Nanocellulose for gel electrophoresis.

HYPOTHESIS: Cellulose nanofibres produced by TEMPO-mediated oxidation can form gels. This study presents a proof-of-concept for gel electrophoresis with nanocellulose (NC). EXPERIMENTS: TEMPO-oxidised cellulose nanofibre dispersion is chemically cross-linked by inducing amide linkages to produce gel slabs for electrophoretic separation. Nanocellulose gel slabs 1 cm thick containing Tris/Borate/EDTA (TBE) buffer were casted. Different cross-linker types and ratios are investigated to assess the migration of conventional electrophoresis tracking dyes. FINDINGS: Tracking dyes (bromophenol blue and orange G) can diffuse within the gel at different rates and therefore separate. Changing the cross-linker length from EDA to HMDA (C2- to C6-chain) increases the overall network pore size resulting in a faster migration rate for both bromophenol blue and orange G. Increasing the cross-linker concentration stabilises the HMDA-NC gel (no extension) during the electrophoresis run without any effect on the dye migration rate. Increasing the voltage increases the migration rates for both orange G and bromophenol blue. Further development is required to cast the gels evenly and to prevent bubble formation during the cross-linking process. This will enable to effectively separate mixtures of proteins. Nanocellulose gels can become a novel substrate for sustainable biomedical separation and diagnostics by electrophoresis.

Nanocellulose Hydrogel for Blood Typing Tests.

The gel test is the most prevalent method for the forward and reverse blood typing tests. It relies on the controlled centrifugation of red blood cells (RBCs) and antibodies through a gel column. This noncontinuous matrix is currently based on microbeads that often lack sensitivity. For the first time, nanocellulose hydrogel is demonstrated as a sustainable and reliable medium for gel-based blood typing diagnostics. Gels with a minimum of 0.3 wt % TEMPO-oxidized cellulose nanofibers (0.92 mmol/g of carboxyl content) separate agglutinated and individual RBCs in the forward test. The addition of glycine is able to balance the osmotic pressure and reduce hemolysis to 5%, while retaining the electrostatic repulsion responsible for the gel network structure and its rheological properties. For the reverse typing, cellulose nanofibers are chemically cross-linked with hexamethylenediamine (HMDA), increasing the gel yield point 8-fold. Sodium chloride is added to achieve the osmolality found in the human plasma and limit cell lysis to 15%, without affecting the gel colloidal stability. Nanocellulose hydrogel constitutes a performant, low cost, and green soft material, providing clear and well-defined results for both blood grouping tests.

Carboxylated nanocellulose foams as superabsorbents.

HYPOTHESIS: Carboxylated nanocellulose fibres formed into foam structures can demonstrate superabsorption capacity. Their performance can be engineered by changing process variables. EXPERIMENTS: TEMPO-oxidised cellulose nanofibres of varying concentration and surface charge are produced from hardwood kraft pulp. Foams were prepared through a 2-step freezing and lyophilisation process. The absorption capacity of water and saline solution (0.9 wt%) were measured as a function of time and related to the foam structure. FINDINGS: The absorption capacity of nanocellulose foams can be manipulated from initial gel properties and processing conditions. Pore structure and distribution of nanocellulose foams are dictated by fibre content and charge density and freezing rate. The best performing foams are at 0.3-0.5 wt%, with a carboxylate concentration of 1.2 mmol/g and frozen at -86 °C before freeze-drying, which can absorb 120 g H2O/g fibre. Fibre surface charge influences the absorption capacity of the foams by dictating the amount of participating carboxylate groups. Absorption capacity in saline (60 g/g) is lower than in deionised water (120 g/g); but is only slightly lower than that of a commercial polyacrylic acid (PAA) SAPs (80 g/g). Nanocellulose foams are attractive renewable alternatives for superabsorbent applications, contributing to a reduction of plastic microspheres.

Pickering Emulsions Electrostatically Stabilized by Cellulose Nanocrystals.

Cellulose Nanocrystals (CNC) are explored to stabilize oil/water emulsions for their ability to adsorb at the oil/water interface. In this work, the role of electrostatic forces in the CNC ability to stabilize oil/water emulsions is explored using canola oil/water and hexadecane/water as model systems. Canola oil/water and Hexadecane/ water (20/80, v/v) emulsions were stabilized with the addition of CNCs using ultrasonication. Emulsion droplet sizes range from 1 to 4 µm as measured by optical microscopy. It is found that CNC can stabilize oil/water emulsions regardless of their charge density. However, reducing the surface charge density, by adding salts and varying pH, can reduce the amount of CNC's required to form a stable emulsion. Just by adding 3 mM Na+ or 1 mM or less Ca+2 to a CNC suspension, the amount of CNC reduced by 30% to stabilized 2 mL of Canola oil. On the other hand, adding salt increases the emulsion volume. The addition of 100 mM Na+ or the reduction of pH below 2 leads to the aggregation of CNC; emulsions formed under these conditions showed gel-like behavior. This work shows the potential of nanocellulose crystal in stabilizing food and industrial emulsions. This is of interest for applications where biodegradability, biocompatibility, and food grade requirements are needed.

Effects of fibre dimension and charge density on nanocellulose gels.

HYPOTHESIS: Carboxylated cellulose nanofibres can produce gels at low concentrations. The effect of pulp source on the nanocellulose fibre dimension and gel rheology are studied. It is hypothesised that fibre length and surface charge influence aspects of the gel rheological properties. EXPERIMENTS: TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl)- mediated oxidised cellulose nanofibres from never-dried hardwood and softwood pulp and containing different charge levels were produced and characterized. Steady-state and dynamic rheological studies were performed to ascertain the effects of pulp type on gel behavior and properties. FINDINGS: Nanocellulose fibres extracted from softwood (SW-TOCN) and hardwood (HW-TOCN) pulp exhibit similar widths but different length dimensions as shown via AFM analysis. Rheological measurements show that the dynamic moduli (G' and G'') of nanocellulose gels are independent of pulp source and are mostly influenced by fibre concentration. Differences in the steady-state behavior (i.e. viscosity) at constant surface charge can be attributed to differences in fibre length. Increasing the surface charge density influences the critical strain and the viscosity at the percolation concentration (0.1 wt%) due to higher electrostatic interactions.

Gelation mechanism of cellulose nanofibre gels: A colloids and interfacial perspective.

HYPOTHESIS: Nanocellulose gels form a new category of sustainable soft materials of industrial interest for a wide range of applications. There is a need to map the rheological properties and understand the mechanism which provides the colloidal stability and gelation of these nanofibre suspensions. EXPERIMENTS: TEMPO (2,2,6,6,-tetramethylpiperidine-1-oxyl)-oxidised cellulose nanofibre gels were investigated at different fibre concentrations, pH and ionic strength. Dynamic and cyclic rheological studies was performed to quantify gel behaviour and properties. Gels were produced at different pH and salt contents to map and understand colloidal stability of the nanocellulose gel. FINDINGS: Rheology indicates gelation asa transitionary state starting at a fibre concentration of 0.1wt.%. The colloidal stability of the nanocellulose gel network is controlled by pH and salt, whereas fibre concentration mainly dictates the dynamic rheological properties. Decreasing pH and adding salt destabilises the gel network by eluting bound water which is correlated with the decrease in electrostatic repulsion between fibres. The gelation and colloidal stability of these nanocellulose gels is driven by electrostatic forces and the entanglement ability of the fibrous system to overlap.