Filaments with Affinity Binding and Wet Strength Can Be Achieved by Spinning Bifunctional Cellulose Nanofibrils

We demonstrate benzophenone (BP) conjugation via amine-reactive esters onto oxidized cellulosic fibers that were used as precursors, after microfluidization, of photoactive cellulose nanofibrils (CNF). From these fibrils, cellulose I filaments were synthesized by hydrogel spinning in an antisolvent followed by fast biradical UV cross-linking. As a result, the wet BP-CNF filaments retained extensively the original dry strength (a remarkable ∼80% retention). Thus, the principal limitation of these emerging materials was overcome (the wet tensile strength is typically <0.5% of the value measured in dry conditions). Subsequently, antihuman hemoglobin (anti-Hb) antibodies were conjugated onto residual surface carboxyl groups, making the filaments bifunctional for their active groups and properties (wet strength and bioactivity). Optical (surface plasmon resonance) and electroacoustic (quartz crystal microgravimetry) measurements conducted with the bifunctional CNF indicated effective anti-Hb conjugation (2.4 mg m^–2), endowing an excellent sensitivity toward Hb targets (1.7 ± 0.12 mg m^–2) and negligible nonspecific binding. Thus, the anti-Hb biointerface was deployed on filaments that captured Hb efficiently from aqueous matrices (confocal laser microscopy of FITC-labeled antibodies). Significantly, the anti-Hb biointerface was suitable for regeneration, while its sensitivity and selectivity in affinity binding can be tailored by application of blocking copolymers. The developed bifunctional filaments based on nanocellulose offer great promise in detection and affinity binding built upon 1D systems, which can be engineered into other structures for rational use of material and space

Adsorption Behavior of Perfluorinated Sulfonic Acid Ionomer on Highly Graphitized Carbon Nanofibers and Their Thermal Stabilities

A systematic adsorption study of perfluorinated sulfonic acid Nafion ionomer on ribbon-type highly graphitized carbon nanofibers (CNFs) was carried out using fluorine-19 nuclear magnetic resonance spectroscopy. On the basis of the values obtained for the equilibrium constant (<i>K</i>_eq, derived from Langmuir isotherm), the ionomer has varying affinities for CNFs (<i>K</i>_eqbetween 5 and 22) as compared to Vulcan (<i>K</i>_eq = 18), depending on surface treatments. However, the interactions are most likely governed by different adsorption mechanisms depending on hydrophilicity/hydrophobicity of the adsorbent carbon. The ionomer is probably adsorbed via the polar sulfonic group on hydrophilic Vulcan, whereas it is adsorbed primarily via hydrophobic −CF₂– backbone on the highly hydrophobic pristine CNFs. Ionomer adsorption behavior is gradually altered from apolar to polar group adsorption for the acid-modified CNFs of decreasing hydrophobicity. This is indicated by the initial decrease and then increase in the value of <i>K</i>_eqwith the increasing strength of the acid treatment. The corresponding carbon–ionomer composite also showed varying thermal stability depending on Nafion orientation. The specific maximum surface coverage (Γ_Smax) of the CNFs is 1 order of magnitude higher than that of Vulcan. The large discrepancy is due to the fact that the ionomers are inaccessible to the internal surface area of Vulcan with high microporosity

High-Throughput Synthesis of Lignin Particles (∼30 nm to ∼2 μm) via Aerosol Flow Reactor: Size Fractionation and Utilization in Pickering Emulsions

An aerosol flow reactor was used for the first time for high-throughput, high yield synthesis of spherical lignin particles with given inherent hydrophilicity, depending on the precursor biomolecule. In situ fractionation via Berner type impactor afforded populations with characteristic sizes ranging from ∼30 nm to 2 μm. The as-produced, dry lignin particles displayed excellent mechanical integrity, even after redispersion under high shear in either mineral oil or water. They were effective in the stabilization of oil-in-water (O/W) Pickering emulsions with tunable droplet size, depending on the dimension of the lignin particles used for emulsification. The emulsion stability correlated with particle concentration as well as the respective lignin type. For the O/W emulsions stabilized with the more hydrophilic lignin particles, negligible changes in phase separation via Ostwald ripening and coalescence were observed over a period of time of more than two months. Together with the fact that the lignin particle concentrations used in emulsification were as low as 0.1%, our results reveal a remarkable ability to endow emulsified systems with high colloidal stability. Overall, we offer a new, high-yield, scalable nanomanufacturing approach to producing dry spherical lignin particles with size control and high production capacity. A number of emerging applications for these organic particles can be envisioned and, as a proof-of-concept, we illustrate here surfactant-free emulsification

Formulation and Composition Effects in Phase Transitions of Emulsions Costabilized by Cellulose Nanofibrils and an Ionic Surfactant

Cellulose nanofibrils (CNF) offer great prospects as a natural stabilizer of colloidal dispersions and complex fluids for application in food, pharma, and cosmetics. In this study, an ionic surfactant (sodium dodecyl sulfate, SDS) was used as emulsifier of oil-in-water and water-in-oil emulsions that were further costabilized by addition of CNF. The adsorption properties of SDS in both, CNF dispersions and emulsions, as well as the influence of composition (CNF and SDS concentration) and formulation (ionic strength, oil, and CNF types) on the phase behavior were elucidated and described in the framework of Windsor systems. At low salinity, the phase transition of emulsions containing CNF and SDS at low concentrations was controlled by molecular transfer in the oil-in-water system. Irregular droplets and “bi-continuous” morphologies were observed at medium and high salinity for systems containing high CNF and SDS concentrations. Water-in-oil emulsions were only possible at high salinity and SDS concentrations in the presence of small amounts of CNF. The results revealed some subtle differences in CNF interfacial activity, depending on the method used for their isolation via fiber deconstruction, either from microfluidization or aqueous counter collision. Overall, we propose that the control of emulsion morphology and stability by addition of CNF opens the possibility of developing environmentally friendly complex systems that display high stability and respond to ionic strength following the expectations of classical emulsion systems