Valorization of Lignocellulose with One-Step Acidified Monophasic Phenoxyethanol Fractionation.

Effective fractionation of lignocelluosic biomass and subsequent valorization of all three major components under mild conditions were achieved. Pretreatment with acidified monophasic phenoxyethanol (EPH) efficiently removed 92.6 % lignin and 80 % xylan from poplar at 110 °C in 60 min, yielding high-value EPH-xyloside, EPH-modified lignin (EPHL), and a solid residue nearly purely composed of carbohydrates. After removing the grafted acetyl groups using 1 % NaOH at 50 °C, the highest enzymatic digestibility reached 92.3 %. EPHL could be recovered in high yield and purity with an uncondensed structure, while xylose was converted to EPH-xyloside, a potential precursor in biomedical industries. Additionally, the acidified monophasic EPH solvent could effectively fractionate biomass from species other than hardwood, achieving over 70 % delignification from recalcitrant pinewood under the same mild conditions, demonstrating the high potential of monophasic EPH pretreatment.

Quantitative correlation analysis between particle liquefaction and saccharification through dynamic changes of slurry rheological behavior and particle characteristics during high-solid enzymatic hydrolysis of sugarcane bagasse.

This study identified the intrinsic relationships among slurry rheology, particle characteristics, and lignocellulosic liquefaction/saccharification based on correlation analysis and principal component analysis during the hydrolysis of sugarcane bagasse pretreated by deep eutectic solvents (DES) and mechanical milling (MM). The DES-MM pretreated lignocellulosic slurry (20% solids) exhibited high apparent viscosity of 1.4 × 104 Pa·s and shear stress of 929.0 Pa under steady state. Glucose production had a negative linear correlation with slurry viscosity (R2, 0.69-0.97), whereas its correlation with yield stress (R2, 0.85-0.98) depended on the particle liquefaction rate. The availability of free water provided a major contribution to improving slurry rheology. However, the size reduction of submillimeter particles and the changes in particle hydrophilicity during liquefaction were not significantly correlated with rheological changes. Various interrelated particle characteristics and rheological changes were integrated into two simple principal variables to predict glucose production with a high R2 of 0.96.

Fractionation of lignin from rice straw using an acidified biphasic solvent system.

To obtain lignin from lignocellulosic biomass, phenoxyethanol (EPH) was employed to construct a biphasic solvent system. The concentration of EPH in this biphasic solvent system was first studied to determine a pretreatment condition for fractionation of lignin. Then, the fractionation of lignin from rice straw was performed under the conditions of temperature 130 °C, cooking time 60 min and sulfuric acid concentration 0.1 M, in 70 % aqueous EPH solvent system. The results showed that 50.97 %, 49.52 % or 82.02 % of the removed lignin with the purity of 89.04 %, 91.30 % or 84.76 % was regenerated from EPH liquor using dimethyl carbonate (DMC), dimethoxymethane (DMM) or diethyl ether (DE) as precipitant, respectively. Additionally, the weight-average molecular weight (Mw) and dispersity index (D) of the regenerated lignin decreased to 4247-4809 g/mol and 1.26-1.60 compared with that of the original lignin (5654 g/mol and 4.78). Finally, the compositional and structural characteristics of lignin, e.g., molecular weight and molecular structure, were also investigated by DSC, HSQC and elemental analysis.

Biphasic fractionation of lignocellulosic biomass based on the combined action of pretreatment severity and solvent effects on delignification.

A novel method based on pretreatment severity and solvent effects on delignification, was introduced to pretreat and fractionate lignocellulose in a 2-phenoxyethanol (EPH) biphasic solvent system. The combined severity factor (CSF) was used to regulate pretreatment severity, and the relative energy difference (RED) of solvent system to lignin was used to evaluate solvent effects. The combined action of pretreatment severity and solvent effects on delignification was first investigated by the response surface regression analysis on the pretreatment of Amorpha. Accordingly, pretreatment and fractionation of Amorpha, poplar and corn straw were then conducted under the optimized conditions. Results showed that >99 % lignin was removed after pretreatment with CSF 3.7845 in a solvent system with RED 0.9371, and 42.94 %, 39.41 % and 70.90 % lignin from Amorpha, poplar and corn straw were respectively regenerated from organosolv liquor after fractionation. Finally, the regenerated products were characterized by FTIR, TG and GPC analysis.

A one-step deconstruction-separation organosolv fractionation of lignocellulosic biomass using acetone/phenoxyethanol/water ternary solvent system.

A novel ternary solvent system for organosolv fractionation of lignocellulosic biomass, named APW process, which is composed of acetone, phenoxyethanol and water with the advantages of monophasic deconstruction and biphasic separation of components was developed. Through fractionation of amorpha as a case study, a monophasic APW solution (acetone/phenoxyethanol/water = 5:11:4, volume ratio) with the best lignin affinity was constructed based on Hansen solubility parameters. According to Taguchi experimental design, the optimal conditions were 130 °C, 70 min, 0.15 M sulfuric acid and 20 LSR. Under optimal conditions, removal of lignin and hemicellulose reached 95.60% and 98.39%, respectively. While 80.48% of cellulose was retained in residue and its digestibility was 80.36%. Then, 83.74% of hemicellulose was recovered from aqueous as sugars, and 35.64% of lignin was recovered by precipitation. Moreover, APW process also have effective fractionation of sugarcane bagasse, corn cob and pine, cellulose and hemicellulose recovery were both over 80%.

Low-temperature sodium hydroxide pretreatment for ethanol production from sugarcane bagasse without washing process.

A low-temperature sodium hydroxide (NaOH) pretreatment for sugarcane bagasse (SCB) was obtained via the surface response design in this study. However, a large quantity of water consumption and wastewater generation which have been the common problems for alkaline pretreatment of lignocellulose still exists in this pretreatment. In order to reduce water consumption and wastewater generation, this study attempted to perform enzymatic hydrolysis and fermentation of NaOH-treated SCB without washing process. It showed that after pretreatment and solid-liquid separation, NaOH-treated SCB could be directly hydrolysed by cellulase via pH and solid-liquid adjustment without washing steps, and the maximum enzymatic hydrolysis efficiency could reach to 70.2%. A domesticated Saccharomyces cerevisiae Y2034 which can endure 6-times diluted BL was obtained, and realized 67.5% ethanol yield from the enzymatic hydrolysate of unwashed NaOH-treated SCB. It provided a clue for converting NaOH-treated lignocellulose to ethanol at low water consumption and wastewater generation.

Environmental enrichment intervention for Rett syndrome: an individually randomised stepped wedge trial.

BACKGROUND: Rett syndrome is caused by a pathogenic mutation in the MECP2 gene with major consequences for motor and cognitive development. One of the effects of impaired MECP2 function is reduced production of Brain Derived Neurotrophic Factor (BDNF), a protein required for normal neuronal development. When housed in an enriched environment, MECP2 null mice improved motor abilities and increased levels of BDNF in the brain. We investigated the effects of environmental enrichment on gross motor skills and blood BDNF levels in girls with Rett syndrome. METHODS: A genetically variable group of 12 girls with a MECP2 mutation and younger than 6 years participated in a modified individually randomised stepped wedge design study. Assessments were conducted on five occasions, two during the baseline period and three during the intervention period. Gross motor function was assessed using the Rett Syndrome Gross Motor Scale (maximum score of 45) on five occasions, two during the baseline period and three during the intervention period. Blood levels of BDNF were measured at the two baseline assessments and at the end of the intervention period. The intervention comprised motor learning and exercise supplemented with social, cognitive and other sensory experiences over a six-month period. RESULTS: At the first assessment, the mean (SD) age of the children was 3 years (1 year 1 month) years ranging from 1 year 6 months to 5 years 2 months. Also at baseline, mean (SD) gross motor scores and blood BDNF levels were 22.7/45 (9.6) and 165.0 (28.8) ng/ml respectively. Adjusting for covariates, the enriched environment was associated with improved gross motor skills (coefficient 8.2, 95%CI 5.1, 11.2) and a 321.4 ng/ml (95%CI 272.0, 370.8) increase in blood BDNF levels after 6 months of treatment. Growth, sleep quality and mood were unaffected. CONCLUSIONS: Behavioural interventions such as environmental enrichment can reduce the functional deficit in Rett syndrome, contributing to the evidence-base for management and further understanding of epigenetic mechanisms. Environmental enrichment will be an important adjunct in the evaluation of new drug therapies that use BDNF pathways because of implications for the strengthening of synapses and improved functioning. TRIAL REGISTRATION: ACTRN12615001286538 .

Feasibility of reusing the black liquor for enzymatic hydrolysis and ethanol fermentation.

The black liquor (BL) generated in the alkaline pretreatment process is usually thought as the environmental pollutant. This study found that the pure alkaline lignin hardly inhibited the enzymatic hydrolysis of cellulose (EHC), which led to the investigation on the feasibility of reusing BL as the buffer via pH adjustment for the subsequent enzymatic hydrolysis and fermentation. The pH value of BL was adjusted from 13.23 to 4.80 with acetic acid, and the alkaline lignin was partially precipitated. It deposited on the surface of cellulose and negatively influenced the EHC via blocking the access of cellulase to cellulose and adsorbing cellulase. The supernatant separated from the acidified BL scarcely affected the EHC, but inhibited the ethanol fermentation. The 4-times diluted supernatant and the last-time waste wash water of the alkali-treated sugarcane bagasse didn't inhibit the EHC and ethanol production. This work gives a clue of saving water for alkaline pretreatment.

Co-extraction of soluble and insoluble sugars from energy sorghum based on a hydrothermal hydrolysis process.

A process for co-extraction of soluble and insoluble sugars from energy sorghum (ES) was developed based on hydrothermal hydrolysis (HH). Two series of ES were investigated: one (N) with a high biomass yield displayed a higher recalcitrance to sugar release, whereas the second (T) series was characterized by high sugar extraction. The highest total xylose recoveries of 87.2% and 98.7% were obtained for N-11 and T-106 under hydrolysis conditions of 180°C for 50min and 180°C for 30min, respectively. Moreover, the T series displayed higher enzymatic digestibility (ED) than the N series. The high degree of branching (arabinose/xylose ratio) and acetyl groups in the hemicellulose chains of T-106 would be expected to accelerate sugar release during the HH process. In addition, negative correlations between ED and the lignin content, crystallinity index (CrI) and syringyl/guaiacyl (S/G) lignin ratio were observed. Furthermore, finding ways to overcome the thickness of the cell wall and heterogeneity of its chemical composition distribution would make cellulose more accessible to the enzyme.

High conversion of sugarcane bagasse into monosaccharides based on sodium hydroxide pretreatment at low water consumption and wastewater generation.

The generation of a great quantity of black liquor (BL) and waste wash water (WWW) has been key problems of the alkaline pretreatment. This work tried to build a sustainable way to recycle the BL for pretreating sugarcane bagasse (SCB) and the WWW for washing the residual solid (RS) of alkali-treated SCB which would be subsequently hydrolysed and fermented. The enzymatic hydrolysis efficiency of the washed RS decreased with the recycling times of BL and WWW increasing. Tween80 at the loading of 0.25% (V/V) could notably improve the enzymatic hydrolysis and had no negative impact on the downstream fermentation. Compared with the non-recycling and BL recycling ways based on alkaline pretreatment, the BL-WWW recycling way could not only maintain high conversion of carbohydrate into monosaccharides and save alkali amount of 45.5%, but also save more than 80% water and generate less than 15% waste water.

Liquid hot water pretreatment of lignocellulosic biomass for bioethanol production accompanying with high valuable products.

Pretreatment is an essential prerequisite to overcome recalcitrance of biomass and enhance the ethanol conversion efficiency of polysaccharides. Compared with other pretreatment methods, liquid hot water (LHW) pretreatment not only reduces the downstream pressure by making cellulose more accessible to the enzymes but minimizes the formation of degradation products that inhibit the growth of fermentative microorganisms. Herein, this review summarized the improved LHW process for different biomass feedstocks, the decomposition behavior of biomass in the LHW process, the enzymatic hydrolysis of LHW-treated substrates, and production of high value-added products and ethanol. Moreover, a combined process producing ethanol and high value-added products was proposed basing on the works of Guangzhou Institute of Energy Conversion to make LHW pretreatment acceptable in the biorefinery of cellulosic ethanol.

Influence of lignin level on release of hemicellulose-derived sugars in liquid hot water.

Lignin layers surrounding hemicelluloses and cellulose in the plant cell walls protect them from deconstruction. This recalcitrance to sugar release is a major limitation for cost-effective industrial conversion of lignocellulosic biomass to biofuels. Many literatures had reported the contribution of lignin removal to cellulose accessibility to enzyme, but less to the hemicellulose hydrolysis. Herein, beech xylan with lignin addition, partly delignified sugarcane bagasse (SB), energy sorghum hybrids (ESH) were treated in liquid hot water (LHW) to investigate the effect of lignin on hemicellulose decomposition. The addition of lignin can enhance the low degree of polymerization of xylooligomers production resulted from the acid catalyzed cleavage of lignin-derived acidic products. However, a negative correlation was observed initially between the lignin level and the total xylose yield from ESH. Furthermore, samples with lignin addition or high lignin content had a great resistant to harsh reaction environment, about 93.5% total xylose lost but only 52.3% released due to the lack of lignin protection for the sample with 100% lignin removal.

Liquid hot water pretreatment of energy grasses and its influence of physico-chemical changes on enzymatic digestibility.

Pennisetum hybrid I, II and switchgrass were pretreated with liquid hot water to enhance the release of sugars. The optimum hydrolysis factor for three energy grasses was 5.98, and the total xylose yield was 88.4%, 98.1% and 83.6% for grass I, II and S. It was indicated that the ratio of syringyl and guaiacyl units of lignin played an important role on the hemicellulose hydrolysis in LHW than branch degree, but latter contributed more on the characterization of xylooligomers degree of polymerization. Moreover, the analysis of multi-scale changes of substrate suggested that cellulose crystallinity index and degree of polymerization seemed no direct relationships for increase of enzymatic digestibility. While lignin barrier was the main factor limiting efficiency of sugar release, and Pennisetum hybrid with low lignin content and high sugar recovery was proved to be a prospective plant feedstock for cellulosic ethanol production.

Pretreatment of sugarcane bagasse with liquid hot water and aqueous ammonia.

Low water consumption operation (LWCO) can reduce the usage of water and energy input for the liquid hot water (LHW) pretreatment of sugarcane bagasse (SB) but causes great negative effects on the saccharification rate of xylose and enzymatic digestibility (ED) of cellulose. Therefore, a combined pretreatment with LHW and aqueous ammonia (LHWAA) was developed. ED of glucan and xylan is enhanced greatly resulted from the removal of hemicellulose and lignin after the LHWAA pretreatment. However, the intriguing results of low lignin removal and ED value were observed at the high reaction temperature of 180°C for the second step pretreatment of AA. It was proposed that lignin or pseudo-lignin droplet redeposited on the surface of residual solids might play a crucial role in determining the ED, so it is indispensable to make the enzyme access to the cellulose by the step of post-treatment with ultrasonic washing or hot washing. Coupled with the process of post-treatment and enzymatic hydrolysis, a high hemicellulose derived sugars recovery of 75.5% and glucose recovery of 87% was obtained for LHWAA pretreatment.

Liquid hot water pretreatment of sugarcane bagasse and its comparison with chemical pretreatment methods for the sugar recovery and structural changes.

Liquid hot water (LHW), dilute hydrochloric acid (HCl) and dilute sodium hydroxide (NaOH) were applied to sugarcane bagasse (SB). Application of the same analytical methods and material balance approaches facilitated meaningful comparisons of glucose and xylose yields from combined pretreatment and enzymatic hydrolysis. All pretreatments enhanced sugar recovery from pretreatment and subsequent enzymatic hydrolysis substantially compared to untreated sugarcane bagasse. Adding Tween80 in the enzymatic hydrolysis process increased the conversion level of glucan/xylan by 0.3-fold, especially for the low pH pretreatment where more lignin was left in the solids. The total sugar recovery from sugarcane bagasse with the coupled operations of pretreatment and 72 h enzymatic digestion reached 71.6% for LHW process, 76.6% for HCl pretreatment and 77.3% for NaOH pretreatment. Different structural changes at the plant tissue, cellular, and cell wall levels might be responsible for the different enzymatic digestibility. Furthermore, a combined LHW and aqueous ammonia pretreatment was proposed to reduce energy input and enhance the sugar recovery.

Hydrolysis of sweet sorghum bagasse and eucalyptus wood chips with liquid hot water.

The chemical composition, hydrolysis products, and kinetics during liquid hot water pretreatment of sweet sorghum bagasse (SSB) and eucalyptus wood chips (EWC) were investigated. Under optimal conditions, a total xylose recovery of 79.6% and 55.6% for SSB and of 74.9% and 84.4% for EWC was achieved after pretreatments in a step-change flow rate reactor (184 °C, 20 ml/min, 8 min, and 10 ml/min, 10 min) and batch stirred reactor (184 °C, 5%w/v, 18 min), respectively. More than 90% of the xylose was recovered as oligomers from SSB, independent of the type of reactor employed. The activation energies of xylan decomposition of SSB in the step-change flow rate reactor was 6.5-fold greater than that of EWC in the batch stirred reactor due to accumulation of acidic products. These findings show that sugar recovery is dependent on the reactor configuration for specific substrates.

Decomposition behavior of hemicellulose and lignin in the step-change flow rate liquid hot water.

Hemicellulose and lignin are the main factors limiting accessibility of hydrolytic enzymes besides the crystallinity of cellulose. The decomposition behavior of hemicellulose and lignin in the step-change flow rate hot water system was investigated. Xylan removal increased from 64.53% for batch system (solid concentration 4.25% w/v, 18 min, 184°C) to 83.78% at high flow rates of 30 ml/min for 8 min, and then 10 ml/min for 10 min. Most of them (80-90%) were recovered as oligosaccharide. It was hypothesized that the flowing water could enhance the mass transfer to improve the sugars recovery. In addition, the solubilization mechanism of lignin in the liquid hot water was proposed according to the results of Fourier transform-infrared spectroscopy and scanning electron microscopy of the water-insoluble fraction and gas chromatography-mass spectrometry of the water-soluble fraction. It was proposed that lignin in the liquid hot water first migrated out of the cell wall in the form of molten bodies, and then flushed out of the reactor. A small quantity of them was further degraded into monomeric products such as vanillin, syringe aldehyde, coniferyl aldehyde, ferulic acid, and p-hydroxy-cinnamic acid. All of these observations would provide important information for the downstream processing, such as purification and concentration of sugars and the enzymatic digestion of residual solid.

High consistency enzymatic saccharification of sweet sorghum bagasse pretreated with liquid hot water.

A laboratory set-up was designed to carry out high consistency enzymatic saccharification of sweet sorghum bagasse (SSB) which was pretreated by liquid hot water (LHW). The effects of two impellers on enzymatic hydrolysis of SSB were investigated. Compared with the double-curved-blade impeller (DCBI), the plate-and-frame impeller (PFI) could improve glucose production by 10%. Tween80 and fed-batch hydrolysis method adopted in this study produced total sugar of 17.06 g/L more than batch hydrolysis and raised the substrate consistency to 30%. At the final substrate loading of 30%, the concentrations of cellobiose, glucose and xylose reached to 15.01 g/L, 88.95 g/L and 9.80 g/L, respectively, and the ethanol concentration reached to 43.36 g/L in the case of cellobiose and xylose were not fermented by Saccharomyces cerevisiae Y2034. This study is an attempt at improvement of enzyme hydrolyzing LHW-pretreated material at high consistency.

The effect of metal salts on the decomposition of sweet sorghum bagasse in flow-through liquid hot water.

The impact of the metal salts NaCl, KCl, CaCl(2), MgCl(2), FeCl(3), FeCl(2), and CuCl(2), particularly the latter, on the decomposition of hemicellulose and lignin from sweet sorghum bagasse in liquid hot water pretreatment processing was studied in an attempt to enhance the recovery of sugars. Transition metal chlorides significantly enhanced the hemicellulose removal compared to the alkaline earth metal chlorides and alkaline metal chlorides, contributing to the formation of a saccharide-metal cation intermediate complex. FeCl(2) greatly increased xylose degradation and about 60% xylan was converted into non-saccharide products. In contrast, an excellent total and monomeric xylose recovery was obtained after the CuCl(2) pretreatment. Most of the lignin was deposited on the surface of the residual solid with droplet morphologies after this pretreatment, and about 20% was degraded into monomeric products. The total recovery of sugars from sweet sorghum bagasse with 0.1% CuCl(2) solution pretreatment and 48 h enzymatic digestibility, reached 90.4%, which is superior to the recovery using hot water pretreatment only.

Acid-catalysed direct transformation of cellulose into methyl glucosides in methanol at moderate temperatures.

Cellulose can be transformed into methyl glucosides in methanol with yields of 50-60% in the presence of several acid catalysts under mild conditions (< or = 473 K); H(3)PW(12)O(40) provides the highest turnover number (approximately 73 in 0.5 h) for the formation of methyl glucosides among many acid catalysts examined.