Investigation of lignin substructures participating in self-assembly for the synthesis of monodisperse lignin spherical particles.

The intricate structure of lignin, characterized by a mix of hydrophilic components and hydrophobic structures from its aliphatic and aromatic constituents, poses challenges in creating monodisperse particles. This is due to the need for precise modulation of self-assembly kinetics. Herein, we explore a correlation between the substructure of lignin and its capacity for self-assembly. We have conducted an in-depth investigation into the interactions between hydrophilic groups, such as phenolic and aromatic-OH, and monolignols with interunit linkages that are involved in the formation of lignin particles (LPs). A high degree of hydrophilicity with a condensed structure is crucial for high supersaturation levels, which in turn determines the growth phase and leads to small LPs. An approach based on tailoring the supersaturation level which is contingent on the structural characteristics of extracted organosolv lignin was used to obtain remarkably uniform LPs with mean diameters of approximately 230 and 480 nm. The results of this study have the potential to serve as a foundation for the preparation of monodisperse LPs derived from various lignin sources as well as for the development of methods to extract lignin containing a specific chemical substructure.

Development of novel recombinant peroxidase secretion system from Pseudomonas putida for lignin valorisation.

Pseudomonas putida is a promising strain for lignin valorisation. However, there is a dearth of stable and efficient systems for secreting enzymes to enhance the process. Therefore, a novel secretion system for recombinant lignin-depolymerising peroxidase was developed. By adopting a flagellar type III secretion system, P. putida KT-M2, a secretory host strain, was constructed and an optimal secretion signal fusion partner was identified. Application of the dye-decolourising peroxidase of P. putida to this system resulted in efficient oxidation activity of the cell-free supernatant against various chemicals, including lignin model compounds. This peroxidase-secreting strain was examined to confirm its lignin utilisation capability, resulting in the efficient assimilation of various lignin substrates with 2.6-fold higher growth than that of the wild-type strain after 72 h of cultivation. Finally, this novel system will lead efficient bacterial lignin breakdown and utilization through enzyme secretion, paving the way for sustainable lignin-consolidated bioprocessing.

Fuzzy Portfolio Selection Using Stochastic Correlation.

Here we have proposed fuzzy portfolio selection model using stochastic correlation (FPSMSC) to overcome limitations both in fuzzy and stochastic world. The newly proposed model not only gets harmonious efficient frontier, but also considers the future movement of stock prices based on fuzzy expertise knowledge. The investment weights of the model have been optimized based on the monthly return data of 18 stocks listed in S&P500 from October 2011 to September 2015. The proposed model has provided higher returns in the whole regime of risk for the period from October 2014 to September 2015, whose monthly return data are used as training data than other available portfolio selection models, i.e., fuzzy portfolio selection models with credibility and possibility and statistic model. Also, the present model has shown the better smoothness of the variations of returns with respect to risk aversion parameter, λ, from the monthly data from October 2015 to September 2016, which is not included to training database. Especially, our model is superior to other models in the regime of 0-0.3 for the risk aversion level. It is demonstrating that the FPSMSC is efficient for the investors who tend to seek the high return in portfolio management. Supplementary Information: The online version contains supplementary material available at 10.1007/s10614-023-10371-w.

Ethanol organosolv lignin as a substitute for commercial antioxidants, focusing on the structural properties and synergistic effect with myricetin.

Lignin has potential as a substitute for natural antioxidants in cosmetics and food industries due to its radical scavenging ability and price competitiveness. The antioxidant activity of lignin depends on its structural properties, and they accordingly have synergy with natural antioxidants. Based on the structural characteristics, the antioxidant activity of ethanol organosolv lignin (EOL) and synergy with myricetin were investigated. The phenolic-OH content was a predominant factor in the antioxidant activity of EOL, and EOL-H with a higher phenolic-OH content and lower IC50 value (0.17 mg/mL) covered a wide synergy range of 1:32-2:1 (EOL:myricetin). The synergistic effect was verified by comparing predicted and actual values based on ESR analysis, and the phenolic-OH ratio (>0.4) of myricetin and EOL for the synergy was suggested. In this respect, the results highlight the potential of lignin with high phenolic-OH content as a substitute for commercial antioxidants with superior activity and broad synergy ranges.

Effect of torrefied biomass on hydrophobicity and mechanical properties of polylactic acid composite.

In this study, the physicochemical properties of torrefied biomass (larch and yellow poplar) were investigated based on torrefaction temperature. The effect of torrefied biomass on the hydrophobicity and mechanical properties of a polylactic acid (PLA) composites was evaluated. Hemicellulose was removed from the biomass during torrefaction, whereas the cellulose and lignin contents increased slightly. The color of the biomass changed from brown to black. The grindability of the torrefied biomass improved as the torrefaction temperature increased, which contributed to the production of fine particles (>100 mesh). A PLA composite was prepared using torrefied biomass (10 %) and polylactic acid. At 280 °C, water contact angle was the highest, regardless of the particle size and biomass species. Tensile strength of the PLA composite was slightly lower than that of PLA alone, regardless of the particle size of torrefied biomass. Nevertheless, the strength increased with the torrefaction temperature, except for larch with a relatively large particle size (<100 mesh). The tensile strength of the control was 68.0 MPa, whereas that of the torrefied biomass ranged from 61.1 to 65.8 MPa.

Thermoplasticity reinforcement of ethanol organosolv lignin to improve compatibility in PLA-based ligno-bioplastics: Focusing on the structural characteristics of lignin.

Commonly, lignin macromolecules have limitations in application to the thermoplastics industries due to poor dispersibility and interfacial compatibility within ligno-bioplastics. In this study, the dispersibility and interfacial compatibility of ethanol organosolv lignin (EOL) in PLA-based ligno-bioplastic were improved by enhancing the thermoplasticity via oxypropylation. Further, three types of EOLs extracted from different severity conditions were applied to investigate the effect of the structural characteristics of EOLs on the changes in the thermal properties. The thermal properties of oxypropylated EOL were dependent on the structural characteristics of the initial EOL as well as the degree of polymerization of propylene oxide. The thermoplasticity of EOLs extracted under mild condition was effectively increased as a new Tg and melting were observed. Based on increased thermoplasticity, the dispersibility and interfacial compatibility of EOL within PLA-based ligno-bioplastic were successfully improved, which compensates for the deterioration in mechanical strength of ligno-bioplastic due to the addition of unmodified EOL. Therefore, oxypropylation of EOL with suitable structural characteristics promises improved availability as a thermoplastic material.

Improving the catalytic performance of xylanase from Bacillus circulans through structure-based rational design.

Endo-1,4-ß-xylanase is one of the most important enzymes employed in biorefineries for obtaining fermentable sugars from hemicellulosic components. Herein, we aimed to improve the catalytic performance of Bacillus circulans xylanase (Bcx) using a structure-guided rational design. A systematic analysis of flexible motions revealed that the R49 component of Bcx (i) constrains the global conformational changes essential for substrate binding and (ii) is involved in modulating flexible motion. Site-saturated mutagenesis of the R49 residue led to the engineering of the active mutants with the trade-off between flexibility and rigidity. The most active mutant R49N improved the catalytic performance, including its catalytic efficiency (7.51-fold), conformational stability (0.7 °C improvement), and production of xylose oligomers (2.18-fold higher xylobiose and 1.72-fold higher xylotriose). The results discussed herein can be applied to enhance the catalytic performance of industrially important enzymes by controlling flexibility.

Techno-economic analysis of producing xylo-oligosaccharides and cellulose microfibers from lignocellulosic biomass.

This study assesses the economic performance of a biorefinery producing xylo-oligosaccharides (XOS) from miscanthus by autohydrolysis and purification based on a rigorous model developed in ASPEN Plus. Varied biorefinery capacities (50-250 oven dry metric ton (ODMT)/day) and three XOS content levels (80%, 90%, 95%) are analyzed. The XOS minimum selling price (XOS MSP) is varied between $3,430-$7,500, $4,030-$8,970, and $4,840-$10,640 per metric ton (MT) for 80%, 90%, and 95% content, respectively. The results show that increasing biorefinery capacity can significantly reduce the XOS MSP and higher purity leads to higher XOS MSP due to less yield, and higher capital and operating costs. This study also explores another system configuration to produce high-value byproducts, cellulose microfiber, by utilizing the cellulose to produce microfiber instead of combusting for energy recovery. The XOS MSP of cellulose microfiber case is $2,460-$7,040/MT and thus exhibits potential economic benefits over the other cases.

Evaluation of Xylooligosaccharides Production for a Specific Degree of Polymerization by Liquid Hot Water Treatment of Tropical Hardwood.

Eucalyptus pellita is known as attractive biomass, and it has been utilized for eucalyptus oil, furniture, and pulp and paper production that causes a significant amount of byproducts. Liquid hot water treatment depending on combined severity factor (CSF) was subjected to isolate hemicellulose fraction from E. pellita and to produce xylooligosaccharides (XOS). The xylan extraction ratio based on the initial xylan content of the feedstock was maximized up to 77.6% at 170 °C for 50 min condition (CSF: 1.0), which had accounted for XOS purity of 76.5% based on the total sugar content of the liquid hydrolysate. In this condition, the sum of xylobiose, xylotriose, and xylotetraose which has a low degree of polymerization (DP) of 2 to 4 was determined as 80.6% of the total XOS. The highest XOS production score established using parameters including the xylan extraction ratio, XOS purity, and low DP XOS ratio was 5.7 at CSF 1.0 condition. XOS production score evaluated using the CSF is expected to be used as a productivity indicator of XOS in the industry (R-squared value: 0.92).

Recent Advances in Sustainable Plastic Upcycling and Biopolymers.

Advances in scientific technology in the early twentieth century have facilitated the development of synthetic plastics that are lightweight, rigid, and can be easily molded into a desirable shape without changing their material properties. Thus, plastics become ubiquitous and indispensable materials that are used in various manufacturing sectors, including clothing, automotive, medical, and electronic industries. However, strong physical durability and chemical stability of synthetic plastics, most of which are produced from fossil fuels, hinder their complete degradation when they are improperly discarded after use. In addition, accumulated plastic wastes without degradation have caused severe environmental problems, such as microplastics pollution and plastic islands. Thus, the usage and production of plastics is not free from environmental pollution or resource depletion. In order to lessen the impact of climate change and reduce plastic pollution, it is necessary to understand and address the current plastic life cycles. In this review, "sustainable biopolymers" are suggested as a promising solution to the current plastic crisis. The desired properties of sustainable biopolymers and bio-based and bio/chemical hybrid technologies for the development of sustainable biopolymers are mainly discussed.

Biosynthesis of polyhydroxyalkanoates from sucrose by metabolically engineered Escherichia coli strains.

Sucrose utilization has been established in Escherichia coli strains by expression of Mannheimia succiniciproducens ß-fructofuranosidase (SacC), which hydrolyzes sucrose into glucose and fructose. Recombinant E. coli strains that can utilize sucrose were examined for their abilities to produce poly(3-hydroxybutyrate) [P(3HB)] and poly(3-hydroxybutyrate-co-lactate) [P(3HB-co-LA)] from sucrose. When recombinant E. coli strains expressing Ralstonia eutropha PhaCAB and SacC were cultured in MR medium containing 20 g/L of sucrose, all recombinant E. coli strains could produce P(3HB) from sucrose. Also, recombinant E. coli strains expressing Pseudomonas sp. MBEL 6-19 PhaC1437, Clostridium propionicum Pct540, R. eutropha PhaAB enzymes along with SacC could produce P(3HB-co-LA) from sucrose. Among the examined E. coli strains, recombinant E. coli XL1-Blue produced the highest contents of P(3HB) (53.60 ± 2.55 wt%) and P(3HB-co-LA) (29.44 ± 0.39 wt%). In the batch fermentations, recombinant E. coli XL1-Blue strains completely consumed 20 g/L of sucrose as the sole carbon source and supported the production of 3.76 g/L of P(3HB) and 1.82 g/L of P(3HB-co-LA) with 38.21 wt% P(3HB) and 20.88 wt% P(3HB-co-LA) contents, respectively. Recombinant E. coli strains developed in this study can be used to establish a cost-efficient biorefinery for the production of polyhydroxyalkanoates (PHAs) from sucrose, which is an abundant and inexpensive carbon source.

Minimal control power of controlled dense coding and genuine tripartite entanglement.

We investigate minimal control power (MCP) for controlled dense coding defined by the channel capacity. We obtain MCPs for extended three-qubit Greenberger-Horne-Zeilinger (GHZ) states and generalized three-qubit W states. Among those GHZ states, the standard GHZ state is found to maximize the MCP and so does the standard W state among the W-type states. We find the lower and upper bounds of the MCP and show for pure states that the lower bound, zero, is achieved if and only if the three-qubit state is biseparable or fully separable. The upper bound is achieved only for the standard GHZ state. Since the MCP is nonzero only when three-qubit entanglement exists, this quantity may be a good candidate to measure the degree of genuine tripartite entanglement.

Evaluation of correlation between glucan conversion and degree of delignification depending on pretreatment strategies using Jabon Merah.

The main purpose of this study was to investigate the glucan conversion rate after enzymatic hydrolysis depending on the treatment methods and conditions with changes in the chemical composition of treated solid fraction of Jabon Merah. The glucan conversion rate (17.4%) was not significantly improved after liquid hot water treatment (1st step) even though most of the hemicellulose was dissolved into liquid hydrolysate. Subsequently, dilute acid, organosolv, and peracetic acid treatment (2nd step) was conducted under various conditions to enhance glucan conversion. Among the 2nd step treatment, the glucan conversion rate of organosolv (max. 46.0%) and peracetic acid treatment (max. 65.9%) was increased remarkably through decomposition of acid-insoluble lignin (AIL). Finally, the glucan conversion rate and AIL content were highly correlated, which was revealed by the R-squared value (0.84), but inhibitory factors including cellulose crystallinity must be considered for advanced glucan conversion from highly recalcitrant biomasses, such as Jabon Merah.

Biomass pretreatments capable of enabling lignin valorization in a biorefinery process.

Recent techno-economic studies of proposed lignocellulosic biorefineries have concluded that creating value from lignin will assist realization of biomass utilization into valuable fuels, chemicals, and materials due to co-valorization and the new revenues beyond carbohydrates. The pretreatment step within a biorefinery process is essential for recovering carbohydrates, but different techniques and intensities have a variety of effects on lignin. Acidic and alkaline pretreatments have been shown to produce diverse lignins based on delignification chemistry. The valorization potential of pretreated lignin is affected by its chemical structure, which is known to degrade, including inter-lignin condensation under high-severity pretreatment. Co-valorization of lignin and carbohydrates will require dampening of pretreatment intensities to avoid such effects, in spite of tradeoffs in carbohydrate production.

Optimization of enzymatic hydrolysis conditions for extraction of pectin from rapeseed cake (Brassica napus L.) using commercial enzymes.

The aims of this study were to extract pectin from rapeseed cake (RSC) by enzymatic hydrolysis using commercial enzymes (Celluclast and Alcalase) and to investigate the effects of different reaction conditions, such as enzymatic hydrolysis time, enzyme-RSC ratio, and Celluclast-Alcalase ratio, on the degradation of RSC and pectin yield. RSC was treated using a combined extraction process that consisted of a fat removal process, enzymatic hydrolysis, and isopropanol/ethanol precipitation. After the fat removal process and enzymatic hydrolysis, defatted-RSC was suitably decomposed, and the loss of liberated reducing sugars was minimized when the hydrolysis condition reached a hydrolysis time of 270 min or an enzyme-RSC ratio of 1:50. Based on these results, various Celluclast-Alcalase ratios were applied. Alcalase led to the destruction of protein-carbohydrate complex in defatted-RSC, whereas Celluclast cleaved some linkages of carbohydrate slightly. As a result, the highest pectin yield was 6.85% at the Celluclast-Alcalase ratio of 1:4.

Structural properties of pretreated biomass from different acid pretreatments and their effects on simultaneous saccharification and ethanol fermentation.

The aim of this study was to investigate the effects of different acid pretreatments on the hydrolysis of biomass and ethanol production. Maleic, oxalic, and sulfuric acids were used individually as catalysts. The fermentable sugar concentration in hydrolysate was high at more than 30 g/L, which obtained at the dicarboxylic acid pretreatment. On the structural change of pretreated biomass, the S/G ratio ranged from 1.7 to 2.0, which was lower than that of raw material. The amount of phenolic OH group was significantly increased by acid pretreatment, which ranged 17.5-32.8%, compared to 4.7% of the raw material. The amounts of phenolic OH group in lignin sensitively affected simultaneous saccharification and fermentation. The maleic acid pretreated biomass, which included 17.5% of the phenolic OH group, was very effective for attaining high glucose yields and ethanol yield, after simultaneous saccharification and fermentation. At the same time, the highest ethanol yield was 0.48.

Involvement of extracellular and intracellular enzymes of Ceriporia sp. ZLY-2010 for biodegradation of polychlorinated biphenyls (PCBs).

This study examined the interrelation between the biodegradation of polychlorinated biphenyls (PCBs) by Ceriporia sp. ZLY-2010 and its fungal enzyme systems. The degradation rates of Aroclor 1254 and 1260 were 29.01% on day 5 and 36.80% on day 10, respectively. MnP (Manganese dependent peroxidase) and laccase activities showed the greatest increases in the samples containing Aroclors, indicating that extracellular enzymes of Ceriporia sp. ZLY-2010 were affected by the addition of Aroclors. However, the relationship between the biodegradation rate and extracellular enzymes might be obscured by the complexity of the biodegradation process. Cytochrome P450 monooxygenase was inhibited and the biodegradation rate of the Aroclor decreased by adding the inhibitor 1-aminobenzotriazole. Two-dimensional gel electrophoresis showed that intracellular enzymes play a significant role in the biodegradation of Aroclor. Complex extracellular and intracellular enzyme systems in Ceriporia sp. ZLY-2010 play an important role in degrading PCBs. Physiological changes of Ceriporia sp. ZLY-2010 caused by PCBs appeared to affect biodegradation of PCBs. However, it is necessary to further study the unidentified enzymes related to the biodegradation of Aroclor.

Effects of combination processes on the extraction of pectins from rapeseed cake (Brassica napus L.).

In this study, rapeseed cake (RSC) was used as a source of pectins due to its high carbohydrate content. Different combinations of treatments were applied to investigate the effect of combination processes on the extraction of pectin from RSC. The treatments chosen for combination were a fat removal process (FRP) (solvent extraction using an alcohol-benzene mixture), a chemical treatment (CT) (hydrolysis using 1% hydrochloric acid), and an enzymatic hydrolysis (EH). After the combined processes, pectins were extracted by isopropanol/ethanol precipitation and the residues were analysed by HPLC or an elemental analyser. The pectin yields and galacturonic acid contents were increased by FRP because 72.13% of the total fat was removed; additionally, EH had a similar effect. However, CT decreased the yields because the treatment was too harsh and the galacturonic acid broke down. Pectin yields and galacturonic acid contents were highest in the combination process FRP/EH (6.23% and 64.23%, respectively).

Antifungal efficacy of environmentally friendly wood preservatives formulated with enzymatic-hydrolyzed okara, copper, or boron salts.

Okara, an organic waste product obtained from soy milk production, was used with copper chloride or sodium borate to formulate new wood preservatives as a substitute for expensive wood preservatives, such as copper-azole-based preservatives and ammoniacal copper quaternary. Before formulating the preservatives, okara was hydrolyzed by enzymes (cellulase, pectinase, and protease) to augment penetration and fix the biocide salts of the preservatives into wood blocks. The preservatives were injected into wood blocks by vacuum pressure to measure the treatability of the preservatives. The treated wood blocks were placed in hot water for 3 d to measure leachability. The treatability and leachability of the preservatives were affected by the type and loading amount of enzymes and the addition of sodium borate into okara-based wood preservative formulations. The treatability and leachability of the preservatives formulated with copper chloride and okara hydrolysates were 63.38 and 3.15%, and those of the preservatives with copper chloride, okara hydrolysates, and sodium borate were 61.47 and 3.32%, respectively. Despite the hot water leaching, wood blocks treated with preservatives formulated with 2% cellulase, pectinase, and protease hydrolyzed okara, CuCl(2), and sodium borate showed only 1.98% average weight loss against Fomitopsis palustris over 12 weeks. Microscopic observation revealed how okara-based preservatives work in wood blocks. Okara has potential as a raw material for cost-effective and environmentally friendly wood preservatives.

Enzymatic saccharification of biologically pretreated Pinus densiflora using enzymes from brown rot fungi.

Enzymatic saccharification of lignocellulosic biomass was performed using culture filtrates of brown rot fungi including Gloeophyllum sepiarium, Fomitopsis pinicola, and Laetiporus sulphureus. Biological treatment with white rot fungi was used as pretreatment prior to enzymatic saccharification. Endoglucanase, beta-glucosidase, xylanase and cellobiohydrolase activities were determined from concentrated culture filtrates of the brown rot fungi. L. sulphureus has the highest endoglucanase, beta-glucosidase, and xylanase activities, and F. pinicola has the highest cellobiohydrolase activity. When enzymes from L. sulphureus were used along with the lignocellulosic biomass pretreated with Stereum hirsutum as the carbon source, the total sugar yield was 11.36 mg/0.25 g of dry weight biomass, with the highest activities of cellulase and hemicellulase. In order to increase the sugar yield, the enzymes from L. sulphureus were mixed with those from F. pinicola, which showed high cellobiohydrolase activity. This caused an increase in the sugar yield from 11.36 mg to 15.22 mg. When temperature was increased to 50 degrees C, the total sugar yield increased to 17.74 mg for the same reaction time. The crystallinity of lignocellulosic biomass decreased from 68.4% to 60.2%, when lignocellulosic biomass pretreated with S. hirsutum was hydrolyzed using enzymes from L. sulphureus.