diffusing hard disks: an effective medium approach.

We propose an effective medium theory to analyze the kinetics of nonsequential adsorption of colloidal particles, including transport and blocking effects, valid at all values of surface coverage. The theory is applied to the irreversible adsorption of diffusing hard disks obtaining a kinetic law, which is in excellent agreement with nonsequential computer simulations at all densities of adsorbed particles.