Deep eutectic solvent pretreatment of cellulose and development of hydrophobic foaming material.

This work aims to investigate the effects of deep eutectic solvents (DES) on the chemical and physical structure of cellulose. Choline chloride-oxalic acid and choline chloride-oxalic acid-glycerol were selected as solvents and cotton fibers was sued as raw materials to explore the difference between cotton fibers treated separately with two different DES. According to yield analysis, ternary solvents alleviated the degradation of cellulose when comparing to binary solvents, resulting in over 90 % of cellulose being obtained. Particularly, there is an esterification reaction of cellulose during treatment with the DES system, which also affects the performance of the subsequent products. Through the simple use of mechanical foaming with polyvinyl alcohol and the palm wax impregnation process, foams with a water contact angle greater than 140° and excellent mechanical properties can be obtained. The resultant foam material has 5 % linear elastic area, and prominent compressive strength providing potential use in the packaging industry in the replacement of plastic.

Super flexible, self-healing, and self-adhesive double network hydrogel reinforced by okara cellulose nanofibrils.

Inspired by the mussel, tannic acid (TA) was modified onto the surface of self-made cellulose nanofibrils (CNFs) to prepare TA@CNFs, which was introduced into borax crosslinked polyvinyl alcohol (PVA) to prepare PTC double-network hydrogel with self-healing properties. Through the comparative observation of TEM images and infrared spectra before and after tannic acid modification, the formation of TA@CNFs was proved. The introduction of TA@CNFs greatly increases the fracture stress of PTC hydrogel, which is more than 10 times higher than that of PVA hydrogel without TA@CNFs, and has high fracture strain (1723 %). Moreover, PTC hydrogel has the ability of rapid self-healing, which can heal to the original form within two minutes. In addition, the temperature response ability of PTC hydrogel makes it capable of reshaping. The self-adhesion ability of PTC hydrogel enables it to adhere to the human epidermis to detect motion signals, as sensitive and as stable as a flexible sensor.

Nanolignin-containing cellulose nanofibrils (LCNF)-enabled multifunctional ratiometric fluorescent bio-nanocomposite films for food freshness monitoring.

Herein, the nanolignin-containing cellulose nanofibrils (LCNF)-enabled ratiometric fluorescent bio-nanocomposite film is developed. Interestingly, the inclusion of LCNF in the cellulose-based film enhances the detecting performance of food freshness, such as high sensitivity to biogenic amines (BAs) (limit of detection (LOD) of up to 1.83 ppm) and ultrahigh discernible fluorescence color difference (ΔE = 113.11). The underlying mechanisms are the fluorescence resonance energy transfer (FRET), π - π interaction, and cation - π interaction between LCNF and fluorescein isothiocyanate (FITC), as well as the increased hydrophobicity due to lignin, which increases the interactions of amines with FITC. Its color stability (up to 28 days) and mechanical property (49.4 Mpa) are simultaneously improved. Furthermore, a smartphone based detecting platform is developed to achieve access to food safety. This work presents a novel technology, which can have a great potential in the field of food packaging and safety.

Cellulose microspheres enhanced polyvinyl alcohol separator for high-performance lithium-ion batteries.

Separators typically play an important role in enhancing the electrochemical performance of lithium-ion batteries (LIBs), while the preparation of separators suffers good electrochemical performance and high stability. In this study, regenerated porous cellulose microspheres (RCM) were innovatively fabricated and the biodegradable RCM/Polyvinyl alcohol (PVA) separators were successfully prepared through simple mixing and solvent substitution. Interestingly, the RCM with rich carboxylic groups, not only function as nanofillers that increases the strength properties of the three-dimensional porous network, but also enhances Li+ transfer (due to the COO- and Li+ interactions), resulting in outstanding Li+ transference number (0.54) of the RCM/PVA separator. In addition, the RCM/PVA separator shows excellent thermal stability and high liquid absorption rate (481.25 %). The LiFePO4/3 % RCM-HCl/PVA/Li cell displayed a high discharge capacity of 152.6 mAh·g-1 after 200 cycles at 1C. This work provides a new light on the fabrication of biodegradable separators for LIBs via a novel and cost-effective strategy.

Luminescence regulation of lanthanide-doped nanorods in chiral photonic cellulose nanocrystal films.

A new design for chiral photonic cellulose nanocrystal films was developed by co-assembling lanthanide-doped nanorods (NRs) into chiral cellulose nanocrystals, in which the photonic band gap (PBG) could be tuned in the visible range by changing the mass fraction of flexible agents, such as polyvinyl alcohol (PVA) and ethylene glycol (EG). Due to the PBG effect, the luminescence modulation in such nanocrystal films had been realized. The down-conversion luminescence from NaGd30Y60F4:5%Tb3+, 5%Eu3+ NRs and up-conversion luminescence from NaGd40Y40F4:18%Yb3+, 2%Er3+ NRs could be enhanced by 28 % and 18 % respectively, on account of the band edge effect. The luminescence would be inhibited when the luminescence overlapped with the stop band of the PBG. These results implied that the biocompatible photonic cellulose nanocrystal films are ideally suited for applications in optical coding, optical resonators and biocompatible lasers.

Efficient separation of bagasse lignin by freeze-thaw-assisted p-toluenesulfonic acid pretreatment.

Lignin separation is an important procedure that benefits multiple industries and in particular biomass transformation efforts. In this study, bagasse lignin was separated by freeze-thaw-assisted p-toluenesulfonic acid (p-TsOH) pretreatment. The optimal conditions were freezing temperature -60 °C, freezing time 8.0 h, thawing temperature 15 °C, p-TsOH concentration 60%, pretreatment temperature 70 °C, and time 20 min. Lower acid concentrations and temperatures were used compared with traditional p-TsOH pretreatment. The efficiency and selectivity of lignin separation were improved. It was attributed to freeze-thawing, which provided a more efficient physical channel for the effective penetration of p-TsOH. The separation, extraction and purity of lignin were improved to 89.76%, 78.22% and 77.89%, respectively. High separation, high extraction, high purity and large molecular weight lignin samples were obtained. In addition, the recovery and reuse of p-TsOH was enhanced. This provided a new method for the efficient and clean separation of lignin.

Design of Structural Parameters of Cutters for Tea Harvest Based on Biomimetic Methodology.

Owing to their sharp teeth, crickets can eat through new shoots of the stalks of tea plants. Inspired by the special geometrical structure of the teeth of crickets, this study designed a biomimetic cutter to reduce the force and energy required to cut the stalks of tea plants. Therefore, four biomimetic cutters were considered: a, b, c, and d. Cutter a was a traditional cutter used for comparison with the other three cutters, which were biomimetic. The cutters were manufactured using 3D printing technology and assessed by a texture tester at different loading speeds (5, 10, and 15 mm/s, respectively). The results show that cutter c delivered better performance compared to cutter a at loading speeds of 5, 10, and 15 mm/s, respectively. However, at 15 mm/s loading speed, the maximum cutting forces required for cutters b and c were 9.43% and 6.04% lower, respectively, than that for cutter a (9.021 N). Similarly, the energies consumed by cutters b and c were 13.8% and 4.24% lower than that consumed by cutter a (1.225 J). In addition, cutter c delivered the best results compared to others. Based on the study results, it was concluded that the biomimetic cutters can thus help to optimize the tea harvest.

Plant-based nanocellulose: A review of routine and recent preparation methods with current progress in its applications as rheology modifier and 3D bioprinting.

"Nanocellulose" have captivated the topical sphere of sturdily escalating market for sustainable materials. The review focuses on the comprehensive understanding of the distinct surface chemistry and functionalities pertaining to the renovation of macro-cellulose at nanodimensional scale to provide an intuition of their processing-structure-function prospective. The abundant availability, cost effectiveness and diverse properties associated with plant-based resources have great economical perspective for developing sustainable cellulose nanomaterials. Hence, emphasis has been given on nanocellulose types obtained from plant-based sources. An overarching goal is to provide the recent advancement in the preparation routes of nanocellulose. Considering the excellent shear thinning/thixotropic/gel-like behavior, the review provids an assemblage of publications specifically dealing with its application as rheology modifier with emphasis on its use as bioink for 3D bioprinting for various biomedical applications. Altogether, this review has been oriented in a way to collocate a collective data starting from the historical perspective of cellulose discovery to modern cellulosic chemistry and its renovation as nanocellulose with recent technological hype for broad spanning applications.

Microdesigned Nanocellulose-Based Flexible Antibacterial Aerogel Architectures Impregnated with Bioactive Cinnamomum cassia.

This work is strategically premeditated to study the potential of a herbal medicinal product as a natural bioactive ingredient to generate nanocellulose-based antibacterial architectures. In situ fibrillation of purified cellulose was done in cinnamon extract (ciE) to obtain microfibrillated cellulose (MFC). To this MFC suspension, carboxylated cellulose nanocrystals (cCNCs) were homogeneously mixed and the viscous gel thus obtained was freeze-dried to obtain lightweight and flexible composite aerogel architectures impregnated with ciE, namely, ciMFC/cCNCs. At an optimal concentration of 0.3 wt % cCNCs (i.e., for ciMFC/cCNCs_0.3), an improvement of around 106% in compressive strength and 175% increment in modulus were achieved as compared to pristine MFC architecture. The efficient loading and interaction of ciE components, specifically cinnamaldehyde, with MFC and cCNCs resulted in developing competent antibacterial surfaces with dense and uniform microstructures. Excellent and long-term antimicrobial activity of the optimized architectures (ciMFC/cCNCs_0.3) was confirmed through various antibacterial assays like the zone inhibition method, bacterial growth observation at OD600, minimum inhibitory concentration (MIC, here 1 mg/mL), minimum bactericidal concentration (MBC, here 3-5 mg/mL), and Live/Dead BacLight viability tests. The changes in the bacterial morphology with a disrupted membrane were further confirmed through various imaging techniques like confocal laser scanning microscopy, FESEM, AFM, and 3D digital microscopy. The dry composite architecture showed the persuasive capability of suppressing the growth of airborne bacteria, which in combination with antibacterial efficiency in the wet state is considered as an imperative aspect for a material to act as the novel biomaterial. Furthermore, these architectures demonstrated excellent antibacterial performance under real "in use" contamination prone conditions. Hence, this work provides avenues for the application of crude natural extracts in developing novel forms of advanced functional biomaterials that can be used for assorted biological/healthcare applications such as wound care and antimicrobial filtering units.

Bio-extract amalgamated sodium alginate-cellulose nanofibres based 3D-sponges with interpenetrating BioPU coating as potential wound care scaffolds.

In this work, sodium alginate (SA) based "all-natural" composite bio-sponges were designed for potential application as wound care scaffold. The composite bio-sponges were developed from the aqueous amalgamation of SA and cellulose nanofibres (CNFs) in bio-extracts like Rice water (Rw) and Giloy extract (Ge). These sponges were modified by employing a simple coating strategy using vegetable oil-based bio-polyurethane (BioPU) to tailor their physicochemical and biological properties so as to match the specific requirements of a wound care scaffold. Bio-sponges with shared interpenetrating polymeric network structures were attained at optimized BioPU coating formulation. The interpenetration of BioPU chains within the sponge construct resulted in the formation of numerous micro-networks in the interconnected microporous structure of sponges (porosity ≥75%). The coated sponge showed a superior mechanical strength (compressive strength ~3.8 MPa, compressive modulus ~35 MPa) with appreciable flexibility and recoverability under repeated compressive loading-unloading cycles. A tunable degradation behaviour was achieved by varying BioPU coating concentrations owing to the different degree of polymer chain entanglement within the sponge construct. The physical entanglement of BioPU chains with core structural components of sponge improved their structural stability by suppressing their full fragmentation in water-based medium without affecting its swelling behaviour (swelling ratio > 1000%). The coated sponge surface has provided a suitable moist-adherent physical environment to support the adhesion and growth of skin cells (HaCaT cells). The MTT (3-(4,5-dimethyl thiazolyl-2)-2,5-diphenyltetrazolium bromide) assay and hemolytic assay revealed the non-toxic and biocompatible nature of coated sponges in vitro. Moreover, no signs of skin erythema or edema were observed during in vivo dermal irritation and corrosion test performed on the skin of Sprague Dawley (SD) rats. Our initial observations revealed the credibility of these sponges as functional wound care scaffolds as well as its diverse potential as a suitable substrate for various tissue engineering applications.

Design and Synthesis of Fluorescent Nanocelluloses for Sensing and Bioimaging Applications.

Recent materials research based on fluorescent nanocelluloses (NCs) used in the field of sensing and bioimaging is reviewed. Many designed morphologies have been reported, such as nanoparticles, fibers, nanopapers, hydrogels and aerogels, that have been produced by physical or chemical methods. In the field of sensing and bioimaging, these studies have involved, but not been limited to, special optical properties including fluorescence, long-lived luminescence, polarized light, and/or aggregation-induced emission. The fluorescence sensing platforms can be categorized according to stimuli such as pH and temperature, as well as the presence of toxic compounds, and anions and metal cations. In addition, NCs exhibit unique low toxicity, good biocompatibility, biodegradability and cell membrane penetration, and can be modified into fluorescent nanoprobes for in vivo imaging and tracing. As an excellent platform for fluorescent sensing and bioimaging, NCs are bound to be increasingly studied and widely applied in the field of production and life sciences.

Efficient dissolution of lignin in novel ternary deep eutectic solvents and its application in polyurethane.

Novel ternary deep eutectic solvents (DESs) were designed to efficiently dissolve the lignin for synthesizing the lignin-containing rigid polyurethane foam (LRPUF). These ternary DESs were constituted by choline chloride (ChCl), two hydrogen bond donors - glycerol (Gly) and polyethylene glycol (PEG-400). The maximum solubility of lignin in the sample DES-2 (ChCl:Gly:PEG-400 = 1:2:2) could up to 66.70 g/100 g solvent at 60 °C due to the hydrogen bonds are the main driving force, which was confirmed by the largest hydrogen bond basicity parameter ß value and disappearance of crystalline peak. The main structure of the lignin did not change after dissolution in DES-2. The content of phenolic and total hydroxyl groups of the regenerated lignin increased, with reduction in their average molecular weights and polydispersity, indicating that the dissolution and regeneration of lignin in these ternary DESs can make it more homogeneous. The regenerated lignin was partially replacing for polyols in the LRPUF synthesis, the lignin replacement rate could up to 58.6% with good mechanical properties. The findings add to our understanding for efficient dissolution of lignin in DESs and for synthesizing the highly LRPUF.

Photoluminescent lignin hybridized carbon quantum dots composites for bioimaging applications.

Carbon quantum dots (CQDs) have attracted considerable interests because of their unique luminescence properties and promising applications in bioimaging. Lignin hybridized CQDs (L-CQDs) are facilely synthesized by one-pot hydrothermal method with different molar ratios of citric acid and ethanediamine. The morphology and chemical structures of L-CQDs are investigated by TEM, FT-IR, XPS, 2D-HSQC NMR spectra. The resultant L-CQDs with near spherical morphology are less than 10 nm in diameter, which are essentially composed of main interunit linkages and aromatic ring structures. The L-CQDs exhibit the excitation-dependent photoluminescence behavior with emission maximum ranging from 454 to 535 nm under excitation at 375-460 nm. The maximum emission of the L-CQDs red-shift to a longer wavelength with a decrease in intensity as the excitation wavelengths are gradually increased. L-CQDs show the low cytotoxicity and good cellular biocompatibility, demonstrating the great potential of the L-CQDs for bioimaging applications.

Formate-assisted analytical pyrolysis of kraft lignin to phenols.

The effect of sodium formate (SF), calcium formate (CF) and nickel formate (NF) as additives on analytical pyrolysis performance of kraft lignin was conducted. The results showed that these formates promoted the releasing of volatiles, leading to the rapid degradation of kraft lignin. High relative content of monophenols (53.77%), especially of guaiacol (23.65%), were achieved from the pyrolysis of pure lignin. The relative content of guaiacol was dramatically decreased after the adding of formates in kraft lignin. The relative content of polyphenols such as 3-methylcatechol and 4-methylcatechol reached to 16.97%, 16.23% and 21.95% with the formates of SF, CF and NF, respectively. The NF showed the highest selectivity of polyphenols and hydrocarbons. The increase of polyphenols and hydrocarbons from NF was the synergetic effect of the hydrogen radical reaction from the formic functional groups under the catalysis of Ni and/or NiO produced from the NF pyrolysis process.

Lewis acid-catalyzed biphasic 2-methyltetrahydrofuran/H2O pretreatment of lignocelluloses to enhance cellulose enzymatic hydrolysis and lignin valorization.

Lewis acid-catalyzed pretreatment in a biphasic system consisting of bio-based solvent 2-methyltetrahydrofuran (2-MeTHF) and water for a highly integrated one-pot catalytic transformation of lignocelluloses have been achieved. The aim of this work was to study the effects of different Lewis acid catalysts and pretreatment temperatures on the structural characteristics of precipitated lignin and enzymatic hydrolysis of the pretreated substrates, as well as the quantitative analysis of precipitates, solid residues, soluble carbohydrates and inhibitors. After the AlCl3-catalyzed biphasic 2-MeTHF/H2O pretreatment at 180 °C, its maximum cellulose conversion rate was enhanced by 7.4-fold as compared to the raw material. The precipitated lignin exhibited the representative structure, relatively low molecular weight and high purity for preparing value-added aromatic chemicals or renewable polymers. Overall, AlCl3-catalyzed biphasic 2-MeTHF/H2O pretreatment may offer a promising approach for enhancing enzymatic hydrolysis and obtaining valorized lignin by-product.

Extraction, isolation and characterization of nanocrystalline cellulose from industrial kelp (Laminaria japonica) waste.

Kelp (Laminaria japonica) is an economically important type of algae cultured in East Asia. Kelp waste is a by-product from the extraction of commercial alginate from kelp. This work reports the isolation of nanocrystalline cellulose (NCC) from the cellulose extracted from the kelp waste. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) show that the crystallinity index of the isolated kelp NCC was 69.4%, which was slightly higher than that of kelp cellulose as well as maintained the cellulose I crystalline form and typical cellulose chemical structure. In thermogravimetric analysis (TGA), kelp NCC showed decreased thermostability and a higher residual mass. Transmission electronic microscopy (TEM) confirmed the ordinary rod-like shape of the produced NCC with various dimensions. The kelp NCC aqueous dispersions displayed the expected characteristic optical and gel effects. Studies on the variables and the orthogonal experiment of NCC preparation contributed a maximum yield of 52.3%. The exploration on the preparation of kelp NCC in this study lays foundations for future applications.

The pattern of cell wall deterioration in lignocellulose fibers throughout enzymatic cellulose hydrolysis.

Cell wall deterioration throughout enzymatic hydrolysis of cellulosic biomass is greatly affected by the chemical composition and the ultrastructure of the fiber cell wall. The resulting pattern of cell wall deterioration will reveal information on cellulose activity throughout enzymatic hydrolysis. This study investigates the progression and morphological changes in lignocellulose fibers throughout enzymatic hydrolysis, using (transmission electron microscopy) TEM and field emission scanning electron microscopy (FE-SEM). Softwood thermo-mechanical pulp (STMP) and softwood bleached kraft pulp (SBKP), lignocellulose substrates containing almost all the original fiber composition, and with lignin and some hemicellulose removed, respectively, was compared for morphology changes throughout hydrolysis. The difference of conversion between STMP and SBKP after 48 h of enzymatic hydrolysis is 11 and 88%, respectively. TEM images revealed an even fiber cell wall cross section density, with uneven middle lamella coverage in STMP fibers. SKBP fibers exhibited some spaces between cell wall and lamella layers due to the removal of lignin and some hemicellulose. After 1 h hydrolysis in SBKP fibers, there were more changes in the fiber cross-sectional area than after 10 h hydrolysis in STMP fibers. Cell wall degradation was uneven, and originated in accessible cellulose throughout the fiber cell wall. FE-SEM images illustrated more morphology changes in SBKP fibers than STMP fibers. Enzymatic action of STMP fiber resulted in a smoother fiber surface, along with fiber peeling and the formation of ribbon-disjunction layers. SBKP fibers exhibited structural changes such as fiber erosion, fiber cutting, and fiber splitting throughout enzymatic hydrolysis.

Effects of SPORL and dilute acid pretreatment on substrate morphology, cell physical and chemical wall structures, and subsequent enzymatic hydrolysis of lodgepole pine.

The effects of pretreatment by dilute acid and sulfite pretreatment to overcome recalcitrance of lignocellulose (SPORL) on substrate morphology, cell wall physical and chemical structures, along with the subsequent enzymatic hydrolysis of lodgepole pine substrate were investigated. FE-SEM and TEM images of substrate structural morphological changes showed that SPORL pretreatment resulted in fiber separation, where SPORL high pH (4.2) pretreatment exhibited better fiber separation than SPORL low pH (1.9) pretreatment. Dilute acid pretreatment produced very poor fiber separation, consisting mostly of fiber bundles. The removal of almost all hemicelluloses in the dilute acid pretreated substrate did not overcome recalcitrance to achieve a high cellulose conversion when lignin removal was limited. SPORL high pH pretreatment removed more lignin but less hemicellulose, while SPORL low pH pretreatment removed about the same amount of lignin and hemicelluloses in lodgepole pine substrates when compared with dilute acid pretreatment. Substrates pretreated with either SPORL process had a much higher cellulose conversion than those produced with dilute acid pretreatment. Lignin removal in addition to removal of hemicellulose in SPORL pretreatment plays an important role in improving the cellulose hydrolysis of the substrate.

Silicone/graphite coating for on-target desalting and improved peptide mapping performance of matrix-assisted laser desorption/ionization-mass spectrometry targets in proteomic experiments.

In two-dimensional gel electrophoresis-based proteomic experiments matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) peptide mass fingerprinting is often the technique of choice in identifying proteins. Here, we present a novel surface coating technique for MALDI-MS targets that improves manual and automatic sample analysis. A mixture of silicone and graphite is spread in the form of a thin layer over the target. Due to the hydrophobicity of the coating, aqueous solutions can be applied to relatively small spots very precisely using a robotic system. At least four times more liquid can be concentrated on the same area compared to uncoated steel targets. alpha-cyano-4-hydrocinnamic acid crystallizes in form of very small crystals evenly distributed over the surface. The search for "hot spots" during the analysis is not necessary, which supports the automatic acquisition of data. The homogeneous crystal layer can be very effectively washed on-target without encountering major sample losses. This efficient washing and the focused application of aqueous samples replace expensive and time-consuming reversed phase micro column based sample clean-ups. When analyzing peptide mixtures, the signal intensities are up to five times higher than with preparations of the same un-desalted samples on steel targets, since four times more sample can be loaded. The mass resolution remains unaffected by the surface coating. After usage the coating can be removed, followed by a new coating avoiding any carry-over of sample to the next analysis. All these properties make the precoating of MALDI-MS targets with a silicone/graphite layer an ideal technique for routine analysis in large-scale proteomic experiments.