Ranking the solubility of ammonia in ionic liquids using near infrared spectroscopy and multivariate curve resolution.

We rank the expected solubilities of ammonia in three hydroxyl ionic liquids - [HOEMIm][BF4], [HOEMIm][NTf2] and [Ch][NTf2] - in the temperature range 20-105 °C by analyzing the cations and anions available for interaction with ammonia. As this availability depends on ion-pair formation in ionic liquids, in this paper it is evaluated using the concentration and spectral profiles recovered in the analysis of their near infrared spectra by the multivariate resolution curve - alternating least squares method. The results indicate that the main effect of temperature on ion pairs is to decrease the number of structural configurations with cooperative hydrogen bonds between cation and cation, although in a lesser extent the number of cation-anion interactions increases. Regardless of the type of ionic liquid cation, the cation-anion interactions are higher in the tetrafluorborate ionic liquid than in the imide ionic liquid, hydroxyl imidazolium or choline. Assuming that the solubility of ammonia is limited by the concentration profile values representative of the cation-cation interactions, we deduce that at temperatures higher than 80 °C, ammonia solubility increases in the following order [HOEMIm][BF4] < [HOEMIm][NTf2] < [Ch][NTf2]. At lower temperatures, this order varies with the ammonia concentration in the NH3/ILs mixtures considered. We deduce that if the ammonia concentration is relatively low, the ammonia solubility will be governed by the evolution of cation-anion interaction in the ionic liquids and the solubility order is the same as at higher temperatures. However, when the ammonia concentration is higher, the ammonia solubility in the [Ch][NTf2] ionic liquid is lower than in the hydroxyl-ionic liquids. This conclusion is supported by the experimental vapor-liquid equilibria (VLE) data of ammonia-/ILs mixtures with ammonia mass fractions between 0.2 and 0.8.

Use of Cross-Linked Poly(ethylene glycol)-Based Hydrogels for Protein Crystallization.

Poly(ethylene glycol) (PEG) hydrogels are highly biocompatible materials extensively used for biomedical and pharmaceutical applications, controlled drug release, and tissue engineering. In this work, PEG cross-linked hydrogels, synthesized under various conditions, were used to grow lysozyme crystals by the counterdiffusion technique. Crystallization experiments were conducted using a three-layer arrangement. Results demonstrated that PEG fibers were incorporated within lysozyme crystals controlling the final crystal shape. PEG hydrogels also induced the nucleation of lysozyme crystals to a higher extent than agarose. PEG hydrogels can also be used at higher concentrations (20-50% w/w) as a separation chamber (plug) in counterdiffusion experiments. In this case, PEG hydrogels control the diffusion of the crystallization agent and therefore may be used to tailor the supersaturation to fine-tune crystal size. As an example, insulin crystals were grown in 10% (w/w) PEG hydrogel. The resulting crystals were of an approximate size of 500 µm.