Antibacterial, antioxidant and fruit packaging ability of biochar-based silver nanoparticles-polyvinyl alcohol-chitosan composite film.

Silver nanoparticles were prepared by loading Ag+ into biochar of waste barley distillers' grains shell by reduction with trisodium citrate, and this silver-loaded biochar was introduced into polyvinyl alcohol-chitosan. Various analysis with Fourier Transform Infrared spectroscopy, X-ray diffraction, Thermogravimetric analysis, and water contact angle revealed that biochar-based silver nanoparticle was incorporated into the polyvinyl alcohol-chitosan film, the biochar-based silver nanoparticles-polyvinyl alcohol-chitosan (C-Ag-loaded PVA/CS) composite film had good thermostability and hydrophobicity. Through the analysis via disk diffusion method, the composite containing 3 % of biochar-based silver nanoparticles-polyvinyl alcohol-chitosan had high antibacterial activity (inhibition zone: 18 mm against E. coli and 15 mm against S. aureus), and the bacterial membrane permeability was measured, indicating that C-Ag-loaded PVA/CS composite film could destroy the cell membrane, release intracellular substances, and have high antioxidant activity. During the storage, the weight loss rate of the biochar-based silver nanoparticles-polyvinyl alcohol-chitosan plastic wrap group was 0.14 %, and the titratable acid content only decreased by 0.061 %, which had a good effect on extending the shelf life of blueberries. The C-Ag-loaded PVA/CS composite film could also delay deterioration of blueberries and prolong storage time. Overall, this composite film had potential in food packaging and extending food shelf-life aspects.

Efficient co-production of reducing sugars and xylooligosaccharides via clean hydrothermal pretreatment of rape straw.

Hydrothermal treatment was applied to pretreat rape straw for the efficient co-production of reducing sugars and xylooligosaccharides. It was observed that hydrothermal treatment using water as solvent and catalyst destructed the compact structure of rape straw and increased its enzymatic digestion efficiency from 24.6% to 92.0%. Xylooligosaccharide (3.3 g/L) was acquired after the treatment under 200 °C for 60 min (severity factor Log Ro = 4.7). With increasing pretreatment intensity from 3.1 to 5.4, the hemicellulose removal increased from 14.4% to 100%, and the delignification was raised from 12% to 44%. Various characterization proved that the surface morphology of treated material showed a porous shape, while the cellulose accessibility, lignin surface area and lignin hydrophobicity were greatly improved. Consequently, hydrothermal pretreatment played a vital role in the sustainable transformation of biomass to valuable biobased compounds, and had a wide range of application prospects in lignocellulosic biorefining.

Ultraviolet blocking ability, antioxidant and antibacterial properties of newly prepared polyvinyl alcohol-nanocellulose­silver nanoparticles-ChunJian peel extract composite film.

In this work, nanocellulose (CNC) from waste water chestnut (WCT) shell was firstly used for preparing nanocomposite films, by using ChunJian peel extract (CJPE) as a green reducing agent to synthesize silver nanoparticles (AgNPs), and then loading them into polyvinyl alcohol-nanocellulose (PVA-CNC) matrix, a multifunctional nanocomposite material that could be used in food packaging was developed. The prepared films were tested for mechanical strength, barrier properties, thermal properties, antibacterial, antioxidant and biocompatibility through various characterizations. The PVA-CNC-AgNPs-CJPE film had good thermostability, mechanical strength, barrier properties, and biocompatibility. Compared with pure PVA film and PVA-CNC film, PVA-CNC-AgNPs-CJPE could shield over 95 % of the UVB (320-275 nm) spectrum and UVC (275-200 nm) spectrum and most of the UVA (400-320 nm). By disk diffusion analysis, the inhibition zones of PVA-CNC-AgNPs-CJPE film against E. coli, P. aeruginosa, S. aureus and E. faecalis were 22.3 mm, 25.0 mm, 22.0 mm and 19.3 mm, respectively. The milk antibacterial simulation test confirmed that PVA-CNC-AgNPs-CJPE film could effectively limit bacterial reproduction and prolong the shelf life of milk. PVA-CNC-AgNPs-CJPE film had excellent UV barrier properties, good antioxidant properties and high-efficiency antibacterial activity, which is expected to be widely used in sustainable nanocomposite food packaging.

Efficient co-production of xylooligosaccharides, furfural and reducing sugars from yellow bamboo via the pretreatment with biochar-based catalyst.

The research on the efficient use of biomass to produce chemical products has received extensive attention. In this work, a novel heterogeneous biocarbon-based heterogeneous catalyst AT-Sn-YB was prepared using yellow bamboo (YB) as a carrier, and its physical properties were proved to be good by various characterization and stability experiments. In the γ-valerolactone/water (3:1, v/v) medium containing 100 mM CuCl2, the use of AT-Sn-YB (3.6 wt%) under 170 °C for 20 min was applied to catalyze YB into furfural (80.3% yield), accompanied with 2.8 g/L xylooligosaccharides. The YB solid residue obtained from treatment was efficiently saccharified to reducing sugars (17.2 g/L). Accordingly, comprehensive understanding of efficiently co-producing xylooligosaccharides, furfural and reducing sugars from YB was demonstrated via the pretreatment with biochar-based catalyst. This study innovatively used a new type of solid acid to complete the efficient co-production of chemical products, and realized the value-added utilization of yellow bamboo.

Chemobiocatalytic transfromation of biomass into furfurylamine with mixed amine donor in an eco-friendly medium.

Biobased furfurylamine (FAM) is a versatile platform molecule for producing additives, pharmaceuticals, and pesticides. Recombinant E. coli HNND-AlaDH was created by co-expressing L-alanine dehydrogenase (AlaDH) and mutated Aspergillus terreus ω-transaminase (HNND), aiming to convert furfural (FUR) into FAM using inexpensive L-alanine and isopropylamine as mixed amine donors. In ChCl:FA:OA (10 wt%), pineapple peel, bagasse, barley shell, peanut shell, and corn stalk could be efficiently transformed into FUR under 170 °C for 10 min. Pineapple peel produced a high titer of FUR (183.3 mM). Additionally, the viscosity, surface tension and polarity of ChCl:FA:OA were explored. The biomass-derived FUR was fully transformed to FAM by HNND-AlaDH with amine donor (1:1:1 of L-Ala/isopropylamine/FUR mol/mol/mol) within 300 min. Accordingly, the FAM productivity was 0.58 g/(g xylan in pineapple peel). This chemobiocatalytic strategy established through the combination of chemocatalysis and biocatalysis could be applied to convert renewable biomass into valuable organic amines.

Efficient production of hydroxymethyl-2-furfurylamine by chemoenzymatic cascade catalysis of bread waste in a sustainable approach.

In this study, efficient and sustainable conversion of waste bread (WB) to 5-hydroxymethyl-2-furoamine (HMFA) was achieved in a cascade reaction in betaine:malonic acid (B:MA) - water. 5-HMF (30.3 wt% yield) was synthesized from WB (40.0 g/L) in B:MA - water (B:MA, 18 wt%) in 45 min at 190 °C. By using the newly created recombinant E. coli HNILGD-AlaDH cells expressing L-alanine dehydrogenase (AlaDH) and ω-transaminase mutant HNILGD as biocatalyst, the WB-valorized 5-HMF was biologically aminated into HMFA in a high yield (92.1%) at 35 °C for 12 h through in situ removal of the amino transfer by-products of the amine donor, greatly reducing amine donor dosage (from D-Ala/5-HMF = 16/1 to D-Ala/5-HMF = 2/1, mol/mol) and improving the productivity of HMFA (0.282 g HMFA per g WB). This two-step chemical-enzymatic cascade reaction strategy with B:MA and HNILGD-AlaDH whole-cell provides a new idea for the chemoenzymatic synthesis of valuable furan chemicals from waste biomass.

Biological valorization of lignin-derived vanillin to vanillylamine by recombinant E. coli expressing ω-transaminase and alanine dehydrogenase in a petroleum ether-water system.

Vanillylamine, as an important drug precursor and fine chemical intermediate, has great economic value. By constructing a strategy of double enzyme co-expression, one newly constructed recombinant E. coli HNIQLE-AlaDH expressing ω-transaminase from Aspergillus terreus and alanine dehydrogenase from Bacillus subtilis was firstly used aminate lignin-derived vanillin to vanillylamine by using a relatively low dosage of amine donors (vanillin:L-alanine:isopropylamine = 1:1:1, mol/mol/mol). In addition, in a two-phase system (water:petroleum ether = 80:20 v/v), the bioconversion of vanillin to vanillylamine was catalyzed by HNIQLE-AlaDH cell under the ambient condition, and the vanillylamine yield was 71.5%, respectively. This double-enzyme HNIQLE-AlaDH catalytic strategy was applied to catalyze the bioamination of furfural and 5-hydroxymethylfurfural with high amination efficiency. It showed that the double-enzyme catalytic strategy in this study promoted L-alanine to replace D-alanine to participate in bioamination of vanillin and its derivatives, showing a great prospect in the green biosynthesis of biobased chemicals from biomass.

Comprehensive understanding of enzymatic saccharification of Betaine:Lactic acid-pretreated sugarcane bagasse.

Green solvents, especially deep eutectic solvents (DESs), are widely applied to pretreat biomass for enhancing its enzymatic hydrolysis. In this work, lactic acid was selected as the hydrogen-bond-donor to prepare Betaine-base DES (Betaine:LA), The DES was utilized to pretreat sugarcane bagasse (SCB) at 160 ℃ for 80 min (severity factor LogR0 = 3.67). The influences of Betaine:LA treatment on the chemical composition, crystal and microstructure structure of cellulose, and cellulase digestion were investigated. The results showed that the lignin (47.1%) and xylan (44.6%) were removed, the cellulase digestibility of Betaine:LA-treated SCB was 4.2 times that of the raw material. This improved efficiency was attributed to the enhanced accessibility of cellulose, the weakened surface area of lignin, the declined hydrophobicity, and the decreased crystallinity of cellulose. Several compelling linear correlations were fitted between enzymatic hydrolysis and these alterations of physicochemical features, comprehensively understanding enzymatic saccharification of Betaine:LA-pretreated SCB.

Combined sulfuric acid and choline chloride/glycerol pretreatment for efficiently enhancing enzymatic saccharification of reed stalk.

In this study, an efficient combination of pretreatment solvents involving Choline chloride/Glycerol (ChCl/Gly) and H2SO4 was firstly developed to assess the pretreatment performance and determine optimal pretreatment conditions. The results illustrated that the H2SO4-[ChCl/Gly] combination efficiently removed lignin (52.6%) and xylan (80.5%) from the pretreated reed stalk, and subsequent enzymatic hydrolysis yielded 91.1% of glucose. Furthermore, several characterizations were conducted to examine the structural and morphological changes of the reed stalk, revealing apparently enhanced accessibility (128.4 to 522.6 mg/g), reduced lignin surface area (357.9 to 229.5 m2/g), and substantial changes on biomass surface. Based on the aforementioned study, possible mechanisms for the H2SO4-[ChCl/Gly] pretreatment of reed stalks were proposed. The comprehensive understanding of combined H2SO4-[ChCl/Gly] pretreatment system for enhancing the saccharification of the reed stalk was interpreted in this work. Overall, this novel approach could be efficiently applied to pretreat and saccharify reed stalks, empowering the biomass refining industry.

Improved enzymatic saccharification of bulrush via an efficient combination pretreatment.

Glycerol (Gly) was selected as hydrogen-bond-donor for preparing ChCl-based DES (ChCl:Gly), and the mixture of ChCl:Gly (20 wt%) and NaOH (4 wt%) was utilized for combination pretreatment of bulrush at 100 °C for 60 min (severity factor LogRo = 1.78). The effects of DES pretreatment on the chemical composition, microstructure, crystal structure, and cellulase hydrolysis were explored. NaOH-ChCl:Gly could remove lignin (80.1%) and xylan (66.8%), and the enzymatic digestibility of cellulose reached 87.9%. The accessibility of bulrush was apparently increased to 645.2 mg/g after NaOH-ChCl:Gly pretreatment. The hydrophobicity and lignin surface area were reduced to 1.56 L/g and 417 m2/g, respectively. The crystallinity of cellulose was increased from 20.8% to 55.6%, and great changes in surface morphology were observed, which explained the improvement of enzymatic hydrolysis efficiency. Overall, DES combined with alkali treatment could effectively promote the removal of lignin and xylan in bulrush, thus the relative saccharification activity was greatly affected.

Improved biotransformation of lignin-valorized vanillin into vanillylamine in a sustainable bioreaction medium.

Lignin is a critical biopolymer for creating a large number of highly valuable biobased compounds. Vanillin, one of lignin-derived aromatics, can be used to synthesize vanillylamine that is a key fine chemical and pharmaceutical intermediate. To produce vanillylamine, a productive whole-cell-catalyzed biotransformation of vanillin was developed in deep eutectic solvent - surfactant - H2O media. One newly created recombinant E. coli 30CA cells expressing ω-transaminase and L-alanine dehydrogenase was employed to transform 50 mM and 60 mM vanillin into vanillylamine in the yield of 82.2% and 8.5% under 40 °C, respectively. The biotransamination efficiency was enhanced by introducing surfactant PEG-2000 (40 mM) and deep eutectic solvent ChCl:LA (5.0 wt%, pH 8.0), and the highest vanillylamine yield reached 90.0% from 60 mM vanillin. Building an effective bioprocess was utilized for transamination of lignin-derived vanillin to vanillylamine with newly created bacteria in an eco-friendly medium, which had potential application for valorization of lignin to value-added compounds.

Enhancing enzymatic saccharification of sunflower straw through optimal tartaric acid hydrothermal pretreatment.

Sunflower straw, a usually neglected and abundant agricultural waste, has great potential for contributing to environmental protection realizing its high-value of valorization if utilizing properly. Because hemicellulose contains amorphous polysaccharide chains, relatively mild organic acid pretreatment can effectively reduce its resistance. Through hydrothermal pretreatment, sunflower straw was pretreated in tartaric acid (1 wt%) at 180 °C for 60 min to enhance its reducing sugar recovery. After tartaric acid-assisted hydrothermal pretreatment, 39.9% of lignin and 90.2% of xylan were eliminated. The reducing sugar recovery increased threefold, while the solution could be effectively reused for four cycles. The properties of more porous surface, improved accessibility, and decreased surface lignin area of sunflower straw were observed through various characterizations, which explained the improved saccharide recovery and provided a basis for the mechanism of tartaric acid-assisted hydrothermal pretreatment. Overall, this tartaric acid hydrothermal pretreatment strategy greatly provided new impetus for the biomass refinery.

Significantly enhanced enzymatic hydrolysis of waste rice hull through a novel surfactant-based deep eutectic solvent pretreatment.

The potential of green solvents, specifically deep eutectic solvents (DESs), has piqued the interest of researchers in the field of lignocellulose pretreatment. To enhance the enzymatic digestion efficiency of waste rice hull (RCH), an effective pretreatment approach was developed using the DES [AA][CATB], which was made with acetic acid (AA) and cetyltrimethylammonium bromide (CTAB). The results showed that [AA][CATB] improved enzymatic saccharification by 3.7 times compared to raw RCH and efficiently eliminated lignin and removed xylan. The improvement in enzymatic hydrolysis efficiency was then interpreted by a series of characterizations that showed a great morphological changed RCH with an obvious accessibility increase and a lignin surface area and hydrophobicity reduction. This work demonstrates that functional, and easily recoverable DESs have potential for improving the efficiency of lignocellulose pretreatment in biorefineries, providing a promising approach for developing green solvents and achieving more sustainable and efficient biorefinery processes.

Enhancing enzymatic hydrolysis of waste sunflower straw by clean hydrothermal pretreatment.

Hydrothermal pretreatment is an effective way to change the lignocellulose structure and improve its saccharification. An efficient hydrothermal pretreatment of sunflower straw was conducted when the severity factor (LogR0) was 4.1. 58.8% of xylan and 33.5% of lignin were removed at 180 °C for 120 min with a solid-to-liquid ratio of 1:15. A series of characterizations (such as X-ray diffraction, Fourier Transform infrared spectroscopy, scanning electron microscopy, chemical component analysis, cellulase accessibility) proved that hydrothermal pretreatment destroyed sunflower straw surface structure, enlarged its pores, and enhanced the accessibility to cellulase (371.2 mg/g). After the enzymatic saccharification of treated sunflower straw for 72 h, 68.0% yield of reducing sugar and 61.8% yield of glucose were achieved, and 3.2 g/L xylo-oligosaccharide was obtained in the filtrate. Overall, this easy-to-operate and green hydrothermal pretreatment could effectively destroy the surface barrier of lignocellulose, help remove lignin and xylan, and increase the enzymatic hydrolysis efficiency.

Improved production of adipic acid from a high loading of corn stover via an efficient and mild combination pretreatment.

Adipic acid is one kind of important organic dibasic acid, which has crucial role in manufacturing plastics, lubricants, resins, fibers, etc. Using lignocellulose as feedstock for producing adipic acid can reduce production cost and improve bioresource utilization. After pretreated in the mixture of 7 wt% NaOH and 8 wt% ChCl-PEG10000 at 25 °C for 10 min, the surface of corn stover became loose and rough. The specific surface area was increased after the removal of lignin. A high loading of pretreated corn stover was enzymatically hydrolyzed by cellulase (20 FPU/g substrate) and xylanase (15 U/g substrate), and the yield of reducing sugars was as high as 75%. Biomass-hydrolysates obtained by enzymatic hydrolysis were efficiently fermented to produce adipic acid, and the yield was 0.48 g adipic acid per g reducing sugar. A sustainable approach for manufacturing adipic acid from lignocellulose via a room temperature pretreatment has great potential in future.

A novel cetyltrimethylammonium bromide-based deep eutectic solvent pretreatment of rice husk to efficiently enhance its enzymatic hydrolysis.

Deep eutectic solvent (DES) has caught widely attention of researchers in biomass pretreatment. As a highly efficient surfactant, cetyltrimethylammonium bromide (CTAB) was expected to be used for synthesizing new DESs with additional functions in pretreatment. In this work, an efficient pretreatment method using a mixture of CTAB and lactic acid (LA) as a novel functional DES was established to improve enzymatic digestion efficiency of rice husk (RH). The results showed that DES CTAB:LA effectively removed lignin (51.5%) and xylan (79.9%) and the enzymatic hydrolysis activity of CTAB:LA-treated RH was 5 times that of RH. Then, a series of characterization demonstrated that a substantial accessibility increased, a hydrophobicity and lignin surface area decreased, and great surface morphology alternation were observed on the treated RH, which explained the increase in enzymatic hydrolysis efficiency. Overall, the discovery of more functional DESs might be motivated and biorefinery pretreatment processes might be greatly promoted.

Effective one-pot chemoenzymatic cascade catalysis of biobased feedstock for synthesizing 2,5-diformylfuran in a sustainable reaction system.

2,5-Diformylfuran, which can be prepared via the oxidation of biobased HMF, has received considerable attention because of its potential applications in producing furan-based chemicals and functional materials, such as biofuels, polymers, fluorescent material, vitrimers, surfactants, antifungal agents and medicines. This work aimed to develop an efficient one-pot process for chemoenzymatic transformation of biobased substrate to 2,5-diformylfuran with deep eutectic solvent (DES) Betaine:Lactic acid ([BA][LA]) catalyst and oxidase biocatalyst in [BA][LA]-H2O. Using waste bread (50 g/L) and D-fructose (18.0 g/L) as feedstocks in [BA][LA]-H2O (15:85, vol/vol), the yields of HMF were 32.8% (15 min) and 91.6% (90 min) at 150 °C, respectively. These prepared HMF could be biologically oxidized to 2,5-diformylfuran by Escherichia coli pRSFDuet-GOase, achieving a productivity of 0.631 g 2,5-diformylfuran/(g fructose) and 0.323 g 2,5-diformylfuran/(g bread) after 6 h under the mild performance condition. This bioresourced intermediate 2,5-diformylfuran was effectively synthesized from biobased feedstock in an environmentally-friendly system.

Transformation of bread waste into 2,5-furandimethanol via an efficient chemoenzymatic approach in a benign reaction system.

Via combination catalysis with deep eutectic solvent lactic acid:betaine (chemocatalyst) and HMFOMUT cell (biocatalyst: E. coli HMFOMUT whole-cell), one-pot manufacture of 2,5-furandimethanol from waste bioresource was constructed in a chemoenzymatic approach. With bread waste (50 g/L) as substrate, the 5-hydroxymethylfuran yield reached 44.2 Cmol% (based on bread waste) by lactic acid:betaine (15 wt%) at 180 °C for 15 min. With glucose as co-substrate, HMFOMUT could transform 5-hydroxymethylfurfural (150 mM) to 2,5-furandimethanol (84.5 % yield) after 1 day at 37 °C and pH 7.0. In lactic acid:betaine-H2O, HMFOMUT effectively converted bread-derived 5-hydroxymethylfurfural into 2,5-furandimethanol in a productivity of 700 kg 2,5-furandimethanol per kg 5-hydroxymethylfurfural (230 kg 2,5-furandimethanol per kg bread). In an eco-friendly lactic acid:betaine system, an effective one-pot chemoenzymatic strategy was firstly developed to convert bread waste into 2,5-furandimethanol, which would reduce the operation cost and has potential application value for valorizing waste food bioresource into value-added furan.

Preparation of a biobased polyelectrolyte complex from chitosan and sodium carboxymethyl cellulose and its antibacterial characteristics.

Using chitosan (CTS) and sodium carboxymethyl cellulose (CMCNa) as raw biobased materials, polyelectrolyte complex (PEC), which is the product of strong electrostatic interaction between two bio-based polyelectrolytes with opposite charges, was attempted to prepare. To enlarge the reactive contact area between CTS and CMCNa, the crosslinked vacuolar structure of PEC was prepared without addition of cross-linked agent. The preparation conditions had a significant impact on the yield of PEC and the bibulous rate of PEC. When pH, mass ratio of CMC-Na-to-CTS, stirring speed and reaction system temperature were 5, 1:2 [(1 wt% CMCNa, 2 wt% CTS), CMC-Na:CTS = 1:1 (v/v)], 800 rpm, 2 min and 25 °C, the yield of PEC reached 71.2 %. The prepared PEC was characterized by XRD and FT-IR. Afterwards, the antibacterial performance of PEC was examined. The prepared PEC had certain bacteriostatic effect on gram-positive and gram-negative bacteria. The bacteriostasis ratios of PEC against Escherichia coli and Staphylococcus aureus were 18.7 % and 31.3 %, respectively. By controlling the combination parameters of the preparation system, an effective strategy was successfully developed for preparation of biobased PEC with bacteriostatic and crosslinked vacuolar structure through simple physical blending without the application of additional crosslinker.

An efficient chemoenzymatic cascade strategy for transforming biomass into furfurylamine with lobster shell-based chemocatalyst and mutated ω-transaminase biocatalyst in methyl isobutyl ketone-water.

To date, an efficient process for manufacturing valuable furan compounds from available renewable resources has gained great attention via a chemoenzymatic route. In this study, a sulfonated tin-loaded heterogeneous catalyst CLUST-Sn-LS using lobster shell as biobased carrier was prepared to convert corncob (75.0 g/L) into furfural (122.5 mM) at 170 °C for 30 min in methyl isobutyl ketone (MIBK)-H2O biphasic system (2:1, v/v). To improve furfurylamine yield, a novel recombinant E. coli TFTS harboring robust mutant Aspergillus terreus ω-transaminase [hydrophilic threonine (T) at position 130 was site-directed mutated to hydrophobic phenylalanine (F)] was constructed to transform 300-500 mM furfural into furfurylamine (90.1-93.6 % yield) at 30 °C and pH 7.5 in MIBK-H2O. Corncob was converted to furfurylamine in MIBK-H2O with a high productivity of 0.461 g furfurylamine/(g xylan). This constructed chemoenzymatic method coupling bio-based chemocatalyst CLUST-Sn-LS and mutant ω-transaminase biocatalyst in a biphasic system could efficiently convert lignocellulose into furfurylamine.