Characterization of microcrystalline cellulose prepared from long and short fibers and its application in ibuprofen tablets.

As a bio-based material, microcrystalline cellulose (MCC) has been applied in many fields including pharmaceuticals, foods, and cosmetics in recent years. However, traditional preparation methods of MCC are facing many challenges due to economic and eco-environmental issues. In this study, softwood dissolved pulp was sieved to long fiber (LF) and short fiber (SF), and subsequently to prepare LF-MCC and SF-MCC by hydrochloric acid hydrolysis at different acid dosages (3-7 wt%), reaction times (30-90 min), and temperatures (75-95 °C). The as-obtained MCC products were compared in terms of morphology, size, crystallinity, and chemical structure. The results indicated that the crystallinity and yield of LF-MCC were high, with maximum values of 78.41 % and 98.68 %, respectively. The particle size distribution of SF-MCC was more uniform in the range of 20-80 µm, with a maximum of 59.44 % at 20-80 µm occupancy proportion. Moreover, SF-MCC had a typical rod-like shape and larger surface area as well as better thermal behavior than LF-MCC. When LF-MCC and SF-MCC were used as fillers in the production of ibuprofen tablets, the tablets added with LF-MCC exhibited higher hardness, friability, dissolution rate, and shorter disintegration time. Therefore, this work is very beneficial for the preparation and application of MCC.

Preparation and Characterization of Pullulan-Based Packaging Paper for Fruit Preservation.

Improving the shelf lives of fruits is challenging. The biodegradable polysaccharide pullulan exhibits excellent film-forming ability, gas barrier performance, and natural decomposability, making it an optimal material for fruit preservation. To overcome problems of high cost and film porosity of existing packaging technologies, we aimed to develop pullulan-based packaging paper to enhance the shelf lives of fruits. A thin paper coating comprising a mixture of 15 wt.% pullulan solution at various standard viscosities (75.6, 77.8, and 108.5 mPa·s) with tea polyphenols (15:2) and/or vitamin C (150:1) improved the oxygen transmission rate (120-160 cm3 m-2·24 h·0.1 MPa), water vapor transmission rate (<5.44 g·mm-1 m-2·h·kPa), maximum free radical clearance rate (>87%), and antibacterial properties of base packaging paper. Grapes wrapped with these pullulan-based papers exhibited less weight loss (>4.41%) and improved hardness (>16.4%) after 10 days of storage compared to those of control grapes (wrapped in untreated/base paper). Grapes wrapped with pullulan-based paper had >12.6 wt.% total soluble solids, >1.5 mg/g soluble protein, >0.44 wt.% titratable acidity, and ≥4.5 mg 100 g-1 ascorbic acid. Thus, pullulan-based paper may prolong the shelf life of grapes with operational convenience, offering immense value for fruit preservation.

Lignocellulosic biomass pretreatment with a lignin stabilization strategy and valorization toward multipurpose fractionation.

Lignocellulosic biomass has emerged as a promising alternative with sustainable advantages for the production of a wide range of renewable products and value-added chemicals. In this study, a pretreatment strategy that use a fully recyclable acid hydrotrope (p-TsOH aqueous solution) to extract lignin and employ glyoxylic acid (GA) to stabilize lignin was proposed for biomass valorization toward multipurpose fractionation. 83.0 % of lignin was dissolved out by p-TsOH hydrotrope (80 wt%) with GA addition to form GA-stabilized product at 80 o C for 15 min. The stabilized lignin was subsequently used as an additive in the preparation of lignin-based suncream. Notably, the incorporation of 4 wt% lignin nanospheres into an SPF15 sunscreen yielded a measured SPF of 59.94. Furthermore, the depolymerization of uncondensed lignin into aromatic monomers yielded a high lignin-oil yield of 84.2 %. Additionally, direct heating of the pretreatment liquor facilitated the conversion of monosaccharides into furfural, achieving a desired yield of 53.7 % without the addition of any acid catalyst. The pretreatment also enhanced the enzymatic hydrolysis of glucan, resulting in a saccharification yield of 98.4 %. Moreover, short-term ultrasonication of the pretreated substrate yielded pulp suitable for papermaking. Incorporating 15 wt% fibers into the produced paper sheets led to a 5.3 % increase in tear index and a 25.4 % increase in tensile index. This study presents a viable pretreatment strategy for the multipurpose fractionation of lignocellulosic biomass, offering potential avenues for biomass valorization.

Recent advances in sustainable preparation of cellulose nanocrystals via solid acid hydrolysis: A mini-review.

As a green and renewable nanomaterial, cellulose nanocrystals (CNC) have received numerous attention due to the unique structural features and superior physicochemical properties. Conventionally, CNC was isolated from lignocellulosic biomass mostly depending on sulfuric or hydrochloric acid hydrolysis. Although this approach is effective, some critical issues such as severe equipment corrosion, excessive cellulose degradation, serious environmental pollution, and large water usage are inevitable. Fortunately, solid acid hydrolysis is emerging as an economical and sustainable CNC production technique and has achieved considerable progress in recent years. Herein, the preparation of CNC by solid acid hydrolysis was summarized systematically, including organic solid acids (citric, maleic, oxalic, tartaric, p-toluenesulfonic acid) and inorganic solid acids (phosphotungstic, phosphoric, and Lewis acid). The advantages and disadvantages of organic and inorganic solid acid hydrolysis methods were evaluated comprehensively. Finally, the challenges and opportunities in the later exploitation and application of solid acid hydrolysis to prepare CNC in the industrial context are discussed. Considering the future development of this technology in the large-scale CNC production, much more efforts should be made in lowering CNC processing cost, fabricating high-solid-content and re-dispersible CNC, developing value-added applications of CNC, and techno-economic analysis and life cycle assessment on the whole process.

Production of nanocellulose using acidic deep eutectic solvents based on choline chloride and carboxylic acids: A review.

Nowadays, nanocellulose production processes with numerous merits of green, eco-friendly, and cost-effective are in urgent need. Acidic deep eutectic solvent (ADES), as an emerging green solvent, has been widely applied in the preparation of nanocellulose over the past few years, owing to its unique advantages, including non-toxicity, low cost, easy synthesis, recyclability, and biodegradability. At present, several studies have explored the effectiveness of ADESs in nanocellulose production, particularly those based on choline chloride (ChCl) and carboxylic acids. Various acidic deep eutectic solvents have been employed, with representative ones such as ChCl-oxalic/lactic/formic/acetic/citric/maleic/levulinic/tartaric acid. Herein, we comprehensively reviewed the latest progress of these ADESs, focusing on the treatment procedures and key superiorities. In addition, the challenges and outlooks of ChCl/carboxylic acids-based DESs implementation in the fabrication of nanocellulose were discussed. Finally, some suggestions were proposed to advance the industrialization of nanocellulose, which would help for the roadmap of sustainable and large-scale production of nanocellulose.

Light-colored lignin extraction by ultrafiltration membrane fractionation for lignin nanoparticles preparation as UV-blocking sunscreen.

A wide range of applications are available for kraft lignin (KL). However, the dark color and wide size distribution of KL make it challenging to use in cosmetics and nanoparticle preparation. In this study, we fractionated KL from a paper-making enterprise using ultrafiltration membrane fractionation, and obtained four kinds of lignin with different molecular weights, namely ultrafiltration lignin (UL). Following that, lignin nanoparticles (ULNPs) were formed by self-assembly from four types of UL. Analyzing the UL and ULNP properties, the low molecular weight lignin, such as ULA, exhibited good antioxidant properties (89.47 %, 5 mg/mL), high brightness (ISO% = 7.55), high L⁎ value (L⁎ = 72.3) and low polydispersity index (PDI = 1.41). The ULNP showed a narrow size distribution (0.8-1.4 m) and high dispersibility in sunscreen. When ULNP was added to sunscreen with 5 % load, its sun protection factor (SPF) value increased from 14.93 to 63.74. Therefore, this study offered an effective way for the comprehensive utilization of pulping waste KL.

A cascade valorization of Kenaf stalk for the preparation of lignin sunscreens and papermaking.

Lignin has been regarded as a potential natural sun screening agent. However, the dark color of traditional industrial lignin hinders its application in the field of skincare. In this study, a green and facile approach was developed to extract light-colored lignin. p-Toluenesulfonic acid (p-TsOH) was used to separate lignin and fibers from Kenaf stalks. During the isolation of lignin, formaldehyde was added to preserve the ß-O-4 bonds of lignins in the form of stable acetals. The obtained lignin was further employed to prepare nanoparticles (LNPs) as sunscreen additives. After adding 4 wt% LNPs, the SPF values of the cream increased from 7.05 to 27.84. The residual fibers from the Kenaf stalks can be utilized for papermaking as the raw materials. by mixing them with softwood pulp to reduce the consumption of commercial pulp. With the addition of 5 wt% residual fibers in commercial softwood pulp, the produced paper showed better mechanical properties. The ring crush strength index and tear index of the samples increased from 2.49 N·m/g and 4.63 mN·m2/g to 2.62 N·m/g and 4.75 mN·m2/g, respectively. This study paved a way for the comprehensive utilization of Kenaf stalks towards not only papermaking but also daily chemical products.

Nanogrinding/ethanol activation facilitating lignin fractionation for preparation of monodispersed lignin nanoparticles.

Lignin nanoparticles (LNPs), as one of green and sustainable biological macromolecules, have attracted great attention owing to their promising potentials in many valorized fields. However, the lignin heterogeneity seriously restricts the controllable preparation of LNPs. Herein, a facile nanogrinding activation combining anhydrous ethanol dissolution process was developed to efficiently homogenize lignin prior to gradient ethanol fractionation. Two lignin fractions were obtained from nanogrinding activation/ethanol dissolution followed by gradient ethanol fractionation: L-fractions and S-fractions. Therefore, monodispersed LNPs with unique concave hollow nanostructure and large particle size, and monodispersed LNPs with solid core nanostructure and small particle size were successfully prepared from L-fractions and S-fractions, respectively, via a GVL/water anti-solvent method. The proposed LNPs formation mechanisms facilitated by nanogrinding activation/ethanol dissolution treatment were demonstrated. This study put forwards a facile and green integrated approach for monodispersed LNPs preparation with controllable morphology and particle size.

Cellulose-based superhydrophobic wrinkled paper and electrospinning film as green tribolayer for water wave energy harvesting.

Water waves are viable low-carbon and renewable sources of power that can be optionally combined with triboelectric nanogeneration (TENG). Herein, we report on the synthesis of a TENG device based on green wrinkled paper tribolayers (W-TENG) assembled in grids (G-TENG) with channels that enable contact-separation modes involving metal balls that roll in phase with the waves. The paper's wrinkle wavelength and amplitude were adjusted by using a crepe blade at a given angle with respect to a drying cylinder, as well as the speed and torque. Polar hierarchical superhydrophobic cellulose micro/nanostructures, proposed as positive tribolayers with enhanced contact area and triboelectric density. The negative (biodegradable) tribolayers were prepared by electrospinning aqueous suspensions of polyvinyl alcohol and poly (ethylene oxide) reinforced with cellulose nanofibers. The charge transfer by the W-TENG reached up to 40 nC in air and retained 27 nC under 85 % relative humidity, ~5 and 7 times higher than those measured in planar TENG counterparts. A G-TENG array charging time (100-µF capacitor) of ~188 s was measured when the voltage of the capacitor raised to ~1.5 V. Overall, we introduce a new, scalable TENG system that is demonstrated for its remarkable ability to harvest blue energy.

Fabrication Mechanisms of Lignin Nanoparticles and Their Ultraviolet Protection Ability in PVA Composite Film.

Lignin is an indispensable and essential compound present in plants. It is a renewable resource and a green alternative to traditional petroleum energy. The rational utilization of lignin can reduce the environmental damage caused by traditional industrial development. The preparation of lignin nanoparticles (LNPs) using the self-assembly method is one of the most favorable ways to achieve high value-added utilization of lignin. However, the process requires an in-depth understanding of the sphere-forming mechanism of lignin self-assembly and the interaction of self-assembly forces. We used the same raw materials and two different preparation methods to prepare LNPs. The results revealed that the variation in the order of the dropwise addition of lignin solution and deionized water produced LNPs with varying average sizes. The sphere-forming mechanisms of the two kinds of lignin nanoparticles were discussed for the preparation of UV-resistant polyvinyl alcohol (PVA) polymeric films. During lignin spherification, the faster the solution reaches the supersaturation state, the faster the spherogenesis rate is, the smaller the size is, and the narrower the particle size distribution is. The lignin micro/nanospheres are produced by exploiting the π-π bonding interactions in lignin itself. The lignin micro/nanospheres are then mixed with PVA to form a film to obtain a lignin-PVA composite film material with an anti-UV effect.

High performance bio-supercapacitor electrodes composed of graphitized hemicellulose porous carbon spheres.

A template-free and one-step carbonization process was developed for fabricating graphitic porous carbon spheres (GPCSs) on hemicelluloses as the electrode material for supercapacitors. This method is green, low-energy, and less time consuming compared to the conventional two-step process (pore-forming and graphitizing). It uses K2FeO4, a mild activating agent that fulfills synchronous activation and graphitization. The GPCSs is regular spherical shape, have high nanoporosity, a large specific surface area (1,250 m2 g-1), and have a high graphitization degree. A unique structural advantage includes a rich interconnected conductive network for electron transfer that shortens the ion transport distance of the electrolyte. Remarkably, the GPCSs electrode displays outstanding electrochemical performance including high specific capacitance (262 F g-1 at 1.0 A g-1), rate capability energy (80%, 20 A g-1), and excellent cycling stability (95%, 10,000 cycles). This work represents a powerful methodology to develop sustainable and low-cost energy storage devices from hemicellulose.

Recent advanced application of lignin nanoparticles in the functional composites: A mini-review.

In recent years, lignin nanoparticles (LNP) have gained tremendous and deep research in the field of functional composites because of their many advantages such as abundant, non-toxic, affordable, green, eco-friendly, biodegradable and biocompatible features along with antioxidant, antibacterial and UV-absorbing abilities. At present, numerous pioneering works have been devoted to the development of LNP-based composites with multiple functions. Herein, we comprehensively reviewed the latest research progress correlated with LNP-filled functional composites. This overview focused on the application of LNP as reinforcement, crosslinker, UV-protectant, antioxidant, antimicrobial and adhesive agents for functional composites. Additionally, the challenges and future outlooks for further exploiting and utilization of LNP in the functional composites were discussed.

Design of co-continuous structure of cellulose/PAA-based alkaline solid polyelectrolyte for flexible zinc-air battery.

In order to prepare high ionic conductivity and robust mechanical properties of alkaline solid polyelectrolyte (ASPE) for applications in flexible wearable devices, a co-continuous structure membrane was designed using in-situ polymerization to introduce cross-linked polyacrylic acid (N-PAA) into the cellulose network constructed by regenerated degreasing cotton (RDC). The resultant ASPE membrane showed high ionic conductivity (430 mS·cm-1 at 25 °C), strong mechanical properties, and excellent alkaline stabilities, proving the viability of cellulose for use in energy storage systems. Surprisingly, the sandwich-shaped zinc-air battery assembled using RDC/N-PAA/KOH membranes as electrolytes exhibits superior values of cycling stability, discharge time, specific capacity (731.5 mAh·g-1), peak power density (40.25 mW·cm-2), and mechanical flexibility. Even under bending conditions, the zinc-air batteries still possess stable energy supply performance, suggesting this novel solid polyelectrolyte has promising application for wearable technology.

Recent advances in lignosulfonate filled hydrogel for flexible wearable electronics: A mini review.

With the rapid development of flexible wearable devices, various polymer hydrogels have gained immense progress due to their adjustable mechanical properties, high conductivity, super sensitivity, good biocompatibility and adaptable wearability. Lignosulfonate (LS), generating from the sulfite pulping industry, was emerged as a promising filler in polymer hydrogels with great potential for multifunctional wearable electronics. Herein, we comprehensively review the latest research progress associated with LS-based hydrogels. Firstly, the function mechanism of lignosulfonate in diverse polymer hydrogels was introduced in detail. Then, the rational design strategies of LS filled multifunctional hydrogels was summarized as toughening filler, adhesive agent, conductive filler dispersant, UV protectant and catalysts. Finally, the future development of LS filled hydrogel for flexible wearable electronics was proposed.

Alkylation modification for lignin color reduction and molecular weight adjustment.

The application of industrial kraft lignin is limited by its low molecular weight, dark color, and low solubility. In this work, an efficient crosslinking reaction with N,N-Dimethylformamide (DMF) and 1,6-dibromohexane was proposed for adjusting the molecular weight and color of lignin. The chemical structure of alkylation lignin was systematically investigated by gel permeation chromatography (GPC), ultraviolet spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, and 2D heteronuclear single quantum correlation nuclear magnetic resonance (HSQC NMR) spectra. After the alkylation modification, the molecular weights of the lignin were increased to 1643%. The resinol (ß-ß), ß-aryl ether (ß-O-4), and phenylcoumaran (ß-5) linkages were still the main types of the linkages. The formation of ß-ß linkage would be inhibited at high temperatures. The color reduction of lignin can be attributed to the low content of chromophores and low packing density. This alkylation lignin will be a new and general approach for developing molecular weight-controlled and light-colored lignins, which can find more applications in cosmetics, packing, and other fields.

Responsive and patterned cellulose nanocrystal films modified by N-methylmorpholine-N-oxide.

A type of cellulose solvent, i.e., aqueous N-methylmorpholine- N-O xide (NMMO) solutions, was used to modify cellulose nanocrystal (CNC) photonic films. CNC films can be swollen by NMMO, resulting in red-shifted reflected colors. The swelling effect is supposed to come from NMMO permeation into the crystalline regions of individual CNCs and intercalating in between CNC particles. When NMMO was removed, the reflected colors of CNC films blue shifted because of the reduced helical pitches. NMMO-treated CNC films display reversible responsive colors to humidity changes in several minutes. Increasing NMMO content allows CNC films to enlarge the responsive color range. Aqueous NMMO can be used as an ink to depict responsive photonic patterns on CNC films. This post-treatment approach to producing responsive colors and photonic patterns in CNC films may be applied to the areas of sensor, anti-counterfeiting, and decoration.