Features of stable radical generation in lignin on exposure to nitrogen dioxide

The mechanism of stable radical generation in lignin under the action of nitrogen dioxide and NO₂ - air mixture is considered. The formation of phenoxyl, iminoxyl and acylaminoxyl radicals has been detected by EPR. The proposed mechanism involves a primary oxidative reaction of phenol groups with dimers of NO₂ (nitrosyl nitrate) resulting in the formation of phenoxyl radicals and nitric oxide. In the subsequent recombination of phenoxyl radicals and nitric oxide, nitroso compounds and oximes are formed. By reaction of oximes with radicals NO₂, stable iminoxyl radicals are formed. This mechanism is confirmed by kinetic dependencies obtained over a wide range of NO₂ concentrations. From IR spectroscopy measurements it follows that hydroxyl groups of non-phenolic structures of lignin are oxidised to aldehydes producing acylaminoxyl radicals by reaction with NO₂. The kinetic data show that the adsorption of NO₂ on the lignin surface is the rate-determining factor in stable radical formation.     

Determination of the carboxylic acids in acidic and basic process samples by capillary zone electrophoresis

Capillary zone electrophoresis (CZE) with indirect UV detection was used in developing a method for the simultaneous determination of inorganic anions, aliphatic and heterocyclic organic acids in various processed samples. The analytes were determined simultaneously in 10 min using an electrolyte containing 20 mM 2,3-pyrazine dicarboxylic acid, 65 mM tricine, 2 mM BaCl₂, 0.5 mM cetyltrimethylammonium bromide, and 2 M urea at pH 8.06. Linear plots for the analytes were obtained in the concentration range of 2–150 mg L⁻¹. Relative standard deviations (RSDs) of peak areas during a 3-day analysis period varied from 5.5% for glycolate to 9.5% for oxalate. RSDs of migration times varied between 0.4% and 1.1%. The detection limit (at S/N 3) was 1 mg L⁻¹ for all the analytes studied. The proposed method was successfully demonstrated for the determination of carboxylic acids in eight oxygen treated samples of commercial softwood and hardwood kraft lignin and two red wine samples of Pinot Noir grapes. In the kraft lignin samples the concentrations of carboxylic acids correspond to the oxidation time. The acid concentrations of wine varied considerable.     

Structural characterization of lignins isolated from Caragana sinica using FT-IR and NMR spectroscopy

In order to efficiently explore and use woody biomass,six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic solvents and alkaline solutions.The lignin structures were characterized by Fourier transform infrared spectroscopy(FT-IR) and 1D and 2D Nuclear Magnetic Resonance(NMR).FT-IR spectra revealed that the core of the lignin structure did not significantly change during the treatment under the conditions given.The results of 1H and 13C NMR demonstrated that ...     

Characterization of selected paper documents from the archives of Palazzo Ducale (Venice), Italy using various analytical techniques

The paper manufacturing process remained unchanged for many centuries, until, in the nineteenth century, the crisis of rags led industrialized countries to patent new production processes with different raw materials. This study deals with this period of transition by analyzing four samples stored at the archives of Superintendency Beni Architettonici per il Paesaggio e per il Patrimonio Storico Artistico ed Etnoantropologico (BAPPDAD) of Venice Lagoon, based in the Palazzo Ducale.The samples were analyzed by FT-IR (ATR), SEM-EDS, HPLC-MS/MS and Py-GC/MS. These techniques allow the characterization of various raw materials and adhesives used in various stages of paper production.These analyses have found a gradual introduction of ground wood in the composition of papers from the mid-nineteenth century, and the use of rosin as glue only in more recent documents.     

Ruthenium‐Catalyzed C?C Bond Cleavage in Lignin Model Substrates

Ruthenium–triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox‐neutral C C bond cleavage of the β‐O‐4 lignin linkage of 1,3‐dilignol model compounds. A mechanistic pathway involving a dehydrogenation‐initiated retro‐aldol reaction for the C C bond cleavage was proposed in line with experimental data and DFT calculations.     

纺丝法制备木质素基碳纤维的研究进展

目前全球制备碳纤维主要以聚丙烯腈(PAN)或沥青为原丝,但是这类碳纤维制备成本高,限制了其自动化工业领域的大规模应用。木质素由于具有较高的含碳量和碳化收率高,其可以作为前驱体来制备碳纤维。作为一种新型材料,木质素基碳纤维因其具有价格低廉、环保、原料丰富、可实现废弃资源再生利用等优点而备受关注。本文详细介绍了木质素的分类及结构特征,阐述了不同纺丝方法制备的碳纤维的力学性能,并对其未来发展进行展望。     

Use of biopolymers for the removal of heavy metals produced by the oil industry—A feasibility study

The possibility of using lignin from the paper industry’s black liquor to absorb nickel (Ni) and vanadium (V), was studied. The work comprised two stages: first, the identification of lignin’s main functional groups and the surface characterization of the solid; second, an experimental study of lignin’s behavior towards the Ni and V cations. Results revealed the presence of aromatic groups as well as substituted methoxy groups on the lignin’s surface. This explains lignin’s adsorptive capacity exhibited in the experimental evaluations. The removal of Ni and V ions was higher than expected solely through the physical adsorption mechanism. This higher capacity is associated with a proposed complex formation on the surface of the lignin. For Ni(II), lignin showed a higher adsorption compared to commercial adsorbents. In the case of V, the behavior is reversed, in order to elucidate this result, further research is recommended.     

Lignin biodegradation by the ascomyceteChrysonilia sitophila

The lignin biodegradation process has an important role in the carbon cycle of the biosphere. The study of this natural process has developed mainly with the use of basidiomycetes in laboratory investigations. This has been a logical approach since most of the microorganisms involved in lignocellulosic degradation belong to this class of fungi. However, other microorganisms such as ascomycetes and also some bacteria, are involved in the lignin decaying process. This work focuses on lignin biodegradation by a microorganism belonging to the ascomycete class,Chrysonilia sitophila. Lignin peroxidase production and characterization, mechanisms of lignin degradation (lignin model compounds and lignin in wood matrix) and biosynthesis of veratryl alcohol are outstanding. Applications of C.sitophila for effluent treatment, wood biodegradation and single-cell protein production are also discussed.     

纳米木质素/二氧化硅基微胶囊的制备及在自愈合涂层中的应用

利用磷酸化改性木质素/二氧化硅复合纳米颗粒(PAL/SiO₂)作为壁材包埋活性组分异佛尔酮二异氰酸酯(IPDI)制备微胶囊(PAL/SiO₂-IPDI). 通过加入少量反应活性更高的聚合多甲基多二异氰酸酯(PMDI), 与水反应形成聚脲, 以增加微胶囊的壁厚. 采用光学显微镜、 扫描电子显微镜(SEM)和激光粒度分析仪(DLS)研究了PAL/SiO₂复合纳米粒子掺杂量, 水油比和剪切速率对微胶囊表面形貌、 粒径和壁厚的影响. 结果表明, 所制备的微胶囊呈现规整球形, 壁厚为2.36~3.50 μm, 平均粒径为40.3~201.5 μm. IPDI作为芯材包埋在微胶囊中, 芯材含量约为82.8%. 将制备的PAL/SiO₂-IPDI微胶囊添加到环氧树脂中得到自愈合环氧树脂涂层. 其在高盐浓度溶液中的抗侵蚀测试结果显示, 添加质量分数4%的PAL/SiO₂-IPDI微胶囊的环氧树脂涂层在划破后能够快速愈合, 显著降低基底的腐蚀电流和腐蚀速率. 纳米压痕实验表明, 环氧涂层的硬度为249.99 MPa, 而添加PAL/SiO₂-IPDI微胶囊后硬度增加到302.98 MPa, 弹性模量也有提高.