Influence of Low-Molar-Mass Xyloglucans on the Rheological Behavior of Concentrated Cellulose Nanocrystal Suspensions.

Hydrogels were prepared at high solid contents (70-100 g/L) with cellulose nanocrystals (CNC) and very short xyloglucans (XGs). At 70 g/L, CNCs form cholesteric liquid crystals regularly spaced by a distance of 30 nm. This structure was preserved after adsorption of XG with a molar mass (Mw) of 20,000 g/mol (XG20) but was lost at 40,000 g/mol (XG40). Rheological measurements discriminated domains where an increasing Mw from XG20 to XG40 gave rise to drastic changes in storage moduli (on 3 orders of magnitude). At 40,000 g/mol, transient systems were obtained and a re-entrant glass-gel-glass transition was observed with increasing XG concentrations. This was interpreted in terms of the length and stiffness of the chain in relation to the inter-CNC distance. Liquid-to-glass-to-gel transitions were attributed to an XG adsorption type according to train or trail conformations or interconnected structures. Such tunable properties may further have implications on the in vivo role of XG during cell wall extension.

Edge-On (Cellulose II) and Face-On (Cellulose I) Adsorption of Cellulose Nanocrystals at the Oil-Water Interface: A Combined Entropic and Enthalpic Process.

Nanocelluloses can be used to stabilize oil-water surfaces, forming so-called Pickering emulsions. In this work, we compare the organization of native and mercerized cellulose nanocrystals (CNC-I and CNC-II) adsorbed on the surface of hexadecane droplets dispersed in water at different CNC concentrations. Both types of CNCs have an elongated particle morphology and form a layer strongly adsorbed at the interface. However, while the layer thickness formed with CNC-I is independent of the concentration at 7 nm, CNC-II forms a layer ranging from 9 to 14 nm thick with increasing concentration, as determined using small-angle neutron scattering with contrast-matched experiments. Molecular dynamics (MD) simulations showed a preferred interacting crystallographic plane for both crystalline allomorphs that exposes the CH groups (100 and 010) and is therefore considered hydrophobic. Furthermore, this study suggests that whatever the allomorph, the migration of CNCs to the oil-water interface is spontaneous and irreversible and is driven by both enthalpic and entropic processes.

Exploiting Complex Formation between Polysaccharides and Protein Microgels To Influence Particle Stabilization of W/W Emulsions.

Protein particles were complexed with polysaccharides, and the effect on their capacity to stabilize water-in-water (W/W) emulsions was investigated. Protein microgels were formed by heating aqueous solutions of whey protein isolate. The microgels were subsequently mixed with anionic or cationic polysaccharides: κ-carrageenan (κ-car) or chitosan, respectively. The molar mass and radius of the complexes formed in dilute microgel suspensions (40 mg/L) were characterized by light scattering techniques as a function of the pH and the composition. The structure and stability of complexes formed at a higher microgel concentration (3 g/L) were studied by confocal laser scanning microscopy. It was found that small stable complexes can be formed with κ-car between pH 4.3 and pH 5.5 and with chitosan between pH 4.1 and pH 6.5, that is, both below and above the isoionic point of the microgels (pI = 5.0). Complexation with polysaccharides stabilized aqueous suspensions of microgels in the pH range where they flocculated in the absence of polysaccharides (4.3-5.5). W/W emulsions were produced by mixing dextran and poly(ethylene oxide) solutions. Microgels added to these emulsions spontaneously form a layer around the dispersed droplets, which inhibits coalescence to different extents depending on the conditions. The effect of complexation on the structure of the emulsions was investigated as a function of the pH. It is shown that stable liquid-like emulsions can be obtained in the pH range where emulsions containing only microgels flocculate.

Water-In-Water Emulsion Gels Stabilized by Cellulose Nanocrystals.

Particle-stabilized water-in-water emulsions were prepared by mixing dextran and poly(ethylene oxide) (PEO) in water and adding cellulose nanocrystals (CNC). The CNC formed a layer at the surface of the dispersed droplets formed by the PEO-rich phase. Excess CNC partitioned to the continuous dextran phase. Aggregation of CNC at different rates was induced by adding NaCl between 10 and 100 mM. In the presence of more than 2 g/L CNC, fast aggregation led to the formation of an emulsion gel showing no signs of creaming. Confocal laser scanning microscopy showed that the emulgels were formed by a continuous network of CNC in which the randomly distributed droplets were embedded. The gel stiffness was measured with oscillatory shear rheology and found to increase strongly with increasing CNC concentration ( C). The dispersed droplets were elastically active and increased the gel stiffness at low C. However, up to C = 10 g/L, the yield stress was too small to inhibit the flow when the gels were tilted. At C < 2 g/L, creaming was observed until the network of connected droplets became sufficiently dense to be strong enough to resist buoyancy.

Design of Pickering Micro- and Nanoemulsions Based on the Structural Characteristics of Nanocelluloses.

The development of biobased materials with lower environmental impact has seen an increased interest these last years. In this area, nanocelluloses have shown a particular interest in research and industries. Cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF) are both known to stabilize oil-water interfaces, forming the so-called Pickering emulsions which are surfactant-free, highly stable emulsions armored by a layer of solid particles. This work describes the emulsion's characteristics and properties according to particle size, shape and surface chemistry in order to produce controlled micro- and nanoemulsions stabilized by nanocelluloses. For this purpose, four nanocelluloses which vary in source, length, width, and surface charge density were used. Isolated droplets were produced by CNCs and interconnected droplets by CNFs that led to distinct drop size (micro- and nanosized), organization of nanoparticles at the surface of the droplets, stability, and mechanical properties through rheological measurements. This work gives a precise description of the resulting emulsions and shows the ability to produce nanosized droplets for CNC and TEMPO oxidized CNF but not for the less fibrillated CNF using HP-homogenizer. Individual noncreaming droplets with average diameters as low as 350 nm were achieved for cotton CNCs and TEMPO oxidized CNFs.

Structural Description of the Interface of Pickering Emulsions Stabilized by Cellulose Nanocrystals.

The cotton cellulose nanocrystals (CNCs) used in this study are rod-like particles with dimensions in the nanoscale (195 nm long, 23 nm width and 6 nm thick) able to stabilize Pickering emulsions. The adsorption of CNCs at an oil-water interface has been investigated by small angle neutron scattering (SANS) with and without surface charge, and varying CNC concentration from 2 to 5 g/L. Average thicknesses of the interfacial CNC layer around the emulsion droplets of 7 and 18 nm were determined for charged and uncharged CNC, respectively, regardless of their concentration in suspension. This suggests that CNC particles lie as a monolayer varying in surface density. Using several phase contrast variations, the neutron wave vector (Q) dependence with the intensity showed that CNCs are in contact with the oil phase only via the surface of the CNC and not immersed in oil since the Porod behavior is observed over the whole Q-range revealing no deformation of the oil surface at a nanometer scale. This result promotes the postulate that the (2 0 0) crystalline plane of the CNC directly interacts with the interface.

Gelation Kinetics and Network Structure of Cellulose Nanocrystals in Aqueous Solution.

Cellulose nanocrystals (CNC) are rod-like biosourced nanoparticles that are widely used in a range of applications. Charged CNC was obtained by acid extraction from cotton and dispersed in aqueous solution using ultrasound and characterized by light scattering. Aggregation and gelation of CNC induced by addition of NaCl was investigated by light scattering as a function of the NaCl concentration (30-70 mM), the CNC concentration (0.5-5 g/L), and the temperature (10-60 °C). Formation of fractal aggregates was observed that grow with time until they percolate and form a weak system spanning network. The aggregation rate and gel time were found to decrease very steeply with increasing NaCl concentration and more weakly with increasing CNC concentration. A decrease of the gel time was also observed with increasing temperature for T > 20 °C. The structure of the CNC networks was studied using confocal laser scanning microscopy and light scattering. The local structure of the networks was fractal and reflected that of the constituting aggregates. The gels were homogeneous on length scales larger than the correlation length, which decreased with increasing CNC concentration. The CNC gels flowed when tilted for C < 12 g/L and sedimentation was observed macroscopically for C < 4 g/L due to the collapse of the CNC network under gravity. The speed and extent of sedimentation was investigated as a function of the ionic strength and the CNC concentration. Gelled CNC could be completely redispersed by applying ultrasound.

Influence of charge density and ionic strength on the aggregation process of cellulose nanocrystals in aqueous suspension, as revealed by small-angle neutron scattering.

Aggregation of rodlike colloidal particles is investigated here through the aggregation process by either increasing ionic strength or decreasing surface charge density of cellulose nanocrystals (CNCs). The form factor of the nanoparticles is characterized up to the Guinier plateau using small-angle neutron scattering (SANS) extended to very small scattering vector Q. Ionic strength, above the threshold of screening charges, brings aggregative conditions that induced fractal organizations for both charged and uncharged CNCs. These two structures display respective fractal dimensions of 2.1 for charged CNCs at high ionic strength and 2.3 for desulfated CNCs over more than a decade of the scattering vector Q, irrespective of salinity, revealing a denser structuration for neutral particles. This is discussed in the framework of aggregation of rodlike particles with an aspect ratio higher than 8. Furthermore, dilution of the rod gel led to disentanglement of the network of fractal aggregates with a subsequent macroscopic sedimentation of the suspensions, with a characteristic time that depends upon the ionic strength and surface charge density. It revealed a threshold independent of salt content around 2.5 g/L and the metastable out-of-equilibrium character of CNC suspensions.

Kinetic aspects of the adsorption of xyloglucan onto cellulose nanocrystals.

In this work, the adsorption of a neutral flexible polysaccharide, xyloglucan (XG), onto thin cellulose nanocrystal (CNC) surfaces has been investigated to get more insight into the CNC-XG association. Gold-coated quartz crystals were spin-coated with one layer of CNC, and XG adsorption was monitored in situ using a quartz crystal microbalance with dissipation (QCM-D). The adsorption of XG under flow at different concentrations did not result in the same surface concentration, which evidenced a kinetically controlled process. In an attempt to describe the binding of XG to CNCs, adsorption data were fitted to a kinetic model comprising a contribution from XG adsorption onto uncovered CNC surfaces and a contribution from XG adsorption after rearrangement. Kinetic studies evidenced the presence of two adsorption regimes as a function of XG concentration. For low XG concentrations, the kinetic constant for chain rearrangement is comparable to the kinetic constant for adsorption. This fact implies a rearrangement and alignment of XG molecules on CNCs. Differently, for higher XG concentrations, the kinetic constant related to the conformational rearrangement decreases, indicating that XG molecules have no time to laterally rearrange before new XG molecules adsorb.

Impact of ionic strength on chitin nanocrystal-xyloglucan multilayer film growth.

The impact of the ionic strength on the film growth has been studied for the architectures composed of chitin nanocrystals (ChiNC) and xyloglucan (XG) to better understand the fabrication process of multilayer films. The formation of ChiNC-XG assemblies was monitored by quartz crystal microbalance with dissipation (QCM-D) and multilayer films were fabricated by the spin-coating assisted layer-by-layer (LbL) procedure. Films were prepared from 1 g L(-1) ChiNC dispersions at pH 4 without and with the addition of NaCl (0 and 5 mM, respectively) and 0.5 g L(-1) XG solutions in water. Distinct growth pattern and structural characteristics were found for the films prepared from ChiNC at 0 and 5 mM NaCl. Specifically, films assembled without salt exhibited lower mass deposition and film growth failed after 5 (ChiNC-XG) bilayers. Differently, at 5 mM NaCl higher amounts of both polymers (ChiNC and XG) were adsorbed; therefore, the films were thicker, and the deposition succeeded up to 10 bilayers. Atomic force microscopy (AFM) revealed an almost completely covered surface after the adsorption of ChiNC at 5 mM NaCl whereas salt-free ChiNC dispersions resulted in lower surface coverage. These results reliably concluded that the fabrication of (ChiNC-XG) films requires the screening of the charges to promote the layers stability.

Preparation of double Pickering emulsions stabilized by chemically tailored nanocelluloses.

Nanocelluloses are bio-based nanoparticles of interest as stabilizers for oil-in-water (o/w) Pickering emulsions. In this work, the surface chemistry of nanocelluloses of different length, nanofibrillated cellulose (NFC, long) and cellulose nanocrystals (CNC, short), was successfully tailored by chemical modification with lauroyl chloride (C12). The resulting nanofibers were less hydrophilic than the original and able to stabilize water-in-oil (w/o) emulsions. The combination of the two types of nanocelluloses (C12-modified and native) led to new surfactant-free oil-in-water-in-oil (o/w/o) double emulsions stabilized by nanocellulose at both interfaces. Characterization was performed with respect to droplet size distribution, droplet stability over time, and stability after centrifugation. Nanocellulose-based Pickering emulsions can be designed with a substantial degree of control, as demonstrated by the stability of the chemically tailored NFC double emulsions. Furthermore, it was demonstrated that increased nanofiber length leads to increased stability.

Chitin nanocrystal-xyloglucan multilayer thin films.

For the first time, the adsorption of xyloglucan (XG) on chitin nanocrystals (ChiNC) surface was proved using quartz crystal microbalance with dissipation (QCM-D) and by successfully building up spin-coated assisted layer-by-layer (LbL) structures on solid substrates. Several parameters in the adsorption process, such as ChiNC concentrations (0.5-3.0 g L(-1)), number of layers, or the outmost layer material (ChiNC or XG), were investigated to better understand the fabrication process of multilayer films. The thickness of the homogeneous film increased linearly with the number of bilayers, with an average thickness per bilayer of 12.3 nm. Additionally surface morphology was studied by atomic force microscopy (AFM), which revealed an almost completely covered surface after the adsorption of ChiNC. The final structures were found to have semireflective properties capable of being tuned by adjusting the ChiNC dispersion parameters.

Chitin nanocrystals for Pickering high internal phase emulsions.

Chitin is a natural polymer of glucosamine bearing N-acetyl groups. Chitin nanocrystals (ChiNCs), resulting from the acid hydrolysis of amorphous regions of chitin, are crystalline positively charged rod-like particles. ChiNCs show some interfacial properties and very efficiently stabilize oil/water interfaces, leading to the so-called Pickering emulsions. In accordance with the irreversible adsorption of particles, these Pickering emulsions proved stable over time, with constant emulsion volume for several months, even though natural creaming may occur. The emulsions produced are not clearly susceptible to ionic strength or pH in terms of average droplet diameter. However, when mixed with a large amount of oil, high internal phase emulsions (HIPE) containing up to 96% of internal phase are formed as a gel with a texture that can be modulated from soft to solid gel by adjusting concentration, pH, and ionic strength.

Surfactant-free high internal phase emulsions stabilized by cellulose nanocrystals.

Cellulose nanocrystals (CNCs) are rod-like colloidal particles that irreversibly adsorb at the oil-water interface to produce ultrastable emulsions. When the internal phase fraction is increased, these CNCs can produce gel-like oil-in-water high internal phase emulsions (HIPEs) in which more than 90% of the hydrophobic phase is stabilized by less than 0.1% wt. of CNCs. However, a one-step preparation of HIPEs is not possible, and incorporation of the high internal phase fraction requires the prior preparation of Pickering emulsions. We propose that this two-step process to create CNC HIPEs relies on a swelling process of the droplets that does not desorb the CNCs from the interface, decreasing the coverage ratio of the droplets and leading to coalescence. As a result, this process leads to a drops deformation and a new interfacial networking organization as revealed by confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) images.

Modulation of surface properties of cellulose nanocrystals through adsorption of tannic acid and alkyl cellulose derivatives.

Cellulose nanocrystals (CNCs) are hydrophilic nanoparticles that cannot be dispersed in non-polar solvents or hydrophobic polymer matrices. Here, we demonstrate the tunable modification of CNC surfaces by physical adsorption of tannic acid (TA) and two alkyl cellulose derivatives (ACDs), methyl cellulose (MC) and ethyl cellulose (EC), while maintaining their sustainable nature. We compare the impact of ACD adsorption when mixed with CNCs to CNCs precoated with tannic acid (CNC@TA), varying ACD weight fractions in CNC suspensions. Our results show that CNC@ACD and CNC@TA@ACD aqueous suspensions display good colloidal stability in water, while their surface properties are altered. We use a wide range of analytical techniques to characterize these suspensions, with a focus on their interaction with water. The two selected ACDs adsorb on both CNCs and CNC@TA at low fractions (ACD ≤ 10 % w/w), followed by an intermediate region of saturation between 10 % and 30 % w/w. At fractions above 30 % w/w, we observe the formation of CNC- or CNC@TA-reinforced ACD composites. Most samples can be redispersed in water upon freeze-drying, except for EC-rich samples redispersible in toluene. Our facile method for preparing ACD-coated CNCs allows for the creation of a range of nanomaterials with modulable wetting and emulsification properties.

Interactions between proteins and cellulose in a liquid crystalline media: Design of a droplet based experimental platform.

Model systems are needed to provide controlled environment for the understanding of complex phenomena. Interaction between polysaccharides and proteins in dense medium are involved in numerous complex systems such as biomass conversion or plant use for food processing or biobased materials. In this work, cellulose nanocrystals (CNCs) were used to study proteins in a dense and organized cellulosic environment. This environment was designed within microdroplets using a microfluidic setup, and applied to two proteins, bovine serum albumin (BSA) and a GH7 endoglucanase, relevant to food and plant science, respectively. The CNC at 56.5 g/L organized in liquid crystalline structure and the distribution of the proteins was probed using synchrotron deep-UV radiation. The proteins were homogeneously distributed throughout the volume, but BSA significantly disturbed the droplet global organization, preferring partition in hydrophilic external micelles. In contrast, GH7 partitioned with the CNCs showing stronger non-polar interaction but without disruption of the system organization. Such results pave the road for the development of more complex polysaccharides - proteins in-vitro models.

Modulation of cellulose nanocrystals amphiphilic properties to stabilize oil/water interface.

Neutral cellulose nanocrystals dispersed in water were shown in a previous work to stabilize oil/water interfaces and produce Pickering emulsions with outstanding stability, whereas sulfated nanocrystals obtained from cotton did not show interfacial properties. To develop a better understanding of the stabilization mechanism, amphiphilic properties of the nanocrystals were modulated by tuning the surface charge density to investigate emulsifying capability on two sources of cellulose: cotton linters (CCN) and bacterial cellulose (BCN). This charge adjustment made it possible to determine the conditions where a low surface charge density, below 0.03 e/nm(2), remains compatible with emulsification, as well as when assisted by charge screening regardless of the source. This study discusses this ability to stabilize oil-in-water emulsions for cellulose nanocrystals varying in crystalline allomorph, morphology, and hydrolysis processes related to the amphiphilic character of nonhydrophobized cellulose nanocrystal.

New Pickering emulsions stabilized by bacterial cellulose nanocrystals.

We studied oil in water Pickering emulsions stabilized by cellulose nanocrystals obtained by hydrochloric acid hydrolysis of bacterial cellulose. The resulting solid particles, called bacterial cellulose nanocrystals (BCNs), present an elongated shape and low surface charge density, forming a colloidal suspension in water. The BCNs produced proved to stabilize the hexadecane/water interface, promoting monodispersed oil in water droplets around 4 µm in diameter stable for several months. We characterized the emulsion and visualized the particles at the surface of the droplets by scanning electron microscopy (SEM) and calculated the droplet coverage by varying the BCN concentration in the aqueous phase. A 60% coverage limit has been defined, above which very stable, deformable droplets are obtained. The high stability of the more covered droplets was attributed to the particle irreversible adsorption associated with the formation of a 2D network. Due to the sustainability and low environmental impact of cellulose, the BCN based emulsions open opportunities for the development of environmentally friendly new materials.

Formulation of re-dispersible dry o/w emulsions using cellulose nanocrystals decorated with metal/metal oxide nanoparticles.

This study describes for the first time the preparation of re-dispersible surfactant-free dry eicosane oil emulsion using cellulose nanocrystals (CNCs) using the freeze-drying technique. Surface properties of CNCs constitute a critical point for the stability of o/w emulsions and thus can affect both the droplet size and dispersion properties of the emulsion. Therefore, surface modification of CNCs was performed to understand its effect on the size of the obtained re-dispersible dry o/w eicosane emulsion. Decoration of the CNC surface with metal and metal oxide nanoparticles was conducted through the available alcoholic groups of glycosidic units of CNC, which played a dual role in reducing and stabilizing nanoparticles. Of these nanoparticles, silver (AgNPs), gold (AuNPs), copper oxide (CuO-NPs), and iron oxide (Fe3O4-NPs) nanoparticles were prepared via a facile route using alkali activated CNCs. Thorough characterizations pertaining to the as-prepared nanoparticles and their re-dispersible dry eicosane o/w emulsions were investigated using UV-vis spectroscopy, TEM, XRD, particle size, zeta potential, and STEM. Results confirmed the ability of CNCs to stabilize and/or reduce the formed nanoparticles with different sizes and shapes. These nanoparticles showed different shapes and surface charges accompanied by individual morphologies, reflecting on the stability of the re-dispersed dry eicosane emulsions with droplet sizes varying from 1.25 to 0.5 µm.

Hydroxyl groups on cellulose nanocrystal surfaces form nucleation points for silver nanoparticles of varying shapes and sizes.

In this study, we investigate the interactions between the cellulose surface and Ag nanoparticles (AgNPs) for the purpose of manufacturing hybrid nanomaterials using bacterial cellulose nanocrystals (BCNs) as a model substrate. We focus on the role of the BCN surface chemistry on the AgNP nucleation obtained by chemical reduction of Ag+ ions. Homogeneous hybrid suspensions of BCN/AgNP are produced, regardless of whether the BCNs are quasi-neutral, negatively (TBCNs) or positively charged (ABCNs). The characterization of BCN/AgNP hybrids identifies the -OH surface groups as nucleation points for AgNPs, of about 20 nm revealing that surface charges only improve the accessibility to OH groups. X-ray Absorption technics (XANES and EXAFS) revealed a high metallic Ag0 content ranging from 88% to 97%. Moreover, the grafting of hydrophobic molecules on a BCN surface (HBCNs) does not prevent AgNP nucleation, illustrating the versatility of our method and the possibility to obtain bifunctional NPs. A H2O2 redox post-treatment on the hybrid induces an increase in AgNPs size, up to 90 nm as well as a shape variation (i.e., triangular). In contrast, H2O2 induces no size/shape variation for aggregated hybrids, emphasizing that the accessibility to -OH groups ensures the nucleation of bigger Ag nano-objects.