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The usage of low-cost, readily available, or even disposable, single-use membranes in macromolecules' purification and separation is still in the development phase. In this research, highly porous (>95 %), water- and compression stable cation-exchange membranes were prepared by freeze-casting using cellulose nanofibrils (CNF) and citric acid (CA) acting as a crosslinker and source of weak anionic (carboxylic) surface groups arising from the mono-esterified CA. The membranes were characterized by different analytical techniques, and evaluated for the ionic adsorption efficacy of different proteins in dead-end filtration mode using a Tri-buffer of pH 8. The membrane's internal microstructure (porosity and density) with the available (quantity and access) carboxylic groups was confirmed, to determine not only the proteins' specific (related to the net charged and molecular weight) adsorption dynamic (>52 % of positive Lysozyme/Cytochrome, <8 % of negative BSA/Myoglobin; ≤0.5 g/L) at extremely high flow rates (>3.000 hL/h*MPa*m 2 ), but also their desorption (>97 %) and re-equilibration (using NaCl) with flux recovery (>80 %). Such efficiency was achieved with up to 5 consecutive filtering cycles. The high permeability (>87 %) of the spherical and negatively surface charged microparticles (used as models) also suggests the likelihood of removing larger microbial species, which, while retaining relatively smaller and positively charged proteins, further increases their potential in biopharma applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Background: Cellulose nanofibrils (CNF) are attractive nanomaterials for various biomedical applications due to their excellent biocompatibility and biomimetic properties. However, their immunoregulatory properties are insufficiently investigated, especially in relation to their functionalization, which could cause problems during their clinical application., Methods: Using a model of human dendritic cells (DC), which have a central role in the regulation of immune response, we investigated how differentially functionalized CNF, ie, native (n) CNF, 2,2,6,6-tetramethylpiperidine 1-oxyl radical-oxidized (c) CNF, and 3-aminopropylphosphoric acid-functionalized (APAc) CNF, affect DC properties, their viability, morphology, differentiation and maturation potential, and the capacity to regulate T cell-mediated immune response., Results: Nontoxic doses of APAcCNF displayed the strongest inhibitory effects on DC differentiation, maturation, and T helper (Th) 1 and Th17 polarization capacity, followed by cCNF and nCNF, respectively. These results correlated with a specific pattern of regulatory cytokines production by APAcCNF-DC and their increased capacity to induce suppressive CD8 + CD25 + IL-10 + regulatory T cells in immunoglobulin-like transcript (ILT)-3- and ILT-4- dependent manner. In contrast, nCNF-DC induced predominantly suppressive CD4 + CD25 hi FoxP3 hi regulatory T cells in indolamine 2,3-dioxygenase-1-dependent manner. Different tolerogenic properties of CNF correlated with their size and APA functionalization, as well as with different expression of CD209 and actin bundles at the place of contact with CNF., Conclusion: The capacity to induce different types of DC-mediated tolerogenic immune responses by functionalized CNF opens new perspectives for their application as well-tolerated nanomaterials in tissue engineering and novel platforms for the therapy of inflammatory T cell-mediated pathologies., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

Cellulose-nanofibrils (CNFs) enriched gelatine (GEL) scaffolds were fabricated in-situ by the combined freeze-thawing process and carbodiimide crosslinking chemistry. The original- and variously surface anionised CNFs (carboxylated/CNF-COOH/, and phosphonated with 3-AminoPropylphosphoric Acid/CNF-COOH-ApA/) were used in order to tune the scaffolds' biomimetic structure towards a more intensive mineralization process. The pore size reduction (from 208±35μm to 91±35μm) after 50% v/v of CNFs addition to GEL was identified, while separated pore-walls' alignment vs. shorter, dense and elongated pores are observed when using 80% v/v of original-CNFs vs. anionised-CNFs, all of them possessed osteoid-like compressive strength (0.025-0.40MPa) and elasticity (0.04-0.15MPa). While randomly distributed Ca 2+ -deficient hydroxyapatite/HAp/(Ca/P≈1.4) aggregates were identified in the case of original-CNF prevalent scaffolds after four weeks of incubation in SBF, the more uniform and intensified deposition with HAp-like (Ca/P≈1.69) structures were established using CNF-COOH-Apa. The growth of Mesenchymal Stem Cells (MSCs) was observed on all CNF-containing scaffolds, resulting in more extensive Ca 2+ deposition compared to the positive control or pure GEL scaffold. Among them, the scaffold prepared with the 50% v/v CNF-COOH-ApA showed significantly increased mineralization kinetic as well as the capacity for bone-like patterning in bone tissue regeneration., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Cellulose nanofibrills (CNFs) are attractive biocompatible, natural nanomaterials for wide biomedical applications. However, the immunological mechanisms of CNFs have been poorly investigated. Considering that dendritic cells (DCs) are the key immune regulatory cells in response to nanomaterials, our aim was to investigate the immunological mechanisms of CNFs in a model of DC-mediated immune response. We found that non-toxic concentrations of CNFs impaired the differentiation, and subsequent maturation of human monocyte-derived (mo)-DCs. In a co-culture with CD4(+)T cells, CNF-treated mo-DCs possessed a weaker allostimulatory and T helper (Th)1 and Th17 polarizing capacity, but a stronger capacity to induce Th2 cells and CD4(+)CD25(hi)FoxP3(hi) regulatory T cells. This correlated with an increased immunoglobulin-like transcript-4 and indolamine dioxygenase-1 expression by CNF-treated mo-DCs, following the partial internalization of CNFs and the accumulation of CD209 and actin bundles at the place of contacts with CNFs. Cumulatively, we showed that CNFs are able to induce an active immune tolerance by inducing tolerogenic DCs, which could be beneficial for the application of CNFs in wound healing and chronic inflammation therapies.

The potential of nanoscaled cellulose and enzymatically phosphorylated derivatives as bio-adsorbents to remove metal ions (Ag(+), Cu(2+) and Fe(3+)) from model water and industrial effluents is demonstrated. Introduction of phosphate groups onto nanocelluloses significantly improved the metal sorption velocity and sorption capacity. The removal efficiency was considered to be driven by the high surface area of these nanomaterials as well as the nature and density of functional groups on the nanocellulose surface. Generally, in the solutions containing only single types of metal ions, the metal ion selectivity was in the order Ag(+)>Cu(2+)>Fe(3+), while in the case of mixtures of ions, the order changed to Ag(+)>Fe(3+)>Cu(2+), irrespective of the surface functionality of the nanocellulose. In the case of industrial effluent from the mirror making industry, 99% removal of Cu(2+) and Fe(3+) by phosphorylated nanocellulose was observed. The study showed that phosphorylated nanocelluloses are highly efficient biomaterials for scavenging multiple metal ions, simultaneously, from industrial effluents., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The acetylation efficiency of nanofibrillated cellulose (NFC) with acetic anhydride as acetyl donor was studied using lipase from Aspergillus niger in a mixture of dimethyl sulphoxide (DMSO) and phosphate buffer solution at ambient conditions and in supercritical carbon dioxide (scCO2). The chemical acetylation of NFC with comparable ester content was carried out for comparison. The ATR-FTIR, solid-state CP/MAS (13)C NMR and DSC analyses revealed that, besides the enzyme-catalysed acetylation, predominantly appearing at the C-6 position of cellulose hydroxyls, a strong and stable acyl-enzyme intermediate attachment also occurred on the NFC via Maillard reaction. Enzymatic acetylation via attached acyl-enzyme complex on NFC yielded high hydophobicity (contact angle of 84±9°), whereas the chemical acetylation with comparable ester content resulted in a much lower hydrophobic surface with a contact angle of 33±3°. Finally, the adsorption capacity profiles of lysozyme and BSA proteins on native, chemically and enzymatically acetylated NFC as a function of the pH medium were determined., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The chemo-enzymatic modification of cellulose nanofibers (CNFs) using laccase as biocatalysts and TEMPO or 4-Amino-TEMPO as mediators under mild aqueous conditions (pH 5, 30 °C) has been investigated to introduce surface active aldehyde groups. 4-Amino TEMPO turned out to be kinetically 0.5-times (50%) more active mediator, resulting to oxoammonium cation intermediacy generated and its in situ regeneration during the modification of CNFs. Accordingly, beside of around 750 mmol/kg terminally-located aldehydes, originated during CNFs isolation, the reaction resulted to about 140% increase of C6-located aldehydes at optimal conditions, without reducing CNFs crystallinity. While only the C6-aldehydes were wholly transformed into the carboxyls after additional post-treatment using NaOH according to the Cannizzaro reaction, the post-oxidation with air-oxygen in EtOH/water medium or NaClO2 resulted to no- or very small amounts of carboxyls created, respectively, at a simultaneous loss of all C6- and some terminal-aldehydes in the latter due to the formation of highly-resistant hemiacetal covalent linkages with available cellulose hydroxyls. The results indicated a new way of preparing and stabilizing highly reactive C6-aldehydes on cellulose, and their exploitation in the development of new nanocellulose-based materials., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Graphical abstract Abstract The antimicrobial polypeptide ε-poly(l -lysine) (ε-PL) was electrostatically incorporated to poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) electrospun nanofibers. ε-PL loading and distribution was assessed by infrared spectra, ζ-potential measurements and the primary amino reactive dye fluorescamine. Functionalized fibers with 485 ± 140 nm diameter, could be loaded with 0.57–0.74 g ε-PL (g dressing)−1 that released at a constant rate of 5.4 ± 2.8 mg ε-PL (g dressing day)−1. Such a dressings resulted in two orders of magnitude lower bacterial colonization than non-functionalized PAA-PVA after 14 days of incubation. Bacterial impairment was attributed to the damage of cell membranes and the formation of intracellular reactive oxygen species. ε-PL functionalized nanofibers did not display cytotoxicity to human corneal epithelial cells, HCEpC, in 24 h MTT assays. However, the viability of rapidly growing tumoral HeLa cells decreased >50% under the same conditions. The prepared biocompatible nanofibrous dressings with durable antibacterial activity show potential application as wound dressings and other biomedical uses. [ABSTRACT FROM AUTHOR]

Phenol removal from aqueous medium was studied by the batch method using novel and fully biobased solvent-cast films prepared from cellulose nanofibrils (CNFs) and in situ synthesised hydroxyapatite (HAp) by the wet-chemical precipitation method and different concentrations of HAp precursors and weight mass of CNFs. The chemical and morphological structures of as-prepared films were investigated by X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy, while their physical properties were determined by water contact angle and swelling kinetic measurements. The HAp precursor leads to a surface modification of CNFs, which increases its activity by forming differently structured, sized and distributed HAp particles, influencing the phenol adsorption kinetic and capacity. The phenol adsorption was faster and higher (~64 mg g) in an acidic solution (pH 2) compared to the original phenol solution pH (pH 7.4, ~30 mg g) using films with unevenly-distributed and positively-charged calcium-richer HAp particles synthesised on the CNFs' surface, being reflected also in its higher water swelling properties, compared to their hybrid counterparts. The phenol adsorption is identified to follow pseudo-second order kinetic and intra-particle diffusion models. A highly-efficient reusing ability of the selected film with 86% adsorption capacity of the initial value at the third sequential regeneration cycle, is also confirmed. A super-hydrophilic nature of the films with high water-diffusing and transport properties, as well as low swelling, indicates their potential in the development of highly-effective adsorbents and, potentially, filter membranes for water purification. [ABSTRACT FROM AUTHOR]

Cellulose nanofibrils (CNFs), unique and promising natural materials have gained significant attention recently for biomedical applications, due to their special biomechanical characteristics, surface chemistry, good biocompatibility and low toxicity. However, their long bio-persistence in the organism may provoke immune reactions and this aspect of CNFs has not been studied to date. Therefore, the aim of this work was to examine and compare the cytocompatibility and immunomodulatory properties of CNFs in vitro. CNFs (diameters of 10-70 nm; lengths of a few microns) were prepared from Norway spruce ( Picea abies) by mechanical fibrillation and high pressure homogenisation. L929 cells, rat thymocytes or human peripheral blood mononuclear cells (PBMNCs) were cultivated with CNFs. None of the six concentrations of CNFs (31.25 µg/ml-1 mg/ml) induced cytotoxicity and oxidative stress in the L929 cells, nor induced necrosis and apoptosis of thymocytes and PBMNCs. Higher concentrations (250 µg/ml-1 mg/ml) slightly inhibited the metabolic activities of the L929 cells as a consequence of inhibited proliferation. The same concentrations of CNFs suppressed the proliferation of PBMNCs to phytohemaglutinine, a T-cell mitogen, and the process was followed by down-regulation of interleukin-2 (IL-2) and interferon-γ production. The highest concentration of CNFs inhibited IL-17A, but increased IL-10 and IL-6 production. The secretion of pro-inflammatory cytokines, IL-1β and tumor necrosis factor-α as well as Th2 cytokine (IL-4), remained unaltered. In conclusion, the results suggest that these CNFs are cytocompatible nanomaterial, according to current ISO criteria, with non-inflammatory and non-immunogenic properties. Higher concentrations seem to be tolerogenic to the immune system, a characteristic very desirable for implantable biomaterials. [ABSTRACT FROM AUTHOR]

This study confirms the enzyme-mediated phosphorylation of cellulose nanofibers (CNF) by using hexokinase and adenosine-5′-triphosphate in the presence of Mg-ions, resulting in a phosphate group's creation predominantly at C-6-O positioned hydroxyl groups of cellulose monomer rings. A proof-of-concept is provided using C CPMAS, P MAS nuclear magnetic resonance, attenuated total reflectance-Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) analyzing methods. The degree of substitution (DS) is determined by elemental analysis and compared to DS estimated by XPS analysis. From the thermal degradation measurements using thermo-gravimetric analysis, the C-6-O phosphorylation was found to noticeably prevent the CNF derivatives from weight loss in the pyrolysis process, thus, providing them flame-resistance functionality. Furthermore, phosphorylation significantly enhanced adsorption capacity of Fe ions making them interesting for fabrication of biobased filters and membranes. Finally, the biomimetic growth of Ca-P crystals (hydroxyapatite) in simulated body fluid was characterized by scanning electron microscopy and energy dispersive X-ray, showing potential application as biomedical materials. [ABSTRACT FROM AUTHOR]