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Cell walls of so-called “wood-materials” are constituted by a complex, highly anisotropic and hierarchically organized nanocomposite, characterized by stiff crystalline cellulose nano-fibers, parallel to each other, and embedded in a softer and less anisotropic matrix of hemicelluloses, lignin and water. This matrix is hygroscopic, and therefore swells with increasing humidity. Consequently, wood cells undergo large dimensional changes. A minimal model of wood secondary cell walls to predict water absorption has recently been developed by Bertinetti and co-workers [1] in the form of an Equation of State (EOS) that represents equivalently the water sorption versus relative humidity, as considered in chemical engineering, or the relation between osmotic pressure and volume of solutes, in the physical chemistry equation of state approach initiated by Jean Perrin. We extend hereby this model to the presence of electrolytes adsorbed in the gel part wood cell wall and compare compression wood cell walls to the extreme case of coir.

The interaction between surfaces displaying end-grafted hydrophilic polymer brushes plays important roles in biology and in many wet-technological applications. In this context, the conformation of the brushes upon their mutual approach is crucial, because it affects interaction forces and the brushes' shear-tribological properties. While this aspect has been addressed by theory, experimental data on polymer conformations under confinement are difficult to obtain. Here, we study interacting planar brushes of hydrophilic polymers with defined length and grafting density. Via ellipsometry and neutron reflectometry we obtain pressure–distance curves and determine distance-dependent polymer conformations in terms of brush compression and reciprocative interpenetration. While the pressure–distance curves are satisfactorily described by the Alexander-de-Gennes model, the pronounced brush interpenetration as seen by neutron reflectometry motivates detailed simulation-based studies capable of treating brush interpenetration on a quantitative level.

Wood cell walls when contacted with humid atmosphere or an aqueous solution containing electrolytes or polymers undergo the phenomenon of swelling. In this work, experimental data were produced to quantify the effects of the adsorption water and solutes, which were introduced in the material by equilibration with a solution used as osmotic reservoir. For this reason, different environmental setups have been developed, allowing the control of temperature, water chemical potential, and ionic strength during the sorption process. The aim of this paper is to describe three experimental setups, focused on different levels: at the nanometric scale, small-angle scattering at controlled humidity; at the mesoscopic scale, environmental scanning electron microscopy; and at the macroscopic scale, tensile stage involving immersion of samples in solutions. Applicability and efficiency of the three setups are described. Moreover, it was shown how the combination of the results obtained via the three methodologies can be compared to expectations from a general Equation of State (EOS approach), where wood swelling with water and salt solutions is presented as the dependence of the distance between adjacent cellulose fibrils on the osmotic pressure. The total pressure calculated takes into account chemical, colloidal and mechanical terms in the force balance of the wood cell wall.

Collagen is the most abundant protein in mammals and its primary role is to serve as mechanical support in many extracellular matrices such as those of bones, tendons, skin or blood vessels. Water is an integral part of the collagen structure, but its role is still poorly understood, though it is well-known that the mechanical properties of collagen depend on hydration. Recently, it was shown that the conformation of the collagen triple helix changes upon water removal, leading to a contraction of the molecule with considerable forces. Here we investigate the influence of mineralization on this effect by studying bone and turkey leg tendon (TLT) as model systems. Indeed, TLT partially mineralizes so that well-aligned collagen with various mineral contents can be found in the same tendon. We show that water removal leads to collagen contraction in all cases generating tensile stresses up to 80MPa. Moreover, this contraction of collagen puts mineral particles under compression leading to strains of around 1%, which implies localized compressive loads in mineral of up to 800MPa. This suggests that collagen dehydration upon mineralization is at the origin of the compressive pre-strains commonly observed in bone mineral.

Aqueous alkyltrimethylammonium bromides, or dialkyldimethylammonium ones, were mixed with sodium alkyl sulfates and dialkanesulfonates. Depending on the overall surfactant concentration, charge and/or mole ratios, cat-anionic vesicles were formed by mixing nonstoichiometric amounts of oppositely charged species. The resulting vesicles are thermodynamically and kinetically stable. ζ-potential and dynamic light scattering characterized the systems. As a rule, cat-anionic vesicles have sizes in the 10(2)-10(3) nm range and bear significant amounts of surface charges. At fixed surfactant concentration, the vesicle surface charge density scales with mole ratios and tends to zero as the latter approach unity. Conversely, the hydrodynamic radius diverges when the cationic/anionic mole ratio is close to 1. The double-layer thickness and surface charge density are controlled by mole ratios and addition of NaBr, which plays a role in vesicle stability. The salt screens the surface charge density and modulates both vesicle size and double-layer thickness. Slightly higher concentrations of NaBr induce the transition from vesicles toward lamellar phases. The electrokinetic properties of cat-anionic dispersions were analyzed by dielectric relaxation experiments. The measured properties are sensitive to vesicle size distributions. In fact, the relaxation frequency shifts in proportion to vesicle polydispersity. Model calculations proposed on that purpose supported the experimental findings.

The effects of salt impregnation are studied within wood cell walls, occurring upon soaking from concentrated salt solutions. Osmotic deswelling is in some cases followed by ion specific swelling linked to Hofmeister effects. Taking into account microstructure, this study models the free energy changes associated with the ions and water uptake at molecular, colloidal, and macroscopic mechanical scales, to show that slow swelling until osmotic equilibrium originates from charge separation of the salt diffused into wood cell wall material. Kinetic effects as well as mechanical effects linked to transfer of species and swelling of the interstitial matrix between cellulose crystals are discussed. Predictions by minimal models taking into account nonelectrostatic ion complexation allow to estimate the order of magnitude of the nonelectrostatic binding free energy of adsorbed chaotropic anions and complexed divalent cations to be 8 and 10 kJ mole–1, respectively.

Nonstoichimetric mixtures of two oppositely charged surfactants, such as sodium dodecylsulfate and hexadecyltrimethylammonium bromide or tetradecyltrimethylammonium bromide and tetraethylammonium perfluorooctanesulfonate, a fluorinated species, form vesicles in dilute concentration regimes of the corresponding phase diagrams. Vesicles size and charge density are tuned by changing the mole ratio between oppositely charged species, at fixed overall surfactant content. They are also modulated by adding neutral electrolytes, or raising T. In the investigated regions, mixtures made of sodium dodecylsulfate/hexadecyltrimethylammonium bromide show ideality of mixing, the other non ideality and phase separation. The formation of unilamellar vesicles occurs in the sodium dodecylsulfate/hexadecyltrimethylammonium bromide mixture, but not in the other. DLS, viscosity, and electrophoretic mobility quantified the above effects. Surface charge density, surface tension, elasticity, and osmotic pressure concur to the stability of unilamellar vesicles and a balance between the above contributions is demonstrated. The results are relevant for practical applications of vesicles as carriers in biomedicine.