Browse
Submit Data
Databases
API
Help

Dataset Information

41 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cleavage of Organosolv Lignin to Phenols Using Nitrogen Monoxide and Hydrazine.

ABSTRACT: From the variety of methods known for the depolymerization of organosolv lignin, a broad range of diversely substituted aromatic compounds are available today. In the present work, a novel two-step reaction sequence is reported, which is focused on the formation of phenols. While the first step of the depolymerization strategy comprises the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-catalyzed oxidation of organosolv lignin with nitrogen monoxide so that two waste materials are combined, cleavage to the phenolic target compounds is achieved in the second step employing hydrazine and potassium hydroxide under Wolff-Kishner-type conditions. Besides the fact that the novel strategy proceeds via an untypical form of oxidized organosolv lignin, the two-step sequence is further able to provide phenols as cleavage products, which bear no substituent at the 4-position.

SUBMITTER: Hofmann LE

PROVIDER: S-EPMC8340100 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Cleavage of Organosolv Lignin to Phenols Using Nitrogen Monoxide and Hydrazine.

Hofmann Laura Elena LE Altmann Lisa-Marie LM Fischer Oliver O Prusko Lea L Xiao Ganyuan G Westwood Nicholas J NJ Heinrich Markus R MR

ACS omega 20210723 30

From the variety of methods known for the depolymerization of organosolv lignin, a broad range of diversely substituted aromatic compounds are available today. In the present work, a novel two-step reaction sequence is reported, which is focused on the formation of phenols. While the first step of the depolymerization strategy comprises the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-catalyzed oxidation of organosolv lignin with nitrogen monoxide so that two waste materials are combined, cle ...[more]

PMID: 34368527

Similar Datasets

Lignin Refinery Using Organosolv Process for Nanoporous Carbon Synthesis.

Project description:Porous carbon has been widely used for many applications e.g., adsorbents, catalysts, catalyst supports, energy storage and gas storage due to its outstanding properties. In this paper, characteristics of porous carbon prepared by carbonization of lignin from various biomasses are presented. Various biomasses, i.e., mangosteen peel, corncob and coconut shell, were processed using ethanol as an organosolv solvent. The obtained lignin was characterized using a Fourier transform infrared (FTIR) spectrophotometer and a viscosimeter to investigate the success of extraction and lignin properties. The results showed that high temperature is favorable for the extraction of lignin using the organosolv process. The FTIR spectra show the success of lignin extraction using the organosolv process because of its similarity to the standard lignin spectra. The carbonization process of lignin was performed at 600 and 850 °C to produce carbon from lignin, as well as to investigate the effect of temperature. A higher pyrolysis temperature will produce a porous carbon with a high specific surface area, but it will lower the yield of the produced carbon. At 850 °C temperature, the highest surface area up to 974 m2/g was achieved.

| S-EPMC7435991 | biostudies-literature

Isolating High Antimicrobial Ability Lignin From Bamboo Kraft Lignin by Organosolv Fractionation.

Project description:Lignin from different biomasses possess biological antioxidation and antimicrobial activities, which depend on the number of functional groups and the molecular weight of lignin. In this work, organosolv fractionation was carried out to prepare the lignin fraction with a suitable structure to tailor excellent biological activities. Gel permeation chromatography (GPC) analysis showed that decreased molecular weight lignin fractions were obtained by sequentially organosolv fractionation with anhydrous acetone, 50% acetone and 37.5% hexanes. Nuclear magnetic resonance (NMR) results indicated that the lignin fractions with lower molecular weight had fewer substructures and a higher phenolic hydroxyl content, which was positively correlated with their antioxidation ability. Both of the original lignin and fractionated lignins possessed the ability to inhibit the growth of Gram-negative bacteria (Escherichia coli and Salmonella) and Gram-positive bacteria (Streptococcus and Staphylococcus aureus) by destroying the cell wall of bacteria in vitro, in which the lignin fraction with the lowest molecular weight and highest phenolic hydroxyl content (L3) showed the best performance. Besides, the L3 lignin showed the ability to ameliorate Escherichia coli-induced diarrhea damages of mice to improve the formation of intestinal contents in vivo. These results imply that a lignin fraction with a tailored structure from bamboo lignin can be used as a novel antimicrobial agent in the biomedical field.

| S-EPMC8188334 | biostudies-literature

Direct Precipitation of Lignin Nanoparticles from Wheat Straw Organosolv Liquors Using a Static Mixer.

Project description:Micro- and nanosize lignin shows improved properties compared to standard lignin available today and has been gaining interest in recent years. Lignin is the largest renewable resource with an aromatic skeleton on earth but it is used for relatively low-value applications. Lignin in micro- to nanoscale; however, could facilitate rather valuable applications. Current production methods consume high amounts of solvents for purification and precipitation. The process investigated in this work uses the direct precipitation of lignin nanoparticles from organosolv pretreatment extract in a static mixer and can reduce solvent consumption drastically. The pH value, ratio of antisolvent to organosolv extract and flowrate in the mixer were investigated as precipitation parameters in terms of the resulting particle properties. Particles with dimensions ranging from 97.3 to 219.3 nm could be produced, and at certain precipitation parameters, carbohydrate impurities reach values as low as in purified lignin particles. Yields were found independent of the precipitation parameters with 48.2 ± 4.99%. Results presented in this work can be used to optimize precipitation parameters with emphasis on particle size, carbohydrate impurities or the solvent consumption.

| S-EPMC7145315 | biostudies-literature

Thermal Properties of Ethanol Organosolv Lignin Depending on Its Structure.

Project description:In general, lignin exhibits unpredictable and nonuniform thermal properties due to the structural variations caused by the extraction processes. Therefore, a systematic understanding of the correlation between the extraction conditions, structural characteristics, and properties is indispensable for the commercial utilization of lignin. In this study, the effect of extraction conditions on the structural characteristics of ethanol organosolv lignin (EOL) was investigated by response surface methodology. The structural characteristics of EOL (molecular weight, hydroxyl content, and intramolecular coupling structure) were significantly affected by the extraction conditions (temperature, sulfuric acid concentration, and ethanol concentration). In addition, the correlation between the structural characteristics and thermal properties of the extracted EOLs was estimated. The relevant correlations between the structural characteristics and thermal properties were determined. In particular, EOLs that had a low molecular weight, high phenolic hydroxyl content, and low aryl-ether linkage content exhibited prominent thermal properties in terms of their initial decomposition rate and a high glass transition temperature, T g. Correspondingly, EOL-PLA blends prepared using three EOL types exhibited improved thermal properties (starting point of thermal decomposition and maximum decomposition temperature) compared to neat PLA and had thermal decomposition behaviors coincident with the thermal properties of the constituent EOLs.

| S-EPMC7818625 | biostudies-literature

Characterization of Organosolv Birch Lignins: Toward Application-Specific Lignin Production.

Project description:Organosolv pretreatment represents one of the most promising biomass valorization strategies for renewable carbon-based products; meanwhile, there is an overall lack of holistic approach to how extraction conditions affect the suitable end-usages. In this context, lignin extracted from silver birch (Betula pendula L.) by a novel hybrid organosolv/steam-explosion treatment at varying process conditions (EtOH %; time; catalyst %) was analyzed by quantitative NMR (1H-13C HSQC; 13C NMR; 31P NMR), gel permeation chromatography, Fourier transform infrared (FT-IR), Pyr-gas chromatography-mass spectroscopy (GC/MS), and thermogravimetric analysis, and the physicochemical characteristics of the lignins were discussed regarding their potential usages. Characteristic lignin interunit bonding motifs, such as β-O-4', β-β', and β-5', were found to dominate in the extracted lignins, with their abundance varying with treatment conditions. Low-molecular-weight lignins with fairly unaltered characteristics were generated via extraction with the highest ethanol content potentially suitable for subsequent production of free phenolics. Furthermore, β-β' and β-5' structures were predominant at higher acid catalyst contents and prolonged treatment times. Higher acid catalyst content led to oxidation and ethoxylation of side-chains, with the concomitant gradual disappearance of p-hydroxycinnamyl alcohol and cinnamaldehyde. This said, the increasing application of acid generated a broad set of lignin characteristics with potential applications such as antioxidants, carbon fiber, nanoparticles, and water remediation purposes.

| S-EPMC7893791 | biostudies-literature

Solubility of Organosolv Lignin in γ-Valerolactone/Water Binary Mixtures.

Project description:The solubility of lignin in a mixture of γ-valerolactone (GVL) and water at different weight ratios was measured using the Hildebrand solubility parameters. Based on the molecular structure of lignin, its solubility parameter (δ-value) was calculated as 25.5 MPa1/2 . The δ-value for aqueous GVL solvent increased from 23.1 MPa1/2 for pure GVL to 45.6 MPa1/2 for pure water. Therefore, the lignin solubility was predicted to increase with increasing GVL concentration in the aqueous mixture up to approximately 92-96 wt % of GVL. A ternary diagram describing the phase behavior of water-GVL-lignin mixtures at room temperature was constructed based on the experimental results. The three-component system exhibited a complex behavior with a liquid-liquid and solid-liquid-liquid phase split. The efficiency of the selected fractionation trials in a previous work was validated using the ternary solubility diagram. A promising recovery pathway and lignin isolation method were deduced from the results of this work.

| S-EPMC6586022 | biostudies-literature

Organosolv Lignin-Based Wood Adhesive. Influence of the Lignin Extraction Conditions on the Adhesive Performance.

Project description:Ethanol organosolv alfa grass lignins were extracted in the presence of sulfuric acid or Lewis acids (Sc(OTf)₃, FeCl₃) as catalysts and subjected to a comprehensive structural characterization by solid state 13C NMR, GPC, MALDI-TOF, and ASAP-MS/MS. The impact of the severity of the treatment and of the nature of the acid catalyst on the recovered lignin structure was investigated. The lignins isolated at high severity were highly recondensed and partly composed of regular structures composed of furan-like rings. The alfa (Stipa tenacissima L.) organosolv lignins were used for the preparation of formaldehyde-free adhesives which were characterized by TMA and used for the preparation of particleboard without any addition of synthetic resin. It has been demonstrated for the first time that: (1) the addition of 10% to 30% of organosolv alfa lignin in a tannin-based adhesive improved the adhesive performance; and (2) the conditions of the lignin extraction strongly impact the lignin-based adhesive performances. The highly recondensed lignin extracted with sulfuric acid as a catalyst allowed the production of resins with improved performances. Formulations composed of 50% glyoxalated alfa lignin and 50% of Aleppo Pine tannins yielded good internal bond strength results for the panels (IB = 0.45 MPa) and satisfied relevant international standard specifications for interior-grade panels.

| S-EPMC6431968 | biostudies-literature

Composition of Lignin-to-Liquid Solvolysis Oils from Lignin Extracted in a Semi-Continuous Organosolv Process.

Project description:The interest and on-going research on utilisation of lignin as feedstock for production of renewable and sustainable aromatics is expanding and shows great potential. This study investigates the applicability of semi-continuously organosolv extracted lignin in Lignin-to-Liquid (LtL) solvolysis, using formic acid as hydrogen donor and water as solvent under high temperature-high pressure (HTHP) conditions. The high purity of the organosolv lignin provides high conversion yields at up to 94% based on lignin mass input. The formic acid input is a dominating parameter in lignin conversion. Carbon balance calculations of LtL-solvolysis experiments also indicate that formic acid can give a net carbon contribution to the bio-oils, in addition to its property as hydrogenation agent. Compound specific quantification of the ten most abundant components in the LtL-oils describe up to 10% of the bio-oil composition, and reaction temperature is shown to be the dominating parameter for the structures present. The structural and quantitative results from this study identify components of considerable value in the LtL-oil, and support the position of this oil as a potentially important source of building blocks for the chemical and pharmaceutical industry.

| S-EPMC5297854 | biostudies-literature

Acid-catalysed α-O-4 aryl-ether bond cleavage in methanol/(aqueous) ethanol: understanding depolymerisation of a lignin model compound during organosolv pretreatment.

Project description:The selective lignin conversion into bio-based organic mono-aromatics is a major general challenge due to complex structure itself/additional macromolecule modifications, caused by the cleavage of the ether chemical bonds during the lignocellulosic biomass organosolv pulping in acidified aqueous ethanol. Herein, the acido-lysis of connected benzyl phenyl (BPE), being a representative model compound with α-O-4 linkage, was investigated in methanol, EtOH and 75 vol% EtOH/water mixture solutions, progressing each time with protonating sulfuric acid. The effect of the physical solvent properties, acidity of the reaction process media and temperature on rate was determined. Experiments suggested BPE following SN1 mechanism due to the formation of a stable primary carbocation/polarity. The product species distribution in non-aqueous functional alcohols was strongly affected. The addition of H2O was advantageous, especially for alkoxylation. Yield was reduced by a factor of 3, consequently preserving reactive hydroxyl group. Quantitative experimental results indicated key performance parameters to achieve optimum. Organosolv lignins were further isolated under significantly moderate conditions. Consecutive structural differences observed supported findings, obtained when using BPE. H2O presence was again found to grant a higher measured -OH content. Mechanistic pathway analysis thus represents the first step when continuing to kinetics, structure-activity relationships or bio-refining industrial resources.

| S-EPMC7338503 | biostudies-literature

Acid-Catalyzed α-O-4 Aryl-Ether Cleavage Mechanisms in (Aqueous) γ-Valerolactone: Catalytic Depolymerization Reactions of Lignin Model Compound During Organosolv Pretreatment.

Project description:In this study, acidolysis of benzyl phenyl ether (BPE), being a representative lignin model compound with the α-O-4 linkage, was examined in γ-valerolactone (GVL) and a GVL/water mixture, each time acidified with sulfuric acid. The product distribution was strongly affected by water used as a cosolvent, which was found to be advantageous by inhibiting the formation of larger structures and introducing reactive OH groups instead. The experimental results indicate the GVL/water ratio as an important parameter to attain an optimal hydrolytic α-ether bond cleavage. Differences between the organosolv lignins (molecular weight distribution, OH group content, and structural features with reaction time), isolated under moderate reaction conditions, supported the findings obtained using BPE. A beneficial effect of the added water is reflected in the higher aliphatic OH group content and less intact structure. Analysis of the reaction mechanism represents an initial step toward kinetics and structure-activity correlation of biorefining industrial resources.

| S-EPMC7735783 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data