Programmed multimaterial assembly by synergized 3D printing and freeform laser induction.

In nature, structural and functional materials often form programmed three-dimensional (3D) assembly to perform daily functions, inspiring researchers to engineer multifunctional 3D structures. Despite much progress, a general method to fabricate and assemble a broad range of materials into functional 3D objects remains limited. Herein, to bridge the gap, we demonstrate a freeform multimaterial assembly process (FMAP) by integrating 3D printing (fused filament fabrication (FFF), direct ink writing (DIW)) with freeform laser induction (FLI). 3D printing performs the 3D structural material assembly, while FLI fabricates the functional materials in predesigned 3D space by synergistic, programmed control. This paper showcases the versatility of FMAP in spatially fabricating various types of functional materials (metals, semiconductors) within 3D structures for applications in crossbar circuits for LED display, a strain sensor for multifunctional springs and haptic manipulators, a UV sensor, a 3D electromagnet as a magnetic encoder, capacitive sensors for human machine interface, and an integrated microfluidic reactor with a built-in Joule heater for nanomaterial synthesis. This success underscores the potential of FMAP to redefine 3D printing and FLI for programmed multimaterial assembly.

Tuning thermal and graphitization behaviors of lignin via complexation with transition metal ions for the synthesis of multilayer graphene-based materials.

Thermal conversion of kraft lignin, an abundant renewable aromatic substrate, into advanced carbon materials including graphitic carbon and multilayer/turbostratic graphene has recently attracted great interest. Our innovative catalytic upgrading approach integrated with molecular cracking and welding (MCW) enables mass production of lignin-derived multilayer graphene-based materials. To understand the critical role of metal catalysts in the synthesis of multilayer graphene, this study was focused on investigating the effects of transition metals (i.e., molybdenum (Mo), nickel (Ni), copper (Cu), and iron (Fe)) on thermal and graphitization behaviors of lignin. During the preparation of metal-lignin (M-lignin) complexes, Fenton-like reactions were observed with the formation of Fe- and Cu-lignin complexes, while Ni ions strongly interacted with oxygen-containing surface functional groups of lignin and Mo oxyanions weakly interacted with lignin through ionic bonding. Different chelation mechanisms of transition metal ions with lignin influenced the stabilization, graphitization, and MCW steps involved in thermal upgrading. The M-lignin complex behaviors in each of the three steps were characterized. It was found that multilayer graphene-based materials with nanoplatelets can be obtained from the Fe-lignin complex via MCW operation at 1000 °C under methane (CH4). Raman spectra indicated that Fe- and Ni-lignin complexes experienced a higher degree of graphitization than Cu- and Mo-lignin complexes during thermal treatment.

Prebiotic inulin enhances gut microbial metabolism and anti-inflammation in apolipoprotein E4 mice with sex-specific implications.

Gut dysbiosis has been identified as a crucial factor of Alzheimer's disease (AD) development for apolipoprotein E4 (APOE4) carriers. Inulin has shown the potential to mitigate dysbiosis. However, it remains unclear whether the dietary response varies depending on sex. In the study, we fed 4-month-old APOE4 mice with inulin for 16 weeks and performed shotgun metagenomic sequencing to determine changes in microbiome diversity, taxonomy, and functional gene pathways. We also formed the same experiments with APOE3 mice to identify whether there are APOE-genotype dependent responses to inulin. We found that APOE4 female mice fed with inulin had restored alpha diversity, significantly reduced Escherichia coli and inflammation-associated pathway responses. However, compared with APOE4 male mice, they had less metabolic responses, including the levels of short-chain fatty acids-producing bacteria and the associated kinases, especially those related to acetate and Erysipelotrichaceae. These diet- and sex- effects were less pronounced in the APOE3 mice, indicating that different APOE variants also play a significant role. The findings provide insights into the higher susceptibility of APOE4 females to AD, potentially due to inefficient energy production, and imply the importance of considering precision nutrition for mitigating dysbiosis and AD risk in the future.

Direct Induction of Porous Graphene from Mechanically Strong and Waterproof Biopaper for On-Chip Multifunctional Flexible Electronics.

Graphene with a 3D porous structure is directly laser-induced on lignocellulosic biopaper under ambient conditions and is further explored for multifunctional biomass-based flexible electronics. The mechanically strong, flexible, and waterproof biopaper is fabricated by surface-functionalizing cellulose with lignin-based epoxy acrylate (LBEA). This composite biopaper shows as high as a threefold increase in tensile strength and excellent waterproofing compared with pure cellulose one. Direct laser writing (DLW) rapidly induces porous graphene from the biopaper in a single step. The porous graphene shows an interconnected carbon network, well-defined graphene domains, and high electrical conductivity (e.g., ≈3 Ω per square), which can be tuned by lignin precursors and loadings as well as lasing conditions. The biopaper in situ embedded with porous graphene is facilely fabricated into flexible electronics for on-chip and paper-based applications. The biopaper-based electronic devices, including the all-solid-state planer supercapacitor, electrochemical and strain biosensors, and Joule heater, show great performances. This study demonstrates the facile, versatile, and low-cost fabrication of multifunctional graphene-based electronics from lignocellulose-based biopaper.

Sonoprocessing improves phenolics profile, antioxidant capacity, structure, and product qualities of purple corn pericarp extract.

For the first time, purple corn pericarp (PCP) was converted to polyphenol-rich extract using two-pot ultrasound extraction technique. According to Plackett-Burman design (PBD), the significant extraction factors were ethanol concentration, extraction time, temperature, and ultrasonic amplitude that affected total anthocyanins (TAC), total phenolic content (TPC), and condensed tannins (CT). These parameters were further optimized using the Box-Behnken design (BBD) method for response surface methodology (RSM). The RSM showed a linear curvature for TAC and a quadratic curvature for TPC and CT with a lack of fit > 0.05. Under the optimum conditions (ethanol (50%, v/v), time (21 min), temperature (28 °C), and ultrasonic amplitude (50%)), a maximum TAC, TPC, and CT of 34.99 g cyanidin/kg, 121.26 g GAE/kg, and 260.59 of EE/kg, respectively were obtained with a desirability value 0.952. Comparing UAE to microwave extraction (MAE), it was found that although UAE had a lower extraction yield, TAC, TPC, and CT, the UAE gave a higher individual anthocyanin, flavonoid, phenolic acid profile, and antioxidant activity. The UAE took 21 min, whereas MAE took 30 min for maximum extraction. Regarding product qualities, UAE extract was superior, with a lower total color change (ΔE) and a higher chromaticity. Structural characterization using SEM showed that MAE extract had severe creases and ruptures, whereas UAE extract had less noticeable alterations and was attested by an optical profilometer. This shows that ultrasound, might be used to extract phenolics from PCP as it requires lesser time and improves phenolics, structure, and product qualities.

Updating the status quo on the extraction of bioactive compounds in agro-products using a two-pot multivariate design. A comprehensive review.

Extraction is regarded as the most crucial stage in analyzing bioactive compounds. Nonetheless, due to the intricacy of the matrix, numerous aspects must be optimized during the extraction of bioactive components. Although one variable at a time (OVAT) is mainly used, this is time-consuming and laborious. As a result, using an experimental design in the optimization process is beneficial with few experiments and low costs. This article critically reviewed two-pot multivariate techniques employed in extracting bioactive compounds in food in the last decade. First, a comparison of the parametric screening methods (factorial design, Taguchi, and Plackett-Burman design) was delved into, and its advantages and limitations in helping to select the critical extraction parameters were discussed. This was followed by a discussion of the response surface methodologies (central composite (CCD), Doehlert (DD), orthogonal array (OAD), mixture, D-optimal, and Box-Behnken designs (BBD), etc.), which are used to optimize the most critical variables in the extraction of bioactive compounds in food, providing a sequential comprehension of the linear and complex interactions and multiple responses and robustness tests. Next, the benefits, drawbacks, and possibilities of various response surface methodologies (RSM) and some of their usages were discussed, with food chemistry, analysis, and processing from the literature. Finally, extraction of food bioactive compounds using RSM was compared to artificial neural network modeling with their drawbacks discussed. We recommended that future experiments could compare these designs (BBD vs. CCD vs. DD, etc.) in the extraction of food-bioactive compounds. Besides, more research should be done comparing response surface methodologies and artificial neural networks regarding their practicality and limitations in extracting food-bioactive compounds.

Lignin-containing Nanocellulose for in situ Chemical-Free Synthesis of AgAu-based Nanoparticles with Potent Antibacterial Activities.

Lignin-containing nanocelluloses (LNCs) have the properties of both lignin and nanocellulose and could overcome the limits of both individual components in metallic nanoparticle synthesis. However, studies on LNCs are still limited, and the potential of such nanomaterials for metallic nanoparticle synthesis has not been fully unraveled. In this study, monometallic silver, gold nanoparticles, and Ag-Au-AgCl nanohybrids were synthesized in situ utilizing LNCs in a chemical-free approach. The parameters, including Ag+ and Au3+ concentrations as well as [Au3+]/[Ag+] ratios, were investigated for their effects on the nanoparticle synthesis. The characterizations, including UV-vis spectrophotometry, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR), confirmed the coexistence of Ag, Au, and AgCl while indicating the key role of lignin and oxygen-containing functional groups in the nanoparticle synthesis. The as-synthesized AgNPs-, AuNPs-, and nanohybrids-LNC samples were tested for their antibacterial activities. In comparison to the monometallic AgNPs-LNC sample, nanohybrids-LNC synthesized with 0.063 mM Au3+ loading showed superior antibacterial activities with minimum inhibitory concentrations (MICs) at 5 µg/mL against Gram-positive Staphylococcus aureus and 10 µg/mL against Gram-negative Salmonella typhimurium with controlled Ag+ release. The results indicated that LNCs can be used to synthesize metallic nanoparticles, and the resultant Ag-Au-AgCl nanohybrids were a potent antibacterial agent with reduced environmental impacts.

High lignin-containing nanocelluloses prepared via TEMPO-mediated oxidation and polyethylenimine functionalization for antioxidant and antibacterial applications.

Lignin-containing nanocelluloses (LNCs) have attracted tremendous research interest in recent years due to less complex extraction processes and more abundant functionality compared to lignin-free nanocelluloses. On the other hand, traditional defibrillation primarily based on bleached pulp would not be readily applied to lignin-containing pulps due to their complex compositions. This study was focused on LNC extraction from lignin-containing pulp via 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation. Three types of switchgrass pulp with varying composition were prepared using different acid-catalyzed pretreatments. The pulps contained as high as 45.76% lignin but minor/no hemicellulose, corresponding to up to 23.72% lignin removal and 63.75-100% hemicellulose removal. TEMPO-mediated oxidation yielded 52.9-81.9% LNCs from respective pulps. The as-produced LNCs possessed aspect ratios as high as 416.5, and carboxyl contents of 0.442-0.743 mmol g-1 along with ζ-potential of -50.4 to -38.3 mV. The TEMPO-oxidized LNCs were further modified by polyethylenimine (PEI), which endowed the LNCs with positive charges plus antioxidant and antibacterial activities. Specifically, the PEI-modified LNCs almost fully scavenged 2,2'-azino-bis-3-ethylbenzthiazoline-6-sulphonic acid (ABTS) radicals at 50 mg L-1 and suppressed the growth of Gram-positive Staphylococcus aureus at 250 µg mL-1.

Microbial Conversion of Lignin-Based Compounds into Carotenoids by Rhodococci.

Lignin valorization is considered an integral part for an economically viable biorefinery. However, heterogenous nature of lignin imposes a big challenge for upgrading diverse lignin-derived intermediates and subsequent downstream processing. To overcome this challenge, we proposed to explore unique convergent pathways in Rhodococus strains to funnel lignin-derived compounds into single target products. A feasible bioprocess for co-production of lipids and carotenoids from lignin by Rhodococci was developed. This process would potentially extract more values from lignin via biological upgrading.

A novel carboxylated polyacrylonitrile nanofibrous membrane with high adsorption capacity for fluoride removal from water.

To deal with the drinking water safety caused by fluoride, a novel carboxylated polyacrylonitrile nanofibrous membrane (C-PAN NFM) is designed and fabricated massively for the first time by adopting synchronously biaxial stretching and carboxylation. The C-PAN NFM is composed of the layered stack structure by cross-linked nanofibers. Due to its high specific surface area, excellent hydrophilicity, a large amount of carboxyl and amine groups, C-PAN NFM owns high fluoride adsorption capacity and outstanding selectivity. Both the carboxylation and acid treatment of C-PAN NFM improved the fluoride adsorption capacity remarkably. Specifically, C-PAN NFM shows excellent reusability without secondary pollution. The fluoride adsorption behavior of C-PAN NFM is dominated by chemical adsorption, and the adsorption mechanism is mainly driven by hydrogen bonding and ion exchange. The mass-produced C-PAN NFM is a novel polyacrylonitrile-based porous membrane that shows a great application potential for fluoride removal with good efficiency and recyclability.

Molecular Entrapment of Polymers by Pyrogallol[4]arenes.

Macromolecular recognition systems are difficult to construct because extremely high recognition ability is required to form a stable host-guest complex toward macromolecules. Herein, we report a novel host-guest recognition motif based on C-propylpyrogallol[4]arene (PgC3) and a commercially available polymer, polyethylene glycol (PEG). The results show that PgC3 can selectively entrap PEG with higher molecular weights to form bilayered host-guest complex structures. Interestingly, this host-guest recognition is strong enough that PgC3 is able to adsorb PEG from an aqueous solution efficiently.

Biomass-derived porous graphene for electrochemical sensing of dopamine.

Cost-effective valorization of biomass into advanced carbon remains a challenge. Here we reported a facile and ultrafast laser writing technique to convert biomass into porous graphene for electrochemical sensing. Laser-induced graphene (LIG) was synthesized from a fully biomass-based film composed of kraft lignin (KL) and cellulose nanofibers (CNFs). The LIG-based electrode was applied to detect dopamine using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. Dopamine with a concentration ranging from 5 to 40 µM was detected linearly, with a sensitivity of 4.39 µA µM-1 cm-2. Our study eliminated the use of synthetic polymer for lignin-based film formation. It demonstrated the feasibility of using the film fully composed of biomass for LIG formation. Furthermore, derived LIG electrodes were shown to have high electrochemical sensing performance.

Laser-Induced Graphene Derived from Kraft Lignin for Flexible Supercapacitors.

Porous graphene was photothermally induced from kraft lignin via direct laser writing. This laser-induced graphene (LIG) possessed a hierarchical structure with a three-dimensional (3D) interconnected network ideal for its transfer from the kraft lignin/poly(ethylene oxide) (KL/PEO) film onto polydimethylsiloxane (PDMS). The resultant LIG/PDMS composite was shown to keep the intrinsic porous structure and electrically active sites of LIG. The supercapacitors (SCs) fabricated using the LIG/PDMS composite exhibited good electrochemical performance and excellent cyclic stability. More than 90% capacitance was retained after 10 000 cycles. Moreover, due to their high flexibility, the SCs were able to endure bending deformation without significantly sacrificing their capacitance. The proposed technology for the fabrication of flexible SCs based on lignin-derived LIG demonstrated great potential to use a low-cost, renewable material for the manufacture of portable and wearable electronics.

One-pot selective conversion of lignocellulosic biomass into furfural and co-products using aqueous choline chloride/methyl isobutyl ketone biphasic solvent system.

This study investigated simultaneous lignocellulose fractionation and conversion in a one-pot reaction using an aqueous choline chloride/methyl isobutyl ketone (ChCl/MIBK) biphasic solvent system. Under the optimized condition (170 °C, 60 min, 0.6 wt% H2SO4, 10.7 wt% solid loading), the biphasic solvent solubilized 96% xylan in raw switchgrass, which was simultaneously converted to furfural with a yield of 84.04%. The biphasic solvent was also able to selectively extract lignin, which had a high purity (93.1%), and uncondensed moieties (i.e., Hibbert's ketone), as well as decreased molecular weight and polydispersity index. The resultant pulp was enriched with cellulose (73.3%), which can be completely hydrolyzed into glucose within 48 h via enzymatic hydrolysis. Aqueous ChCl was successfully recycled and reused for atleast three cycles with similar performance in switchgrass fractionation. This study demonstrated that aqueous ChCl/MIBK biphasic system was an effective solvent system for co-production of furfural, high quality technical lignin and digestible cellulose for further upgrading.

Effect of Dibasic Calcium Phosphate Incorporation on Cellulose Nanocrystal/Chitosan Hydrogel Properties for the Treatment of Vertebral Compression Fractures.

Vertebral compression fractures account for approximately 700,000 out of the 1.5 million total osteoporotic fractures that occur annually in the USA. There is growing interest in substituting currently utilized clinical treatments for vertebral compression fractures with an injectable, degradable, and bioactive system. In this research we studied the osteoinductive effect of calcium phosphate incorporation into cellulose nanocrystal/chitosan hydrogels with varying ratios of carbonate as an ionic crosslinker and genipin as a covalent crosslinker. As calcium and phosphate ions have been shown to be osteoinductive in time and concentration dependent manners, dibasic calcium phosphate was chosen as a bioactive additive due to its desirable controlled ion delivery potential. Gelation time, swelling ratio, erosion, compressive strength, and ion release behavior of different dibasic calcium phosphate incorporated hydrogels were evaluated. Mesenchymal stem cells were then exposed to mechanically competent hydrogels found capable of maintaining calcium and phosphate concentrations within the established bioactive range in order to assess their cytotoxicity and osteoinductivity. Our results demonstrate that hydrogels with higher covalent crosslinking possessed better mechanical properties and stabilities as well as more controlled calcium and phosphate ion release. Interestingly, dibasic calcium phosphate incorporation not only improved hydrogel bioactivity but also resulted in greater compressive strength.

Inductive co-crosslinking of cellulose nanocrystal/chitosan hydrogels for the treatment of vertebral compression fractures.

Vertebral compression fractures are a very common consequence of osteoporosis for which injection of a non-biodegradable, non-bioactive, mechanically-stiff polymer bone cement into the vertebral body is the most common treatment. Recently, there has been growing interest in using bioactive, degradable, and bone biomechanics-matching products as an alternative approach for treating these fractures. In this research, we focused on creating injectable, chitosan-based hydrogels that can convey mechanical strength similar to vertebral bone as well as possess inherent osteoinductivity. First, we investigated the effects of three different factors - 1) bioactive phosphate ionic crosslinking; 2) genipin covalent crosslinking; 3) mechanically reinforcing cellulose nanocrystal incorporation - on the material properties of chitosan-based hydrogels. Mesenchymal stem cells were then exposed to hydrogels with optimum mechanical properties and stability in order to assess the biological effects of the bioactive phosphate ionic crosslinker. Our results show that hydrogels with higher ionic and covalent crosslinking ratios supplemented with neutral cellulose nanocrystals possessed desirable compressive strength and stability. Also, the significant osteoinductivity of these composite hydrogels demonstrated their potential to function as an injectable system for the future treatment of vertebral compression fractures.

Ternary deep eutectic solvents for effective biomass deconstruction at high solids and low enzyme loadings.

Ternary deep eutectic solvents (DESs) were developed to enable rapid and high-solid biomass pretreatment as well as concentrated sugar hydrolysate production. Six ternary DESs constituted choline chloride (ChCl) or guanidine hydrochloride (GH) as a hydrogen bond acceptor (HBA), ethylene glycol (EG) or propylene glycol (PG) or glycerin (GLY) as a polyol-based hydrogen bond donor (HBD), and p-toluenesulfonic acid (PTSA) as an acidic HBD. GH-EG-PTSA was the most effective, evidenced by 79% xylan and 82% lignin removal in only 6 min at 120 °C and 10 wt% solid loading. Even at 35 wt% solid loading, both GH-EG-PTSA and ChCl-EG-PTSA still removed more than 60% xylan and lignin in 30 min. Using a 20% solid loading and a low enzyme loading of 5 mg protein/g solid, 128 g/L glucose and 20 g/L xylose was obtained, with a glucose yield of 78.4%. Overall, this study demonstrated novel and high-performance ternary DESs for effective lignocellulose deconstruction.

Transforming lignin into porous graphene via direct laser writing for solid-state supercapacitors.

Cost-effective valorization of lignin into carbon-based electrode materials remains a challenge. Here we reported a facile and ultrafast laser writing technique to convert lignin into porous graphene as active electrode material for solid-state supercapacitors (SCs). During laser writing, alkaline lignin experienced graphitization. By controlling laser parameters such as power the porous structure and graphitization degree can be well modulated. Graphene obtained at 80% of laser power setting (LIG-80) had higher graphene quality and more porous structure than that obtained at the lower power levels (i.e., 50%, 70%). TEM images revealed that LIG-80 had few-layer graphene structure with fringe-like patterns. LIG-80 proved to be an active electrode material for SCs with a specific capacitance as high as 25.44 mF cm-2 in a H2SO4/PVA gel electrolyte, which is comparable or even superior to SCs based on pristine LIG obtained from other carbon precursors. Taken together, our proposed technical route for lignin-based LIG and subsequent application in SCs would not only open a new avenue to lignin valorization, but also produce porous graphene from a renewable carbon precursor for energy storage applications.

Deep eutectic solvent pretreatment enabling full utilization of switchgrass.

In this study, an acidified, aqueous DES comprising choline chloride: glycerol (ChCl:Gly) was used to fractionate switchgrass into three major streams under a relatively mild condition: cellulose-rich pulp, lignin, and xylose-rich liquor. The pulp showed good digestibility with about 89% glucose yield. The solvent can be recycled successfully and reused for at least four more pretreatment cycles while maintaining its pretreatment capability. The solvent recycling also improved the lignin recovery from the pretreatment liquor. Lignin recovered from different pretreatment cycles had the ß-O-4 bonds preserved, and shared similar structures with native lignin. Using the pretreatment liquor as a substrate, the oleaginous yeast Rhodotorula toruloides produced 18.7 g/L biomass with lipid and carotenoid titers of 8.1 g/L and 15.0 mg/L, respectively. Overall, this study demonstrated a green process integrating chemical and biological methods toward full utilization of lignocellulosic biomass.

Ultrafast fractionation of lignocellulosic biomass by microwave-assisted deep eutectic solvent pretreatment.

Deep eutectic solvents (DESs) have received increasing attention in recent years as designer solvents for bioprocessing. In this study, ultrafast microwave-assisted DES pretreatment was developed for lignocellulose fractionation. The pretreatment was conducted for 45 s with microwave irradiation at 800 W using a DES composed of choline chloride and lactic acid (ChCl: LA). The results indicated that such pretreatment was highly effective in removing lignin and xylan while retaining most of cellulose in the pretreated solids. The ultrafast fractionation increased the cellulose digestibility by 2-5 folds. Switchgrass gave a similar glucose yield to corn stover but experienced less cellulose loss during the pretreatment. Miscanthus was also substantially fractionated but showed lower digestibility than switchgrass and corn stover. Lignin was readily recoverable with relatively high purity from all the pretreatment liquor. Our study demonstrated an innovative ultrafast pretreatment process with superior effectiveness for biomass fractionation and cellulose digestibility improvement as well as lignin extraction.