Modulating the isotopic hydrogen-deuterium exchange in functionalized nanocellulose to optimize SANS contrast.

Contrast matching by isotopic exchange in cellulose allows visualizing functional groups, biomolecules, polymers and nanoparticles embedded in cellulosic composites. This isotopic exchange varies the scattering length density of cellulose to match its contrast with the background network. Here, contrast matching of microcrystalline-cellulose (MCC) and the functionalized nanocellulose-fiber (CNF) and cellulose nanocrystals (CNC) are elucidated by small angle neutron scattering (SANS). Results show no isotopic exchange occurs for the CNF surface functionalized with carboxyl nor for the CNC-High with a high sulfate groups concentration. Both CNC-Low, with low sulfate groups, and MCC exchange 1H with 1D in D2O. This is due to the high exchange probability of the labile C6 position primary -OH group. The structure of thermo-responsive poly-N-isopropylacrylamide (PNIPAM) chains grafted onto CNF (PNIPAM-grafted-CNF) was extracted by CNF contrast matching near the lower critical solution temperature. Contrast matching eradicates the CNF scattering to retain only the scattering from the grafted-PNIPAM chains. The coil to globule thermo-transition of PNIPAM was revealed by the power law variation from q-1.3 to q-4 in SANS. Isotopic exchange in functionalized cellulosic materials reveals the nano- and micro-scale structure of its individual components. This improved visualization by contrast matching can be extended to carbohydrate polymers to engineer biopharmaceutical and food applications.

Vapor deposition strategy for implanting isolated Fe sites into papermaking nanofibers-derived N-doped carbon aerogels for liquid Electrolyte-/All-Solid-State Zn-Air batteries.

Single-atom catalysts (SACs), with precisely controlled metal atom distribution and adjustable coordination architecture, have gained intensive concerns as efficient oxygen reduction reaction (ORR) electrocatalysts in Zn-air batteries (ZAB). The attainment of a monodispersed state for metallic atoms anchored on the carbonaceous substrate remains the foremost research priority; however, the persistent challenges lie in the relatively weak metal-support interactions and the instability of captured single atom active sites. Furthermore, in order to achieve rapid transport of O2 and other reactive substances within the carbon matrix, manufacturing SACs based on multi-stage porous carbon substrates is highly anticipated. Here, we propose a methodology for the fabrication of carbon aerogels (CA)-supported SACs utilizing papermaking nanofibers, which incorporates advanced strategies for N-atom self-doping, defect/vacancy introduction, and single-atom interface engineering. Specifically, taking advantages of using green and energy-efficient feedstocks, combining with a direct pore-forming template volatilization and chemical vapor deposition approach, we successfully developed N-doped carbon aerogels immobilized with separated iron sites (Fe-SAC@N/CA-Cd). The obtained Fe-SAC@N/CA-Cd exhibited substantially large specific surface area (SBET = 1173 m2/g) and a multi-level pore structure, which can effectively mitigate the random aggregation of Fe atoms during pyrolysis. As a result, it demonstrated appreciable activity and stability in catalyzing the ORR progress (E1/2 = 0.88 V, Eonset = 0.96 V). Furthermore, the assembled liquid electrolyte-state Zn-air batteries (LES-ZAB) and all-solid-state Zn-air battery (ASS-ZAB) also provides encouraging performance, with a peak power density of 169 mW cm-2 for LES-ZAB and a maximum power density of 124 mW cm-2 for ASS-ZAB.

Improved anti-biofilm activity and long-lasting effects of novel serratiopeptidase immobilized on cellulose nanofibers.

Today, enzymatic treatment is a progressive field in combating biofilm producing pathogens. In this regard, serratiopeptidase, a medicinally important metalloprotease, has been recently highlighted as an enzyme with proved anti-biofilm activity. In the present study, in order to increase the long-lasting effects of the enzyme, serratiopeptidase and the novel engineered forms with enhanced anti-biofilm activity were immobilized on the surface of cellulose nanofibers (CNFs) as a natural polymer with eminent properties. For this, recombinant serratiopeptidases including the native and previously designed enzymes were produced, purified and conjugated to the CNF by chemical and physical methods. Immobilization was confirmed using different scanning and microscopic methods. The enzyme activity was assessed using casein hydrolysis test. Enzyme release analysis was performed using dialysis tube method. Anti-biofilm activity of free and immobilized enzymes has been examined on Staphylococcus aureus and Pseudomonas aeruginosa strains. Finally, cytotoxicity of enzyme-conjugated CNFs was performed by MTT assay. The casein hydrolysis results confirmed fixation of all recombinant enzymes on CNFs by chemical method; however, inadequate fixation of these enzymes was found using cold atmospheric plasma (CAP). The AFM, FTIR, and SEM analysis confirmed appropriate conjugation of enzymes on the surface of CNFs. Immobilization of enzymes on CNFs improved the anti-biofilm activity of serratiopeptidase enzymes. Interestingly, the novel engineered serratiopeptidase (T344 [8-339ss]) exhibited the highest anti-biofilm activity in both conjugated and non-conjugated forms. In conclusion, incorporation of serratiopeptidases into CNFs improves their anti-biofilm activities without baring any cytotoxicity. KEY POINTS: • Enzymes were successfully immobilized on cellulose nanofibers using chemical method. • Immobilization of enzymes on CNFs improved their anti-biofilm activity. • T344 [8-339ss] exhibited the highest anti-biofilm activity in both conjugated and non-conjugated forms.

Effect of temperature on the conformation and functionality of poly(N-isopropylacrylamide) (PNIPAM)-grafted nanocellulose hydrogels.

HYPOTHESIS: Poly(N-isopropylacrylamide) [PNIPAM]-grafted cellulose nanofibers (CNFs) are new thermo-responsive hydrogels which can be used for a wide range of applications. Currently, there is no clear understanding of the precise mechanism by which CNFs and PNIPAM interact together. Here, we hypothesize that the physical crosslinking of grafted PNIPAM on CNF inhibits the free movement of individual CNF, which increases the gel strength while sustaining its thermo-responsive properties. EXPERIMENTS: The thermo-responsive behaviour of PNIPAM-grafted CNFs (PNIPAM-g-CNFs), synthesized via silver-catalyzed decarboxylative radical polymerization, and PNIPAM-blended CNFs (PNIPAM-b-CNFs) was studied. Small angle neutron scattering (SANS) combined with Ultra-SANS (USANS) revealed the nano to microscale conformation changes of these polymer hybrids as a function of temperature. The effect of temperature on the optical and viscoelastic properties of hydrogels was also investigated. FINDINGS: Grafting PNIPAM from CNFs shifted the lower critical solution temperature (LCST) from 32 °C to 36 °C. Below LCST, the PNIPAM chains in PNIPAM-g-CNF sustain an open conformation and poor interaction with CNF, and exhibit water-like behaviour. At and above LCST, the PNIPAM chains change conformation to entangle and aggregate nearby CNFs. Large voids are formed in solution between the aggregated PNIPAM-CNF walls. In comparison, PNIPAM-b-CNF sustains liquid-like behaviour below LCST. At and above LCST, the blended PNIPAM phase separates from CNF to form large aggregates which do not affect CNF network and thus PNIPAM-b-CNF demonstrates low viscosity. Understanding of temperature-dependent conformation of PNIPAM-g-CNFs engineer thermo-responsive hydrogels for biomedical and functional applications.

Mechanical strength predictability of full factorial, Taguchi, and Box Behnken designs: Optimization of thermal settings and Cellulose Nanofibers content in PA12 for MEX AM.

Optimization of reinforced nanocomposites for MEX 3D-printing remain strong industrial claims. Herein, the efficacy of three modeling methods, i.e., full factorial (FFD), Taguchi (TD), and Box-Behnken (BBD), on the performance of MEX 3D printed nanocomposites was investigated, aiming to reduce the experimental effort. Filaments of medical-grade Polyamide 12 (PA12) reinforced with Cellulose NanoFibers (CNF) were evolved. Besides the CNF loading, 3D printing settings such as Nozzle (NT) and Bed (BΤ) Temperatures were optimization goals aiming to maximize the mechanical response. Three parameters and three levels of FFD were compliant with the ASTM-D638 standard (27 runs, five repetitions). An L9 orthogonal TD and a 15 runs BBD were compiled. In FFD, wt.3%CNF, 270 °C NT, and 80 °C BΤ led to 24% higher tensile strength compared to pure PA12. TGA, RAMAN, and SEM analyses interpreted the reinforcement mechanisms. TD and BBD exhibited fair approximations, requiring 7.4% and 11.8% of the FFD experimental effort.

Electrochemical monitoring of 4-chlorophenol as a water pollutant via carbon paste electrode amplified with Fe3O4 incorporated cellulose nanofibers (CNF).

A crucial problem that needs to be resolved is the sensitive and selective monitoring of chlorophenol compounds, especifically 4-chlorophenol (4-CP), one of the most frequently used organic industrial chemicals. In light of this, the goal of this study was to synthesize Fe3O4 incorporated cellulose nanofiber composite (Fe3O4/CNF) as an amplifier in the development of a modified carbon paste electrode (CPE) for 4-CP detection. Transmission electron microscopy (TEM) was used to evaluate the morphology of the synthesized nanocatalyst, while differential pulse voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV) techniques were implemented to illuminate the electrochemical characteristics of the fabricated sensor. The ultimate electrochemical sensor (Fe3O4/CNF/CPE) was used as a potent electrochemical sensor for monitoring 4-CP in the concentration range of 1.0 nM-170 µM with a limit of detection value of 0.5 nM. As a result of optimization studies, 8.0 mg Fe3O4/CNF was found to be the ideal catalyst concentration, whereas pH = 6.0 was chosen as the ideal pH. The 4-CP's oxidation current was found to be over 1.67 times greater at ideal operating conditions than it was at the surface of bare CPE, and its oxidation potential decreased by about 120 mV. By using the standard addition procedure on samples of drinking water and wastewater, the suggested capability of Fe3O4/CNF/CPE to detect 4-CP was further investigated. The recovery range was found to be 98.52-103.66%. This study paves the way for the customization of advanced nanostructure for the application in electrochemical sensors resulting in beneficial environmental impact and enhancing human health.

High-Resolution Magic-Angle Spinning NMR Spectroscopy for Evaluation of Cell Shielding by Virucidal Composites Based on Biogenic Silver Nanoparticles, Flexible Cellulose Nanofibers and Graphene Oxide.

Antiviral and non-toxic effects of silver nanoparticles onto in vitro cells infected with coronavirus were evaluated in this study using High-Resolution Magic-Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) spectroscopy. Silver nanoparticles were designed and synthesized using an orange flavonoid-hesperetin (HST)-for reduction of silver(I) and stabilization of as obtained nanoparticles. The bio-inspired process is a simple, clean, and sustainable way to synthesize biogenic silver nanoparticles (AgNP@HST) with diameters of ∼20 nm and low zeta potential (-40 mV), with great colloidal stability monitored for 2 years. The nanoparticles were used for the fabrication of two types of antiviral materials: colloids (AgNP@HST spray) and 3D flexible nanostructured composites. The composites, decorated with AgNP@HST (0.05 mmol L-1), were made using cellulose nanofibers (CNF) obtained from orange peel and graphene oxide (GO), being denominated CNF@GO@AgNP@HST. Both materials showed high virucidal activity against coronaviruses in cell infection in vitro models and successfully inhibited the viral activity in cells. HR-MAS 1H-NMR technique was used for determining nanomaterials' effects on living cells and their influences on metabolic pathways, as well as to study viral effects on cells. It was proven that none of the manufactured materials showed toxicity towards the intact cells used. Furthermore, viral infection was reverted when cells, infected with the coronavirus, were treated using the as-fabricated nanomaterials. These significant results open possibilities for antiviral application of 3D flexible nanostructured composite such as packaging papers and filters for facial masks, while the colloidal AgNP@HST spray can be used for disinfecting surfaces, as well as a nasal, mouth, and eye spray.

Novel 3D porous aerogels engineered at nano scale from cellulose nano fibers and curcumin: An effective treatment for chronic wounds.

Traditional cotton gauze derived from cellulose has many limitations in the processes of wound healing. To overcome these hassles, we used cellulose nanofibers (CNF) incorporated with curcumin for the fabrication of wound healing 3D porous aerogel. Cellulose nanofibers synthesized from plant waste are promising sustainable nanomaterials due to their biocompatibility and biodegradability. Ionic cross linking with sodium alginate was performed to maintain the mechanical strength. SEM results revealed highly porous architecture that effectively promoted wound healing, as a result of macro- and micro-porous architecture and curcumin. In-vitro drug release studies showed a slow and steady release pattern. The 3D porous nano bio aerogel with curcumin significantly promoted the migration of fibroblast cells and had excellent antimicrobial activity against pathogenic microorganisms. In-vivo studies showed angiogenesis without rejection or inflammation of the scaffold. From the observations, we can conclude that this novel 3D porous aerogel can be used to treat chronic wounds.

Dialdehyde modified cellulose nanofibers enhanced the physical properties of decorative paper impregnated by aldehyde-free adhesive.

Impregnated decorative paper was an important wood-based panel finishing material. However, traditional impregnated decorative paper was impregnated with melamine-formaldehyde resin, which will release formaldehyde and harm the human health. To solve this problem, small molecule polyacrylate-polyethylene glycol (PEG) adhesive was used to achieve the non-formaldehyde addition of the impregnation system. The dialdehyde modified CNF (D-CNF), modified by sodium periodate (NaIO4), and triethylenediamine were introduced to enhance the surface properties of the impregnated decorative paper. The results showed that the incorporation of D-CNF and triethylenediamine imparted excellent physical strength and surface properties to impregnated decorative paper. When the dosage of 0.3 wt% D-CNF and 3 mL/100 g triethylenediamine in the compound emulsion, the hardness, abrasion resistant value and surface bonding strength of impregnated decorative paper adhered fiberboard reached 3H, 330 r of damage and 1.13 MPa, respectively. Thus, it could be effectively used for making high-performance formaldehyde-free impregnated decorative paper.

Sustainable production of cellulose nanofiber gels and paper from sugar beet waste using enzymatic pre-treatment.

Removal of non-cellulosic polymers from vegetable pulp to obtain cellulose nanofibers (CNF) is normally achieved by chemical pre-treatments which requires several washing steps. In the present study, it is demonstrated how incubation of sugar beet pulp at pH 9, followed by treatment with polysaccharide-degrading enzymes and subsequent bleaching can be done in a one-pot procedure to make CNF. The new method consumes 67% less water and removes non-cellulosic polysaccharides with similar efficiency as a chemical method. In addition, CNF produced by the new method contained slightly more pectin and formed gels with 2.7 times higher storage modulus. Nanopapers cast from chemically- and enzymatically produced CNF showed similar mechanical properties. However, without the pH 9 incubation step, the enzymes accessibility to cell-wall polymers was limited resulting in lower gel and paper strengths. In conclusion, the new method offers a sustainable route for producing high quality CNF from sugar beet waste.

Fabrication of single-crystalline gold nanowires on cellulose nanofibers.

Cellulose nanofibers (CNF) are promising nanomaterials for functional inks and printed sensors, although the potential applications are currently limited by the available functionalization methods. This work outlines a convenient method to grow a novel and highly conductive network of single-crystalline gold nanowires (AuNW) on CNF for use in conductive inks and printed sensors. The CNF are able to reduce Au (III) precursors to Au (0) monomers and generate nucleation sites for the subsequent monomer-by-monomer growth of Au nanocrystals; sodium citrate is used to control the reduction kinetics and the crystal growth. The growth of these AuNW/CNF materials is a three-step process of redox reaction, isotropic nucleation and anisotropic crystallization: the morphology and crystal structure of Au nanocrystals on CNF can be controlled by adjusting the reaction temperature and concentrations of citrate and CNF. The AuNW/CNF materials obtained have been formulated into highly conductive and atmospherically stable inks for use in either directly writing or screen printing. We have demonstrated AuNW/CNF-printed sensors with highly controllable electrical conductivity as well as excellent stability against rinsing and immersion by water and ethanol.

Reinforcement of Polylactic Acid for Fused Deposition Modeling Process with Nano Particles Treated Bamboo Powder.

The focus of this report was to understand the tensile properties and dynamic mechanical properties of bamboo powder (BP) reinforced polylactic acid (PLA) composite filaments which were treated with nano calcium carbonate (CaCO3), cellulose nanofibers (CNF), and micro-crystalline cellulose (MCC) using impregnation modification technology. The storage modulus (E') of nano CaCO3-BP/PLA, MCC-BP/PLA, and CNF-BP/PLA composite filaments increased compared with BP/PLA composite filaments before the glass transition temperature Tg. When the temperature was above Tg, the reinforcement effect of nano CaCO3, MCC, and CNF gradually became less apparent. The loss modulus (E'') and loss factor (tan δmax) of the nano CaCO3-BP/PLA, MCC-BP/PLA, and CNF-BP/PLA composite filaments was higher than that of BP/PLA composite filaments produced by the "one-step" method. The tensile strength (TS) results showed a similar trend. Compared with the control samples, the TS of nano CaCO3-BP/PLA, MCC-BP/PLA, and CNF-BP/PLA composite filaments produced by the "one-step" method (and the "two-step" method) increased by 40.33% (and 10.10%), 32.35% (and -8.61%), and 12.32% (and -12.85%), respectively. The TS of nano CaCO3-BP/PLA, MCC-BP/PLA, and CNF-BP/PLA composite filaments produced by the "one-step" method was slightly higher than those produced by the "two-step" method. The elongation at break (EAB) of BP/PLA composite filaments was higher than that of BP/PLA samples treated with nano CaCO3, MCC, or CNF. The PLA and modified BP were readily accessible through a simple mixing process. The rheological investigation of such mixtures showed that nano CaCO3, CNF, and MCC have different effects on the processability and rheological properties of composites.

Cellulose Nanofibers from Softwood, Hardwood, and Tunicate: Preparation-Structure-Film Performance Interrelation.

This work reveals the structural variations of cellulose nanofibers (CNF) prepared from different cellulose sources, including softwood (Picea abies), hardwood (Eucalyptus grandis × E. urophylla), and tunicate (Ciona intestinalis), using different preparation processes and their correlations to the formation and performance of the films prepared from the CNF. Here, the CNF are prepared from wood chemical pulps and tunicate isolated cellulose by an identical homogenization treatment subsequent to either an enzymatic hydrolysis or a 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation. They show a large structural diversity in terms of chemical, morphological, and crystalline structure. Among others, the tunicate CNF consist of purer cellulose and have a degree of polymerization higher than that of wood CNF. Introduction of surface charges via the TEMPO-mediated oxidation is found to have significant impacts on the structure, morphology, optical, mechanical, thermal, and hydrophobic properties of the prepared films. For example, the film density is closely related to the charge density of the used CNF, and the tensile stress of the films is correlated to the crystallinity index of the CNF. In turn, the CNF structure is determined by the cellulose sources and the preparation processes. This study provides useful information and knowledge for understanding the importance of the raw material for the quality of CNF for various types of applications.

Method to reinforce polylactic acid with cellulose nanofibers via a polyhydroxybutyrate carrier system.

The elastic moduli of PLA reinforced with 5 and 10wt.% CNF with the carrier, at a frequency (ω) of 0.07, were 67% and 415% higher, respectively, than that of neat PLA. The shear viscosity at a shear rate of 0.01 (η0.01) for PLA+10wt.% CNF was 32% higher than that of the neat PLA matrix. The η0.01 of PLA reinforced with 5wt.% CNF and the PHB carrier was similar to neat PLA. The tensile and flexural moduli of elasticity of the nanocomposites continuously increased with increased CNF loading. The results of the mechanical property measurements are in accordance with the rheological data. The CNF appeared to be better dispersed (less-aggregated nanofibers) in the PLA reinforced with 5wt.% CNF and the PHB carrier. Possible applications for the composites studied in this research are packaging materials, construction materials, and auto parts for interior applications.

Rheological properties of micro-/nanofibrillated cellulose suspensions: wall-slip and shear banding phenomena.

The rheological properties of enzymatically hydrolyzed and TEMPO-oxidized microfibrillated/nanofibrillated cellulose (MFC/NFC) aqueous suspensions were investigated in oscillation and steady-flow modes and were compared with the morphology of the studied materials. The flow instabilities, which introduce an error in the rheological measurements, were discovered during flow measurements. A wall-slip (interfacial slippage on the edge of geometry tools and suspension) was detected at low shear rates for two types of NFC suspensions while applying cone-plate geometry. A roughening of the tool surfaces was performed to overcome the aforementioned problem. Applying to TEMPO-oxidized NFC, a stronger suspension response was detected at low shear rates with higher values of measured shear stress. However, a shear banding (localization of shear within a sample volume) became more pronounced. The use of serrated tools for enzymatically hydrolyzed NFC produced lower shear stress at the moderate shear rates, which was influenced by water release from the suspension.