Cation-exchange performance of a citric-acid esterified cellulose nanofibrous membrane for highly-selective proteins' permeability and adsorption capacity.

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*m2), 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.

Antibacterial and degradation properties of dialdehyded and aminohexamethylated nanocelluloses.

Dialdehyde cellulose nanofibrils (CNF) and nanocrystals (CNC) were prepared via periodate oxidation (CNF/CNC-ox) and subsequently functionalized with hexamethylenediamine (HMDA) via a Schiff-base reaction, resulting in partially crosslinked micro-sized (0.5-10 µm) particles (CNF/CNC-ox-HMDA) with an aggregation and sedimentation tendency in an aqueous media, as assessed by Dynamic Light Scattering and Scanning Electron Microscopy. The antibacterial efficacy, aquatic in vivo (to Daphnia magna) and human in vitro (to A594 lung cells) toxicities, and degradation profiles in composting soil of all forms of CNF/CNC were assessed to define their safety profile. CNF/CNC-ox-HMDA exhibited higher antibacterial activity than CNF/CNC-ox and higher against Gram-positive S. aureus than Gram-negative E. coli, yielding a bacteria reduction of >90 % after 24 h of exposure at the minimum (≤2 mg/mL), but potentially moderately/aquatic and low/human toxic concentrations (≥50 mg/L). The presence of anionic, un/protonated amino-hydrophobized groups in addition to unconjugated aldehydes of hydrodynamically smaller (<1 µm) CNC-ox-HMDA increased the reduction of both bacteria to log 9 at ≥4 mg/mL and their bactericidal activity. While only CNF/CNC-ox can be considered as biosafe and up to >80 % biodegradable within 24 weeks, this process was inhibited for the CNF/CNC-ox-HMDA. This indicated their different stability, application and disposal after use (composting vs. recycling).

Cationised Fibre-Based Cellulose Multi-Layer Membranes for Sterile and High-Flow Bacteria Retention and Inactivation.

Low-cost, readily available, or even disposable membranes in water purification or downstream biopharma processes are becoming attractive alternatives to expensive polymeric columns or filters. In this article, the potential of microfiltration membranes prepared from differently orientated viscose fibre slivers, infused with ultrafine quaternised (qCNF) and amino-hydrophobised (aCNF) cellulose nanofibrils, were investigated for capturing and deactivating the bacteria from water during vacuum filtration. The morphology and capturing mechanism of the single- and multi-layer structured membranes were evaluated using microscopic imaging and colloidal particles. They were assessed for antibacterial efficacy and the retention of selected bacterial species (Escherichia coli, Staphylococcus aureus, Micrococcus luteus), differing in the cell envelope structure, hydrodynamic biovolume (shape and size) and their clustering. The aCNF increased biocidal efficacy significantly when compared to qCNF-integrated membrane, although the latter retained bacteria equally effectively by a thicker multi-layer structured membrane. The retention of bacterial cells occurred through electrostatic and hydrophobic interactions, as well as via interfibrous pore diffusion, depending on their physicochemical properties. For all bacterial strains, the highest retention (up to 100% or log 6 reduction) at >50 L/h∗bar∗m2 flow rate was achieved with a 4-layer gradient-structured membrane containing different aCNF content, thereby matching the performance of industrial polymeric filters used for removing bacteria.

Biocompatible antimicrobial electrospun nanofibers functionalized with ε-poly-l-lysine.

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 ±â€¯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 ±â€¯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.

Enhanced catalytic activity of the surface modified TiO2-MWCNT nanocomposites under visible light.

Fusing multiwall carbon nanotubes (MWCNTs) with TiO2 at the nano-scale level promotes the separation of those electron-hole charges generated upon UV and daylight irradiation. In this study, we investigated facile sonochemical synthesis, combined with the calcination process for the preparations of TiO2-MWCNT composites with different mole ratios of titanium and carbon. In order to produce stable nano dispersions we exploited an innovative biotechnology-based approach for the covalent functionalizations of TiO2-MWCNTs with in-situ synthesized soluble phenoxazine dye molecules. The none and functionalized TiO2-MWCNTs composites were analyzed by a range of analytical techniques including XRD, Raman, XPS, SEM and UV-vis diffuse reflectance spectroscopy (DRS), and dynamic light scattering (DLS). The photocatalytic activity was evaluated toward the liquid-phase degradation of MB in aqueous solution under both UV and visible light irradiation. TiO2-MWCNTs with optimized mole ratio exhibit much higher photocatalytic activity and stability than bare TiO2. The as-prepared TiO2-MWCNTs photocatalyst possessed good adsorptivity of dyes, extended light absorption range and efficient charge separation properties simultaneously. The results indicated that the soluble phenoxazine dyes and amino-benzenesulfonic acid monomers were covalently grafted on to the surfaces of TiO2-MCNTs, which promoted good aquatic dispersibility and extended light absorption, resulting in increased photocatalytic efficiency.

New findings about the lipase acetylation of nanofibrillated cellulose using acetic anhydride as acyl donor.

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.