Catalytic Performance and Electrophoretic Behavior of an Yttrium-Organic Framework Based on a Tricarboxylic Asymmetric Alkyne.

A new Y-based metal-organic framework (MOF) GR-MOF-6 with a chemical formula of {[YL(DMF)2]·(DMF)}n {H3L = 5-[(4-carboxyphenyl)ethynyl] isophthalic acid; DMF = N,N-dimethylformamide} has been prepared by a solvothermal route. Structural characterization reveals that this novel material is a three-dimensional MOF in which the coordination of the tritopic ligand to Y(III) metal ions leads to an intercrossing channel system extending over three dimensions. This material has proven to be a very efficient catalyst in the cyanosilylation of carbonyls, ranking second in catalytic activity among the reported rare earth metal-based MOFs described so far but with the lowest required catalyst loading. In addition, its electrophoretic behavior has been studied in depth, providing a zero-charge point between pH 4 and 5, a peak electrophoretic mobility of -1.553 µm cm V-1 s-1, and a ζ potential of -19.8 mV at pH 10.

Nanoemulsion stability: experimental evaluation of the flocculation rate from turbidity measurements.

The coalescence of liquid drops induces a higher level of complexity compared to the classical studies about the aggregation of solid spheres. Yet, it is commonly believed that most findings on solid dispersions are directly applicable to liquid mixtures. Here, the state of the art in the evaluation of the flocculation rate of these two systems is reviewed. Special emphasis is made on the differences between suspensions and emulsions. In the case of suspensions, the stability ratio is commonly evaluated from the initial slope of the absorbance as a function of time under diffusive and reactive conditions. Puertas and de las Nieves (1997) developed a theoretical approach that allows the determination of the flocculation rate from the variation of the turbidity of a sample as a function of time. Here, suitable modifications of the experimental procedure and the referred theoretical approach are implemented in order to calculate the values of the stability ratio and the flocculation rate corresponding to a dodecane-in-water nanoemulsion stabilized with sodium dodecyl sulfate. Four analytical expressions of the turbidity are tested, basically differing in the optical cross section of the aggregates formed. The first two models consider the processes of: a) aggregation (as described by Smoluchowski) and b) the instantaneous coalescence upon flocculation. The other two models account for the simultaneous occurrence of flocculation and coalescence. The latter reproduce the temporal variation of the turbidity in all cases studied (380≤[NaCl]≤600 mM), providing a method of appraisal of the flocculation rate in nanoemulsions.

Carboxylated core-shell particles: II. Experimental and theoretical comparison of salt-induced swelling.

In a previous work [1] we showed that the swelling behavior of carboxylated core-shell particles (PS-PC) can be modified using a specific sample preparation route or favoring the hydrophobic attractive interaction by other way, i.e. controlling the temperature. In that paper, we found that the swelling was promoted in those particles which were initially in a highly swollen state (pH⩾10) while it was hindered for those particles which were not previously in this trigger pH. In this work, we present a discussion of the salt-induced swelling of the same carboxylated core-shell system (PS-PC) with two tuned swelling behaviors: the former, called A-2, exhibits promoted swelling while in the latter, called B-1, the swelling is greatly suppressed because of a compact conformation of the polymer shell is induced [1]. Good agreement between experimental, numerical and theoretical results at all pH values is obtained for promoted particles (A-2). On the other hand, the salt-induced swelling behaviors shown by hindered particles (B-1) corroborate that polymer restructuring includes assembly among ionic groups which affect their ionization degree and also the electrosteric interaction between particles. Finally, the salt-induced swelling behavior shown by the B-1 system at pH 8.6 resembles the Pincus regime predicted by scaling theory.

Carboxylated core-shell particles: I. A system showing hindered swelling behavior.

We study the swelling behavior of carboxylated core-shell particles. It is well-known that these particles swell with increasing pH due to the electrostatic repulsion between carboxylate groups. Our results reveal that the swelling behavior is affected by the preparation method. We find that the swelling is promoted in those particles which were initially in a highly swollen state (pH>or=10). However, the swelling is hindered for those particles which were not previously in this trigger pH. In the hindered systems, a compact conformation of the polymer shell is induced by hydrophobic attractions between the non-charged segments which compete against the swelling driving force. In addition, an interesting hysteresis behavior emerges when promoted systems are subjected to a heating-cooling cycle; a new stable system appears with a less extended polymer shell conformation. Furthermore, salt-induced swelling experiments corroborate not only polymer restructuring but also assembly among carboxylate groups which affects their ionization grade.

Phase behaviour of a model colloid-polymer mixture at low colloid concentration.

The phase behaviour of a colloid-polymer mixture is studied at very low colloid concentrations (below 0.5%). The size ratio between the polymer and the colloidal particles is around 0.09, so that the colloids experience short-range attractions. At these low volume fractions, fluid-crystal coexistence is found at moderate polymer concentrations and the kinetics of crystallization are analyzed by turbidimetry. At higher polymer concentrations, clustering of the particles occurs, but some of them remain in a diluted, gas, phase composed mainly of single particles. These states do not correspond to vapor-liquid coexistence, as shown by studying the density of the gas phase. Strong interactions induce flocculation of the system, producing fractal aggregates with dimension df ≈ 1.8, compatible with diffusion limited cluster aggregation (DLCA). These results are discussed in connection with the phase diagram of colloid-polymer mixtures, obtained at much higher colloid concentrations. For low colloid volume fractions, below ∼0.05%, no clustering of the particles is observed for any polymer concentration.

Experimental phase diagram of symmetric binary colloidal mixtures with opposite charges.

The phase behavior of equimolar mixtures of oppositely charged colloidal systems with similar absolute charges is studied experimentally as a function of the salt concentration in the system and the colloid volume fraction. As the salt concentration increases, fluids of irreversible clusters, gels, liquid-gas coexistence, and finally, homogeneous fluids, are observed. Previous simulations of similar mixtures of Derjaguin-Landau-Verwey-Overbeek (DLVO) particles indeed showed the transition from homogeneous fluids to liquid-gas separation, but also predicted a reentrant fluid phase at low salt concentrations, which is not found in the experiments. Possibly, the fluid of clusters could be caused by a nonergodicity transition responsible for the gel phase in the reentrant fluid phase. Liquid-gas separation takes a delay time after the sample is prepared, whereas gels collapse from the beginning. The density of the liquid in coexistence with a vapor phase depends linearly on the overall colloid density of the system. The vapor, on the other hand, is comprised of equilibrium clusters, as expected from the simulations.