Tannin-encapsulated electrospun nanofibrous membrane of cellulose nanowhiskers-reinforced polysulfone for colorimetric detection of iron(III).

A nanocomposite of tannic acid and cellulose nanowhiskers (CNW)-reinforced polysulfone (PSF) was used to develop a metallochromic nanofibrous membrane sensor for iron(III) in aqueous media. Tannic acid was used as an active detecting probe, whereas the CNW@PSF composite was employed as a hosting material. Cellulose nanowhiskers (7-12 nm) were obtained from microcrystalline cellulose (MCC). According to the coloration parameters, a bathochromic shift from colorless (415 nm) to purple (561 nm) occurs when ferric cations bind to the phenolic hydroxyls of the tannic acid probe. The concentration of ferric was found to be directly correlated to the extent of the color change, demonstrating a detection limit of 0.1-250 ppm. This could be attributed to the creation of a coordinative complex between ferric ions and phenolic tannic acid. The generated nanofibers were inspected by energy-dispersive X-ray (EDX) and scanning electron microscopy (SEM). The electrospun nanofibrous membrane showed an average diameter between 75 and 150 nm. The tannic acid-containing nanofibers are remarkably reusable and simple. The tannic acid-encapsulated polysulfone nanofibrous membrane was used to detect various metal ions, demonstrating a high selectivity for Fe3+. The ideal pH range for the identification of Fe3+ was determined to be in the range of 4.25-6.75.

A one-dimensional bacterial cellulose nano-whiskers-based binary-drug delivery system for the cancer treatment.

It's currently a challenge to design a drug delivery system for chemotherapy with high drug contents and minimal side effects. Herein, we constructed a novel one-dimensional binary-drug delivery system for cancer treatment. In this drug delivery system, drugs (doxorubicin (DOX) and resveratrol (RES)) self-assemble on bacterial cellulose nano-whiskers (BCW) and are subsequently encapsulated by polydopamine (PDA) with high encapsulation efficiencies (DOX: 81.53 %, RES: 70.32 %) and high drug loading efficiencies (DOX: 51.54 %, RES: 36.93 %). The cumulative release efficiencies can reach 89.27 % for DOX and 80.05 % for RES in acidic medium within 96 h. The BCW/(DOX + RES)/PDA can enter tumor cells easily through endocytosis and presents significant anti-cancer effects. Furthermore, the released-RES plays a protective role in normal cells through up-regulation of antioxidant enzymes activities and scavenging of reactive oxygen species. Taken together, the one-dimensional BCW/(DOX + RES)/PDA binary-drug delivery system can be used for the anticancer treatment along with slight side effects.

Green Biodegradable Polylactide-Based Polyurethane Triblock Copolymers Reinforced with Cellulose Nanowhiskers.

A novel series of biodegradable polylactide-based triblock polyurethane (TBPU) copolymers covering a wide range of molecular weights and compositions were synthesized for potential use in biomedical applications. This new class of copolymers showed tailored mechanical properties, improved degradation rates, and enhanced cell attachment potential compared to polylactide homopolymer. Triblock copolymers, (TB) PL-PEG-PL, of different compositions were first synthesized from lactide and polyethylene glycol (PEG) via ring-opening polymerization in the presence of tin octoate as the catalyst. After which, polycaprolactone diol (PCL-diol) reacted with TB copolymers using 1,4-butane diisocyanate (BDI) as a nontoxic chain extender to form the final TBPUs. The final composition, molecular weight, thermal properties, hydrophilicity, and biodegradation rates of the obtained TB copolymers, and the corresponding TBPUs were characterized using 1H-NMR, GPC, FTIR, DSC, and SEM, and contact angle measurements. Results obtained from the lower molecular weight series of TBPUs demonstrated potential use in drug delivery and imaging contrast agents due to their high hydrophilicity and degradation rates. On the other hand, the higher molecular weight series of TBPUs exhibited improved hydrophilicity and degradation rates compared to PL-homopolymer. Moreover, they displayed improved tailored mechanical properties suitable for utilization as bone cement, or in regeneration medicinal applications of cartilage, trabecular, and cancellous bone implants. Furthermore, the polymer nanocomposites obtained by reinforcing the TBPU3 matrix with 7% (w/w) bacterial cellulose nanowhiskers (BCNW) displayed a ~16% increase in tensile strength, and 330% in % elongation compared with PL-homo polymer.

Insights into chitosan-based cellulose nanowhiskers reinforced nanocomposite material via deep eutectic solvent in green chemistry.

In the present work, the synthesis of cellulose nanowhiskers (CNW)/chitosan nanocomposite films via deep eutectic solvents (DES) changing the chemical structures were carried out. It was observed that a pure chitosan film has broadband at 3180-3400 cm-1, indicating amide and hydroxyl groups. Upon CNW incorporation, the peak gets sharper and stronger and shifts to a greater wavelength. Further, the addition of DES infuses more elements of amide into the nanocomposite films. Moreover, the mechanical properties incorporating CNW filler into a chitosan matrix show an enhancement in tensile strength (TS), Young's modulus (YM), and elongation at break. The TS and YM increase while the elongation decrease as the CNW concentration increases. The YM of biocomposite films is increased to 723 MPa at 25% CNW into chitosan films. Besides, the TS has enhanced to 11.48 MPa at 15% CNW concentration in the biocomposite films. The elongation at break has decreased to 11.7% at 25% CNW concentration. Hence, incorporating CNW into the chitosan matrix via DES can still improve the mechanical properties of the nanocomposite films. Therefore, the application of DES results in a lower YM and TS as the films are hygroscopic. In conclusion, DES can be considered the new green solvent media for synthesizing materials. It has the potential to replace ionic liquids due to its biodegradability and non-toxic properties while preserving the character of low-vapour pressure. Besides that, chitosan can be used as potential material for applications in process industries, such as the biomedical and pharmaceutical industries. Thus, DES can be used as a green solvent and aim to reduce the toxic effect of chemicals on the environment during chemical production.

A Review on Fully Bio-Based Materials Development from Polylactide and Cellulose Nanowhiskers.

This review covers the development of eco-friendly, bio-based materials based on polylactide (PLA) and cellulose nanowhiskers (CNWs). As a biodegradable polymer, PLA is one of the promising materials to replace petroleum-based polymers. In the field of nanocomposites, CNWs offer many advantages; they are made from renewable resources and exhibit beneficial mechanical and thermal properties in combination with polymer matrix. A wide range of surface modifications has been done to improve the miscibility of CNW with the PLA homopolymer, which generally gives rise to hydrophobic properties. PLA-CNW nanocomposite materials are fully degradable and sustainable and also offer improved mechanical and thermal properties. Limitations pertaining to the miscibility of CNWs with PLA were solved through surface modification and chemical grafting on the CNW surfaces. Further development has been done by combining PLA-based material via stereocomplexation approaches in the presence of CNW particles, known as bio-stereo-nanocomposite PLA-CNW. The combination of stereocomplex crystalline structures in the presence of well-distributed CNW particles produces synergetic effects that enhance the mechanical and thermal properties, including stereocomplex memory (melt stability). The bio-based materials from PLA and CNWs may serve as eco-friendly materials owing to their sustainability (obtained from renewable resources), biodegradability, and tunability properties.

Osteogenesis enhancement using poly (l-lactide-co-d, l-lactide)/poly (vinyl alcohol) nanofibrous scaffolds reinforced by phospho-calcified cellulose nanowhiskers.

Electrospun poly (l-lactide-co-d, l-lactide) (PLDLLA)/poly (vinyl alcohol) (PVA) nanofibers were reinforced by various contents (0-1 wt%) of phospho-calcified cellulose nanowhiskers (PCCNWs) as scaffolds in bone applications. The hydrophilicity and rate of hydrolytic degradation of PLDLLA were improved by introducing 10 wt% of PVA. PCCNWs with inherent hydrophilic properties, high aspect ratio, and large elastic modulus enhanced the hydrophilicity, accelerated the rate of degradation, and improved the mechanical properties of the nanofibrous samples. Moreover, calcium phosphate and phosphate functional groups on the surface of PCCNWs possessing act as stimulating agents for cellular activities such as proliferation and differentiation. Besides the physico-chemical properties investigation of PLDLLA/PVA-PCCNWs nanofibrous samples, their cytotoxicity was also studied and they did not show any adverse side effect. Incorporation of PCCNWs (1 wt%) into the PLDLLA/PVA nanofibrous samples showed more enzymatic activities and deposited calcium. The micrograph images of the morphology of human mesenchymal stem cells (hMSCs) cultured on the nanofibrous sample containing 1 wt% of PCCNWs after 14 days of cell differentiation revealed their high potential for bone tissue engineering.

Pilot-Scale Production of Cellulosic Nanowhiskers With Similar Morphology to Cellulose Nanocrystals.

This study describes a class of cellulosic nanomaterials, cellulosic nanowhiskers (CNWs), and demonstrates scaled-up production with acid recovery using less expensive equipment made of common stainless steel rather than glass-lined steel. CNWs produced using concentrated maleic acid (MA) hydrolysis followed by mechanical fibrillation have morphology similar to MA-produced cellulose nanocrystals (CNCs) and sulfuric-acid-produced CNCs (S-CNCs) but differ in crystallinity. Applications of CNWs as a substitute for CNCs for which morphology and surface charge, rather than crystallinity, are the pertinent characteristics are presented. The tested CNW suspensions have a wider viscosity range of 0.001 to 1000 Pa.s over a variety of shear rates of 0.01 to 1000 1/s compared to S-CNCs of 0.001 to 0.1 Pa.s and are better suited for applications such as rheology modification and 3D printing. This study proposes CNWs as a less expensive and sustainable replacement for CNCs in applications that do not require crystalline properties.

Self-Assembly of Surface-Acylated Cellulose Nanowhiskers and Graphene Oxide for Multiresponsive Janus-Like Films with Time-Dependent Dry-State Structures.

For the first time Janus-like films of surface-acylated cellulose nanowhiskers (CNWs) with or without graphene oxide (GO) via one-step evaporation-driven self-assembly process are reported, which have reconstructible time-dependent micro-/nanostructures and asymmetric wettability. The heterogeneous aggregation of CNWs on rough Teflon substrates favors the formation of uniform films, leading to hydrophobic smooth bottom surface. The homogeneous nucleation of residual CNWs in bulk suspensions promotes the growth of patchy microspheres with an average diameter of 22.7 ± 2.1 µm, which precipitate on the top surface leading to enhanced hydrophobicity. These patchy microspheres are thermoresponsive and vanish after heating at 60 °C within 1 min, while they are reconstructed at room temperature with time-dependent evolving micro-/nanostructures in dry state within 2 d. The thermoresponsive transition of patchy microparticles leads to accompanied switchable change between transparency and opacity of Janus-like films. Furthermore, the incorporation of GO generates more patchy microspheres with an average diameter of 13.5 ± 1.3 µm on the top surface of hybrid Janus-like films. Different distributions of CNWs and GO in Janus-like films and the solvent-responsive self-assembled patchy microparticles of CNWs facilitate their reversible actuation by showing fast curling in THF within 6 s and flattening in water for at least 25 cycles.

Analysis and physicochemical properties of cellulose nanowhiskers from Pennisetum purpureum via different acid hydrolysis reaction time.

Cellulose nanowhisker (NWC) was extracted by hydrolysing Pennisetum purpureum (PP) fibres with acid and alkali. They were subjected to different periods of acid hydrolysis; 30, 45, and 60 min. NWC morphology and physicochemical properties were characterised by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), particle size analyser, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and thermogravimetric analysis. NWC3, which underwent the longest hydrolysis time, showed the smallest width and length, under TEM. All samples presented a needle-like shape under TEM and AFM; uneven lengths and irregular shapes under FESEM; and a broad range of distribution, with the particle size analyser. All samples exhibited a good crystallinity index (CrI)-72.0 to 74.6%. The highest CrI% corresponded to 60 min of acid hydrolysis. Thermogravimetric analysis showed thermal stability between 310.72 °C and 336.28 °C. Thus, cellulose nanowhisker from PP fibres, have high potential as bio-nanocomposites.

Novel halochromic cellulose nanowhiskers from rice straw: Visual detection of urea.

Colorimetric nanocomposite film sensor was fabricated by incorporating TCFH spectroscopic probe into cellulose nanowhiskers (CNW)/Urease enzyme matrix. CNW-TCFH can be used as disposable molecular biosensor in which CNW is the probe carrier comprising high surface area-to-volume ratio, urease is the catalyst and TCFH is the molecular probe. Tricyanofuran-hydrazone (TCFH) spectroscopic probe was prepared. UV-vis absorption spectra demonstrated solvatochromic behavior and a reversible color change of the tricyanofuran-hydrazone probe solution in acetone under acid/base conditions. CNW were reinforced with sodium alginate biopolymer to introduce biocomposite film. This CNW-TCFH film biosensor responds through visible color shift from light yellow to pink when exposed to urea in aqueous media. The morphology properties of CNW and CNW-TCFH films were examined by different tools. The photophysical properties of the prepared TCFH probe, including solvatochromism and pH sensory, were also studied.

Detection of hydrogen peroxide (H2O2) using a colorimetric sensor based on cellulose nanowhiskers and silver nanoparticles.

Hydrogen peroxide (H2O2) is an important compound for several industrial sectors, but it becomes harmful to human health under high concentrations. Thus, the development of simple, low cost and fast analytical methods capable to detect and monitor H2O2 is fundamentally important. In the present study, we report a simple route for synthesizing silver nanoparticles (AgNPs) in the presence of a nanostructured polysaccharide (cellulose nanowhiskers) to produce a hybrid material, which was employed as a colorimetric probe for H2O2 detection. Our results revealed that AgNPs tend to experience catalytic decomposition when exposed to H2O2, causing a decrease of AgNPs absorption band at 410 nm in accordance with H2O2 concentration. This decrease was linearly dependent on H2O2 concentration (in the ranges 0.01-30 µM and 60-600 µM), yielding limits of detection of 0.014 µM and 112 µM, respectively. The easy-to-interpret H2O2 sensor also proved to be suitable for real samples analysis even in the presence of other interfering substances.

Conductive electrospun nanofibers containing cellulose nanowhiskers and reduced graphene oxide for the electrochemical detection of mercury(II).

Mercury is a heavy metal highly deleterious for the environment being associated to several diseases. Thus, novel and expedite techniques capable of detecting this heavy metal in water, even at trace levels, are highly sought for human and environmental safety purposes. Here we developed a novel electrochemical sensor for detecting mercury(II) using a green hybrid nanoarchitecture composed of reduced graphene oxide (rGO), cellulose nanowhiskers (CNW) and polyamide 6 (PA6) electrospun nanofibers. Scanning transmission electron microscopy (STEM), ultraviolet-visible (UV-VIS) absorption and Fourier transform infrared (FTIR) spectroscopies and termogravimetric analysis (TGA) were employed to elucidate the morphology and composition of CNW:rGO hybrid system. The hybrid composite proved to enhance charge transference properties, which was evaluated by cyclic voltammetry (CV) experiments. Due to the excellent electrical properties of graphene, the nanocomposite (PA6/CNW:rGO) was applied in the electrochemical detection of very low concentrations of mercury in water samples, improving the sensor sensibility. Moreover, the PA6/CNW/rGO electrode demonstrated stability, high selectivity, low detection limit and wide dynamic linear range for the detection of mercury(II).

Biomimetic nanocomposite based on hydroxyapatite mineralization over chemically modified cellulose nanowhiskers: An active platform for osteoblast proliferation.

Functionalized-cellulose nanowhiskers (CNWs) were obtained and used to improve hydroxyapatite (HAp) growth by the biomimetic method. CNWs were obtained through HCl hydrolysis and then submitted to chemical functionalization with carboxylate or amine groups that can induce selective HAp mineralization efficiently. Functionalized-CNWs were tested against HAp growth through the biomimetic method using a simulated body fluid (SBF) as a medium during 14 and 28 days of mineralization. Both chemical surface nature (bearing carboxylate or amine reactive groups) and contact time with SBF influenced the nucleation and growth of HAp crystals over CNWs surface. Nanocomposites immersed for 28 days showed a higher amount of HAp crystals compared to bare CNWs or the ones immersed for 14 days. Biocompatibility of the nanomaterials immersed for 14 days in SBF was evaluated through cell viability test using pre-osteoblasts (MC3T3-E1). In general, functionalized-CNWs containing HAp crystals deposited through biomimetic method showed promising results, with CNWs bearing amine groups showing a slightly larger biocompatibility compared to the ones bearing carboxylate groups during an incubation period of 24 h.

Cellulose nanowhiskers decorated with silver nanoparticles as an additive to antibacterial polymers membranes fabricated by electrospinning.

Antimicrobial films based on distinct polymer matrices, poly (vinyl alcohol) (PVA) or poly (N-isopropylacrylamide) (PNIPAAm), and silver nanoparticles (AgNPs) immobilized onto cellulose nanowhiskers (CWs) were successfully prepared by either casting or electrospinning. CWs were first functionalized with carboxylate groups (labeled as CWSAc) and later they were immersed in a silver nitrate solution (AgNO3). After Ag+ ions anchored in the COO- groups are chemically reduced to produce AgNPs. The CWSAc/AgNPs biological activity was evaluated against Staphylococcus aureus (S. aureus), Bacillus Subtilis (B. subtilis), Escherichia coli (E. coli), and Candida albicans (C. albicans). The materials were more effective against C. albicans that showed a MIC of 15.6 µg/mL. In the process of AgNPs synthesis, the activity of the stabilizing agent (gelatin) and concentration of precursor and reducing agents were evaluated. The synthesized polymeric films displayed good antimicrobial activity against S. aureus, E. coli, and Pseudomonas aeruginosa (P. aeruginosa) bacteria. The PVA films with CWSAc/AgNPs showed diameter of the inhibition halo of up to 11 mm. The results obtained displayed that the films obtained have a potential application to be used in different fields such as packaging, membrane filtration, wound dressing, clothing and in different biomedical applications.

Flexible and transparent films produced from cellulose nanowhisker reinforced agarose.

Transparent and flexible nanocomposite films with a range of Agarose to Cellulose Nano-Whisker (CNW) ratios were produced using never-dried CNWs. The incorporation of never-dried CNWs within Agarose played an important role in the surface roughness (Ra 7-15 nm) and light transparency of the films (from 84 to 90%). Surface induced crystallisation of Agarose by CNWs was also found with increasing percentage of crystallinity (up to 79%) for the nanocomposite films, where CNW acted as nucleating sites. The enhanced tensile strength (ca. 30% increase) and modulus (ca. 90% increase) properties of the nanocomposite films compared to the control Agarose film indicated the effectiveness of the nanowhiskers incorporation. The storage modulus of the nanocomposite films increased also to be tripled Agarose alone as the CNWs content reached 43%. The swelling kinetics of the nanocomposites revealed that addition of CNWs reduced the long-term swelling capacity and swelling rate of the nanocomposite.

Mechanically improved polyvinyl alcohol-composite films using modified cellulose nanowhiskers as nano-reinforcement.

Cellulose nanowhiskers (CWs) extracted from cotton fibers were successfully modified with distinct anhydrides structures and used as additives in poly(vinyl alcohol) (PVA) nanocomposite films. The surface modification of CWs was performed with maleic, succinic, acetic or phthalic anhydride to compare the interaction and action the carboxylic groups into PVA films and how these groups influence in mechanical properties of the nanocomposites. CWs presented a high degree of crystallinity and good dispersion in water, with average length at the nanoscale. The addition of specific amounts (3, 6 and 9 wt.%) of modified-CWs increased up to 4.4 times the storage modulus (PVA88-CWSA 9 wt.%), as observed from dynamic mechanical analysis (DMA), compared to the bare PVA films. A significant increase in mechanical properties such as tensile strength, elastic modulus, and elongation at break showed a close relationship to the amount and chemical surface characteristics of CWs added, suggesting that these modified-CWs could be explored as reinforcement additives in PVA films.

Designed cellulose nanocrystal surface properties for improving barrier properties in polylactide nanocomposites.

Nanocomposites are an opportunity to increase the performance of polymer membranes by fine-tuning their morphology. In particular, the understanding of the contribution of the polymer matrix/nanofiller interface to the overall transport properties is key to design membranes with tailored selective and adsorptive properties. In that aim, cellulose nanocrystals (CNC)/polylactide (PLA) nanocomposites were fabricated with chemically designed interfaces, which were ensuring the compatibility between the constituents and impacting the mass transport mechanism. A detailed analysis of the mass transport behaviour of different permeants in CNC/PLA nanocomposites was carried out as a function of their chemical affinity to grafted CNC surfaces. Penetrants (O2 and cyclohexane), which were found to slightly interact with the constituents of the nanocomposites, provided information on the small tortuosity effect of CNC on diffusive mass transport. The mass transport of water (highly interacting with CNC) and anisole (interacting only with designed CNC surfaces) exhibited non-Fickian, Case II behaviour. The water vapour caused significant swelling of the CNC, which created a preferential pathway for mass transport. CNC surface grafting could attenuate this phenomenon and decrease the water transport rate. Anisole, an aromatic organic vapour, became reversibly trapped at the specifically designed CNC/PLA interface, but without any swelling or creation of an accelerated pathway. This caused the decrease of the overall mass transport rate. The latter finding could open a way to the creation of materials with specifically designed barrier properties by designing nanocomposites interfaces with specific interactions towards permeants.

Fabrication of cellulose nanowhiskers reinforced chitosan-xylan nanocomposite films with antibacterial and antioxidant activities.

Antibacterial and antioxidant chitosan-xylan/cellulose nanowhiskers (CNW) nanocomposite films were successfully prepared using CNW as nanofillers. The structure and morphology of the nanocomposite films were investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), and scanning electron microscopy (SEM). The optical transmittance, thermal stability, mechanical property, and swelling property of the nanocomposite films were also evaluated. These results revealed the microstructure of the films and confirmed the good miscibility between chitosan-xylan and CNW. The improvements of tensile strength and elongation at break of the nanocomposite films confirmed the reinforcement effects of CNW. Moreover, the inhibitory effects against S. aureus and E. coli and the ABTS+ scavenging activity indicated antibacterial and antioxidant functions of the nanocomposite films. In this work, the prepared chitosan-xylan/CNW nanocomposite films, combined the antibacterial property of chitosan, the antioxidant property of xylan, and good mechanical property of CNW, could be potentially applied in food and health-related areas.

Cellulose nanowhiskers improve the methylene blue adsorption capacity of chitosan-g-poly(acrylic acid) hydrogel.

Cellulose nanowhiskers (CNWs, 90% crystalline) were used to enhance the adsorption capacity of chitosan-g-poly(acrylic acid) hydrogel. The composites up to 20w/w-% CNWs showed improved adsorption capacity towards methylene blue (MB) as compared to the pristine hydrogel. At 5w/w-% CNWs the composite presented the highest adsorption capacity (1968mg/g). The maximum removal of MB (>98% of initial concentration 2000mg/L) was achieved quickly (60min) at room temperature, pH 6, and at low ionic strength (0.1M). Adsorption mechanism was explained with the Langmuir type I model suggesting the formation of a MB monolayer on the adsorbent surface. The interaction between the adsorbent and MB molecules was explained by chemisorption, as suggested by the pseudo-second-order kinetic model. Desorption experiments showed that 75% of loaded-MB could be recovered from the adsorbent by its immersion in a pH 1 solution. Additional experiments showed the post-utilized composite could be regenerated and reused for at least 5 consecutive adsorption/desorption cycles with minimum efficiency loss (∼2%).

Hybrid materials for bone tissue engineering from biomimetic growth of hydroxiapatite on cellulose nanowhiskers.

Cellulose nanowhiskers (CNWs) with different surface composition were used to generate the biomimetic growth hydroxyapatite (HAp). Hybrids materials primarily consist of CNWs with HAp content below 24%. CNWs were produced by different inorganic acid hydrolyses to generate cellulose particles with surface groups to induce HAp mineralization. In the present study, we evaluate the use of CNWs prepared from hydrochloric acid, sulfuric acid and phosphoric acid. HAp growth was obtained from the biomimetic method using a simulated body fluid concentration of 1.5M (SBF). The sulfonate and phosphonate groups on the CNW surface have a direct impact on the nucleation and growth of HAp. HAp/CNW were also compared with the physical mixture method using HAp nanoparticles prepared by chemical precipitation. The bioactivity and biocompatibility of the hybrid materials were assessed by cell viability studies using fibroblast cells (L929). The materials obtained from the biomimetic method have superior biocompatibility/bioactivity compared to the material synthesized by the wet chemical precipitation method with an incubation period of 24h.