Quantitative Determination of Metal Ion Adsorption on Cellulose Nanocrystals Surfaces.

Nanocellulose is a bio-based material that holds significant potential in the field of water purification. Of particular interest is their potential use as a key sorbent material for the removal of metal ions from solution. However, the structure of metal ions adsorbed onto cellulose surfaces is not well understood. The focus of this work is to determine quantitatively the three-dimensional distribution of metal ions of different valencies surrounding negatively charged carboxylate functionalized cellulose nanocrystals (CNCs) using anomalous small-angle X-ray scattering (ASAXS). These distributions can affect the water and ionic permeability in these materials. The data show that increasing the carboxylate density on the surface of the CNCs from 740 to 1100 mmol/kg changed the nature of the structure of the adsorbed ions from a monolayer into a multilayer structure. The monolayer was modeled as a Stern layer around the CNC nanoparticles, whereas the multilayer structure was modeled as a diffuse layer on top of the Stern layer around the nanoparticles. Within the Stern layer, the maximum ion density increases from 1680 to 4350 mmol of Rb+/(kg of CNC) with the increase in the carboxylate density on the surface of the nanoparticles. Additionally, the data show that CNCs can leverage multiple mechanisms, such as electrostatic attraction and the chaotropic effect, to adsorb ions of different valencies. By understanding the spatial organization of the adsorbed metal ions, the design of cellulose-based sorbents can be further optimized to improve the uptake capacity and selectivity in separation applications.

In Vitro and in Vivo Analyses of the Effects of Source, Length, and Charge on the Cytotoxicity and Immunocompatibility of Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) are an emergent, sustainable nanomaterial that are biosourced, abundant, and biodegradable. On account of their high aspect ratio, low density, and mechanical rigidity, they have been employed in numerous areas of biomedical research including as reinforcing materials for bone or tissue scaffolds or as carriers in drug delivery systems. Given the promise of these materials for such use, characterizing and understanding their interactions with biological systems is an important step to prevent toxicity or inflammation. Reported herein are studies aimed at exploring the in vitro and in vivo effects that the source, length, and charge of the CNCs have on cytotoxicity and immune response. CNCs from four different biosources (cotton, wood, Miscanthus x Giganteus, and sea tunicate) were prepared and functionalized with positive or negative charges to obtain a small library of CNCs with a range of dimensions and surface charge. A method to remove endotoxic or other impurities on the CNC surface leftover from the isolation process was developed, and the biocompatibility of the CNCs was subsequently assayed in vitro and in vivo. After subcutaneous injection, it was found that unfunctionalized (uncharged) CNCs form aggregates at the site of injection, inducing splenomegaly and neutrophil infiltration, while charged CNCs having surface carboxylates, sulfate half-esters, or primary amines were biologically inert. No effect of the particle source or length was observed in the in vitro and in vivo studies conducted. The lack of an in vitro or in vivo immune response toward charged CNCs in these experiments supports their use in future biological studies.

Improved Concrete Materials with Hydrogel-Based Internal Curing Agents.

This research article will describe the design and use of polyelectrolyte hydrogel particles as internal curing agents in concrete and present new results on relevant hydrogel-ion interactions. When incorporated into concrete, hydrogel particles release their stored water to fuel the curing reaction, resulting in reduced volumetric shrinkage and cracking and thus increasing concrete service life. The hydrogel's swelling performance and mechanical properties are strongly sensitive to multivalent cations that are naturally present in concrete mixtures, including calcium and aluminum. Model poly(acrylic acid(AA)-acrylamide(AM))-based hydrogel particles with different chemical compositions (AA:AM monomer ratio) were synthesized and immersed in sodium, calcium, and aluminum salt solutions. The presence of multivalent cations resulted in decreased swelling capacity and altered swelling kinetics to the point where some hydrogel compositions displayed rapid deswelling behavior and the formation of a mechanically stiff shell. Interestingly, when incorporated into mortar, hydrogel particles reduced mixture shrinkage while encouraging the formation of specific inorganic phases (calcium hydroxide and calcium silicate hydrate) within the void space previously occupied by the swollen particle.