Cellulose aerogel beads and monoliths from CO2-based reversible ionic liquid solution.

The CO2-based reversible ionic liquid solution of 1,1,3,3-tetramethylguanidine (TMG) and ethylene glycol (EG) in dimethyl sulfoxide (DMSO) after capturing CO2, (2[TMGH]+[O2COCH2CH2OCO2]2-/DMSO (χRILs = 0.1), provides a sustainable and effective platform for cellulose dissolution and homogeneous utilization. Highly porous cellulose aerogel beads and monoliths were successfully prepared via a sol-gel process by extruding cellulose solution into different coagulation baths (NaOH aqueous solution or alcohols) and exposing the cellulose solution in open environment, respectively, and followed by different drying techniques, including supercritical CO2-drying, freeze-drying and air-drying. The effect of the coagulation baths and drying protocols on the multi-scale structure of the as-prepared cellulose aerogel beads and monoliths were studied in detail, and the sol-gel transition mechanism was also studied by the solvatochromic parameters determination. High specific surface area of 252 and 207 m2/g for aerogel beads and monoliths were achieved, respectively. The potential of cellulose aerogels in dye adsorption was demonstrated.

Noble-metal-free Co-N-C catalyst derived from cellulose-based poly(ionic liquid)s for highly efficient oxygen reduction reaction.

Noble-Metal-Free nitrogen-doped carbon-based materials are promising electrocatalysts for oxygen reduction reaction (ORR), yet it remains a great challenge to construct efficient porous non-noble metal nitrogen-doped carbon (M-N-C) catalysts with uniform distribution, due to the easy aggregation of metals. Herein, we reported the synthesis and assessment of a novel and efficient noble-metal-free catalyst for oxygen reduction reaction (ORR) from pyrolysis of a cobalt-containing cellulosic poly(ionic liquid) (Co-N-C). The prepared Co-N-C catalyst possesses high surface area, hierarchical porous structure, well-dispersed Co nanoparticles and large amounts of low-coordinated Co active sites. Especially, the Co-N-C-850 sample exhibits a high ORR activity (Eonset = 0.827 V, E1/2 = 0.74 V) that can rival 20 wt% commercial Pt/C (Eonset = 0.833 V, E1/2 = 0.71 V) in alkaline media. Moreover, the Co-N-C-850 sample also shows excellent anti-methanol poisoning activity and long-term stability toward ORR compared with commercial Pt/C. Our study provides a promising avenue both for the development of non-noble M-N-C catalysts for fuel cells and the functional utilization of cellulose.

Facile preparation of cellulose/lignosulfonate derivatives composite films with high UV-shielding and gas barrier properties.

Herein, a serial of full cellulose and lignosulfonate derivatives (LS), including sodium lignosulfonate (LSS), calcium lignosulfonate (LSC), lignosulfonic acid (LSA), composite films were generated through dissolving cellulose in reversible carbon dioxide (CO2) ionic liquids solvent system (TMG/EG/DMSO/CO2 solvent system), followed by a facile solution-gelation transition and absorption strategy. The findings indicated that LS aggregated and embedded inside the cellulose matrix via H-bond interaction. The cellulose/LS derivatives composite films showed good mechanical properties which the tensile strength reaches the maximum value of 94.7 MPa in MCC3LSS film. While for the MCC1LSS film, the breaking strain increases to 11.6 %. The outstanding UV shielding effect and high transmittance in the visible region of composite films were also achieved and the shielding performance of the whole UV region (200-400 nm) tended to 100 % for MCC5LSS film. In addition, thiol-ene click reaction was selected as model reaction to verify the UV-shielding performance. It was also found that the oxygen and water vapor barrier performances of composite films were evidently associated with the intense H-bond interaction and tortuous path effect. The OP and WVP of MCC5LSS film were 0 and 6 × 10-3 g·µm/m2·day·kPa, respectively. These outstanding properties make them with great potential for packaging field.

The synthesis of multifunctional cellulose graft alternating copolymers of 3,4-dihydrocoumarin and epoxides in DBU/DMSO/CO2 solvent system.

Cellulose graft copolymers having well-defined structures could incorporate the characteristics of both the cellulose skeleton and side chains, providing a new method for the preparation functionalised cellulose derivatives. Herein, a series of multifunctional cellulose grafted, alternating 3,4-dihydrocoumarin (DHC) and epoxide (EPO) copolymers (cell-g-P(DHC-alt-EPO)) were prepared in a metal-free DBU/DMSO/CO2 solvent system without adding additional catalyst. Four examples of cell-g-P(DHC-alt-EPO) with tunable thermal and optical properties were synthesized by copolymerization of DHC with styrene oxide (SO), propylene oxide (PO), cyclohexene oxide (CHO) or furfuryl glycidyl ether (FGE) onto cellulose. The nonconjugated cell-g-P(DHC-alt-EPO) showed UV absorption properties with the maximum absorption peak at 282 nm and 295 nm and photoluminescence performance. A clustering-triggered emission mechanism was confirmed and consistent with DFT theoretical calculations. In DMSO solution, the copolymer (DHCSO5) with DP of 11.64 showed ACQ behaviour as the concentration increased. In addition, DHCSO5 had good antioxidant capacity with an instantaneous radical scavenging activity of 2,2-diphenyl-1-picrylhydrazine (DPPH) up to 65 % at a concentration of 40 mg/ ml and increased to 100 % after 30 min. Thus, the multifunctional cell-g-P(DHC-alt-EPO) materials had a variety of potential applications in the fields of fluorescent printing, bio-imaging, UV- shielding and antioxidants.

Engineering chitosan into fully bio-sourced, water-soluble and enhanced antibacterial poly(aprotic/protic ionic liquid)s packaging membrane.

The design and facile preparation of water-soluble and eco-friendly polymer packaging membrane materials is a fascinating research topic, particularly in terms of the increasing concerns on potential microplastics pollution in ecosystem. In this study, taking advantages of the structural features of chitosan (CS) and betaine hydrochloride (BHC), fully bio-sourced and water-soluble poly(aprotic/protic ionic liquid)s (PAPILs) were successfully designed and prepared through the reaction of the amino groups in CS and carboxyl groups in BHC. The structure and thermo-properties of the PAPILs were elucidated by a series of characteristic methods. The rheological properties of the PAPILs aqueous solutions were also investigated. Moreover, water-soluble PAPILs membrane with a smooth surface morphology and a tensile strength of 62.9 MPa was successfully prepared. The PAPILs membrane also exhibited satisfactory biocompatibility, excellent antibacterial activities and high oxygen barrier property. Together with these outstanding material performance and functionality, as a "proof of concept", the potential use of the PAPILs membrane as water-soluble packaging material for laundry detergent capsule and pesticide was preliminarily demonstrated. These findings provide significant insights for the design of sustainable and functional packaging materials by using natural resources.

Eugenol-derived Organic Liquids as an In-Situ CO2 Capturing and Conversion System for Eugenol-based Polycarbonate Synthesis.

The significant development of catalytic biomass conversion has provided a large library of chemicals ready for subsequent upgrading to polymerisable monomers for the design and preparation of sustainable polymers. In this study, hydroxyethylation of eugenol by using green ethylene carbonate as alkylation reagent and cheap tetrabutylammonium iodide ionic liquids as green solvents and catalysts produced 2-(4-allyl-2-methoxyphenoxy)ethan-1-ol with a 85% yield, which could be used to construct an in situ CO2 capture and conversion system by taking the reversible chemistry of alcoholic compounds with CO2 in the presence of superbases, on which α,ω-diene functionalized carbonate monomers were successfully prepared and were applied in thiol-ene click and acyclic diene metathesis polymerisation (ADMET), producing a series of poly(thioether carbonate)s and unsaturated aromatic aliphatic polycarbonates with moderate molecular weights and satisfactory thermal properties. The structures of the formed CO2 reversible ILs, the polymerisable monomers and the corresponding polymers were fully characterized by various technologies.

An unexpected reaction between 5-hydroxymethylfurfural and imidazolium-based ionic liquids at high temperatures.

A new compound was detected during the production of 5-hydroxymethylfurfural (HMF) from glucose and cellulose in the ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) at high temperatures. Further experiments found that it was derived from the reaction of HMF with [Bmim]Cl. The structure of new compound was established as 1-butyl-2-(5'-methyl-2'-furoyl)imidazole (BMI) based on nuclear magnetic resonance and mass spectrometry analysis, and a possible mechanism for its formation was proposed. Reactions of HMF with other imidazolium-based ionic liquids were performed to check the formation of BMI. Our results provided new insights in terms of side reactions between HMF and imidazolium-based ionic liquids, which should be valuable for designing better processes for the production of furans using biomass and related materials.

Dissolution pretreatment of cellulose by using levulinic acid-based protic ionic liquids towards enhanced enzymatic hydrolysis.

In this study, an economically competitive and sustainable levulinic acid-based protic ionic liquids were identified to be good solvents for the dissolution pretreatment of cellulose towards enhanced enzymatic hydrolysis. The influences of protic ionic liquids species, dissolution pretreatment time, and pretreatment temperature on the physico-chemical structures of cellulose were systematically investigated by various analytical techniques. The findings indicate that the pretreatment efficiency was correlated to the basicity of the organic bases, and the presence of ketone group in the levulinate anion with particular hydrogen bonding forming ability via keto-enol tautomerism. The DBN derived protic ionic liquids exhibited best performance at 100 °C in 1 h, as evidenced by a 94% glucose yield. This solvent system was also suitable for the dissolution pretreatment of corn stover-based lignocellulosic biomass for sugars production, although a higher temperature and longer pretreatment time was required. Furthermore, the solvent system could be recycled and reused.

Carboxylcellulose hydrogel confined-Fe3O4 nanoparticles catalyst for Fenton-like degradation of Rhodamine B.

Facile preparation of functional hydrogel materials for environmental catalysis is a hot research topic of soft materials science and green catalysis. In this study, a carboxylcellulose hydrogel confined Fe3O4 nanoparticles composite catalyst (Fe3O4@CHC) with magnetic recyclability has been synthesized by taking the advantages of the newly developed cellulose solution in tetramethyl guanidine/DMSO/CO2 through in situ acylation using mixed cyclic anhydrides and ion exchange reaction. The achieved Fe3O4@CHC hydrogel catalyst was shown to be an more efficient and better Fenton-like catalyst for decomposition of the organic dye rhodamine B (RhB) in the presence of hydrogen peroxide, with almost complete decomposition occurring within 180 min, in comparison with Fe3O4@cellulose hydrogel (CH) with excellent recyclability. This work provided a facile strategy for the preparation of hydrogel-based functional composite green catalytic materials, which has potential applications in green catalysis.

A preliminary study on polycaprolactone and gelatin-based bilayered tubular scaffolds with hierarchical pore size constructed from nano and microfibers for vascular tissue engineering.

Due to the insufficient endothelialization and the poor colonization of smooth muscle cells (SMCs), small-diameter vascular tissue engineering is still challenging. An ideal vascular graft is expected to effectively support the formation of endothelial monolayer and the colonization of SMCs. In this study, we proposed a bilayered scaffold with hierarchical pore size constructed from nano and microfibers by electrospinning PCL-PEG-PCL (PCE) and a blend of PCE and gelatin (PCEG) sequentially. The structural features of nano and microfibers were tuned by the concentration of PCE and the proportion of PCE/gelatin in electrospun solution respectively. The results demonstrated the best nanofiber morphology and relatively high mechanical properties were achieved in 18% PCE (w/v) (PCE18) and PCE and gelatin with a weight ratio of 7:3 (P7G3) at a concentration of 18% (w/v) electrospun membranes. The in vitro co-culturing studies of cells and membranes indicated all the PCE membranes supported the proliferation and spreading of endothelial cells and the further endothelialization of the membranous surface, while PCEG membranes facilitated the migration inward of SMCs. Taking the porosity and mechanical properties into consideration, PCE18 and P7G3 were chosen to construct the inner and outer layers of the bilayered scaffold with hierarchical pore size respectively. The circumferential ring test demonstrated that the bilayered scaffold has good mechanical property both in dry and wet state. After cells were co-cultured with this bilayered scaffold for 7 days, the results manifested a continuous endothelial monolayer has formed on the luminal surface and the SMCs have started to colonized from outer layers, indicating the vast potential of this bilayered scaffold in vascular remodeling and regeneration.

Reversible covalent chemistry of carbon dioxide unlocks the recalcitrance of cellulose for its enzymatic saccharification.

To overcoming the natural recalcitrance of cellulose for glucose production via enzymatic hydrolysis, a new strategy of destroying hydrogen bond donor to reconstruct cellulose's hydrogen bonding network was developed via a mild reversible reaction of cellulose with CO2 catalyzed by organic bases. The reaction dynamics of cellulose with CO2 in the presence of organic bases was studied by using in situ IR. Investigation also included how the organic bases in pretreatment media and pretreatment parameters including CO2 pressure, pretreatment temperature and time affected the physical-chemical structure of cellulose by Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and Atomic force microscopy (AFM) and subsequent enzymatic scarification of cellulose. The findings showed that dissolution activation efficiency significantly correlated to various parameters, that can be optimized to be the tetramethyl guanidine (TMG)/CO2/DMSO solvent system at 50 °C, 2 MPa of CO2 for 2 h, by which a complete transformation the cellulose crystalline structure from I to II, and 100% glucose yield were achieved. The recyclability and usability are also investigated.

Biomimetic dual-oriented/bilayered electrospun scaffold for vascular tissue engineering.

Natural blood vessels have a multi-layered, cell-specific oriented spatial structure, mimicking of this structure is a promising way for blood vessel regeneration. In this study, a newly developed dual-oriented/bilayered small-diameter tubular scaffold was electrospun using a mixture of poly (ε-caprolactone) (PCL), poly (D, L-lactide-co-glycolide) (PLGA) and gelatin. The nanofiber orientations of the bilayers were spatially perpendicular to each other, aiming at guiding cell-specific orientation of smooth muscle cells (SMCs) and endothelial cells (ECs) in vitro respectively. The results showed that the hydrophilicity of scaffold was greatly improved by gelatin, and the mechanical property of this scaffold was the best among all. The in vitro degradation demonstrated that by mixing of three biodegradable polymers, a relatively fast degradation rate was achieved. After SMCs and ECs were seeded on scaffolds, cell viability, cellular morphology, and cytoskeleton behavior were investigated. The results revealed that as-electrospun scaffolds could promote both SMCs and ECs proliferation. Moreover, topographic cues offered by oriented nanofibers could guide the growth and orientation of SMCs and ECs. Therefore, the dual-oriented/bilayered electrospun scaffold is a superior structural and functional analogue to natural blood vessel and a potential candidate for vascular tissue engineering.

Capturing CO2 to reversible ionic liquids for dissolution pretreatment of cellulose towards enhanced enzymatic hydrolysis.

To overcome the natural recalcitrance of cellulose for glucose production in aqueous media catalyzed by enzyme, in this study, a dissolution pretreatment strategy was developed by using in situ formed CO2-based reversible ionic compounds (RICs)/DMSO mixed organic electrolytes under mild conditions. The influences of the constitution of RICs, CO2 pressure, dissolution pretreatment time on the physic-chemical structure of cellulose were investigated systematically by FTIR, XRD, SEM, AFM towards in-depth understanding of the correlations between the pretreatment conditions, micro-scale structure and enzymatic saccharification of cellulose. The results showed that the tetramethyl guanidine (TMG) based RICs solvent system [TMGH]2+[O2COCH2CH2OCO2]2-/DMSO (XRICs = 0.1, XRICs: the mole fraction of the formed RICs in the mixture) presented the best performance, which was evidenced by 100% glucose yield after the dissolution-regeneration pretreatment strategy under mild conditions (T = 60 °C, Pco2 = 2.0 MPa, t = 2 h). Furthermore, the solvent system have good recyclability and usability.

Individual and binary mixture effects of bisphenol A and lignin-derived bisphenol in Daphnia magna under chronic exposure.

In recent years, many new chemicals have been synthesized from biomass with an aim for sustainable development by replacing the existing toxic chemicals with those having similar properties and applications. However, the effects of these new chemicals on aquatic organisms remain relatively unknown. In this study, the effects of bisphenol A (BPA) and lignin-derived bisphenol (LD-BP, a BPA analogue) on Daphnia magna were evaluated. The animals were exposed to BPA, LD-BP, and their binary mixture at concentrations (2-2000 µg L-1) for 21 days. The expression of various biochemical markers and the effects on growth, molting, and reproduction parameters were examined. The results showed that the weight of daphnids significantly increased after exposure to BPA, LD-BP, and the binary mixture relative to that of the control animals. The activity of superoxide dismutase was significantly inhibited by LD-BP and the binary mixture. At the highest exposure concentration of the binary mixture, the activities of acetylcholinesterase and α-glucosidase, fecundity, and the number of neonates per brood were significantly altered. Our results showed that the effects of BPA and LD-BP on D. magna were generally comparable, except for the effect on the weight at their environmentally relevant concentrations (e.g., <20 µg L-1). The effects on the reproduction of D. magna could be mainly due to the shift in energy redistribution under BPA and LD-BP exposures. Our results implied that exposures to both BPA and LD-BP could potentially cause deleterious effects at the population level in D. magna.

Fast dissolution pretreatment of the corn stover in gamma-valerolactone promoted by ionic liquids: Selective delignification and enhanced enzymatic saccharification.

The dissolution of corn stover was investigated in gamma-valerolactone (GVL) assisted by ionic liquids. An enhanced subsequent enzymatic saccharification was reached with a total reducing sugar yield of 0.69 g.g-1 and a glucose of 0.38 g.g-1 within 24 h. The treatment effects on the physical-chemical features of corn stover in terms of the natural recalcitrance to the subsequent biological digest were systematically investigated using composition analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The structures of the associated enzymatic hydrolysis lignin (EHL) and ionic liquid extracted lignin (IEL) were characterized by gel permeation chromatography (GPC), fourier transform infra-red spectroscopy (FTIR), phosphorous nuclear magnet resonance spectrometry (31P NMR), and heteronuclear single quantum coherence spectroscopy (HSQC) for an in-depth understanding of the delignification process and the basic structural information for further lignin valorization.

Thorough chemical modification of wood-based lignocellulosic materials in ionic liquids.

Homogenous acylation and carbanilation reactions of wood-based lignocellulosic materials have been investigated in ionic liquids. We have found that highly substituted lignocellulosic esters can be obtained under mild conditions (2 h, 70 degrees C) by reacting wood dissolved in ionic liquids with acetyl chloride, benzoyl chloride, and acetic anhydride in the presence of pyridine. In the absence of pyridine, extensive degradation of the wood components was found to occur. Highly substituted carbanilated lignocellulosic material was also obtained in the absence of base in ionic liquid. These chemical modifications were confirmed by infrared spectroscopy, (1)H NMR, and quantitative (31)P NMR of the resulting derivatives. The latter technique permitted the degrees of substitution to be determined, which were found to vary between 81% and 95% for acetylation, benzoylation, and carbanilation, accompanied by similarly high gains in weight percent values. Thermogravimetric measurements showed that the resulting materials exhibit different thermal stabilities from those of the starting wood, while differential scanning calorimetry showed discrete new thermal transitions for these derivatives. Scanning electron microscopy showed the complete absence of fibrous characteristics for these derivatives, but instead, a homogeneous porous, powdery appearance was apparent. A number of our reactions were also carried out in completely recycled ionic liquids, verifying their utility for potential applications beyond the laboratory bench.

Facile transformation of hydrophilic cellulose into superhydrophobic cellulose.

Superhydrophobic cellulose-based materials coupled with transparent, stable and nanoscale polymethylsiloxane coating have been successfully achieved by a simple process via chemical vapor deposition, followed by hydrolyzation and polymerization.

The acute toxicity of bisphenol A and lignin-derived bisphenol in algae, daphnids, and Japanese medaka.

Risk assessing newly synthesized chemicals prior to their applications is extremely important, if we want to ensure substitution of risky chemicals with more benign ones. During the past two decades, many analogs of bisphenol A (BPA) have been manufactured, while their toxicity remains less studied. The aim of this study was to compare the acute toxicity of a synthesized lignin-derived BPA (LD-BP) with that of BPA in representative aquatic organisms including two algal species (Chlorella pyrenoidosa and Scenedesmus obliquus), a cladoceran species (Daphnia magna), and the Japanese medaka (Oryzias latipes). The results revealed that the two algal species showed different responses to the two chemicals. For C. pyrenoidosa, both BPA and LD-BP stimulated growth within 48 h of exposure, except for the 50 mg L-1 of LD-BP treatment. After 96 and 144 h of exposures, BPA stimulated the growth of C. pyrenoidosa at low-exposure concentrations but inhibited its growth at high concentrations, while LD-BP caused a concentration-dependent response in C. pyrenoidosa. S. obliquus exhibited a monotonic concentration-response curve for both BPA and LD-BP exposures. For both D. magna and O. latipes, concentration-responses were monotonic with 96 h-LC50 of BPA and LD-BP of 11.7 and 5.0 mg L-1 and 9.4 and 4.1 mg L-1, respectively. Our results demonstrate that LD-BP is more toxic than BPA in the representative aquatic organisms, and it can pose higher ecological risk to the aquatic ecosystem than BPA.

Tungsten Carbide: A Remarkably Efficient Catalyst for the Selective Cleavage of Lignin C-O Bonds.

A remarkably effective method for the chemoselective cleavage of the C-O bonds of typical ß-O-4 model compounds and the deconstruction of lignin feedstock was developed by using tungsten carbide as the catalyst. High yields of C-O cleavage products (up to 96.8 %) from model compounds and liquid oils (up to 70.7 %) from lignin feedstock were obtained under low hydrogen pressure (0.69 MPa) in methanol. The conversion efficiency was determined to a large extent by solvent effects and was also affected by both the electronic and steric effects of the lignin model compounds. In situ W2 C/activated carbon (AC)-catalyzed hydrogen transfer from methanol to the substrate was proposed to be responsible for the high performance in methanol solvent. The conversion of 2-(2-methoxyphenoxy)-1-phenylethanol showed that the catalyst could be reused five times without a significant loss in activity for C-O bond cleavage, whereas the selectivity to value-added styrene increased markedly owing to partial oxidation of the W2 C phase according to X-ray diffraction, Raman spectroscopy, and transmission electron microscopy characterization. 2 D-HSQC-NMR spectroscopy analysis showed that W2 C/AC exhibited high activity not only for ß-O-4 cleavage but also for the deconstruction of more resistant α-O-4 and ß-ß linkages, so that a high yield of liquid oil was obtained from lignin. Corn stalk lignin was more liable to be depolymerized than birch lignin owing to its loosened structure (scanning electron microscopy results), larger surface area (BET results), and lower molecular weight (gel-permeation chromatography results), whereas its liquid oil composition was more complicated than that of birch wood lignin in that the former lignin contained more p-hydroxyphenyl units and the former contained noncanonical units.

Cellulose Dissolution and In†Situ Grafting in a Reversible System using an Organocatalyst and Carbon Dioxide.

Cellulose is a promising renewable material, but cannot easily be processed homogeneously owing to the stiffness of the molecules and the dense packing of its chains, due to intermolecular hydrogen bonds. Cellulose processability can be improved by chemical modification. The reversible reaction of cellulose with carbon dioxide in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) allows dissolution of cellulose in dimethyl sulfoxide (DMSO). This DMSO solution is an effective medium for grafting L-lactide (LLA) from cellulose by ring-opening polymerization (ROP) under mild conditions, allowing to prepare cellulose-graft-poly(L-lactide) co-polymers with a molar substitution (MSPLLA ) of poly(L-lactide) in the range of 0.37-5.32, at 80 °C. This makes DBU not only an important reagent to achieve cellulose dissolution, but it also acts as organocatalyst for the subsequent ring-opening polymerization process. Characterization of the structure and thermal properties of the co-polymers by a variety of techniques reveals that they have a single glass-transition temperature (Tg ), which decreases with increasing MSPLLA . Thus, the modification results in a transformation of the originally semirigid cellulose into a thermoplastic material with tunable Tg . The carbon dioxide dissolution strategy is an efficient platform for cellulose derivatization by homogeneous organocatalysis.