Diaminated Cellulose Beads as a Sustainable Support for Industrially Relevant Lipases.

Environmentally persistent polystyrene or polyacrylic beads are used as supports in enzyme large-scale bioprocesses, including conversion glucose isomerization for high-fructose corn syrup production, hydrolysis of lactose, and synthesis of active pharmaceutical ingredients. In this paper, we report the development of a novel sustainable and scalable method to produce diaminated cellulose beads (DAB) as highly efficient alternative supports for industrially relevant lipases. Regenerated cellulose beads were grafted with diaminated aliphatic hydrocarbons via periodate oxidation and reductive amination. The oxidation step indicated that aldehyde content can be easily tuned through the reaction time and concentration of reactants. Reductive amination of dialdehyde cellulose was more efficient as the length of the diaminated hydrocarbon compound increased. Morphological analysis of DAB showed that cellulose chemical grafting enabled the preservation of the bead shape and internal structure upon freeze-drying. Enzymatic degradability studies demonstrated that chemical functionalization did not undermine enzyme cellulose hydrolysis. The addition of aminated moieties on cellulose dramatically increased absorption efficiency for all industrially relevant lipases used, reaching 100% for Thermomyces lanuginosus lipase (TLL). Storage and recyclability experiments demonstrated that enzymes were retained and recyclable for at least nine cycles, although the activity gradually declined after each cycle. Medium chain triacylglycerol hydrolysis in a SpinChem reactor using TLL immobilized on 1,6 DAB exhibited higher activity compared to acrylic beads (588 vs 459 U/g) suggesting that biodegradable cellulose-based materials could be a valid and attractive alternative to plastics carriers.

Cellulose Acetate Microbeads for Controlled Delivery of Essential Micronutrients.

The controlled delivery of micronutrients to soil and plants is essential to increase agricultural yields. However, this is today achieved using fossil fuel-derived plastic carriers, posing environmental risks and contributing to global carbon emissions. In this work, a novel and efficient way to prepare biodegradable zinc-impregnated cellulose acetate beads for use as controlled release fertilizers is presented. Cellulose acetate solutions in DMSO were dropped into aqueous antisolvent solutions of different zinc salts. The droplets underwent phase inversion, forming solid cellulose acetate beads containing zinc, as a function of zinc salt type and concentration. Even higher values of zinc uptake (up to 15.5%) were obtained when zinc acetate was added to the cellulose acetate-DMSO solution, prior to dropping in aqueous zinc salt antisolvent solutions. The release profile in water of the beads prepared using the different solvents was linked to the properties of the counter-ions via the Hofmeister series. Studies in soil showed the potential for longer release times, up to 130 days for zinc sulfate beads. These results, together with the efficient bead production method, demonstrate the potential of zinc-impregnated cellulose acetate beads to replace the plastic-based controlled delivery products used today, contributing to the reduction of carbon emissions and potential environmental impacts due to the uptake of plastic in plants and animals.

Continuous production of cellulose microbeads by rotary jet atomization.

The replacement of plastic microbeads with biodegradable alternatives is essential due to the environmental persistence of plastics and their accumulation within the human food chain. HYPOTHESIS: Cellulose microbeads could be such alternative, but their production is hindered by the high viscosity of cellulose solutions. It is expected that this viscosity can be harnessed to induce filament thinning of jets of cellulose solutions to create droplets with diameters within the micrometre range, which can then be converted to solid cellulose microbeads via phase inversion. EXPERIMENTS: A 3D printed rotating multi-nozzle system was used to generate jets of cellulose dissolved in solutions of [EMIm][OAc] and DMSO. The jets were subject to Rayleigh breakup to generate droplets which were captured in an ethanol anti-solvent bath, initiating phase-inversion, and resulting in regeneration of the cellulose into beads. FINDINGS: Control of both process (e.g. nozzle dimensions) and operational (e.g. rotational speed and pressure) parameters has allowed suppression of both satellite droplets generation and secondary droplet break-up, and tuning of the filament thinning process. This resulted in the continuous fabrication of cellulose microbeads in the size range 40-500 µm with narrow size distributions. This method can produce beads in size ranges not attainable by existing technologies.

Stable Cellulose Nanofibril Microcapsules from Pickering Emulsion Templates.

Electrostatic attractions are essential in any complex formation between the nanofibrils of the opposite charge for a specific application, such as microcapsule production. Here, we used cationized cellulose nanofibril (CCNF)-stabilized Pickering emulsions (PEs) as templates, and the electrostatic interactions were induced by adding oxidized cellulose nanofibrils (OCNFs) at the oil-water interface to form microcapsules (MCs). The oppositely charged cellulose nanofibrils enhanced the solidity of interfaces, allowing the encapsulation of Nile red (NR) in sunflower oil droplets. Microcapsules exhibited a low and controlled release of NR at room temperature. Furthermore, membrane emulsification was employed to scale up the preparation of microcapsules with sunflower oil (SFO) encapsulated by CCNF/OCNF complex networks.