磺甲基化木质素的辣根过氧化物酶催化聚合研究

以碱木质素为原料,采用磺甲基化反应,得到磺甲基化木质素(SAL),并进一步采用辣根过氧化物酶(HRP)催化以提高其分子量,制备了高分子量高磺化度磺甲基化木质素(HPSAL).采用凝胶渗透色谱、红外光谱、核磁共振氢谱、紫外光谱和顶空气相色谱等研究了改性前后SAL的结构特征.结果表明,经HRP催化后,与SAL相比,HPSAL的重均分子量和磺化度显著增加,分别提高20倍和30%以上,羧基含量升高,而甲氧基和酚羟基含量降低.HRP使SAL形成酚氧自由基,活化其酚羟基的邻、对和侧链Cβ位,增加磺化反应活性,而磺化度的提高又有利于增加HRP催化SAL的聚合反应活性,其聚合方式主要为β-O-4'、β-β'、β-1'和β-5'联结.分子模拟结果表明,甲氧基含量的降低和磺酸基含量的增加能显著提高以β-O-4'连接键为主的聚合反应活性.     

漆酶改性木质素磺酸钠的结构表征及吸附特征

采用漆酶对木质素磺酸钠(木钠)进行改性, 通过凝胶渗透色谱、 电位滴定、 红外光谱和核磁共振等测试方法研究了漆酶改性木钠的结构特征, 结果表明, 漆酶改性对木钠的磺酸基及表面电荷含量影响很小; 在漆酶对木钠的改性过程中既有解聚作用, 又有聚合作用, 反应初期, 漆酶使木钠发生脱甲基反应及部分链接键的断裂, 使酚羟基含量增大和分子量降低, 随着改性时间的延长, 酚羟基含量减少, 分子量变大, 聚合作用占主导地位. 采用静电逐层自组装技术研究了漆酶改性对木钠吸附特征的影响, 紫外光谱以及原子力显微镜的研究结果表明, 当漆酶改性时间为2 h时, 在平板上的吸附量及吸附膜的表面粗糙度最大, 木钠分子呈扁长的椭球形, 而改性时间为36 h时, 木钠聚合为近似球形的大分子结构, 空间位阻增大, 吸附量及吸附膜的表面粗糙度降低.     

Ce掺杂固体酸活化的碱木质素的抗氧化性能

采用共沉淀法,将硝酸铈与硝酸锆溶液混合,制备了掺杂CeO_2的ZrO_2载体,再通过浸渍焙烧法负载S_2O_8~(2-)制备了稀土固体酸催化剂,将其应用于碱木质素多羟基活化反应.通过Hamment指示剂法、X射线小角衍射(XRD)分析、BET比表面积和硫含量测定,研究了不同Ce掺杂比例对固体酸的酸强度、载体晶型和比表面积的影响.用该固体酸催化木质素氢化反应后,木质素的酚羟基和总羟基含量及还原能力提高,对1,1-二苯基-2-三硝基苦肼(DPPH)自由基及2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)自由基的清除能力增强.实验结果表明,与S_2O_8~(2-)/ZrO_2相比,掺杂Ce后,催化剂S_2O_8~(2-)/ZrO_2-CeO_2的比表面积增大,硫含量增加,反应后木质素酚羟基和总羟基含量分别从1.52%和2.31%提高至3.35%和10.35%,总羟基含量显著提高.这表明掺杂Ce后的催化剂对碱木质素氢化活化反应具有良好的催化作用,同时保留了木质素芳香环不饱和键,且活化后的木质素具有较好的抗氧化能力.     

微量热法研究漆酶和3,4,5-三羟基苯甲酸的反应

用LKB－2107型微量热系统,在不同的温度(pH＝7.4)条件下,测定了3,4,5－三羟基苯甲酸与漆酶反应的摩尔反应烙、米氏常数、反应速率常数、漆酶的活性并计算了结合能、活化自由能、活化能和活化烟等.在此基础上,应用过渡态理论,从能量变化的角度,对其催化过程进行了分析.由活化摘(△S_≠^T＜0)得出酶－底物过渡态的结构较酶－底物复合物更为有序的结论.     

顺[1-溴-2-羟基-2-(对-甲氧基苯基)乙基]膦酸二异丙酯的羟基反应性能的研究

研究了顺[1-溴-2-羟基-2-(对-甲氧基苯基)乙基]膦酸二异丙酯羟基的反应性能。由于膦酸酯基和电负性的溴原子的吸电子作用,羟基氧原子周围的电子云密度降低．从而增强了羟基上质子的酸性并减弱了碱性条件下相应的烷氧基负离子的亲核能力,因而得到了有关羟基与酚进行Mitsunobu脱水反应和酯化反应的特殊反应性能。同时,由于氢键的作用和膦酸酯基团的空问障碍作用,羟基与酰氯的反应活性较低。     

漆酶与酚类模式底物的结合及反应活性的理论研究

通过生物信息学分析、分子动力学模拟及量子化学计算,对21种邻对位取代酚类模式底物与漆酶的结合能力以及反应活性进行了探讨.生物信息学结构比对分析发现漆酶的活性口袋含有Asp/Glu206,Asn/His208,Asn264,Gly392和His458等保守的氨基酸残基(氨基酸残基编号以Trametes versicolor漆酶为例,PDB:1KYA);采用MM-GBSA方法计算了21种酚类模式底物与T.versicolor漆酶的结合自由能.分子力学计算结果表明,漆酶与底物的结合力主要来自Asp206和Asn264等残基与底物分子形成的分子间氢键,并且Phe265残基和酚类底物的芳香环形成π-π相互作用.量子化学计算表明,芳环上取代基的推拉电子效应显著影响协同电子转移的底物去质子化过程,其中推电子能力较强的—NH2,—OH,—OCH3和—CH CHCH3等基团能够明显增强酚羟基反应活性,而吸电子的—CONH2和—Cl则具有相反的效应.     

碱木质素的乙酰化及其球形胶束的制备

以造纸制浆废液中的碱木质素(AL)为原料,通过乙酰氯对其进行化学改性,制备出了乙酰化碱木质素(ACAL).红外光谱和核磁共振谱的结果表明乙酰化反应后AL中的羟基被乙酰基取代.ACAL在四氢呋喃(THF)和水的混合溶剂中能够通过自组装形成纳米级的球形胶束.利用静态光散射测定了胶束形成时的临界含水量,通过动态光散射研究了溶液初始浓度和水的滴加速度对胶束粒径和多分散性的影响,采用透射电镜和原子力显微镜对胶束形貌进行表征.结果表明,碱木质素经乙酰化改性后可用于制备木质素基球形胶束,并且胶束结构具有一定的稳定性,通过改变溶液条件可以在一定范围内调节胶束的粒径大小和多分散性.     

微量热法研究漆酶和3,4,5—三羟基苯甲酸的反应

用ＬＫＢ－２１０７型微量热系统，在不同的温度（ｐＨ＝７．４）的条件下，测定了３，４，５－三羟基苯甲酸与漆酶反应的摩尔反应焓，米氏常数，反应速率常数，漆酶的活性并计算了结合能，活化自由能，活化能和活化熵等。在此基础上，应用过渡态理论，从能量变化的角度，对其催化过程进行了分析，由活化熵（△Ｓ＾≠Ｔ〈０）得出酶－底物过渡态的结构较酶－底物复合物更为有序的结论。     

Pd掺杂Fe催化剂上愈创木酚加氢脱氧理论研究

通过密度泛函理论(DFT)计算研究了愈创木酚在Fe(211)表面上的吸附活化行为和加氢脱氧(HDO)反应性能.讨论了Pd的掺杂和H_2O~*的参与对Fe催化剂活性和选择性的影响.计算结果表明,通过苯环水平吸附在催化剂表面的愈创木酚的稳定性高于仅通过羟基的垂直吸附构型,这有利于苯环, C_(Ar)-OCH_3键和O-CH_3键的活化.在Fe(211)表面上,愈创木酚通过脱甲基再加氢生成邻苯二酚在动力学上比通过脱甲氧基生成苯酚和通过脱羟基生成苯甲醚更有利. Pd掺杂对愈创木酚的吸附稳定性影响较小(0.05 eV),但增加了其加氢脱氧反应的活化能垒,抑制了C_(Ar)-OCH_3, O-CH_3和C_(Ar)-OH键的断裂以及随后加氢生成苯酚,邻苯二酚和苯甲醚的反应过程.在Fe(211)表面上, H_2O~*通过与-CH_3形成氢键作用(H-bonding机理)对反应产生影响,从而降低了愈创木酚脱甲基和脱甲氧基反应的活化能垒.在Fe(211)-1Pd表面上, H_2O~*通过H转移参与反应(H-shuttling机理),促进了愈创木酚向邻苯二酚和苯酚产物的转化,并提高了加氢脱氧反应对苯酚的选择性.     

白藜芦醇清除自由基活性的密度泛函理论研究

采用密度泛函理论(DFT)方法,从静态与动态两大方面分析了白藜芦醇分子酚羟基在不同溶剂中清除自由基活性的能力大小.通过白藜芦醇的结构参数、前线轨道理论、3种抽氢反应机制等方面分析了分子活性位与其性质的关系.探讨了白藜芦醇分子不同位置酚羟基清除·OH和·OOH的抗氧化机理,得到了该分子与·OOH发生抽氢反应时的过渡态结构.计算结果表明,在任何溶剂中白藜芦醇分子C(4')位上酚羟基活性最高,发生抽氢反应时反应热最小,是高活性位点.     

Effect of Lignin Structure Characteristics on the Performance of Lignin Based Phenol Formaldehyde Adhesives

As the second most abundant biopolymer, lignin remains underutilized in various industrial applications. Various forms of lignin generated from different methods affect its physical and chemical properties to a certain extent. To promote the broader commercial utilization of currently available industrial lignins, lignin sulfonate (SL), kraft lignin (KL), and organosolv lignin (OL) are utilized to partially replace phenol in the synthesis of phenol formaldehyde (PF) adhesives. The impact of lignin production process on the effectiveness of lignin-based phenolic (LPF) adhesives is examined based on the structural analysis of the selected industrial lignin. The results show that OL has more phenolic hydroxyl groups, lower molecular weight, and greater number of reactive sites than the other two types of lignins. The maximum replacement rate of phenol by OL reaches 70% w/w, resulting in organosolv lignin phenolic (OLPF) adhesives with a viscosity of 960 mPa·s, a minimal free formaldehyde content of 0.157%, and a shear strength of 1.84 MPa. It exhibits better performance compared with the other two types of lignin-based adhesives and meets the requirements of national standards.     

Structure of Alkali Lignins Fractionated from Ricinus communis and Bagasse. 1. Chemical Constituents

Fractionation of alkali lignins of the soda and sulfate pulping processes of Ricinus communis and bagasse was carried out by using successive equal concentrations of the alkaline reagent. Soda lignins were soluble in organic solvents, while the sulfate ones were sparingly soluble. Thus, two fractions of the sulfate lignins, soluble and insoluble, could be obtained from acetone. The different alkali lignin fractions were subjected to elemental and functional group analyses. For both Ricinus communis and bagasse, the carbon content of the fractions of the various types of lignin is in the order: soluble sulfate > soda > insoluble sulfate, while the methoxy is in the order: soda > soluble sulfate > insoluble sulfate. The phenolic OH content, as well as OH/C₉ of soda lignins of bagasse, are lower than those of soluble sulfate lignins. For Ricinus communis, the phenolic OH content and OH/C₉ is higher for some of the fractions (first three stages of cooking) of soda lignin than the corresponding fractions of kraft (sulfate) lignin, while the reverse takes place for the other fractions. For the same type of lignin, the fractions showed changes in their carbon, methoxyl, and phenolic OH contents. The change may be regular, i.e., increase or decrease with the order of stage of cooking, or irregular. Molecular weights of the different alkali lignins which are soluble in organic solvents ranged between 750 and 840.     

Influence of ozonized kraft lignin on the crystallization of CaCO3

Results are reviewed from a study examining how structural modifications introduced by ozonization enhance the influence of kraft lignin on the crystallization of CaCO(3). Ozone treatment of kraft lignin in an aqueous environment is shown to increase its carboxylic acid and overall oxygen content and reduce its molecular weight. Calcium concentration and temperature were monitored in heated supersaturated solutions containing ozonized kraft lignins to gauge their influence on CaCO(3) crystallization processes. The presence of kraft lignin raises the temperature necessary to induce crystallization. This effect is shown to level off at relatively low lignin concentrations and be dependent on the extent of ozone treatment the kraft lignin has undergone. A linear correlation is found between crystallization temperatures and the carboxylic acid content of ozonized lignin samples indicating the introduction of these functional groups plays an important role in enhancing its inhibitory effect. Scanning electron microscopy images of crystals grown in the presence of kraft lignins show significant morphological modifications. These are consistent with specific or pseudo specific interactions between the lignin and crystal faces of calcite to inhibit growth parallel to its c axis. The influence over crystal morphology demonstrated by modified kraft lignin increases with increasing ozonization. Also presented here are crystallization temperature data for a range of kraft lignin ultrafiltration fractions, which indicate that the optimal (nominal) molecular weight of kraft lignin for inhibiting the crystallization of CaCO(3) lies between 5000 and 10000.     

Strategies for the Removal of Polysaccharides from Biorefinery Lignins: Process Optimization and Techno Economic Evaluation

The utilization of biorefinery lignins as a renewable resource for the production of bio-based chemicals and materials remain a challenge because of the high polysaccharide content of this variety of lignins. This study provides two simple methods; (i) the alkaline hydrolysis-acid precipitation method and (ii) the acid hydrolysis method for the removal of polysaccharides from polymeric biorefinery lignin samples. Both purification strategies are optimized for two different hardwood hydrolysis lignins, HL1 and HL2, containing 15.1% and 10.1% of polysaccharides, respectively. The treated lignins are characterized by polysaccharide content, molecular weight, hydroxyl content, and Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR). Preliminary techno-economic calculations are also carried out for both purification processes to assess the economic potential of these technologies. The results indicate that both protocols could be used for the purification of HL1 and HL2 hydrolysis lignins because of the minimal polysaccharide content obtained in the treated lignins. Nevertheless, from an industrial and economic perspective the acid hydrolysis technology using low acid concentrations and high temperatures is favored over the alkaline hydrolysis-acid precipitation strategy.     

Molecular variability of lignin fractions isolated from wheat straw

Three lignin fractions were isolated from wheat straw internodes and leaves: alkali lignin (LA), milled lignin (LM) and enzyme lignin (LE). Thioacidolysis and alkaline nitrobenzene oxidation were used for the characterisation of the lignin monomeric composition. Esterified and etherifiedp-coumaric and ferulic acids were characterised by alkali hydrolysis and acidolysis, respectively. Lignin fractions from leaves are more condensed than those from internodes. The syringyl/guaiacyl (S/G) ratio is higher in the case of internode lignins. Among the three lignin fractions, LA is the less condensed whereas LM and LE do not present significant structural differences according to their monomeric composition. Finally, the lignin fractions studied differ in their contents and proportions of associated phenolic acids.     

Factors affecting lignin solubility

The solubility of lignin in aqueous NaOH solutions was studied in relation to the lignin molecular weight, temperature, liquid to solid ratio, and ionic strength. A new procedure for determining the content of phenolic hydroxyls in lignin was developed. A formula was suggested for calculating the lignin solubility in aqueous alkali solutions.     

芬顿预处理对木质素快速热解甲氧基脱除规律研究

采用不同H₂O₂含量的芬顿溶液对碱木质素进行预处理，并结合快速热解，探究轻质生物油中含甲氧基化合物含量的变化规律，同时研究了芬顿溶液对木质素结构的影响规律。结果表明，轻质生物油中含甲氧基团的酚类化合物峰面积从AL（未处理碱木质素）的7.3×10⁹下降至13-FML（H₂O₂含量为13 mL/g芬顿溶液预处理碱木质素）的5.2×10⁹，减少了0.29倍。而含甲基团和乙基团的酚类化合物峰面积从AL的3.9×10⁹上升到13-FML的7.2×10⁹，增加了0.85倍。同时，轻质生物油产率从22.4%提高到28.7%。通过FT-IR、¹H NMR和¹³C NMR分析发现，芬顿预处理使木质素凝缩性结构单元减少，甲氧基含量降低，为后续快速热解产生低甲氧基含量的生物油提供了有利条件。     

On the mechanism of the laccase-mediator system in the oxidation of lignin

In an effort to elucidate the role of phenolic and non-phenolic lignin subunits in a laccase mediator (LM) system, vanillyl alcohol was oxidized with laccase in the presence and absence of the mediator 1-hydroxybenzotriazol (HBT). Furthermore, the role of phenolic, aliphatic hydroxyl, and carboxylic acid moieties in lignin degradation was elucidated by selectively blocking them. The modified samples were then subjected to laccase and laccase-HBT treatments. On the basis of this data it was possible to establish the role of this mediator. HBT mediates the oxidation of lignin by inducing side-chain oxidation and oxygen-addition products rather than oxidative coupling reactions.     

磺化木质素系聚合物的结构及其在氧化铝上的吸附特性

以造纸黑液中的碱木质素为主要原料,通过磺化和缩聚反应制备了磺化木质素高分子聚合物SBAL.TEM和1H-NMR测试结果表明SBAL是以木质素的疏水骨架为中心,以磺酸基和羧基组成亲水性侧链的球形结构.GPC测试结果表明其重均分子量达到了24880 Da,是碱木质素的7.38倍,电位滴定测试结果表明,其磺化度达到2.70 mmol.g-1.通过流变曲线、吸附等温线、zeta电位、XPS测试研究了其对氧化铝在水中的分散机理及其吸附特性.掺SBAL的氧化铝浆体,在pH=3～12范围内SBAL对其具有良好的分散降黏作用.溶液pH对SBAL的分子构型和吸附特性有较大的影响,随pH增加,SBAL中磺酸基、羧基和酚羟基逐渐电离,分子的伸展程度逐渐增大.随pH增加,SBAL在氧化铝上的吸附质量减少,吸附层由致密逐渐变得疏松,pH小于等电点时以静电吸附为主,pH大于等电点时以非静电的特性吸附为主.当SBAL的用量小于临界值(0.5 wt%)时,其在氧化铝表面形成单分子层吸附,在颗粒间起到静电排斥作用;当用量大于临界值时,其在颗粒表面形成聚集体吸附而起到空间位阻作用.