Emulsion formation and stabilization by biomolecules: the leading role of cellulose

Emulsion stabilization by native cellulose has been mainly hampered because of its insolubility in water. Chemical modification is normally needed to obtain water-soluble cellulose derivatives. These modified celluloses have been widely used for a range of applications by the food, cosmetic, pharmaceutic, paint and construction industries. In most cases, the modified celluloses are used as rheology modifiers (thickeners) or as emulsifying agents. In the last decade, the structural features of cellulose have been revisited, with particular focus on its structural anisotropy (amphiphilicity) and the molecular interactions leading to its resistance to dissolution. The amphiphilic behavior of native cellulose is evidenced by its capacity to adsorb at the interface between oil and aqueous solvent solutions, thus being capable of stabilizing emulsions. In this overview, the fundamentals of emulsion formation and stabilization by biomolecules are briefly revisited before different aspects around the emerging role of cellulose as emulsion stabilizer are addressed in detail. Particular focus is given to systems stabilized by native cellulose, either molecularly-dissolved or not (Pickering-like effect).Financially support by the Portuguese Foundation for Science and Technology, FCT, via the projects PTDC/AGR-TEC/4814/2014, PTDC/ASP-SIL/30619/2017 and researcher grant IF/01005/2014. RISE Research Institutes of Sweden AB and PERFORM, a competence platform in Formulation Science at RISE, are acknowledged for additional financing. This research has been supported by Treesearch.se.info:eu-repo/semantics/publishedVersio

Cellulose dissolution in an alkali based solvent: influence of additives and pretreatments

The distinction between thermodynamic and kinetics in cellulose dissolution is seldom considered in the literature. Therefore, herein an attempt to discuss this topic and illustrate our hypotheses on the basis of simple experiments was made. It is well-known that cellulose can be dissolved in a aqueous sodium hydroxide (NaOH/H2O) solvent at low temperature but it is here shown that such an alkaline solvent can be considerably improved regarding solubility, stability and rheological properties as a whole if different additives (salts and amphiphilic molecules) are used in the dissolution stage. This work probes new aqueous routes to dissolve cellulose, thereby improving the potential to commercially dissolve cellulose in an inexpensive and environmentally friendly manner.A distinção entre termodinâmica e cinética de dissolução da celulose raramente tem sido considerada na literatura. Neste trabalho, discutimos este tema e fundamentamos as nossas hipóteses recorrendo a experiências simples. É do conhecimento geral que a celulose pode ser dissolvida no solvente aquoso de hidróxido de sódio (NaOH/H2O) a baixa temperatura. Neste trabalho, demonstramos que este solvente alcalino pode ser consideravelmente melhorado em relação à sua estabilidade, solubilidade e propriedades reológicas se forem usados diferentes aditivos (sais e moléculas anfifílicas) na fase de dissolução. Este trabalho indica novos caminhos relativamente à dissolução da celulose em solventes aquosos, de uma forma mais econômica e ambientalmente amigável, aumentando o seu potencial comercial

Probing cellulose amphiphilicity

Cellulose dissolution and regeneration is an increasingly active research field due to the direct relevance for numerous production processes and applications. The problem is not trivial since cellulose solvents are of remarkably different nature and thus the understanding of the subtle balance between the different interactions involved becomes difficult but crucial. There is a current discussion in literature on the balance between hydrogen bonding and hydrophobic interactions in controlling the solution behavior of cellulose. This treatise attempts to review recent work highlighting the marked amphiphilic characteristics of cellulose and role of hydrophobic interactions in dissolution and regeneration. Additionally, a few examples of our own research are discussed focusing on the role of different additives in cellulose solubility. The data does support the amphiphilic behavior of cellulose, which clearly should not be neglected when developing new solvents and strategies for cellulose dissolution and regeneration

Fourier Transform NMR Self-diffusion Studies Of A Nonaqueous Microemulsion System

Self-diffusion coefficients of the components of the microemulsion system glycerol/hexanol/sodium dodecyl sulfate (SDS) were determined in the presence and absence of an oil, p-xylene, and the results were compared with those from corresponding aqueous systems (i.e., glycerol replaced by water). In the aqueous system, the water in the hexanol rich isotropic liquid showed a diffusion coefficient less than 10% of that of free water, while that of hexanol was roughly 80% of that of free hexanol; such restricted motion of the water is consistent with the presence of water as discrete droplets. Partial substitution of p-xylene for hexanol did not affect the diffusion coefficient of water appreciably. In the nonaqueous three-component system, the diffusion coefficients of glycerol, SDS, and hexanol all decreased in concert as the glycerol content increased, e.g., that of hexanol goes from 1.75 x 10-10 m2 s-1 to 2.7 x 10-11 m2 s-1 as the glycerol content ranges from 10 to 80%. The diffusion coefficient of glycerol was always greater than that of neat glycerol by a factor of 5 to 45. As the diffusion coefficients of all components were within a factor of 2, the idea of segregating one or more components into disconnected domains is not supported. There is no support for glycerol droplets but these microemulsions appear to be structureless. © 1987

Associating polymer-surfactant systems

Some recent illustrations of the phase behavior of polymer-amphiphile systems in solution are presented. Surfactant-polymer association is demonstrated for various amphiphilic synthetic and biological polymers both on a macroscopic and on a single molecular level

Polyion Adsorption onto Catanionic Surfaces. A Monte Carlo Study

The adsorption of a single and negatively charged polyion with varying flexibility onto a surface carrying both negative and positive charges representing a charged membrane surface has been investigated by using a simple model employing Monte Carlo simulations. The polyion was represented by a sequence of negatively charged hard spheres connected with harmonic bonds. The charged surface groups were also represented by charged hard spheres, and they were positioned on a hard surface slightly protruding into the solution. The surface charges were either frozen in a liquidlike structure or laterally mobile. With a large excess of positive surface charges, the classical picture of a strongly adsorbed polyion with an extended and flat configuration emerged. However, adsorption also appeared at a net neutral surface or at a weakly negatively charged surface, and at these conditions the adsorption was stronger with a flexible polyion as compared to a semiflexible one, two features not appearing in simpler models containing homogeneously charged surfaces. The presence of charged surface patches (frozen surface charges) and the ability of polarization of the surface charges (mobile surface charges) are the main reasons for the enhanced adsorption. The stronger adsorption with the flexible chain is caused by its greater ability to spatially correlate with the surface charges

Finite and infinite-dimensional symmetries of pure N=2 supergravity in D=4

We study the symmetries of pure N=2 supergravity in D=4. As is known, this theory reduced on one Killing vector is characterised by a non-linearly realised symmetry SU(2,1) which is a non-split real form of SL(3,C). We consider the BPS brane solutions of the theory preserving half of the supersymmetry and the action of SU(2,1) on them. Furthermore we provide evidence that the theory exhibits an underlying algebraic structure described by the Lorentzian Kac-Moody group SU(2,1)^{+++}. This evidence arises both from the correspondence between the bosonic space-time fields of N=2 supergravity in D=4 and a one-parameter sigma-model based on the hyperbolic group SU(2,1)^{++}, as well as from the fact that the structure of BPS brane solutions is neatly encoded in SU(2,1)^{+++}. As a nice by-product of our analysis, we obtain a regular embedding of the Kac-Moody algebra su(2,1)^{+++} in e_{11} based on brane physics.Comment: 70 pages, final version published in JHE