A sustainable process to 100%bio-based nylons integrated chemical and biological conversion of lignocellulose

Considerable progress has been made in recent years to the development of sustainable polymers from bio-based feedstocks.In this study,100%bio-based nylons were prepared via an integrated chemical and biological process from lignocellulose.These novel nylons were obtained by the melt polymerization of 3-propyladipic acid derived from lignin and 1,5-pentenediamine/1,4-butanediamine derived from carbohydrate sugar.Central to the concept is a three-step noble metal free catalytic chemical funnelling sequence(Raney Ni mediated reductive catalytic fractionation-reductive funnelling-oxidative funnelling),which allowed for obtaining a single component 3-propyladipic acid from lignin with high efficiency.The structural and thermodynamic properties of the obtained nylons have been systematically investigated,and thus obtained transparent bio-based nylons exhibited higher Mw(>32,000)and excellent thermal stability(Td5%>265℃).Considering their moderate Tg and good melt strength,these transparent bio-based nylons could serve as promising functional additives or temperature-responsive materials.

Co@CoO:An efficient catalyst for the depolymerization and upgrading of lignocellulose to alkylcyclohexanols with cellulose intact

The depolymerization and upgrading of lignin from raw biomass,while keeping cellulose intact is important in biorefinery and various metal-based catalysts have been used in reductive catalytic fractionation,a key method in"lignin-first"strategy,Recently,we found that a core-shell structured Co@CoO catalyst with CoO shell as the real active site had excellent performance in the hydrogenolysis of 5-hydromethylfurfural to 2,5-dimethylfuran due to its unique ability to dissociate H_(2)and yield active H^(δ-)species(Xiang et al.,2022).In this work,we report a one-pot depolymerization and upgrading of lignocellulose to alkylcyclohexanols,a flavour precursor,with intact cellulose over this unique core-shell structured catalyst,Co@CoO.Lignin model compounds(β-O-4,4-O-5,α-O-4)were first used to clarify the activity of Co@CoO catalyst.Then,the one-pot conversion of various organosolv lignin(birch,pine and poplar)to alkylcyclohexanols was realized with the mass yield of alkylcyclohexanols up to25.8 wt%from birch lignin under the reaction condition of 210℃,1 MPa H_(2),16 h.Finally,the corresponding woody sawdusts were used as feedstocks and found that the Co@CoO catalyst indeed preferentially depolymerized and upgraded the lignin part and obtained the same alkylcyclohexanols products with the retention of cellulose-rich pulp.The collected alkylcyclohexanols were further esterified to obtain valueadded esters,which can be used as flavors.This work will inspire the design of new efficient metal oxide catalysts in lignin fractionation and depolymerization to high-value-added chemicals with intact cellulose.

The case-dependent lignin role in lignocellulose nanofibers preparation and functional application-A review

Lignocellulose nanofibers(LCNFs) as a new material is attracting extensive attention. The pretreatment and mechanical fibrillation are the two main stages involved in the preparation of LCNFs, and lignin plays the important role of these two stages. This review discussed the interaction between lignin and chemicals in the pretreatment stage, and discovered the general law of the effect of lignin in the mechanical fibrillation stage.Lignin exhibits both promotion and inhibition effects on mechanical fibrillation, and the mutual competition between the two effects ultimately affects the energy consumption, morphology and yield of LCNFs. Furthermore, the recent research progress related to the contributions of lignin on the functional application of LCNFs was summarized, aiming to provide profound guidance for the preparation and application of LCNFs.

Advances in catalytic conversion of lignocellulose to chemicals and liquid fuels

In response to the awareness of limited fossil resources and environmental concerns,catalytic conversion of renewable lignocellulose biomass to value-added chemicals and fuels is of great significance and attractive for sustainable chemistry.Division of Biomass Conversion and Bio-Energy attached to Dalian National Laboratory for Clean Energy has devoted themselves to valorization of lignocellulose biomass since launched in 2011.Our research interests focus on breeding of biomass resources(inulin and microalgae),exploration of catalytic and biological technologies,and production of energy chemicals and fuels.Although lignocellulose biomass is renewable and abundant,the way of utilization should be reasonable according to its structural characteristics in view of efficiency and economy.In this review,to celebrate the DICP's 70 th anniversary,we will highlight the major fundamental advances in DICP about the conversion of lignocellulose to value-added chemicals and liquid fuels.Particular attention will be paid to the transformation of cellulose and its derivatives to glycols,acids and nitrogen-containing chemicals,hemicellulose-derived platform molecule furfural to jet fuels and lignin to aromatics using catalytic technologies.

Oscillating Cellulase Adsorption and Enhanced Lignocellulose Hydrolysis upon Ultrasound Treatment

We investigated the effects of ultrasound treatment on cellulase adsorption and lignocellulose hydrolysis.The activity of cellulase remained constant upon lowpower ultrasound treatment(<120 W) and decreased using high-power ultrasound(>280 W).Oscillating cellulase adsorption occurred upon ultrasound treatment with any intensity.The maxima for desorption and adsorption were41.9 and 83.1%,respectively,during 1 h of 90 W ultrasound treatment at 50 °C.A comparison between the shorttime with long-time ultrasound experiments indicated that ultrasound treatment tended to desorb cellulase from substrate.However,ultrasound treatment also led to further surface erosion of biomass,which increased cellulase accessibility.These joint actions of ultrasound treatment induced the oscillating adsorption of cellulase.The increase in cellulase accessibility caused by ultrasound treatment led to a significant enhancement in lignocellulose hydrolysis.

Lignocellulose as an insoluble fiber source in poultry nutrition:a review

Extensive research in recent years into the use of various fiber sources in poultry nutrition has led to the perception that dietary fiber is more than a simple diet diluent.Several studies showed that the feeding of insoluble fiber sources such as oat hulls,sunflower hulls or wood shavings may affect digestive physiology and function improving chickens health and growth performance.In this context,the effect of lignocellulose as an insoluble dietary fiber source is increasingly being investigated.Lignocellulose is a component of plant cell walls and consists mainly of the insoluble carbohydrate polymers cellulose and hemicelluloses as well as the phenolic polymer lignin.Lignocellulose is chemically and physicochemically different from other insoluble fiber sources and thus possibly has different effects on poultry compared to traditional fiber sources.Several studies investigated the effect of dietary lignocellulose on growth performance,nutrient digestibility,gastrointestinal tract development and intestinal microbiota in broilers and laying hens.Studies differed in terms of feed formulation and lignocellulose inclusion level as well as products of different suppliers were used.The results obtained are inconsistent;beneficial,indifferent or detrimental effects of feeding lignocellulose were observed,so that a final assessment of lignocellulose as a“novel”insoluble fiber source is difficult.This review article summarizes the results of studies in connection with the feeding of lignocellulose to poultry,compares them with those that have used other insoluble fiber sources and illuminates the possible mechanisms of action.

Top-down strategy for bamboo lignocellulose-derived carbon heterostructure with enhanced electromagnetic wave dissipation

Biomass-derived residue carbonization has been an important issue for"carbon fixation"and"zero emission",and the carbonized products have multiple application potentials.However,there have been no specific research to study the differences in macro-and micro-morphology,electrical properties and many other aspects of the products obtained from carbonization of pure cellulose,pure lignin or their complex,lignocellulose.In this work,lignocellulose with cellulose to lignin mass ratio of 10:1 is obtained using p-toluenesulfonic acid hydrolysis followed by homogenization process at a controlled condition.Then,carbon heterostructure with fibers and sheets(CH-10)are obtained by pyrolysis at 1500℃.Detailed results imply that the fiber-like carbon structure possesses high crystallinity and low defect density,coming from carbonization of the cellulose content in lignocellulose(LC)nanofibers.Correspondingly,the graphite-like carbon sheet with high defect density and low crystallinity comes from carbonization of the lignin content in LCs.Further investigation indicates CH-10 possesses enhanced polarization and moderate impedance matching which makes it an ideal candidate for electromagnetic wave(EMW)absorption.CH-10 exhibits an excellent EMW absorption performance with a minimum RL value of-50.05 dB and a broadest absorption bandwidth of 4.16 GHz at a coating thickness as thin as 1.3 mm.

Dynamic Changes of Microbial Community for Degradation of Lignocellulose

Dynamic changes of a microbial community for lignocellulose degradation were explored in details. Community composition and development were investigated by the means of denaturing gradient gel electrophoresis （DGGE）, and results showed that the microbial community was constituted of 14 kinds of bacteria and presented the fluctuation in some degrees with fermentation. Furthmore, the result of cluster analysis of DGGE pattern was accordant with growth curve, and the degradation process was divided into three stages： initial stage （0-12 h）, intermediate stage （24-144 h） and end stage （144-216 h）.

Adsorption of Congo Red onto Lignocellulose/Montmorillonite Nanocomposite

Lignocellulose/montmorillonite （LNC/MMT） nanocomposites were prepared and characterized by FTIR and XRD. The adsorption of congo red （CR） on LNC/MMT nanocomposite was studied in detail. The effects of contact temperature, pH value of the dye solutions, contact time and concentration of dye solutions on the adsorption capacities of lignocellulose （LNC）, montmorillonite （MMT） and the nanocomposite were investigated. The adsorption kinetics and isotherms and adsorption thermodynamics of the nanocomposite for CR were also studied. The results show that the adsorption capacity of LNC/MMT nanocomosite is higher than that of LNC and MMT. All the adsorption processes fit very well with the pseudo-second-order and the Langmuir equation. From thermodynamic studies, it is seen that the adsorption is spontaneous and endothermic.

Selective hydrolysis of lignocelluloses from corn stalk in an ionic liquid

Although lots of basic studies , such as the hydrolysis and dissolution of lignocelluloses has made great progress in recent years , the hydrolysates containing complex mixture of pentose and hexose are very hard to be separated , and these process sometimes cause serious environmental problems in practical application of cellulose polymer degradation science.Herein , an efficient two-stage method for selective hydrolysis of lignocelluloses biomass is being developed in this paper by controlling of pH in an ionic liquid.The lignin-hemicelluloses matrix in corn stalk was hydrolyzed into xylose in 23.1% yield in the first stage ; and cellulose-rich residues from the first stage was by farther hydrolyzed to provide a glucose in 26.9%yield.Structure of the products were identified by 13 C NMR.It should be mentioned that , the ionic liquid which can be regenerated and reused throughout the process. The present work significantly opens an a new path to utilize each component of lignocellulose as raw materials producing biofuels , renewable energy and fine chemicals.

Transcriptome Analysis of White-Rot Fungi in Response to Lignocellulose or Lignocellulose-Derived Material Using RNA Sequencing Technology

White-rot fungi are the only organisms that can completely degrade all components of lignocellulosic biomass, including the recalcitrant lignin polymer. Lignin degradation is important for the industrial application of lignocellulosic biomass as a raw material for producing value-added chemicals and materials. Therefore, elucidating the lignin degradation mechanism in white-rot fungi will help researchers develop efficient and eco-friendly methods enabling the production of value-added chemicals from lignocellulosic biomass. A transcriptome analysis is an effective way to compare gene expression patterns between different samples under diverse conditions and can provide insights into biological processes. The democratization of next-generation sequencing technology, especially RNA-sequencing, has made transcriptome sequencing and analysis a common research approach for many laboratories. In this review, we focus on the transcriptome profiles of two well-characterized white-rot fungi (Phanerochaete chrysosporium and Dichomitus squalens) in response to various lignocellulosic materials. The application of RNA-seq technology combining with other techniques remains the best approach for investigating fungal secretomes and elucidating the mechanisms of fungal responses to lignocellulose.

Cellulosomal hemicellulases:Indispensable players for ensuring effective lignocellulose bioconversion

The bioconversion of lignocellulose has attracted global attention,due to the significant potential of agricultural and forestry wastes as renewable zero-carbon resources and the urgent need for substituting fossil carbon.The cellulosome system is a multi-enzyme complex produced by anaerobic bacteria,which comprises cellulases,hemicellulases,and associated enzymatic and non-enzymatic components that promote biomass conversion.To enhance their efficiency in degrading recalcitrant lignocellulosic matrices,cellulosomes have been employed to construct biocatalysts for lignocellulose bioconversion,such as consolidated bioprocessing and consolidated bio-saccharification.Hemicelluloses,the second most abundant polysaccharides in plant cell walls,hold valuable application potential but can also induce inhibitory effects on cellulose hydrolysis,thus highlighting the indispensable roles of hemicellulases within the cellulosome complex.This review evaluated current research on cellulosomal hemicellulases,comparing their types,abundance,and regulation,primarily focusing on eight known cellulosome-producing species of different origins.We also reviewed their growth conditions,their hemicellulose-degrading capabilities,and the inhibitory effects of hemicellulose on cellulosome-based lignocellulose saccharification.Finally,we proposed strategies for targeted enhancement of hemicellulase in cellulosomes to improve lignocellulose bioconversion in future studies.

In-situ polymerization of lignocelluloses of autohydrolysis process with acrylamide

In the present study,the hydrolysates generated via autohydrolysis of spruce wood chips were di-rectly used as feedstock for producing coagulants.The in-situ polymerization of acrylamide(AM)and lignocellulose(LC)of hydrolysates was successfully conducted.The reaction was optimized to generate lignocellulose-acrylamide(LC-AM)with the highest molecular weight(41,060 g/mol)and charge density(-0.25 meq/g)under the optimum conditions,which were 3 h,60◦C,4%(w)initiator based on the dried mass of hydrolysate,and an AM/LC molar ratio of 5.63.A nuclear magnetic resonance(NMR)spectroscopy confirmed the grafting of acrylamide on LC.Other prop-erties of LC-AM were characterized by the elemental analyzer,zeta potential analyzer,gel per-meation chromatography(GPC),and particle charge detector(PCD).The LC-AM was applied as a coagulant for removing ethyl violet dye from a simulated dye solution.The results indicated that 47.2%dye was removed from the solution at a low dosage of 0.2 g/g.The dual flocculation of LC-AM with other polymers for dye removal is suggested to further improve its effectiveness.

Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass

Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.

Preparation of Nanolignocellulose/Chitin Composites with Superior Mechanical Property and Thermal Stability

To resolve the issues of special processing equipment, cumbersome process flow and high cost of thecomposite material. The poplar wood fiber was used as the raw material, which were effectively crosslinked with chitin bythe simple mechanical thermal rubber milling method, then the high performance nanolignocellulose/chitin compositewere obtained by the binderless hot-press method. The nanostructure, chemical structure, surface composition, andthermal stability of nanolignocellulose/chitin composites were investigated by the scanning electron microscopy (SEM),Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric/differential thermogravimetric (TG-DTG), respectively. Results turned out that the nanolignocellulose was laminated bythe grinding and the composite material appeared layered structure after the binderless hot-pressing. Chitin/chitosan fromcrab shell powder can be effectively crosslinked with nanofibrillarized lignocellulose to increase the contact area ofsurface hydroxyl groups. The static bending strength (MOR), modulus of elasticity (MOE) and internal bonding strengthof the nanolignocellulose/chitin composite were 34.13 MPa, 7072 MPa and 0.97 MPa, respectively. Meanwhile, theswelling value of thickness after water absorption was only 9.27%, demonstrating the dimensional stability. According tothe profile density distribution, the density of nano-lignocellulose/chitin composites was relatively uniform, whichindicates that the preparation process is reasonable. The nanolignocellulose/chitin composite has excellent thermalstability, since the mass loss of pyrolysis process is lower than the untreated binderless fiberboard. In this study, a new andeffective methods for preparing composite materials was proposed, which provides some research ideas and theoreticalguidance for the efficient development of new nanolignocellulose composite and waste marine arthropod materials.

Comparison and rapid prediction of lignocellulose and organic elements of a wide variety of rice straw based on near infrared spectroscopy

Rice straw is a major kind of biomass that can be utilized as lignocellulosic materials and renewable energy.Rapid prediction of the lignocellulose(cellulose,hemicellulose,and lignin)and organic elements(carbon,hydrogen,nitrogen,and sulfur)of rice straw would help to decipher its growth mechanisms and thereby improve its sustainable usages.In this study,364 rice straw samples featuring different rice subspecies(japonica and indica),growing seasons(early-,middle-,and late-season),and growing environments(irrigated and rainfed)were collected,the differences among which were examined by multivariate analysis of variance.Statistic results showed that the cellulose content exhibited significant differences among different growing seasons at a significant level(p<0.01),and the contents of cellulose and nitrogen had significant differences between different growing environments(p<0.01).Near infrared reflectance spectroscopy(NIRS)models for predicting the lignocellulosic and organic elements were developed based on two algorithms including partial least squares(PLS)and competitive adaptive reweighted sampling-partial least squares(CARS-PLS).Modeling results showed that most CARS-PLS models are of higher accuracy than the PLS models,possibly because the CARS-PLS models selected optimal combinations of wavenumbers,which might have enhanced the signal of chemical bonds and thereby improved the predictive efficiency.As a major contributor to the applications of rice straw,the nitrogen content was predicted precisely by the CARS-PLS model.Generally,the CARS-PLS models efficiently quantified the lignocellulose and organic elements of a wide variety of rice straw.The acceptable accuracy of the models allowed their practical applications.

Processing and valorization of cellulose,lignin and lignocellulose using ionic liquids

Cellulose,lignin and lignocellulose are important bioresources in the nature.Their effective and environmentally friendly utilization not only reduces dependence on fossil resources but also protects the environment.Recently,a class of novel eco-friendly solvents,ionic liquids,is employed to dissolve and process these bioresources.In this mini-review,we summarized the recent advances of processing and valorization of cellulose,lignin and lignocellulose in ionic liquids.It is expected that this up-to-date survey provides a comprehensive information of this field,and accelerates the development and utilization of the renewable plant biomass resources.

In situ fabrication of Na3V2（PO4）3 quantum dots in hard carbon nanosheets by using lignocelluloses for sodium ion batteries

The rational assembly of quantum dots on two-dimensional(2 D) carbonaceous materials is very promising to produce materials, but remains a challenge. Here, we develop an assembly strategy of growing Na3 V2(PO4)3 quantum dots with superlattice structure(NVP-QDs-SL) for obtaining precise control of the size, distribution and crystallinity. The multifunctional lignocelluloses(LCs) used as a hard carbon source induce heterogeneous nucleation and confined growth of NVP-QDs-SL, leading to the uniform distribution of NVP-QDs-SL in H/S-doped hard carbon ultra-thin nanosheets(HCS). Detailed electrochemical analysis results from sodium-ion batteries of NVP-QDs-SL show that NVP-QDs-SL could trap the electrons inside HCS, significantly enhancing Na ion storage and transfer kinetics. Compared to the common Na3 V2(PO4)3 nanoparticle cathode, the NVP-QDs-SL/HCS cathode exhibits a high reversible capacity of 149.2 m A h g^-1 at a 0.1 C rate, which is far beyond the theoretical capacity of Na3 V2(PO4)3(117.6 m A h g^-1).At the ultrahigh current rate of 100 C, this cathode still remains a high discharge capacity of 40 m A h g-1.Even after cycling at 20 C over 3000 cycles, an ultrahigh coulombic efficiency close to 100% is still obtained,highlighting its excellent long cycling life, remarkable rate performance and energy density.

Activated Carbon from Nipa Palm Fronds(Nypa fruticans)with H_(3)PO_(4) and KOH Activators as Fe Adsorbers

Nipa palm is one of the non-wood plants rich in lignocellulosic content.In this study,palm fronds were converted into activated carbon,and their physical,chemical,and morphological properties were characterized.The resulting activated carbon was then applied as an adsorbent of Fe metal in peat water.The carbonization process was carried out for 60 min,followed by sintering at 400℃ for 5 h with a particle size of 200 mesh.KOH and H_(3)PO_(4) were used in the chemical activation process for 24 h.KOH-activated carbon contained 6.13%of moisture,4.55%of ash,17.02%of volatile matter,and 78.84%of fixed carbon,while its Fe reduction efficiency was 28.09%.The H_(3)PO_(4)-activated carbon contained 4.67%of moisture,2.84%of ash,16.41%of volatile matter,and 80.57%of bonded carbon,and the Fe reduction efficiency was 52.25%.KOH-activated carbon and H_(3)PO_(4)-activated carbon contained fixed carbon of 78.84%and 80.57%,respectively,while their average rates of efficiency of Fe reduction were 22.82%and 39.23%,respectively.Overall,the characteristics of activated nipa carbon met the Indonesian standards(SNI No.06-3730-1995).However,H_(3)PO_(4)-activated carbon was found to be better at adsorbing Fe metal from peat water.

Integrated engineering of enzymes and microorganisms for improving the efficiency of industrial lignocellulose deconstruction

Bioconversion of lignocellulosic biomass to fuels and chemicals represents a new manufacturing paradigm that can help address society’s energy,resource,and environmental problems.However,the low efficiency and high cost of lignocellulolytic enzymes currently used hinder their use in the industrial deconstruction of lignocellu-lose.To overcome these challenges,research efforts have focused on engineering the properties,synergy,and production of lignocellulolytic enzymes.First,lignocellulolytic enzymes’catalytic efficiency,stability,and toler-ance to inhibitory compounds have been improved through enzyme mining and engineering.Second,synergistic actions between different enzyme components have been strengthened to construct customized enzyme cocktails for the degradation of specific lignocellulosic substrates.Third,biological processes for protein synthesis and cell morphogenesis in microorganisms have been engineered to achieve a high level and low-cost production of lignocellulolytic enzymes.In this review,the relevant progresses and challenges in these fields are summa-rized.Integrated engineering is proposed to be essential to achieve cost-effective enzymatic deconstruction of lignocellulose in the future.