Alteration Of Lignin Research Articles

Harnessing Biomass for a Sustainable Future: The Role of Starch and Lignin

The global climate crisis, driven by unchecked industrialization and ecological negligence, compels humanity to seek alternative ways to either avert or mitigate the disastrous environmental phenomena encountered, particularly in recent years. The significant quantities of biomass generated by human activities may serve as important resources for technological applications, and biomass valorization offers dual benefits. This review emphasizes the potential of starch and lignin as adaptable materials for the advancement of sustainable and eco-friendly technologies. By investigating catalytic alterations, we may advance a more sustainable future and tackle the escalating issues of environmental pollution and sustainability. Catalytic alterations of lignin and starch have become essential techniques for their valorization. Biopolymers can be changed into useful chemicals and materials, like levulinic acid, lactic acid, 5-HMF and modified starch, which are used in the paper, textile, and coatings industries. Besides transforming into chemicals, lignin and starch can produce reactive carbon compounds that find application in both classical chemistry and photocatalysis. Additionally, we can use their highly functionalized polymeric matrices as catalysts. We can change the polymeric matrices’ chemical backbone to make them better at speeding up reactions like cross-coupling and multicomponent reactions.

Study of Purified Cellulosic Pulp and Lignin Produced by Wheat Straw Biorefinery

With the world population rising, wheat straw production is expected to reach 687–740 million tons per year by 2050. Its frequent application as a fuel source leads to air, water, and soil pollution. Limited literature exists on methods for separating components of residual wheat straw. Optimal conditions for organosolv pulping of hydrolyzed wheat straw include 3% FeCl3·6H2O as a catalyst, a biomass-to-solvent ratio of 1:15 (m/v), and 50% ethanol:water as cooking liquor at 200 °C for 30 min. Desilication conditions involve extraction with 7.5% Na2CO3 at a biomass-to-solvent ratio of 1:20 (m/v) treated at 115 °C for 60 min. Lignin from hydrolyzed wheat straw showed similar properties to organosolv lignin from untreated straw, with minimal lignin alteration during hydrolysis. Hydrolysis significantly degraded cellulose. A 41% lignin recovery rate with 95% purity was achieved from pre-extracted hydrolyzed straw. Recovered cellulose after silica removal had 2% ash and 87% purity. The innovation of this process lies in the development of a comprehensive, sustainable, efficient, and economically viable biorefinery process that efficiently separates key components of wheat straw, i.e., xylose, lignin, cellulose, and silica, while addressing environmental pollution associated with its traditional use as fuel.

Antimultidrug-resistant bacterial activity of microwave solvolysis lignin from woody biomass

Drug-resistant bacteria are a serious concern for human health. Thus, protective substances need to be urgently developed to inhibit the propagation of such bacteria in living environments. We herein report about antibacterial activity of lignin, which was developed via chemical alteration of native lignin in wood. Japanese cedar (Cryptomeria japonica) wood was degraded via microwave solvolysis in an equivolume mixture of 2 % (w/w) aqueous sulfuric acid, ethylene glycol, and toluene at 190 °C for 60 min and fractionated via extraction with toluene, ethyl acetate, and ethanol. The ethyl acetate extract (jEAE) exhibited ≥ 98.5 % inhibitory activity against the drug- and multidrug-resistant strains of Streptococcus pneumoniae. jEAE also exhibited strong inhibitory activity against two nondrug-resistant S. pneumoniae and one Streptococcus pyogenes strains. Lignin-derived monomers having guaiacyl nuclei were detected as major fragments using pyrolysis gas chromatography–mass spectrometry (GC–MS), indicating that jEAE is a solvolysis lignin. In 1H–13C-edited heteronuclear single quantum coherence nuclear magnetic resonance (NMR), signals of guaiacyl nuclei were observed, but those from side chains of β-O-4, β-5, and 5–5/4-O-β substructures disappeared. 31P NMR revealed that jEAE possesses lower and higher amounts of aliphatic and phenolic OH groups, respectively, than milled wood lignin. The high antidrug-resistant bacterial activity of the structure-altered lignin provides a new approach for suppressing the growth of drug-resistant bacteria using lignocellulosic biomass.

Identification and analysis of ancient ship wood excavated at Nantong hydraulic site

The Nantong Ancient Ship refers to an ancient Chinese wooden ship of the late Ming Dynasty excavated in Nantong city in December 2022. This paper identifies the wood and discusses its related analysis. Wood samples extracted from the Nantong Ancient Ship were studied from the viewpoints of anatomy, physics, and chemistry. Microscopic identification results concluded that willow and Chinese fir were the main wood species used to make this ship. The content of holocellulose in the ancient wood was only 37.9 to 38.9%, while the content of lignin was 55.2 to 56.4%. The cellulose crystallinity of ancient wood was 39 to 42% lower than that of healthy recent wood. Fourier transform infrared (FTIR) spectra revealed that the deterioration of ancient wood caused cellulose and hemicellulose degradation, but no apparent lignin alteration. The results could provide a basis for drawing up a conservation plan for the Nantong Ancient Ship. They could also provide a reference for the research and conservation of other archaeological shipwrecks in China.

Evaluation of guaiacyl lignin aromatic structures using 13CO2 administered Ginkgo biloba L. xylem by quantitative solid- and liquid-state 13C NMR

Abstract Ginkgo biloba L. saplings were cultivated in an airtight growth chamber with 13CO2 for two months. The 13C ratio of the newly developed xylem region was ca. 85%, evaluated by high lateral resolution secondary ion mass spectrometry and thioacidolysis/GC-MS. Quantitative solid-state 13C direct polarisation/magic angle spinning (DP/MAS) NMR measurements with high-speed MAS of 70.0 kHz were conducted for cutting-milled wood (CMW), ball-milled wood (BMW), and enzymatically saccharified lignin (EL) samples. In addition, quantitative liquid-state 13C NMR measurements were carried out for EL in DMSO-d 6. Major lignin aromatic signals were classified into three groups of aromatic carbons of C–H, C–C, and C–O, and their area ratio was compared within these measurements. EL samples in solid- and liquid-state showed nearly the same results. However, the results for CMW and BMW in solid-state NMR suggest the structural alteration of lignin within the sample preparation procedure, including ball milling.

Characteristics of Ancient Shipwreck Wood from Huaguang Jiao No. 1 after Desalination.

Huaguangjiao I refers to the ancient Chinese wooden shipwreck of the South Song Dynasty (1127-1279 AD) discovered in the South China Sea in 1996. From 2008 to 2017, the archaeological waterlogged wood was desalted using deionized water combined with ultrasonic treatment, and desalted using EDTA-2Na, EDTAHO, and NaH2PO4·2H2O solutions. In this paper, the degree of degradation of the modified waterlogged archaeological wood and the moisture and content of the main components were determined. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), nanoindentation (NI), and scanning electron microscopy (SEM) were employed to investigate the state of wood degradation after desalination and desulfurization. The results showed that the water content of the wood was as high as 532~1149%, while the basic density was only 0.14~0.18 g/cm3, indicating that the wood had been seriously degraded. The holocellulose content was only 36-40%. Based on the XRD patterns, the degree of cellulose crystallinity in the modified wood was 14.08%. The elastic modulus and hardness of the ancient shipwreck wood after desalination and desulfurization were 1.28-4.31 and 0.10-0.28 GPa, respectively, according to nanoindentation. In addition, the FTIR spectra revealed that the biological deterioration of the modified wood caused cellulose and hemicellulose degradation, but no apparent lignin alteration occurred. The results could provide knowledge for appropriate dewatering, strengthening, and restoration strategies.

Impact of Natural Degradation on the Aged Lignocellulose Fibers of Moroccan Cedar Softwood: Structural Elucidation by Infrared Spectroscopy (ATR-FTIR) and X-ray Diffraction (XRD)

The aims of this study are to investigate the structure of four historical Moroccan cedar softwood samples of different aging time duration (16th, 17th, 19th, 21st centuries) and compare among these four samples, using two analytical methods, FTIR and XRD, in order to confirm some structural changes and determine the degree of deterioration. The pronounced hemicellulose deterioration was highlighted by a breakdown of IR acetyl groups at 1738 cm−1 from the 19th century sample until aged ones. The cellulose XRD crystallinity index showed an important decrease from recent to oldest samples (51.8 to 20.2%) justifying the damages mainly in the two oldest samples (17th and 16th centuries), also confirmed by FTIR. The alteration of lignin was manifested in the case of the two ancient samples (16th and 17th centuries), proven by the decrease in IR bands related to aromatic nuclei (1595, 1500, 1230 cm−1) evolving towards a new diconjugate C=O formers at 1647 cm−1 (quinone, Ar-CO-Ar, Ar-CO-C=C). For accurate elucidation, the data of two combined techniques were compared and correlated. The obtained results depended on the part of the wood exposed to weathering effects (internal or external) and were influenced by both extended time of aging and effects of natural deterioration agents. The effects of natural aging were investigated in four historical Moroccan cedar softwood samples (16th, 17th, 19th, 21st centuries) using two analytical tools: FTIR and XRD. The pronounced hemicellulose deterioration was highlighted by a breakdown of IR acetyl groups at 1738 cm−1 and declines in the absorption signal at 1268 cm−1 from the 19th century sample until aged ones. The cellulose XRD crystallinity index (CrI) estimation showed an important decrease from recent to oldest samples (51.8 to 20.2%) justifying the damages mainly in the two oldest samples (17th and 16th centuries). These data were also confirmed by FTIR showing a significant reduction in both area profiles of C-O-C (1150–1000 cm−1) and C-H crystalline cellulosic bands (1375, 1318, and 1268 cm−1), respectively. The lignin alteration in both old samples (16th and 17th centuries) was proven by the decrease in IR aromatic skeleton (1595, 1500, and 1230 cm−1) evolving towards a new diconjugate C=O formers at 1647 cm−1 (quinone, Ar-CO-Ar, Ar-CO-C=C). To determine the structural difference and the degree of deterioration, the IR area of C=O band intensities ranging from 1550 to 1800 cm−1 was exploited. For accurate elucidation, the data of two combined techniques were compared and correlated. The obtained results depended on the part of the wood (internal or external) exposed to weathering effects and were influenced by both extended time of aging and effects of natural deterioration agents.

Burn Intensity Drives the Alteration of Phenolic Lignin to (Poly) Aromatic Hydrocarbons as Revealed by Pyrolysis Gas Chromatography-Mass Spectrometry (Py-GC/MS).

High-intensity wildfires alter the chemical composition of organic matter, which is expected to be distinctly different from low-intensity prescribed fires. Herein, we used pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), in conjunction with solid-state 13C nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, to assess chemical alterations from three wildfires and a long-term frequent prescribed fire site. Our results showed that black ash formed under moderate intensity burns contained less aromatic (ArH), polyaromatic hydrocarbon (PAH), and nitrogen-containing compounds (Ntg) but more lignin (LgC) and phenol compounds (PhC), compared to white ash formed under high intensity burns. Both 13C NMR and FT-IR confirmed a higher relative percentage of carboxyl carbon in white ash, indicating the potential for higher water solubility and more mobile carbon, relative to black ash. Compared to wildfires, ash from low-intensity prescribed fire contained less ArH, PAH, and Ntg and more LgC and PhC. Controlled laboratory burning trials indicated that organic matter alteration was sensitive to the burn temperature, but not related to the fuel type (pine vs fir) nor oxygen absence/presence at high burn temperatures. This study concludes that higher burn temperatures resulted in higher (poly)aromatic carbon/nitrogen and lower lignin/phenol compounds.

Structural basis of lignocellulose deconstruction by the wood-feeding anobiid beetle Nicobium hirtum

The details of the lignocellulose deconstruction processes in the digestive systems of wood-feeding insects remain elusive. This study aimed to examine the biochemical conversion of lignocellulose in the digestive system of a wood-feeding anobiid beetle, Nicobium hirtum, one of the most important pests of wooden products in Japan. To this end, N. hirtum larvae were fed with Japanese red pine (softwood) and Japanese beech (hardwood) sapwood diets, as well as an artificial diet containing Shorea wood (hardwood) sapwood sawdust. The structural differences between the original and digested (feces) lignocellulose samples were examined using wet-chemical and two-dimensional (2D) nuclear magnetic resonance (NMR) methods. Cellulose and hemicelluloses, especially mannan in the softwood diet, were preferentially degraded over lignin in the larval digestive system. As a result, lignin was enriched in the digested lignocellulose residues. Lignin compositional analyses based on thioacidolysis and 2D NMR determined that the proportions of oxidized lignin aromatic units were notably increased after digestion. Further, the 2D NMR analyses revealed the accumulation of aldehyde and hydroxypropiovanillone/syringone end-unit structures in lignin, indicating that oxidative and/or reductive modifications of lignin polymers occur in the larval digestive system. Such structural alterations of lignin may facilitate the dissociation of the lignin barrier, thereby liberating polysaccharides for subsequent enzymatic conversion for assimilation and energy.

Enhancement of Interface between Lignocellulosic Fibers and Polypropylene Matrix via the Structure Alteration of Lignin at Elevated Temperatures.

This paper investigated the feasibility of enhancing the interface between lignocellulosic fibers and a polypropylene matrix via structure alteration of lignin at elevated temperatures. Alkali treatment can remove gum substances from lignocellulose fibers effectively at elevated temperatures but easily causes damages to fiber strength. In previous studies on directional delignification of lignocellulosic fibers, loss of fiber strength is avoided but condensation and degradation of lignin are accelerated. So far, few reports have been available on the effect of lignin structures on the interface between fibers and a matrix. In this study, jute fibers with different lignin structures are produced at 100 and 130 °C for reinforcing a polypropylene matrix. The interface between the fibers and matrix is analyzed. The result shows that decrease in aliphatic hydroxyl concentration by 9.5% at 130 °C from 3 to 5 h contributes to a 14.2% decrease in the surface energy of jute fibers. Meanwhile, the polydispersity index of lignin decreases from 1.21 to 1.15. Centralized distribution of lignin molecule-weight and reduction in fiber surface energy improves the interface between the fibers and matrix, which manifests as a 30.8% increase in the impact strength of the composites. Similar improvement is not observed in the composites reinforced with jute fibers at 100 °C, due to the absence of lignin-structure changes. This paper provides a new strategy to improve the interface between lignocellulose fibers and a hydrophobic matrix.

Profiling of Chemical and Structural Composition of Lignocellulosic Biomasses in Tetraploid Rice Straw.

The improvement of the saccharification of rice straw is one of the strategies to reduce the sophisticated pretreatment that results in high cost and is unfriendly to the environment. We explored the cell wall features in tetraploid rice and highlighted the enhanced saccharification of tetraploid with large biomass. Results showed that lignin content and S/G ratio reduced to 17.09% and 0.37, respectively, in tetraploid straw by the determination of the pyGC-MS method. After the pretreatment, the cellulose crystallinity index decreased from 63.22% to 57.65% in tetraploid straw, which is lower than that of pretreated diploid straw. Surface topological analysis of SEM images indicated that tetraploid straw was more susceptible to the pretreatment. Tetraploid straw showed a strong advantage in the process of enzymatic hydrolysis. The enzyme efficiency reached the highest value of 77.60%, and the rate of enzyme reaction was improved to make the reaction saturated earlier than conventional rice. We concluded that the high saccharification has resulted from the alteration of lignin and cellulose in tetraploid rice. Our research provides an improved green feedstock for bioenergy, and the tetraploid rice straw shows the potential utilization value in bioethanol production.

Preserving Aryl Ether Linkages and Higher Yields of Isolated Lignin through Biomass Fibrillation

Ball milling is used for size reduction of biomass for isolating lignin. However, it is known that it can lead to some structural alteration of lignin. Fibrillation using ultrafriction grinding is a newer size reduction technology which was applied to poplar for isolating cellulolytic enzyme lignin. Compositional analysis of poplar, enzymatic hydrolysis yield, water retention value, lignin yield, lignin structural characterization, and lignin molecular weight analysis were carried out to compare lignin isolated from fibrillated and ball milled poplar. By using fibrillation instead of planetary ball milling for size reduction of poplar, higher β-O-4′ linkage content, lignin yield, and molecular weight were obtained. Replacing ball milling with fibrillation for size reduction allows recovery of lignin whose structure is closer to that of lignin in biomass.

Structural characteristics of lignin extracted from Jordanian olive cake using different fractionation conditions

ABSTRACT The chemical structure and properties of lignin-derived from lignocellulosic olive mill waste (Jeft) were investigated. Alkali and dioxane lignins were evaluated regarding the achieved high delignification and high purity of the extracted lignins. The results declared that the major constituents of olive cake are extractives, cellulose, hemicelluloses, and lignin. Furthermore, the olive cake has low relative crystallinity and the ash content does not exceed 2%. The yields of Alkali and Dioxane lignins were 15.3 ± 0.34, and 1.4 ± 0.43%, respectively. For the elucidation of structural features of lignin molecules, lignins samples were also subjected to UV spectroscopy and 1HNMR analysis. The analysis showed that the treatment under acidic condition did not significantly attack the β-aryl ether structure (β-O-4), while the alkali treatment shows an extensive cleavage of the β-aryl-ether linkage with the degradation of ester resulting in a structural alteration of lignin. High Delignification is achieved by dioxane process through progressive enrichment of carboxylic acid group in isolated lignin; also dioxane isolation has little influence on the structure of isolated lignin. Moreover, the results confirmed that Alkali and Dioxane lignin were guaiacyl-syringyl lignin, typical of hardwood lignins.

About Making Lignin Great Again-Some Lessons From the Past.

Lignin, the second most abundant biopolymer on the planet, serves land-plants as bonding agent in juvenile cell tissues and as stiffening (modulus-building) agent in mature cell walls. The chemical structure analysis of cell wall lignins from two partially delignified wood species representing between 6 and 65% of total wood lignin has revealed that cell wall-bound lignins are virtually invariable in terms of inter-unit linkages, and resemble the native state. Variability is recognized as the result of isolation procedure. In native state, lignin has a low glass-to-rubber transition temperature and is part of a block copolymer with non-crystalline polysaccharides. This molecular architecture determines all of lignin's properties, foremost of all its failure to undergo interfacial failure by separation from (semi-) crystalline cellulose under a wide range of environmental conditions. This seemingly unexpected compatibility (on the nano-level) between a carbohydrate component and the highly aromatic lignin represents a lesson by nature that human technology is only now beginning to mimic. Since the isolation of lignin from lignocellulosic biomass (i.e., by pulping or biorefining) necessitates significant molecular alteration of lignin, isolated lignins are highly variable in structure and reflect the isolation method. While numerous procedures exist for converting isolated (carbon-rich) lignins into well-defined commodity chemicals by various liquefaction techniques (such as pyrolysis, hydrogenolysis, etc.), the use of lignin in man-made thermosetting and thermoplastic structural materials appears to offer greatest value. The well-recognized variabilities of isolated lignins can in large part be remedied by targeted chemical modification, and by adopting nature's principles of functionalization leading to inter-molecular compatibility. Lignins isolated from large-scale industrial delignification processes operating under invariable isolation conditions produce polymers of virtually invariable character. This makes lignin from pulp mills a potentially valuable biopolymeric resource. The restoration of molecular character resembling that in native plants is illustrated in this review via the demonstrated (and in part commercially-implemented) use of pulp lignins in bio-degradable (or compostable) polymeric materials.

Expression of a hyperthermophilic endoglucanase in hybrid poplar modifies the plant cell wall and enhances digestibility

BackgroundExpression of glycosyl hydrolases in lignocellulosic biomass has been proposed as an alternative to improve efficiency of cellulosic ethanol production. In planta production of hyperthermophilic hydrolytic enzymes could prevent the detrimental effects often seen resulting from the expression of recombinant mesophilic enzymes to plant hosts. Utilizing lignocellulosic feedstocks to produce hyperthermophilic hydrolases provides additional benefits for ethanol production in the way of transgenic feedstocks serving as both enzyme providers and cellulosic substrates.ResultsIn this study, transgenic hybrid poplar (Populus alba × grandidentata) was generated to express a hyperthermophilic endoglucanase from Thermotoga neapolitana with an optimal temperature over 100 °C. Functional hyperthermoactive endoglucanase was successfully produced in the transgenic events, and altered phenotypic growth was observed in transgenic lines. Moreover, the line with the highest TnCelB expression in both leaf and developing xylem had reduced lignin content and cellulose crystallinity, resulting in a more digestible cell wall. The activation of TnCelB by a post-harvest heat treatment resulted in enhanced saccharification efficiencies of transgenic poplar lines with moderate TnCelB expression and without alteration of cellulose and lignin when not heat-treated. In planta high-level overexpression of a hyperthermophilic endoglucanase paired with heat treatment following harvest, resulted in biomass that was comparable with wild-type lines that underwent a traditional pretreatment for saccharification.ConclusionsOverexpression of hyperthermophilic endoglucanase in feedstock had impacts on plant growth and cell wall composition, especially when the enzyme was highly expressed. Improved glucan saccharification efficiencies from transgenic lines before and after heat treatment could reduce both the economic and environmental costs associated with ethanol production from lignocellulosic biomass.

Biological, chemical and technological characteristics of waterlogged archaeological piles (Quercus petraea (Matt.)Liebl.) of a medieval bridge foundation in Bavaria

The biological, chemical and technological study of waterlogged archaeological piles of oak wood (Quercus petraea (Matt.)Liebl.) of a medieval bridge in Bavaria was primarily undertaken in the context of finding an adequate drying method to assure stable long-term conditions while presenting the archaeological finds in a local history museum. There was a unique chance to study the oak wood preservation of five generations of a bridge foundation from one and the same place. According to the dendrochronological dating of the felling dates of the oaks, the first identified generation is already medieval with an earliest date of 1447, followed by the second generation at about 1572, with the third one at about 1658, the fourth one at about 1727 and the youngest one at about 1787. The experienced selection of the trees in the forest and the subsequent careful manufacture of the piles without any sapwood and obviously their immediate application allowed for studying the alteration of the wood characteristics with increasing years of underground pile exposure. The light microscopical study did not reveal remarkable structural alterations of lignin and cellulose. Microbial activities of erosion bacteria and soft rot could only be detected within the uppermost rounded part of some piles and in their periphery. However, it was informative to see how green and wet manufactured oak wood responds as a sensitive ion-exchange system underground. The iron ions penetrated particularly into the outer heartwood and reacted with the special accessory compounds, such as tannins, essentially within the parenchyma cells. However, the radial distinct gradient had no notable difference between the fifth generation (1787) and the older ones. The uptake of Si-, Ca- and Mg-ions significantly represents an influx with a radial penetration even to the pith. Surprisingly, the monomeric K-ions, which are present in the green woody tissue with a mean value of 330 ppm moved radially out of the wood, down to about 10% compared to the beginning of the underground exposure. Moreover, the shift of the original pH value of about 3.6 of the heartwood to finally a mean of pH 4.6 clearly underlines a correlated efflux effect, which might slightly chemically alter the woody tissue. The changes of the chemical and technological characteristics such as basic density, compression strength, sorption behavior, shrinkage, and ash content actually indicate that over the centuries some change in the chemical characteristics of the heartwood must have occurred.

Effects of maturity on the pyrolytic fingerprint of coals from North Borneo

Pyrolysis-gas chromatography-mass spectrometry (Py-GC–MS) and thermally assisted hydrolysis and methylation (THM-GC–MS) were applied to 27 coal samples of lignite to high volatile bituminous rank (vitrinite reflectance %Ro=0.28–0.66) from the Malaysian states of Sabah and Sarawak on Borneo, to investigate rank effects on molecular properties. The molecular fingerprints of these coals appeared to be controlled by diagenetic and, to a smaller extent, early catagenetic transformations (%Ro 0.28–0.50). The molecular assemblages from immature coals consist mainly of lignin-derived material and long-chain (≥C24) ester-bound polymethylene chains, whereas mature coals are enriched in short (C10–C25) free and/or trapped (isoprenoid) hydrocarbons, alkylated phenols and resinite aromatic derivatives. By comparing a large suite of potential molecular proxies of maturation (indices of pristane formation, resin aromatization, lignin alteration stages, etc.) and other maturity proxies (%Ro, Tmax), rank effects on different coal constituents are illustrated, as well as the suitability of the proxies for specific rank ranges. The results highlight the importance of decarboxylation of long-chain fatty acids (%Ro 0.35–0.40) and the progressive accumulation of resistant aryl-O (probably diaryl ether) bonds at advanced stages of maturity. The coals from Pinangah in Sabah were more mature than those from Sarawak (Mukah and Balingian coalfields), whereas the molecular signature of other coals from northeastern Sabah (Sandakan area) and southeastern Sabah (Silimpopon and Maliau areas) varied across the rank range studied.

Physical and Mechanical Properties of Recycled Polypropylene Composites Reinforced with Rice Straw Lignin

Recycled polypropylene (RPP) and lignin represent by-products produced in enormous amounts worldwide that remain underutilized. This study used rice straw lignin as a filler at various concentrations (0% to 70% w/w) in RPP and virgin polypropylene (PP) composites by melt blending. Structural and morphological alterations of lignin were analyzed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM), respectively. Mechanical properties were evaluated using a universal testing machine (UTM). Results revealed that the tensile strength of the composites decreased as the lignin content increased, presumably due to the low of compatibility degree of lignin and MAPP, as well as the crack formation due to the agglomeration of lignin. However, composites with lignin as a filler showed higher moduli and water absorption capacities, as well as thickness swelling; using lignin as a filler caused a drastic reduction of the elongation at break values. The results indicated that the physical and mechanical properties of RPP and its virgin PP composites had no substantial differences. This indicated that virgin PP could be substituted by recycled polypropylene (RPP) for composite applications with the addition of MAPP.

Unravelling the impact of lignin on cell wall mechanics: a comprehensive study on young poplar trees downregulated for CINNAMYL ALCOHOL DEHYDROGENASE (CAD).

Lignin engineering is a promising tool to reduce the energy input and the need of chemical pre-treatments for the efficient conversion of plant biomass into fermentable sugars for downstream applications. At the same time, lignin engineering can offer new insight into the structure-function relationships of plant cell walls by combined mechanical, structural and chemical analyses. Here, this comprehensive approach was applied to poplar trees (Populus tremula×Populus alba) downregulated for CINNAMYL ALCOHOL DEHYDROGENASE (CAD) in order to gain insight into the impact of lignin reduction on mechanical properties. The downregulation of CAD resulted in a significant decrease in both elastic modulus and yield stress. As wood density and cellulose microfibril angle (MFA) did not show any significant differences between the wild type and the transgenic lines, these structural features could be excluded as influencing factors. Fourier transform infrared spectroscopy (FTIR) and Raman imaging were performed to elucidate changes in the chemical composition directly on the mechanically tested tissue sections. Lignin content was identified as a mechanically relevant factor, as a correlation with a coefficient of determination (r²) of 0.65 between lignin absorbance (as an indicator of lignin content) and tensile stiffness was found. A comparison of the present results with those of previous investigations shows that the mechanical impact of lignin alteration under tensile stress depends on certain structural conditions, such as a high cellulose MFA, which emphasizes the complex relationship between the chemistry and mechanical properties in plant cell walls.

The diversity of methoxyphenols released by pyrolysis-gas chromatography as predictor of soil carbon storage

The variable extent to which environmental factors are involved in soil carbon storage is currently a subject of controversy. In fact, justifying why some soils accumulate more organic matter than others is not trivial. Some abiotic factors such as organo-mineral associations have classically been invoked as the main drivers for soil C stabilization. However, in this research indirect evidences based on correlations between soil C storage and compositional descriptors of the soil organic matter are presented. It is assumed that the intrinsic structure of soil organic matter should have a bearing in the soil carbon storage. This is examined here by focusing on the methoxyphenols released by direct pyrolysis from a wide variety of topsoil samples from continental Mediterranean ecosystems from Spain with different properties and carbon content. Methoxyphenols are typical signature compounds presumptively informing on the occurrence and degree of alteration of lignin in soils. The methoxyphenol assemblages (12 major guaiacyl- and syringyl-type compounds) were analyzed by pyrolysis-gas chromatography-mass spectrometry. The Shannon-Wiener diversity index was chosen to describe the complexity of this phenolic signature. A series of exploratory statistical analyses (simple regression, partial least squares regression, multidimensional scaling) were applied to analyze the relationships existing between chemical and spectroscopic characteristics and the carbon content in the soils. These treatments coincided in pointing out that significant correlations exist between the progressive molecular diversity of the methoxyphenol assemblages and the concentration of organic carbon stored in the corresponding soils. This potential of the diversity in the phenolic signature as a surrogate index of the carbon storage in soils is tentatively interpreted as the accumulation of plant macromolecules altered into microbially reworked structures not readily recognized by soil enzymes. From a quantitative viewpoint, the partial least squares regression models exclusively based on total abundances of the 12 major methoxyphenols were especially successful in forecasting soil carbon storage.