Microsphere-Structured Protein Hydrogel Dielectrics for Capacitive Wearable Sensors.

The desire for healthy living has created a crucial need for portable flexible health-monitoring devices based on biomaterials. Toward this end, we report a microsphere-structured hydrogel that uses bovine serum albumin (BSA) as a dielectric layer for capacitive pressure sensors. We developed a theoretical model that describes how stacking dielectric layers of spheres affects the performance of capacitive sensors. We also prepared a prototype sensor featuring the unique microsphere structure to create capacitive sensors with high sensitivity (360.91 strain sensitivity), excellent cyclical stability, and a long service life (over 5000 stretching-compression cycles). Furthermore, the design of the hydrogel sensor allows for easy integration into fabrics to create devices such as smart wristbands, which can collect a diverse range of health data. Thus, BSA-hydrogel-based sensors not only provide safe wearable devices but also advance the performance of high-sensitivity capacitive sensors.

Design and function of lignin/silk fibroin-based multilayer water purification membranes for dye adsorption.

The treatment of dye wastewater poses a significant challenge to the sewage recycling industries. However, the reduction of secondary pollution resulting from the membrane residues, to maintain high performance, remains a considerable obstacle. A novel approach for the fabrication of multilayer nanofiber structures using a layer-by-layer electrostatic spinning technique with biological materials was reported in this study. Incorporating the chemical adsorption advantages of lignin nanofiber and the physical adsorption advantages of silk fibroin (SF) nanofiber enabled the full realization of excellent dye interception performance. A comparative analysis was conducted on the lignin derived from eucalyptus, pine, and straw to determine the most suitable option. Notably, eucalyptus lignin exhibited superior antimicrobial properties. The adsorption of crystal violet by eucalyptus lignin/SF membrane was consistent with the Freundlich isotherm model and the pseudo-second-order kinetic model, revealing a chemisorption mechanism involving Π-Π conjugation, hydrogen bonding, and the binding of anions and cations. The lignin/SF membrane exhibited a retention rate exceeding 99.5 % for crystal violet, methylene blue, and brilliant green dyes. Furthermore, it demonstrated efficacy in retaining heavy metal ions, including cadmium and copper. The original biomass material imparts the property of rapid degradation to a multilayer membrane that can be used as an effective and eco-friendly water purification material.

Highly stretchable, fast self-healing nanocellulose hydrogel combining borate ester bonds and acylhydrazone bonds.

Self-healing hydrogels have received considerable attention as a promising material for flexible electronic devices given their mechanical durability and structurally tunable properties. In this study, a highly stretchable self-healing hydrogel with dual cross-linking network was developed via borate ester bonds generated by polyvinyl alcohol and borax, and acylhydrazone bonds formed by aldehyde nanocellulose with adipic acid dihydrazide-modified alginate. Compared with the single network hydrogel composed of polyvinyl alcohol and borax, the introduction of dynamic acylhydrazone bonds greatly increases the flexibility of the hydrogel. The elongation rate increased from 480 % to approximately 1440 %, and the self-healing efficiency increased from 84.6 % to 92.7 % after healing for 60 min at ambient temperature without any stimulus. Moreover, the longer the self-healing time, the more evident the self-healing effect of the acylhydrazone bonds. In addition, electrical measurements confirmed a wide working strain range (ca.1000 %), durability, and reliability. Once assembled as a strain sensor, the hydrogel is able to monitor both large and subtle human motions. Besides, this hydrogel exhibited desirable biocompatibility, as demonstrated by in vitro cytotoxicity towards NIH 3T3 cells. These integrated properties make this nanocomposite hydrogel a promising candidate for future applications as green, flexible, and smart sensors.

Comparative investigation of the structural characteristics of tobacco stalk lignin during the DES and alkaline deconstruction toward sustainable materials.

Lignin polymer as a natural aromatic macromolecule presents significant prospects in producing functional and sustainable materials, and achieving a comprehensive characterization will facilitate their target valorization. In the present study, deep eutectic solvent (DES) and alkaline delignification were adopted to deconstruct tobacco stalk before and after hydrothermal pretreatment, obtaining diverse lignin fractions with fascinating characteristics. DES lignin exhibited a higher yield and homogenous molecular structure than MWL. A severe cleavage of the inter-unit linkages in lignin was also observed. This result mostly originated from the efficient delignification of the DES deconstruction system adopted. Moreover, all the recovered lignin fractions exhibited good micro-nanoparticle size that can enhance the valorization of lignin in nanomaterial production, in which the hydrothermal-assisted DES deconstruction promoted the formation of the smaller lignin nanoparticle size. Next, all the recovered lignin presented an excellent UV absorption and structure-related absorption performance or thermal properties. Overall, this work provides an important foundation for further exploiting DES/alkaline delignification lignin that can be applied as an ideal feedstock for producing sustainable functional or micro/nanomaterials.

Facile Construction of Iron/Nickel Phosphide Nanocrystals Anchored on N-B-Doped Carbon-Based Composites with Advanced Catalytic Capacity for 4-Nitrophenol and Methylene Blue.

The search for a simple and effective method to remove organic dyes and color intermediates that threaten human safety from the water environment is urgent. Herein, we report a simple method for constructing iron/nickel phosphide nanocrystals anchored on N-B-doped carbon-based composites, using steam-exploded poplar (SEP) and graphene oxide (GO) as a carrier. The stability and catalytic activity of N-B-NixFeyP/SEP and GO were achieved by thermal conversion in a N2 atmosphere and modifying the Fe/Ni ratio in gel precursors. N-B-Ni7Fe3P/SEP was employed for the catalytic hydrogenation of 4-nitrophenol (4-NP) and methylene blue (MB), using sodium borohydride in aqueous media at room temperature. This showed much better catalytic performances in terms of reaction rate constant (0.016 S-1 and 0.041 S-1, respectively) and the activity factor, K (1.6 S-1·g-1 and 8.2 S-1·g-1, respectively) compared to the GO carrier (0.0053 S-1 and 0.035 S-1 for 4-NP and MB, respectively). The strong interaction between the carrier's morphology and structure, and the vertically grown bimetallic phosphide nanoclusters on its surface, enhances charge transfer, electron transfer kinetics at the interface and Ni-Fe phosphide dispersion on the nanoclusters, and prevents dissolution of the nanoparticles during catalysis, thereby improving stability and achieving catalysis durability. These findings provide a green and simple route to efficient catalyst preparation and provide guidance for the rational selection of catalyst carriers.

Deep eutectic solvent with Lewis acid for highly efficient biohydrogen production from corn straw.

To boost saccharification and biohydrogen production efficiency from corn straw, Lewis acid enhanced deep eutectic solvent (DES) pretreatment using choline chloride/glycerol was developed. A notable enhancement of the enzymatic hydrolysis efficiency from 26.3 % to 87.0 % was acquired when corn straw was pretreated with aqueous DES at 100 °C for 5 h using 2.0 wt% AlCl3. A maximum biohydrogen yield of 114.8 mL/g total solids (TS) was achieved in the sequential dark fermentation stage, which was 2.1 times higher than that of the raw feedstock (37.1 mL/g TS). The enhanced efficient conversion was ascribed to the effective removal of lignin and hemicellulose, which led to the bio-accessibility of the straw. This work provides new sights for the rational design of efficient AlCl3-aided aqueous DES system toward biohydrogen production from lignocellulosic biomass.

Enzymatic Crosslinked Silk Fibroin Hydrogel for Biodegradable Electronic Skin and Pulse Waveform Measurements.

The development of a portable, controllable, and environmentally friendly electronic skin (e-skin) is highly desirable; however, it presents a major challenge. Herein, a biocompatible, biodegradable, and easily usable hydrogel was designed and fabricated as e-skin to enable the transmission of information regarding the spatial pressure distribution. Silk fibroin (SF) was used as the hydrogel skeleton, which endowed the hydrogel with intelligent mechanical sensitivity. During its conditioning in weakly acidic media, the density of the enzymatic crosslink increased and a dense network was formed due to the formation of covalent/hydrogen bonds. Additionally, a conductive SF/polyvinyl alcohol (PVA) hybrid film was molded as a flexible electrode after graphite deposition. The above SF sensing unit based on SF hydrogels and SF/PVA hybrid films showed high strain sensitivity (4.78), fast responsiveness (<0.1 s), good cycling stability (≥10,000), excellent biocompatibility, and biodegradability. Importantly, a coplanar 8 × 8 pixel SF-based e-skin array was successfully fabricated and applied for 3D signal transmission of the object. The SF-based e-skin was capable of precisely tracking the changes in the pulse pressure, the movement of the finger joint, and the vibrations of the vocal cord. Therefore, the current findings provide a solid foundation for future studies exploring the next generation of electronic devices.

Customized Utilization Strategies of Industrial Lignin to Produce Adsorbents and Flocculants Based on Fractionation and Adequate Structural Interpretation.

Lignin, a by-product of pulping and biorefinery, has great potential to replace petrochemical resources for wastewater purification. However, the defects of lignin, such as severe heterogeneity, inferior reactivity and poor solubility, characterize the production process of lignin-based products by high energy consumption and serious pollution. In this study, several lignin fractions with relatively homogeneous structure were first obtained by organic solvent fractionation, and their structures were fully deciphered by various characterization techniques. Subsequently, each lignin component was custom-valued for wastewater purification based on their structural characteristics. Benefiting from the high reactivity and reaction accessibility, the lignin fraction (lignin-1) refined by dissolving in ethanol and n-butanol could been used as a raw material to produce cationic lignin-based flocculant (LBF) in a copolymerization system using green, cheap and recyclable ethanol as solvent. The lignin fraction (lignin-2) extracted by methanol and dioxane showed low reactivity and high carbon content, which was used to produce lignin-based activated carbon (LAC) with phosphoric acid as activator. Moreover, the influences of synthetic factors on the purification capacity were discussed, and the LBF and LAC produced under the optimal conditions showed distinguished purification effect on kaolin suspension and heavy metal wastewater, respectively. Furthermore, the corresponding purification mechanism and external factors were also elaborated. It is believed that this cleaner production strategy is helpful for the valorization of lignin in wastewater resources.

Fast pyrolysis of guaiacyl-syringyl (GS) type milled wood lignin: Product characteristics and CH4 formation mechanism study.

It is anticipated that the insight into the demethylation and mechanism of CH4 formation from natural lignin using in-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ FTIR) combined with two-dimensional perturbation correlation infrared spectroscopy (2D-PCIS) and density functional theory (DFT) calculation analysis would contribute to a deeper insight of bond cleavage mechanism of lignin pyrolysis. Herein, GS-type lignin (poplar MWL) was characterized by Fourier transform infrared spectroscopy (FTIR) and heteronuclear Single-Quantum Correlation Nuclear Magnetic Resonance (HSQC), and its pyrolysis at different temperatures was performed in a lab-scale fixed-bed reactor. The biochar, gaseous and liquid products were qualitative, and quantitative analysis of gases and bio-oil is demonstrated using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The key of CH4 formation is the homolytic cleavage of the methoxyl functional group generating methyl radical and further verified via in-situ FTIR combined with 2D-PCIS and DFT calculation. The study established a new methodology based on multiple factor analysis to evaluate the CH4 formation mechanism in GS-type milled wood lignin at the molecular level, which is of positive significance for increasing lignin valorization and improving the environment.

Lightweight, strong, and form-stable cellulose nanofibrils phase change aerogel with high latent heat.

Phase change material (PCM) is promising for energy storage and release. However, the deformation and leaking during phase change generally limit its application. Herein, a lightweight, strong, and form-stable PCM aerogel was fabricated using Pickering emulsion templating technique. Cellulose nanofibrils (CNFs) were used to stabilize PCM into Pickering emulsion, which was further integrated into a 3D interconnected CNF network forming CNF/PCM composite aerogel. The composite aerogel is strong that can support over 5000 times of its own weight, and demonstrates exceptional form stability at 80 °C, showing no leakage after 20 heating/cooling cycles. The latent heat of CNF/PCM composite aerogel could reach 173.59 J·g-1, approximately 84.4% of the paraffin. The CNF/PCM composite aerogel showed relatively low thermal conductivity of 32.0-37.7 mW·m-1·K-1. The sustainability and impressive thermal regulating properties of the CNF/PCM composite aerogel make it an ideal candidate for applications in smart textile, smart building, batteries, and electronic devices.

Sustainable isolation of nanocellulose from cellulose and lignocellulosic feedstocks: Recent progress and perspectives.

As a type of sustainable nanomaterials, nanocellulose has drawn increasing attention over the last two decades due to its great potential in diverse value-added applications such as electronics, sensors, energy storage, packaging, pharmaceuticals, biomedicine, and functional food. Sourcing nanocellulose from lignocellulose is commonly accomplished via the use of mineral acids, oxidizers, enzymes, and/or intensive mechanical energy. Yet, the economic and environmental concerns associated with these conventional isolation techniques pose major obstacles for commercialization. Considerable progress has been achieved in the last few years in developing sustainable nanocellulose isolation technologies involving organic acid/anhydride, Lewis acid, solid acid, ionic liquid, and deep eutectic solvent. This paper provides a comprehensive review of these alternatives with regard to general procedures and key advantages. Important knowledge gaps, including total biomass utilization, complete life cycle analysis, and health/safety, require urgently bridging in order to develop economically competitive and operationally feasible nanocellulose isolation technology for commercialization.

Antifouling, antibacterial and non-cytotoxic transparent cellulose membrane with grafted zwitterion and quaternary ammonium copolymers.

Copolymer brushes with different ratios of sulfobetaine methacrylate (SBMA) and [2-(Acryloyloxy)ethyl]trimethylammonium chloride (DAC) were grafted from transparent cellulose membrane (CM) via surface-initiated atom transfer radical polymerization (SI-ATRP) method for improving its antifouling and antibacterial performance. Surface concentrated copolymer grafting on the cellulose membranes can be obtained without significantly sacrificing the transparency and mechanical properties. The zwitterionic PSBMA chains of the copolymers can lead to an extremely hydrophilic surface with significantly reduced non-specific protein adsorption and bacterial attachment, therefore, leading to satisfying antifouling and antibacterial property. While the PDAC chains of the copolymers improved antibacterial performance against both Gram-positive and Gram-negative bacteria due to the presence of quaternary ammonium groups, the PDAC modified CM (CM-1) possessed best antibacterial performance, reaching to 95.1 % against S. aureus and 90.5 % against E. coli, respectively. More importantly, the biocompatibility of all grafted CM was retained, leading to over 100 % cell viability.

Flexible and Super Thermal Insulating Cellulose Nanofibril/Emulsion Composite Aerogel with Quasi-Closed Pores.

Because of the prevailing environment and energy challenges, there has been a growing interest in biobased materials for thermal insulation application. Although cellulose aerogel has been considered as an excellent thermal insulating material, its thermal conductivity is generally negatively affected by the interconnected internal pores. Herein, it is demonstrated that a cellulose nanofibril (CNF)/emulsion composite aerogel with quasi-closed internal pores can be facilely fabricated by Pickering emulsion templating and solvent exchange methods. The CNF-stabilized oil-in-water Pickering emulsion (with an average diameter of 1.3 µm) can be converted into quasi-closed pores by sequential solvent exchange to acetone and tert-butanol (TBA), followed by freeze-drying from TBA to suppress the formation of large ice crystals. The presence of quasi-closed pores from emulsion templating is verified by both confocal microscopy and scanning electron microscopy images and is confirmed to reduce thermal conductivity to as low as 15.5 mW/(m K). Compared to the CNF aerogel, increasing emulsion content can lead to better volume retention with significantly reduced density (11.4 mg/cm3), increased mesoporosity, and enhanced specific modulus (18.2 kPa/(mg/cm3)) and specific yield strength (1.6 kPa/(mg/cm3)). In addition, the CNF/emulsion composite aerogel also demonstrates superb flexibility and infrared shielding performance.

Acidic deep eutectic solvent assisted isolation of lignin containing nanocellulose from thermomechanical pulp.

Nanocellulose is a promising material but its isolation generally requires unrecyclable hazardous chemicals and high energy consumption and its overall yield is low due to the use of high purity cellulose as precursor. In order to overcome these shortcomings, in this study, thermomechanical pulp (TMP) was investigated as a precursor for isolating lignin containing nanocellulose (LNC) using an environmentally friendly acidic deep eutectic solvent (DES) pre-treatment. Flat "ribbon" like LNCs (around 7.1 nm wide, 3.7 nm thick) with uniformly distributed lignin nanoparticles of 20-50 nm in diameter were successfully obtained at 57 % yield under optimum pre-treatment conditions (90 °C, 6 h, 1:1 oxalic acid dihydrate to choline chloride ratio). The LNCs exhibit cellulose Iß structure, high lignin content (32.6 %), and high thermal stability (Tmax of 358 °C). In general, green acidic DES pre-treatment has shown high efficiency in converting high lignin content biomass into value-added LNC, which benefits both lignocellulose utilization and environmental protection.

Recycling of pre-hydrolysis liquor to improve the concentrations of hemicellulosic saccharides during water pre-hydrolysis of aspen woodchips.

In this study, the pre-hydrolysis liquor (PHL) was recycled during aspen chip water pre-hydrolysis, and the effects of PHL recycling on the extraction and accumulation of the hemicellulosic saccharides especially that with high molecular weight in the PHL were studied. The results showed that the concentration of hemicellulose saccharides in PHL depended on the pre-hydrolysis temperature and PHL recycling times. Compared to the unrecycled PHL, the concentration of hemicellulosic saccharides in PHL increased significantly when recycling PHL once or twice at 170°C. Furthermore, the amount of high-molecular-weight hemicelluloses (HMHs) in PHL recycled once at 170°C increased from 2.58g/L (unrecycled) to 6.18g/L, but the corresponding average molecular weight of HMHs decreased from 9.2kDa to 7.6kDa. The concentration of hemicellulosic saccharides in PHL decreased with PHL recycling time at 180°C, accompanied by the formation of a significant amount of furfural.

Separation and purification of hemicellulose-derived saccharides from wood hydrolysate by combined process.

Prehydrolysis of wood biomass prior to kraft cooking provides a stream containing hemicellulose-derived saccharides (HDSs) but also undesired non-saccharide compounds (NSCs) that were resulted from lignin depolymerization and carbohydrate degradation. In this study, a combined process consisting of lime treatment, resin adsorption, and gel filtration was developed to separate HDSs from NSCs. The macro-lignin impurities that accounted for 32.2% of NSCs were removed by lime treatment at 1.2% dosage with negligible HDSs loss. The majority of NSCs, lignin-derived phenolics, were eliminated by mixed bed ion exchange resin, elevating NSCs removal to 94.0%. The remaining NSCs, furfural and hydroxymethylfurfural, were excluded from HDSs by gel filtration. Chemical composition analysis showed that xylooligosaccharides (XOS) with the degree of depolymerization from 2 to 6 accounted for 28% of the total purified HDSs.

Fractionation and characterization of saccharides and lignin components in wood prehydrolysis liquor from dissolving pulp production.

Saccharides and lignin components in prehydrolysis liquor (PHL) from kraft-based dissolving pulp production was characterized after being fractionated using membrane filtration. The results showed that the membrane filtration provided a method for organics fractionation with considerable recovery rate, but exhibited some disadvantages. Besides the limited ability in purifying oligosaccharides (OS) due to the overlaps of molecular weight distribution with lignin components, the membrane filtration could not improve the homogeneity of OS as indicated by the analysis of chemical compositions and the degree of polymerization (DP), which may be ascribed to the linear conformation of OS. The characterization of lignin components indicated a great potential for polymer industry because of the remarkable content of phenolic hydroxyl groups (PhOH), especially for low molecular weight (LMW) fraction. It was concluded the organics in PHL provided streams of value-added chemicals. However, the practical significance thereof can be realized and maximized only when they are successfully and completely fractionated.

Selective removal of phenolic lignin derivatives enables sugars recovery from wood prehydrolysis liquor with remarkable yield.

The specific elimination of lignin derivatives from wood hydrolysate without sugar loss has great practical significance to biorefinery and bioenergy. In the present study, a process consisting of calcium hydroxide and anion exchange resin treatments was developed for the purpose of selective removal of lignin from wood prehydrolysis liquor (PHL). Particular emphasis was made on the ionization of phenolic lignin, and the subsequent binding to metallic salts. It was observed that phenolic hydroxyl groups (PhOH) in lignin played an important role in lignin removal. The results showed that up to 95.2% lignin was removed from PHL with 78.8% sugar recovery. This suggested that the proposed process is highly specific to lignin, and therefore can be envisaged as a great contribution to wood-sugar production or bioenergy conversion.

Lignosulfonate-mediated cellulase adsorption: enhanced enzymatic saccharification of lignocellulose through weakening nonproductive binding to lignin.

BACKGROUND: Thermochemical pretreatment of lignocellulose is crucial to bioconversion in the fields of biorefinery and biofuels. However, the enzyme inhibitors in pretreatment hydrolysate make solid substrate washing and hydrolysate detoxification indispensable prior to enzymatic hydrolysis. Sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL) is a relatively new process, but has demonstrated robust performance for sugar and biofuel production from woody biomass in terms of yield and energy efficiency. This study demonstrated the advantage of SPORL pretreatment whereby the presentation of lignosulfonate (LS) renders the hydrolysate non-inhibitory to cellulase (Cel) due to the formation of lignosulfonate-cellulase complexes (LCCs) which can mediate the Cel adsorption between lignin and cellulose, contrary to the conventional belief that pretreatment hydrolysate inhibits the enzymatic hydrolysis unless detoxified. RESULTS: Particular emphasis was made on the formation mechanisms and stability phase of LCCs, the electrostatic interaction between LCCs and lignin, and the redistributed Cel adsorption between lignin and cellulose. The study found that LS, the byproduct of SPORL pretreatment, behaves as a polyelectrolyte to form LCCs with Cel by associating to the oppositely charged groups of protein. Compared to Cel, the zeta potential of LCCs is more negative and adjustable by altering the molar ratio of LS to Cel, and thereby LCCs have the ability to mitigate the nonproductive binding of Cel to lignin because of the enlarged electrostatic repulsion. Experimental results showed that the benefit from the reduced nonproductive binding outweighed the detrimental effects from the inhibitors in pretreatment hydrolysate. Specifically, the glucan conversions of solid substrate from poplar and lodgepole pine were greatly elevated by 25.9% and 31.8%, respectively, with the complete addition of the corresponding hydrolysate. This contradicts the well-acknowledged concept in the fields of biofuels and biorefinery that the pretreatment hydrolysate is inhibitory to enzymes. CONCLUSIONS: The results reported in this study also suggest significant advantages of SPORL pretreatment in terms of water consumption and process integration, that is, it should abolish the steps of solid substrate washing and pretreatment hydrolysate detoxification for direct simultaneous saccharification and combined fermentation (SSCombF) of enzymatic and pretreatment hydrolysate, thereby facilitating bioprocess consolidation. Furthermore, this study not only has practical significance to biorefinery and bioenergy, but it also provides scientific importance to the molecular design of composite enzyme-polyelectrolyte systems, such as immobilized enzymes and enzyme activators, as well as to the design of enzyme separation processes using water-soluble polyelectrolytes.