Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

Decomposition of a β-O-4 lignin model compound over solid Cs-substituted polyoxometalates in anhydrous ethanol: acidity or redox property dependence?

Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone （2-PAP）, was investigated over several ce-sium-exchanged polyoxometalate （Cs-POM） catalysts. Decomposition of 2-PAP can follow two dif-ferent mechanisms： an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox proper-ties of the catalysts. The catalysts of POMs perform the following functions： promoting active hy-drogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen libera-tion and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP （〉99%） with excellent selectivities to the desired products （98.6% for phenol and 91.1% for acetophenone） can be achieved.

Immobilized laccase on magnetic nanoparticles for enhanced lignin model compounds degradation

As a natural aromatic polymer,lignin has great potential but limited industrial application due to its complex chemical structure.Among strategies for lignin conversion,biodegradation has attracted promising interest recently in term of efficiency,selectivity and mild condition.In order to overcome the issues of poor stability and non-reusability of enzyme in the biodegradation of lignin,this work explored a protocol of immobilized laccase on magnetic nanoparticles(MNPs)with rough surfaces for enhanced lignin model compounds degradation.Scanning electron microscope with energy dispersive spectrometer(SEM-EDS),flourier transformation infrared spectroscopy(FTIR)and thermal gravimetric analysis(TGA)were utilized to characterize the immobilization of laccase.The results showed a maximum activity recovery of 64.7%towards laccase when it was incubated with MNPs and glutaraldehyde(GA)with concentrations of 6 mg·ml^-1and 7.5 mg·ml^-1for 5 h,respectively.The immobilized laccase showed improved thermal stability and pH tolerance compared with free laccase,and remained more than 80%of its initial activity after 20 days of storage at 4℃.In addition,about 40%residual activity of the laccase remained after 8 times cycles.Gas chromatography–mass spectrometry(GC–MS)was utilized to characterize the products of lignin model compound degradation and activation,and the efficiency of immobilized laccase was calculated to be 1–5 times that of free laccase.It was proposed that the synergistic effect between MNPs and laccase displays an important role in the enhancement of stability and activity in lignin model compound biodegradation.

Urchin-like Nb_(2)O_(5)hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions

Selective cleavage of robust C−C bonds to harvest value-added aromatic oxygenates is an intriguing but challenging task in lignin depolymerization.Photocatalysis is a promising technology with the advantages of mild reaction conditions and strong sustainability.Herein,we show a novel urchin-like Nb_(2)O_(5)hollow microsphere(U-Nb_(2)O_(5)HM),prepared by one-pot hydrothermal method,are highly active and selective for C_(α)−C_(β)bond cleavage of ligninβ-O-4 model compounds under mild conditions,achieving 94%substrate conversion and 96%C−C bond cleavage selectivity.Systematic experimental studies and density functional theory(DFT)calculations revealed that the superior performance of U-Nb_(2)O_(5)HMs arises from more exposed active sites,more efficient free charge separation and the active(001)facet,which facilitates the activation of Cβ−H bond of lignin models and generate key Cβradical intermediates by photogenerated holes,further inducing the C_(α)−C_(β)bond cleavage to produce aromatic oxygenates.This work could provide some suggestions for the fabrication of hierarchical photocatalysts in the lignin depolymerization system.

Synthesis of a trimeric lignin model compound composed of a-O-4 and b-O-4 linkages under microwave irradiation

A trimeric lignin model compound composed of α-O-4 and β-O-4 linkages was prepared by the microwave-assisted synthesis, which consisted of three steps： （a） the synthesis of 3-methoxy-4- benzyloxyacetophenone （2） from acetovanillone （1）, （b） the bromination of compound 2 to produce 3- methoxy-4-benzyloxy-α-bromoacetophenone （3）, and （c） followed by a nucleophilic substitution of compound （3） to obtain 3-methoxy-4-benzyloxy-α-（3-methoxy-4-（1-propenyl）phenol）-acetophenone （4）. The target product was characterized by MS, 1H NMR and 13C NMR spectroscopy. It was found that the trimeric compound synthesized can be used as a preferable lignin model compound because it contains guaiacyl structural unit （3-methoxy-4-hydroxy phenyl propane） linked by α-O-4 and β-O-4 linkages. In addition, under the conditions of microwave irradiation, the reaction time of each step is significantly reduced, and the selectivity of target product is greatly improved. The yields of each step and the overall sequence are 95.31%. 87.3%. 90.6% and 75.4% （95.31%× 87.3% × 90.6%）. respectively.

Lignin derived absorbent for efficient and sustainable CO_(2) capture

High and cost-efficient capture of CO_(2) is a prerequisite and an inevitable path of carbon emission reduction. To address the challenges(high cost, low efficiency, less sustainability, etc.) of existing petroleum-based CO_(2) absorbents, herein, a class of efficient and sustainable lignin-based absorbents were resoundingly prepared by grafting the active amine group on a lignin derived compound vanillin and alkali lignin. The results demonstrated that vanillin modified by acrylamide achieved the excellent absorption capacity among the three absorbents, whose ability was 0.114 g CO_(2) per gram of absorbent under 25 ℃ and 100 kPa. In addition, the absorbent retained stable absorbability of CO_(2) after 6 cycles.The absorbing capacity of the absorbent formed by the coupling of vanillin and acrylamide to CO_(2) was much greater than their own(i.e. 0 g CO_(2) ·g^(-1)vanillin, 0.01 g CO_(2) ·g^(-1) acrylamide, respectively).Detailed information revealed the multi-site synergistic absorption mechanism, in which CO_(2) has C and O double interactions with the amide group of the absorbent, and single interaction with the hydroxyl oxygen on the benzene ring of the absorbent. The absorption capacity of modified lignin for CO_(2) is as high as 0.12 g CO_(2) per gram of absorbent, which is comparable with that of model compound vanillin.This work not only provides a new idea for the design of bio-absorbents for CO_(2) capture, but explores the application potential of lignin-based materials.

Synthesis and Characterization of Lignin Grafting Modification-based Aliphatic Superplasticizer

Lignin as the main component of black liquor is generally employed to modify aliphatic superplasticizer（AFS）. However, the modification effect is hard to evaluate correctly due to the uncertain molecular structure of lignin and the disturbance from the complexity of black liquor compositions. In this paper, the purified lignin via acid precipitation from straw black liquor is used to modify AFS. The modified AFS named as LAFS for short presents lower molecular mass than AFS. It is assumed that it is due to the single active site of guaiacol segments in lignin by which lignin graft modifies AFS in virtue of methylolation reaction. In order to verify this assumption, guaiacol and dihydro eugenol as the typical segments of lignin macromolecule were selected, respectively, as the simplified model compounds of lignin to modify AFS, and corresponding products are abbreviated in GAFS and DAFS. Both GAFS and DAFS show the lower molecular mass than unmodified AFS. FTIR and TG-DTG analyses prove that lignin is successfully grafted onto AFS. The graft modification of lignin results in a decrease in electrostatic epulsion, but an enhanced steric hindrance. Therefore, although the replacement rate of lignin in LAFS was about 23.3%, the dispersion performance was only slightly affected.

Modelling the Biomass Growth and Enzyme Secretion by the White Rot Fungus <i>Phanerochaete Chrysosporium</i>in Presence of A Toxic Pollutant

The white rot fungus Phanerochaete chrysosporium is well known for its ability to degrade toxic pollutants owing to its efficient extracellular ligninase system. However, biomass growth and enzyme secretion in presence of toxic pollutant is not well understood. In the present study, using the model azo dye Direct Red-80, biomass growth and lignin peroxidase secretion by the fungus was studied during its degradation and a stochastic based model was applied to simulate the behavior of the fungus. Also, glucose concentration in the medium was varied in order to observe its effect on the dye degradation. Results revealed that glucose at an optimum concentration of 10 gL-1 is essential for biomass growth, LiP secretion, as well as the dye decolourization. Modeling the behavior of the fungus with the presence of both glucose and dye has shown significant similarity.

双反应活性中心催化体系降解木质素模型物的研究

以硝酸铜和硝酸铁为原料,制备以活性炭为载体的铜-铁双金属复合催化剂,将其用于活化过硫酸盐,以实现对木质素模型物阿魏酸的降解;探讨催化剂制备的最佳反应条件和反应条件对材料催化活化效率的影响。结果表明,当活性炭质量分数为6%、催化剂(Cu^(2+)∶Fe^(3+)=2∶1,物质的量比)用量为0.03 g/L、过硫酸钠浓度为0.05 mol/L、pH值=7时,反应60 min,能够降解90%的阿魏酸。通过分析降解中间产物发现,阿魏酸可通过一系列氧化反应降解为小分子羧酸。通过电子顺磁共振技术表征表明,该催化体系中的主要反应活性物种是硫酸根自由基和羟基自由基。同时,催化剂具有良好的稳定性和循环利用性。

木质素熔融沉积式3D打印的分子结构-流变学响应关系研究进展

木质素作为自然界储量最大的可再生芳香族生物质资源,开发其高值化加工利用技术是林业生物质产业转型升级的重要途径。近年来,基于3D打印技术制备高性能木质素基复合材料的研究发展迅速。木质素的3D打印可快速、高效构建具有特定功能特性的复合材料,且可灵活调控木质素基复合材料的宏观、微观结构,以使其满足能量传输、药物递送和个性化医疗等需求。然而,由于木质素分子结构复杂多变、分子量分布宽、脆性大等特点,木质素的分子结构-流变学响应关系仍缺乏系统研究,限制了木质素基复合材料的进一步开发和应用。本文基于近年来木质素熔融沉积式3D打印的发展现状,系统总结了木质素分子结构与其熔融流变学的响应关系。首先介绍了木质素的分子结构特性和熔融沉积式3D打印技术,然后重点对比分析了不同木质素分子结构、木质素与热塑性高聚物的共混对其熔融流变学特性和打印性的影响,最后总结了木质素熔融沉积式3D打印面临的挑战,并对木质素熔融沉积式3D打印的发展方向进行了展望,通过更好地理解木质素熔融流变学的构-效关系,促进木质素的高值化利用。

β-5型木质素二聚体热解机理模拟计算

木质素是由苯基丙烷结构通过C—O键和C—C键连接而成的复杂三维网状无定形高聚物,热解是木质素的重要利用方式,探究木质素热解过程中连接键的断裂机理对于开发高效热解技术至关重要。利用密度泛函理论方法,针对典型的β-5连接木质素二聚体模型化合物,探究其热解过程及取代基的影响。计算结果表明,苯环之间五元环的开环反应是最可能发生的初步反应,其中Cα—O键和Cα—Cβ键的键解离能(BDEs)分别为163.9 kJ/mol和212.9 kJ/mol,是最主要的断键开环反应。通过对比甲基、甲氧基、羟基、正丙基等支链对β-5连接键的断裂的影响,发现当两个苯环和β-5连接五元环上分别连接羟基、丙基、羟甲基取代基时,Cα—O键和Cα—Cβ键的BDEs最低。对于不同取代基类型和位点来说,Cα—O键均裂始终是最容易发生的初始反应,而Cα—O键和Cα—Cβ键连续断裂的路径是β-5连接五元环断裂的主要途径。

木质素基高效染料吸附材料制备及其性能研究

本研究采用ZnCl2、KOH和尿素共同活化处理工业碱木质素,经高温碳化(700℃)制备得到木质素基高吸附性能材料(Zn-LB)。将Zn-LB用于亚甲基蓝和甲基橙染料溶液吸附实验,探究了染料种类、吸附温度、多元混合染料体系对Zn-LB吸附性能的影响。结果表明,Zn-LB的比表面积高达2190.3 m^(2)/g。通过Langmuir吸附等温线模型拟合了Zn-LB对亚甲基蓝和甲基橙的最大平衡吸附量分别为1345.9和1732.4 mg/g。此外,Zn-LB对亚甲基蓝的吸附量随温度的升高而升高,表明吸附亚甲基蓝是一个吸热过程;而Zn-LB对甲基橙的吸附则相反,是一个放热过程。

β-O-4型木素模型化合物的合成及其在GIF型仿酶降解体系中的变化(Ⅰ)

研究了一种β O 4型木素模型化合物——— 4 (α (2 甲氧基苯氧基 ) 乙酰基 ) 愈创木酚的合成方法 ,并利用薄层色谱 (TLC)、红外光谱和核磁共振谱 (1H NMR)等手段对它们的化学结构进行了分析与确认。采用由Cu2 + /吡啶 /过氧化氢组成的GIF型仿酶系统对这一木素模型物进行仿酶降解 ,结合高效液相色谱 (HPLC)及GC MS等分析方法 ,分析了该β O 4型木素模型化合物在降解过程中的结构变化 ,并对这种仿酶降解的机理进行了探讨。研究结果表明 :通过利用过量愈创木酚和 4 乙酰基愈创木酚的溴化物的反应并结合羟甲基化可以得到含α 羰基的酚型 β O 4木素模型化合物。GIF仿酶降解体系对β O 4型木素模型物有较强的碎解能力 ,降解后产生较多的脂肪族小分子化合物 ,一部分成为香草醛、香草酸等低分子芳香族化合物 ,该结果可以说明此降解体系能有效导致 β O

改良的大豆种皮过氧化物酶纯化方法及酶的底物氧化特性研究

由大豆壳中分离出一种过氧化物酶 大豆种皮过氧化物酶 (soybeanhullperoxidase ,SHP ,EC 1 .1 1 .1 .7) ,经硫酸铵分级沉淀 ,DEAE SephadexA 50离子交换层析 ,Bio GelP 60凝胶过滤 ,DEAE SephadexA 2 5二次离子交换和SephadexG 1 0 0凝胶过滤纯化了该酶 .分子量为 3.8× 1 0 4u ,薄层等电聚焦电泳测得SHP等电点为 3.9.SHP的底物范围较宽 ,以H2 O2 为电子受体 ,可以氧化多种木素单体模型物 ,包括愈创木酚、2 ,3 二甲氧基酚、2 ,6 二甲氧基酚、3,4 二甲氧基酚、3,5 二甲氧基酚、1 ,2 ,4 三甲氧基苯、阿魏酸、咖啡酸、异丁子香酚和丁香醛联氮 ,提示该酶在木素的生物降解中有潜在的应用价值 .

羟甲基交联碱木质素锰肥的锰离子缓释动力学研究

为改善中国北方土壤缺锰的问题,该文以麦草碱木质素为原料制备了羟甲基碱木质素(HMAL);以物理混合的方式添加硫酸锰,以甲醛、尿素作为交联剂使HMAL发生缩合交联制备了羟甲基交联碱木质素锰肥(CHMAL-Mn)。CHMAL-Mn肥产率为93.7%,CHMAL-Mn肥的锰离子的饱和负载量为48mg/g;其红外光谱表明甲醛成功交联羟甲基碱木质。以7种常见动力学和概率分布的数学模型对CHMAL-Mn肥的锰离子累积释放率的动力学试验数据的进行拟合,以R2、均方误差(e)、精确因子(Af)和偏差因子(Bf)的算数平均值比较模型拟合有效性。结果表明:对CHMAL-Mn肥的锰离子累积释放率的动力学试验数据拟合性最好的模型是Ritger-Peppa模型,其R2、e、Af和Bf的平均值分别为0.9443、0.0083、0.0223和0.0003。当CHMAL-Mn肥的锰负载量为12mg/g时,拟合模型的缓释指数n<0.45,锰离子缓释行为以Fick扩散为主。当CHMAL-Mn肥的锰负载量大于24mg/g时,拟合模型的缓释指数0.45≤n≤0.89,缓释机理为非Fick扩散与骨架溶蚀协同作用。当CHMAL-Mn肥的锰负载量达到饱和值48mg/g时,拟合模型的缓释指数n为0.811,该模型预测CHMAL-Mn肥对锰离子累积缓释率的极大值为79.28%,预测缓释时间为95.92h;模型拟合准确率为96.57%。该研究为可大幅提高碱木质对肥料锰肥的负载量,为碱木质素的综合利用和促进碱木质素在现代农业可降解缓/控释载体领域的应用提供了参考。

β-O-4型木质素模型化合物的合成及其在GIF型仿酶降解体系中的变化(Ⅱ)

深入研究了β-O-4型木质素模型化合物———愈创木基丙三醇-β-愈创木基醚的合成新路线,并利用红外光谱和核磁共振谱对其化学结构进行了分析。采用由Cu2+/吡啶/过氧化氢组成的GIF(GIF sur YVETTE)型仿酶体系对这一木质素模型物进行了仿酶降解的研究,并采用GC-MS、13CNMR等方法分析了该β-O-4型木质素模型化合物在降解过程中的结构变化,在此基础上对这种仿酶降解的机理进行了探讨。研究结果表明:利用溴化铜对4-乙酰基愈创木酚进行溴化后很容易得到4-(α-溴化乙酰基)-愈创木酚中间体,从而提高了合成愈创木基丙三醇-β-愈创木基醚的效率。GIF仿酶降解体系对β-O-4型木质素模型物有较强的碎解能力,降解后产生一系列含羟基、醛基和羧基的芳香族低分子化合物,根据反应产物的结构可以说明β-O-4型木质素模型化合物的主要降解途径为:β-O-4醚键断裂、Cα—Cβ键断裂、Cβ—Cγ键断裂。本研究为该仿酶降解体系在无污染漂白工业上的应用提供理论依据。

木质素模化物键离解能的理论研究

采用密度泛函理论B3P86方法,在6-31G(d,p)基组水平上,对木质素结构中的6种连接方式(β-O-4、α-O-4、4-O-5、β-1、α-1、5-5)的63个木质素模化物的醚键(C-O)和C-C键的键离解能EB进行了理论计算研究。分析了不同取代基对键离解能的影响以及键长与键离解能的相关性。计算结果表明,C-O键的键离解能通常比C-C键的小,在各种醚键中Cα-O键的平均键离解能最小,为182.7 k J/mol;其次是β-O-4连接中的Cβ-O键,苯环和烷烃基上的取代基对醚键的键离解能有较强的弱化作用,C-O键的键长和键离解能的相关性较差。与C-O键相比,C-C键的键离解能受苯环上取代基的影响很小,而烷烃基上的取代基对C-C键的键离解能有较大的影响,C-C键的键离解能和键长之间存在较强的线性关系,C-C键的键长越长,其键离解能越小。

杂色云芝组成型漆酶Ⅰ的纯化和底物专一性

采用合成培养基培养杂色云芝As5 4 8,从发酵液中纯化出一种组成型漆酶同功酶Ⅰ .经超滤浓缩 ,DEAE SephadexA 5 0离子交换层析 ,Bio gelP 10 0凝胶过滤纯化了该酶 .SDS PAGE分析发现 ,该酶分子量为 6 8kD ,薄层等电聚焦测得等电点为 3 5 .漆酶Ⅰ的底物范围较宽 ,以O2 为电子受体 ,可以氧化多种木素单体模型物 ,包括 2 ,6 二甲氧基酚 ,2 ,2′ 联氮 二 (3 乙基 苯并噻唑 6 磺酸 )(ABTS) ,愈创木酚 ,咖啡酸 ,阿魏酸和邻联茴香胺 .结果表明 ,该酶在木质素的生物降解中可能有重要的作用和应用价值 .

Ni基催化剂上木质素模型化合物苯基苯乙醚C–O键的加氢裂解

研究了Ni基催化剂上木质素模型化合物苯基苯乙醚中C–O–C键加氢裂解性能.结果表明,Ni/C催化剂显示出优异的加氢裂解能力,苯基苯乙醚的转化率达到99%以上.Ni/C催化剂的还原方法对裂解选择性有重要影响;氢气还原制备的Ni/C-H催化剂上,C–O–C键裂解选择性为85%.Ru/C和Pd/C催化剂上裂解选择性分别为40%和69%.采用碳热还原方法制备的Ni/C-C催化剂,可以实现高选择性加氢和裂解,C–O–C键裂解选择性达到99%以上,其中芳烃化合物收率为44%.这可能与镍组分和载体碳之间的相互作用有关.

漆酶-助剂体系催化氧化具有α-苄基氢的木素模型物

研究了漆酶—助剂体系催化氧化具有等基氢不同结构的木索非酚型和酚型模型化合物，结果表明非酚型具有苄醇结构的木素模型化合物能发生α位脱氢氧化，但此氧化反应是有限度的，氧化的结果主要生成芳香醛，没有发现进一步被氧化成芳香酸。而具有Cα和Cβ双键的化合物，α位的氢却很稳定，不能被氧化。酚型的本素模型化合物在漆酶的催化反应体系中发生聚合。