2478-38-8Relevant articles and documents
Detection of an O-methyltransferase synthesising acetosyringone in methyl jasmonate-treated tobacco cell-suspensions cultures
Negrel, Jonathan,Javelle, Francine,Wipf, Daniel
, p. 52 - 60 (2014)
Acetosyringone (3′,5′-dimethoxy-4′-hydroxyacetophenone) is a well-known and very effective inducer of the virulence genes of Agrobacterium tumefaciens but the precise pathway of its biosynthesis in plants is still unknown. We have used two tobacco cell lines, cultured in suspension and exhibiting different patterns of accumulation of acetosyringone in their culture medium upon treatment with methyl jasmonate, to study different steps of acetosyringone biosynthesis. In the two cell lines studied, treatment with 100 μM methyl jasmonate triggered a rapid and transient increase in acetovanillone synthase activity followed by a progressive increase in S-adenosyl-L-methionine: 5-hydroxyacetovanillone 5-O-methyltransferase activity which paralleled the rise in acetosyringone concentration in the culture medium. This O-methyltransferase displayed Michaelis-Menten kinetics with an apparent Km value of 18 μM for 5-hydroxyacetovanillone and its activity was magnesium-independent. Its molecular mass was estimated by gel permeation on an FPLC column and was found to be of ca. 81 kDa. 5-Hydroxyacetovanillone was the best substrate among the different o-diphenolic compounds tested as methyl acceptors in the O-methyltransferase assay. No formation of 5- hydroxyacetovanillone could be detected in vitro from 5-hydroxyferuloyl-CoA and NAD in the extracts used to measure acetovanillone synthase activity, indicating that 5-hydroxyacetovanillone is probably formed by direct hydroxylation of acetovanillone rather than by β-oxidation of 5-hydroxyferulic acid. Taken together our results strongly support the hypothesis that acetosyringone biosynthesis in tobacco proceeds from feruloyl-CoA via acetovanillone and 5-hydroxyacetovanillone.
Catalytic C(β)-O Bond Cleavage of Lignin in a One-Step Reaction Enabled by a Spin-Center Shift
Zhu, Qilei,Nocera, Daniel G.
, p. 14181 - 14187 (2021/11/27)
A challenge to the utilization of lignin as a feedstock for aromatic fine chemicals lies in selective cleavage of copious β-O-4 linkages. A photocatalytic strategy for the selective cleavage of the C(β)-O bonds of model substrates and natural lignin extracts is achieved by a redox-neutral, catalytic cycle that does not require stoichiometric reagents. Mechanistic studies reveal the generation of a thiyl radical, which is derived from a cystine-derived H-atom transfer catalyst, initiates a spin-center shift (SCS) that leads to C(β)-O bond cleavage. The SCS reactivity is reminiscent of the C(β)-O bond cleavage chemistry that occurs in the active site of ribonucleotide reductase.
Profiling of the formation of lignin-derived monomers and dimers from: Eucalyptus alkali lignin
Hu, Zhenhua,Li, Suxiang,Lu, Fachuang,Shi, Lanlan,Wang, Chen,Yue, Fengxia,Zhang, Han,Zhao, Chengke
supporting information, p. 7366 - 7375 (2020/11/18)
Lignin is a renewable and the most abundant aromatic source that can be used for extensive chemicals and materials. Although approximately 50 million tons of lignin are produced annually as a by-product of the pulp and paper industry, it is currently underutilized. It is important to know the structural features of technical lignin when considering its application. In this work, we have demonstrated the formation of low-molecular-weight constituents from hardwood (Eucalyptus) lignin, which produces much more low-molecular-weight constituents than softwood (spruce) lignin, after a chemical pulping process, and analyzed the micromolecular compositions in the alkali lignin after fractionation by dichloromethane (DCM) extraction. By applying analytical methods (gel-permeation chromatography, 2D NMR and GC-MS) with the aid of evidence from authenticated compounds, a great treasure trove of lignin-derived phenolic compounds from Eucalyptus alkali lignin were disclosed. Except for some common monomeric products, as many as 15 new lignin-derived monomers and dimers including syringaglycerol, diarylmethane, 1,2-diarylethanes, 1,2-diarylethenes, (arylvinyl ether)-linked arylglycerol dimers and isomeric syringaresinols were identified in the DCM-soluble fraction. Regarding the formation and evolution of the Cα-condensed β-aryl ether structure, a novel route that is potentially responsible for the high content of β-1 diarylethenes and diarylethanes in the lignin low-molecular-weight fraction, in addition to the β-1 (spirodienone) pathway, was proposed. This work not only provides novel insights into the chemical transformation of S-G lignin during the alkali pulping process, but also discovered lignin-derived phenolic monomers and dimers that can potentially be used as raw materials in the chemical or pharmaceutical industries. This journal is
Synthesis of CoFeO mixed oxides via an alginate gelation process as efficient heterogeneous catalysts for lignin depolymerization in water
Hdidou,Khallouk,Solhy,Manoun,Oukarroum,Barakat
, p. 5445 - 5453 (2018/11/20)
A catalytic oxidative fragmentation of a lignin dimer and polymer extracted from wheat straw was successfully performed under eco-friendly conditions: 10% O2/N2 as the oxidizing agent, water as the solvent (pH ≈ 7), and Co3O4, Fe2O3 and CoFeO mixed oxides as heterogeneous catalysts and at temperatures of T = 150 °C and 200 °C. These catalysts unexpectedly showed tunable selectivity that directly depends on the composition of the selected bimetallic nanoparticles. High selectivity for benzoic acid and alkylbenzene (above 50%) was observed over Co50-Fe50 at 200 °C. Under similar conditions, the conversion of wheat organosolv lignin over Co50-Fe50 at 150 °C for 4 h yielded up to 50 wt% of monomeric species (based on dry lignin) and up to 19% of aromatic molecules with high selectivity to aromatic aldehydes (syringaldehyde and vanillin), up to 60%. An important fraction of water-soluble oligomers, with low molecular weights, was also formed during the catalytic treatment. The oxide nanomaterials were readily separated from the residual lignin during the recyclability test. The yield and the product distribution can be tuned by choosing the oxidation parameters: temperature, reaction time, oxygen partial pressure, solvent and catalyst charges.