Probing cellulose-solvent interactions with self-diffusion NMR: Onium hydroxide concentration and co-solvent effects.

The molecular self-diffusion coefficients were accessed, for the first time, in solutions of microcrystalline cellulose, dissolved in 30 wt% and 55 wt% aqueous tetrabutylammonium hydroxide, TBAH (aq), and in mixtures of 40 wt% TBAH (aq) with an organic co-solvent, dimethylsulfoxide (DMSO), through pulsed field gradient stimulated echo NMR measurements. A two-state model was applied to estimate α (i.e., average number of ions that "bind" to each anhydroglucose unit) and Pb (i.e., fraction of "bound" molecules of DMSO, TBAH or H2O to cellulose) parameters. The α values suggest that TBA+ ions can bind to cellulose within 0.5 TBA+ to 2.3 TBA+/AGU. On the other hand, the Pb parameter increases when raising cellulose concentration for TBA+, DMSO and water in all solvent systems. Data suggests that TBAH interacts with the ionized OH groups from cellulose forming a sheath of bulky TBA+ counterions which consequently leads to steric hindrance between cellulose chains.

Microrheology of novel cellulose stabilized oil-in-water emulsions.

Diffusing wave spectroscopy (DWS) is a powerful optical technique suitable to investigate turbid samples in a nondestructive and reproducible way, providing information on the static and dynamic properties of the system. This includes the relative displacement of emulsion droplets over time and changes in the viscoelastic properties. Here, novel and promising cellulose-based oil-in-water (O/W) emulsions were prepared and studied, for the first time, by DWS. Cellulose plays the role of a novel eco-friendly emulsifying agent. The hydrolysis time of cellulose was observed to affect the average size of the emulsion droplets and their stability; the longer the hydrolysis time, the more dispersed and stable the emulsions were found to be. Additionally, a good complementarity between the microrheology (DWS) and macrorheology (mechanical rheometer) data was found. Our work suggests that DWS is a highly attractive method to investigate the stability, aging and microrheology properties of cellulose-based emulsions, providing valuable insights on their microstructure. This technique is thus highly appealing for the characterization and design of novel emulsion formulations.

In situ follow-up of hybrid alginate-silicate microbeads formation by linear rheology.

Hybrid alginate-silicate microbeads of about 10-20 µm were synthesized by combining alginate crosslinking, silica condensation in a one pot approach using a food grade emulsion as template. A fine tuning of the formulation composition (alginate, silica and calcium sources) is necessary in order to obtain core-shell microbeads instead of unshaped and irregular fragments or even perforated spherical beads. Importantly, in situ linear rheology provides insights into the reaction mechanism as a result of the rheological fingerprint profile obtained during beads formation.

Development of carboxymethyl cellulose-chitosan hybrid micro- and macroparticles for encapsulation of probiotic bacteria.

Novel carboxymethyl cellulose-chitosan (CMC-Cht) hybrid micro- and macroparticles were successfully prepared in aqueous media either by drop-wise addition or via nozzle-spray methods. The systems were either physically or chemically crosslinked using genipin as the reticulation agent. The macroparticles (ca. 2mm) formed are found to be essentially of the core-shell type, while the microparticles (ca. 5µm) are apparently homogeneous. The crosslinked particles are robust, thermally resistant and less sensitive to pH changes. On the other hand, the physical systems are pH sensitive presenting a remarkable swelling at pH 7.4, while little swelling is observed at pH 2.4. Furthermore, model probiotic bacteria (Lactobacillus rhamnosus GG) was for the first time successfully encapsulated in the CMC-Cht based particles with acceptable viability count. Overall, the systems developed are highly promising for probiotic encapsulation and potential delivery in the intestinal tract with the purpose of modulating gut microbiota and improving human health.

Cyclodextrin-grafted cellulose: physico-chemical characterization.

Cyclodextrins (CDs) can form inclusion complexes with a wide variety of molecules making them very attractive in different areas, such as pharmaceutics, biochemistry, food chemistry and textile. In this communication we will report on the physico-chemical characterization of cellulose modified with CDs by means of infra-red spectroscopy (FTIR), cross polarization magic angle spinning solid state nuclear magnetic resonance (CP-MAS NMR), polarized optical microscopy (POM) and thermal gravimetric analysis (TGA). Both CP-MAS NMR and FTIR indicate that CDs are chemically attached to cellulose backbone through the formation of ester bonds. Furthermore, the CD-grafted cellulose was dissolved in a "superphosphoric" acid solution but, despite the increase of hydrophilicity due to the modification, POM revealed that grafted cellulose was less soluble when compared to the unmodified polymer. The formation of a complex CD-cellulose network is suggested.

Shear-induced defect formation in a nonionic lamellar phase.

(2)H NMR experiments on a nonionic oriented lamellar phase demonstrate that shear flow induces structural defects in the lamellar structure. These substantial structural changes give rise to a transition from a viscous to a solidlike behavior; the elastic modulus of presheared samples was found to increase, reversibly, with the applied preshear rate. A similar behavior was found when step-cycling the temperature toward the layer-to-multilamellar-vesicle transition and back at constant shear rate. However, while shear rate controls the defect density, the temperature is found to control the defect rigidity. The lamellar phase exhibits a shear-thinning behavior under steady shear conditions, following the power law eta approximately gamma(n), with n approximately -0.4. Both the shear thinning and the elastic behavior are in agreement with the available theoretical models. The observed shear-induced structural defects are reversible and can be regarded as a pretransition prior to the shear-induced formation of multilamellar vesicles.

Size determination of shear-induced multilamellar vesicles by rheo-NMR spectroscopy.

A model for analyzing the deuterium ((2)H) NMR line shapes of D(2)O in surfactant multilamellar vesicle (MLV, "onion") systems is proposed. The assumption of the slow exchange of water molecules between adjacent layers implies that the (2)H NMR line shape is simply given by a sum of Lorentzians if the condition of motional narrowing is also fulfilled. Using the classical two-step model for the NMR relaxation in structured fluids allows us to calculate how the NMR line shape depends on the MLV size. The model is tested on two different MLV systems for which the NMR line shapes are measured as a function of the applied shear rate using rheo-NMR. The MLV sizes obtained are in good agreement with previous data from rheo-small-angle light scattering.

Shear-induced transitions between a planar lamellar phase and multilamellar vesicles: continuous versus discontinuous transformation.

The shear-induced transitions between an oriented lamellar phase and shear-induced multilamellar vesicles (MLVs) in a nonionic surfactant system were studied by deuterium rheo-NMR spectroscopy as a function of time in start-up experiments at several temperatures and shear rates. By starting from an initial state of oriented lamellae and observing the transformation to the final steady state of MLVs and vice-versa, two different mechanisms were found, depending on the direction of the transition and the initial state. The transition is continuous when MLVs are formed, starting from the oriented lamellar phase. On the other hand, a discontinuous nucleation-and-growth process with a coexistence region is observed when transforming MLVs into an oriented lamellar phase.

Viscoelasticity of a nonionic lamellar phase.

The linear viscoelastic properties of a nonionic lamellar phase in C-orientation were studied as a function of temperature by small-amplitude oscillatory measurements in the frequency range 0.5-5 Hz. An almost solid-like elastic response was observed at all studied temperatures, from 42 to 20 degrees C. In this range, the elastic modulus was found to increase strongly with decreasing temperature. The elasticity is attributed to screw dislocations connecting layers in the stack, and the data thus suggest that the density of screw dislocations decreases with increasing temperature. The lamellar phase forms an "onion" texture when continuously sheared at lower temperatures. It is argued that a possible origin for the shear-induced "onion" texture is the instability of the screw dislocations in shear flow. By 2H NMR experimentation, we also find the formation of a random mesh phase at lower temperatures. The presence of equilibrium bilayer perforations, however, does not correlate with the "onion" stability.