Chapter 1. Hairy Cellulose Nanocrystals: Chemistry and Fundamentals

Muthami, Joy; Wamea, Patricia; Pitcher, Mica L.; Sakib, Nurus; Liu, Zeyu; Arora, Sainyam; Kennedy, David C.; Chang, Yin-Jen; Sheikhi, Amir

doi:10.1039/9781788019521-00001

Cited by 6 publications

(9 citation statements)

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“…Cellulose fibrils may undergo a two-step oxidation process to enable the preferential oxidation and partial solubilization of disordered regions, − which are more accessible than the inner crystalline layers. Treatment with (meta)periodate oxidatively cleaves the C2–C3 bond in the repeating units of cellulose chains, yielding dialdehyde-modified cellulose (DAMC).…”

Section: Introductionmentioning

confidence: 99%

Nanoengineering the Redispersibility of Cellulose Nanocrystals

2022

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Enhancing the redispersibility of dried colloidal particles to yield stable dispersions after rehydration is a persistent challenge in the sustainable processing of nanocelluloses due to hydrogen bonding-induced irreversible aggregation. Programming nanocelluloses, such as cellulose nanocrystals (CNC), with moieties that enable colloidal repulsion after rehydration may address this challenge and contribute to the United Nation (UN)'s sustainable development goals (SDGs) of urban development and sustainable living (SDGs 9 and 11) and cradle-to-cradle processing (SDG 12). We hypothesize that imparting electrosteric repulsion to CNC via polyanionic disordered cellulose chains (hairs) protruding from each end may render the dried nanocrystals highly redispersible in aqueous media. Anionic hairy CNC (AHCNC), that is, CNC decorated with dicarboxylated cellulose (DCC) chains, were synthesized by the preferential, successive periodate/chlorite oxidation of the disordered regions of cellulose fibrils, bearing >5 mmol of carboxylate groups per gram. The colloidal properties of AHCNC were compared with those of sulfate half-ester groupfunctionalized CNC and TEMPO-oxidized CNC (TOCNC) after redispersion in aqueous media, followed by comparing the redispersibility of AHCNC and CNC in aqueous solutions containing monovalent or divalent cations and at varying pH. The AHCNC had remarkable aqueous redispersibility even at high ionic strengths and extreme pH. The unique redispersibility mechanism of dried AHCNC relies on the synergistic steric and electrostatic repulsion forces, recuperated upon the rehydration of DCC. This work may open new opportunities for more sustainable and cost-effective handling and processing of nanocelluloses.

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Section: Introductionmentioning

confidence: 99%

Nanoengineering the Redispersibility of Cellulose Nanocrystals

2022

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“…We have recently engineered a bio-based adsorbent based on cellulose, the most abundant biopolymer on earth, named anionic hairy cellulose nanocrystals, i.e., cellulose nanoparticles attached to disordered dicarboxylated cellulose chains bearing a high content (∼5 mmol g –1 ) of carboxylate groups for high-concentration Nd , or drug removal. The formation of hairy cellulose nanocrystals and evidence of hair location on both ends have been discussed in the literature. − The hairs impart the anionic hairy cellulose nanocrystals with a high adsorption capacity for neodymium ions (Nd 3+ ) and partial selectivity against calcium ions (Ca 2+ ) and ferrous ions (Fe 2+ ); however, the Nd 3+ removal percentage remains exceedingly low at a low adsorbate: adsorbent ratio as a result of the colloidal stability of unsaturated nanoparticles. In fact, this is a key bottleneck in using nanoparticles for ion separation and extraction .…”

Section: Introductionmentioning

confidence: 99%

Mussel-Inspired Nanocellulose Coating for Selective Neodymium Recovery

Yeh,

Alexander,

Narasimhalu

et al. 2023

ACS Appl. Mater. Interfaces

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Neodymium (Nd) is one of the most in-demand rare earth elements (REEs) for developing the next generation of magnetic medical devices and clean energy. Eco-friendly and sustainable nanotechnology for REE recovery may be highly suitable to address the limited global supply while minimizing the environmental footprints of current practice, such as solvent extraction. Here, we present a novel one-step mussel-inspired nanocellulose coating (MINC) using bifunctional hairy cellulose nanocrystals (BHCNC), bearing dialdehyde and dicarboxylate groups. The dialdehyde groups enable dopamine-mediated orthogonal conjugation of BHCNC to substrates, such as microparticles, while the high content of dicarboxylate groups yields high-capacity and selective Nd removal against ferric, calcium, and sodium ions. To the best of our knowledge, the MINC-treated substrate provides the most rapid selective removal and recovery of Nd ions even at low Nd concentrations with a capacity that is among the highest reported values. We envision that the MINC will provide new opportunities in developing next-generation bio-based materials and interfaces for the sustainable recovery of REEs and other precious elements.

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“…PVA was a reference for the mobile OH groups bound to flexible polymer chains. In addition, an aqueous dispersion containing hairy-CNCs (which have amorphous chains at both ends of CNCs; hereafter, called HCNCs) (van de Ven and Sheikhi 2016; Sheikhi and van de Ven 2017; Muthami, Wamea et al 2021) was studied and compared. Finally, molecular dynamics (MD) simulations were conducted to calculate the relaxation dynamics of water molecules in contact with the immobile OH groups exposed at the hydrophilic (110) surface of cellulose Iβ.…”

Section: Introductionmentioning

confidence: 99%

Relaxation dynamics of water in the vicinity of cellulose nanocrystals

Chae

Paniagua-Guerra

Pitcher

et al. 2023

Preprint

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Water molecules near cellulose nanocrystals (CNCs; produced via sulfuric acid-catalyzed hydrolysis) are believed to relax slower than those in the bulk liquid, which may result in unique properties of CNC aqueous dispersions. This study analyzed the polarization behavior of water molecules in CNC aqueous dispersions and other reference samples using a dielectric relaxation spectroscopy (DRS) technique in the microwave frequency range (200 MHz – 20 GHz). As the CNC concentration increases, two slow relaxation components become prominent. The comparison with DRS data of aqueous dispersions of nanoporous silica, polyvinyl alcohol (PVA), and hairy CNCs with amorphous chains in both ends suggested that these slow relaxation modes of water near CNC surfaces cannot be attributed to direct hydrogen bonding interactions with the hydroxyl (OH) groups exposed and immobilized at the solid surface. Instead, they are rather similar to the water molecules interacting with OH groups attached to flexible polymer chains. Molecular dynamics (MD) simulations of the polarization behavior of water near the (110) facet of cellulose Ib crystals confirmed that the interactions of water molecules with the cellulose crystal surface do not cause slower relaxations in the frequency range studied via the DRS. These results indicated that the CNC surface cannot be depicted with the crystallographic facets of cellulose Iβ; instead, it resembles a polymer-brush surface on which the short glucan residues or fragments of the strong acid-catalyzed hydrolysis process are swollen and extended into the aqueous phase.

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Chapter 1. Hairy Cellulose Nanocrystals: Chemistry and Fundamentals

Cited by 6 publications

References 0 publications

Nanoengineering the Redispersibility of Cellulose Nanocrystals

Nanoengineering the Redispersibility of Cellulose Nanocrystals

Mussel-Inspired Nanocellulose Coating for Selective Neodymium Recovery

Relaxation dynamics of water in the vicinity of cellulose nanocrystals

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