疏水离子液体中生物不对称还原制备手性醇

针对近平滑假丝酵母全细胞不对称还原2-羟基苯乙酮制备光学纯(R)-苯基乙二醇反应中底物的质量浓度、产量及质量平衡低的问题,运用多相萃取生物转化的原理,比较不同非水介质对不对称还原反应效率的影响,构建具有良好生物相容性和高质量平衡的水/疏水离子液体1-丁基-3-乙基咪唑六氟磷酸盐([BEIM]PF6)双相反应体系。考察该体系下辅助底物种类、辅助底物用量、底物质量浓度、催化剂用量、离子液体比例、p H和反应温度对生物催化反应的影响,通过正交试验设计和响应面法优化不对称还原2-羟基苯乙酮的反应条件,在最优反应条件下,产物质量浓度、产率和质量平衡得率分别达到15.35 g/L、76.8%和84.3%,产物的对映消旋值(e.e.值)大于99.9%。     

大叶桉叶水浸提液成分分析

为进一步明确大叶桉的化学成分,对大叶桉叶水浸提液分别用不同极性的有机溶剂石油醚、乙酸乙酯和正丁醇进行萃取,对各萃取相进行GC-MS分析。结果表明:大叶桉叶水浸提液共含有37种化合物,其中,石油醚萃取相中含有20种,主成分为草酸丁基异己酯(37.24%);乙酸乙酯萃取相中含有16种,主成分为2,2-二亚甲基双[6-(1,1-二甲基乙基-4-甲基)]-苯酚(50.05%);正丁醇萃取相中含有5种,主成分为丙基-2-甲基丁酸酯(54.57%)。在所有成分中,酯类物质居多,也有少量的烯、酮、醇、苯和烷烃。1-甲基,4-(1-甲基乙基)-1,4环己二烯、2,2-二亚甲基[6-(1,1-二甲基乙基)-4-甲基]苯酚、1-十八烯和二十烷为石油醚和乙酸乙酯的共有成分;1、2-苯二甲酸单(2-乙基己基)酯为乙酸乙酯和正丁醇的共有成分。该研究进一步明确了大叶桉的化学成分,为其在医药、化工和化感方面的应用研究奠定了基础。     

生物质原料预处理、组分分离到结构选择性拆分——生物质原料工程学的发展

在石化资源日益匮乏的严峻形势下,生物质将成为未来新一代生物及化工产业的最理想的替代原料.因此,如何使生物质资源成为生物基能源、生物基化学品和生物基材料的通用原料,成为目前世界各国共同关注的焦点和热点.从生物炼制及生物质科学与工程的发展可以看出,原料预处理是实现生物质高效转化的必要手段,而组分分离-定向转化是原料预处理的进一步提升,它可以实现纤维素、半纤维素和木质素的分别转化,但是仍然存在着原子利用率不高、能耗高、工艺路线复杂等问题.鉴于生物质是一个功能大分子体,要使其成为通用原料,应该根据原料结构特点和产物要求,发展结构化功能高值拆分的转化过程,即原料的选择性结构拆分思路.从原料预处理到组分分离,再到选择性结构拆分,实现了原料工程学的发展与逐步成熟,其最终目的是要真正建立以生物质为通用原料的新型工业技术体系和研究平台.     

生物质生物预处理研究进展与展望

木质纤维素生物质分布广、产量大、可再生,用于制备生物基能源、生物基材料和生物基化学品。木质纤维素生物质组成复杂,包含纤维素、半纤维素和木质素等,木质素与半纤维素通过共价键、氢键交联形成独特的“包裹结构”,纤维素含有复杂的分子内与分子间氢键,上述因素制约着其资源化利用。生物预处理以其独特优越性成为生物质研究的重要方面。系统阐述了生物预处理过程中木质素降解和基团修饰对纤维素酶解的影响,纤维素含量及结晶区变化,半纤维素五碳糖利用,微观物理结构的改变。进一步提出了以生物预处理为核心的组合预处理、基于不同功能的多酶协同催化体系、木质纤维素组分分级利用和新型高效细菌预处理工艺是生物预处理未来发展的重要趋势。     

红火蚁告警信息素的GC-EAD分析

[背景]2-乙基-3,6-二甲基吡嗪是红火蚁告警信息素的主要成分,本研究旨在分离、鉴定红火蚁工蚁浸提液中告警信息素成分,分析红火蚁工蚁对告警信息素合成样品混合物的电生理反应。[方法]200 g红火蚁工蚁的正己烷浸提液过硅胶柱,正己烷—丙酮体系洗脱,气相色谱（GC）和气相色谱—质谱联用（GC-MS）分析检测浸提液中含告警信息素的流分,气相色谱—触角电位联用仪（GC-EAD）分析红火蚁工蚁对2-乙基-3,5（6）-二甲基吡嗪混合物的电生理活性。[结果]红火蚁工蚁正己烷浸提液硅胶柱层析分离能够得到含2-乙基-3,6-二甲基吡嗪的流分,GC-MS分析的保留时间在11.45 min。经过GC-EAD分析,发现红火蚁工蚁对2-乙基-3,5（6）-二甲基吡嗪混合物有显著的电生理反应。[结论与意义]红火蚁工蚁对2-乙基-3,6-二甲基吡嗪的电生理反应比2-乙基-3,5-二甲基吡嗪高。     

含离子液体体系中固定化细胞转化甘草酸生成单葡萄糖醛酸基甘草次酸

研究疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6)与醋酸-醋酸钠缓冲液两相体系中,固定化产紫青霉Penicillium purpurogenum Li-3细胞转化甘草酸(GL)生成单葡萄糖醛酸基甘草次酸(GAMG)的反应,并与缓冲液单相体系作为对照.确定了在[BMIM]PF6/缓冲液两相体系中,最适离子液体加入比例、缓冲液pH、反应温度、底物浓度分别为10%、5.8、35℃和6.0mmol/L,在此条件下反应58h,甘草酸转化率为87.03%,比缓冲液单相体系提高了15.02%.离子液体循环使用8次后,回收利用率维持在85.28%.主产物GAMG和副产物甘草次酸(GA)在两相体系中得到有效分离,为后续产物分离带来便利.     

离子液体介导玉米秸秆制备5-羟甲基糠醛

以玉米秸秆为原料,采用离子液体([BMIM]Cl)与二甲基亚砜(DMSO)为溶剂,氯化铬和浓硫酸为催化剂制备5-羟甲基糠醛(5-HMF)。通过考察反应时间、温度、催化剂加入量和固液比等条件,以获得制备5-HMF的最优反应条件,反应产物由高效液相色谱分析。结果表明:酸解后的秸秆,在150℃、固液比为3.8%、m([BMIM]Cl)/m(DMSO)=1、硫酸和氯化铬的质量分数分别6.7%和13.3%(相对于秸秆)的条件下反应80 min时,5-HMF产率较高,为53.3%。     

白星花金龟聚集信息素的分离鉴定及引诱效果

[目的]明确白星花金龟Protaetia brevitarsis Lewis聚集信息素的有效成分,为白星花金龟的绿色防控提供支持.[方法]通过动态顶空法收集白星花金龟雌虫、雄虫和雌雄虫混合挥发物,用气相色谱-质谱(Gas chromatography-mass spectrometry,GC-MS)联用技术对收集的挥发物进行分析鉴定,并利用触角电位(Electroantennogram,EAG)仪和Y型嗅觉仪测定白星花金龟对8种化合物的触角电位和行为选择反应.[结果]白星花金龟雌虫、雄虫和雌雄虫混合挥发物中皆鉴定出8类15种化合物,包括6种烷烃类、2种酚类、2种芳香烃类、1种烯类、1种吡啶类、1种胺类、1种醇类和1种酮类.EAG试验结果表明,白星花金龟对8种化合物都有EAG反应,且不同挥发物间、同种挥发物不同浓度间的EAG反应存在差异.白星花金龟对蒎烷胺、3,4-二甲基-6-乙基苯酚、2,3-二甲基苯乙酮和2,6,10,14-四甲基十七烷4种挥发物的EAG反应相对值在1μg/μtL时达到最大,对萘、苯并噻唑、百里酚和正十四烷4种挥发物的EAG反应相对值在10 μtg/μtL时达到最大.行为选择反应表明,白星花金龟雌成虫、雄成虫对2,3-二甲基苯乙酮有明显趋向性,选择反应率大于70％,对2,6,10,14-四甲基十七烷、萘、苯并噻唑、百里酚和正十四烷5种物质均表现出显著或极显著的驱避效果,对3,4-二甲基-6-乙基苯酚和蒎烷胺表现出了性别上的差异,雄虫对3,4-二甲基-6-乙基苯酚表现出显著的趋向性,对蒎烷胺表现出显著的驱避性,而雌虫对这2种挥发物却无明显反应.[结论]2,3-二甲基苯乙酮对白星花金龟雌成虫、雄成虫有明显的引诱效果,2,6,10,14-四甲基十七烷、萘、苯并噻唑、正十四烷和百里酚有较强的驱避作用,推测2,3-二甲基苯乙酮是白星花金龟聚集信息素的有效组分.     

酸性功能性离子液体催化合成二甘醇二苯甲酸酯

选用6种酸性功能化离子液体作为催化剂,催化苯甲酸和二甘醇酯化合成增塑剂二甘醇二苯甲酸酯(DEDB),通过实验考察反应温度、时间、催化剂种类及用量、原料投料比等工艺因素对合成收率的影响,确定了最佳反应条件:优选1-丁基磺酸-3-甲基咪唑对甲基苯磺酸盐([(CH_2)_4SO_3HMIm]TS)为催化剂,反应温度160℃,时间4.0 h,苯甲酸与二甘醇的摩尔比为2.2∶1,催化剂用量为二甘醇质量的10%,最终发现DEDB产率可达99.1%,且产品具有较高的品质。产物可以通过简单倾倒与离子液体催化剂分离,离子液体具有优异的重复使用性,使用10次后DEDB的产率仍有95.2%。     

α-O-4型木质素二聚体模型物热解解聚机理

为了解木质素α-O-4连接部分的热解机理,以4-(3-羟基-1-苯氧基丙基)-苯酚为α-O-4型木质素二聚体模型化合物,采用密度泛函理论M06-2X/6-31+G(d,p)方法,对该二聚体热解过程中的反应物、中间产物、过渡态、产物进行几何结构的完全优化,通过计算各可能路径的反应能垒,确定了该模型化合物主要通过Cα-O键的均裂和协同断裂的方式发生裂解反应,主要生成苯酚、4-甲基苯酚、4-乙烯基苯酚和香豆醇等酚类产物以及乙醇、甲醇、甲醛等小分子物质,由此首次从理论上揭示了该模型化合物的详细热解解聚过程。     

Thermal decomposition kinetics of wheat straw treated by Phanerochaete chrysosporium

Combining biological pretreatment with thermal processing may offer an alternative strategy for efficient conversion of lignocellulosic biomass into fuels and chemicals. The thermal decomposition kinetics of biologically pretreated wheat straw by Phanerochaete chrysosporium was investigated in this study using thermogravimetry (TG) - deconvoluted thermogravimetry (DTG) techniques and the Friedman method. This study revealed that biological pretreatment reduced the thermal degradation temperature of the biomass significantly. Relying on the thermal behavior of the biologically pretreated wheat straw, we proposed two biomass degradation phases during the biological degradation of wheat straw. The first phase of biodegradation (within 10 days of biological pretreatment) improved the efficiency of pyrolysis by reducing the temperature demand. In the second phase (after 10 days), although the efficiency of pyrolysis displayed the similar trend as the first phase, it showed a significant increase in activation energy demand. This process is greatly influenced by the residual lignin and cellulose ratios in the biomass. These experimental results will be useful in developing a biological pretreatment based thermochemical conversion process for lignocellulosic biomass.     

木质纤维素预处理及高值化技术研究进展

木质纤维素生物质是地球上最丰富的可再生生物资源.随着化石能源的消耗及环境的污染,以取代石化燃料为目标的由生物质向生物燃料的转化受到了广泛的关注.木质纤维素有很强的天然抗降解屏障,需先通过物理、化学及微生物等手段进行预处理,进而以更低的成本和更高的效率转化为生物燃料及其他高附加值产品.本文在总结酸碱等传统预处理方法优缺点...     

Impact of Dilute Sulfuric Acid,Ammonium Hydroxide,and Ionic Liquid Pretreatments on the Fractionation and Characterization of Engineered Switchgrass

Improving plant characteristics for better environmental resilience and more cost-effective transformation to fuels and chemicals is one of the focus areas in biomass feedstock development. In order to bridge lignin engineering and conversion technologies, this study aimed to fractionate and characterize lignin streams from wild-type and engineered switchgrass using three different pretreatment methods, i.e., dilute sulfuric acid (DA), ammonium hydroxide (AH), and aqueous ionic liquid (IL). Results demonstrate the low lignin content and high S/G ratio switchgrass mutant (4CL) was more susceptible to pretreatment and subsequently more digestible by enzymes as compared to wild-type switchgrass and AtLOV1 mutant. In addition, when compared to DA and AH pretreatment, aqueous IL (cholinium lysinate) was demostrated to be an efficient lignin solvent, as indicated by the high (> 80%) lignin solubility and reduced lignin molecular weight. FTIR and differential scanning calorimetry measurements suggest that pretreatment chemistry greatly influenced the structural and compositional changes and thermal properties of the pretreated switchgrass and recovered lignin-rich streams. The comparative data obtained from this work deepen our understanding of how lignin modification impacts the fractionation and properties of biomass feedstocks.     

Pretreatment of Populus tomentosa with Trametes velutina supplemented with inorganic salts enhances enzymatic hydrolysis for ethanol production

Different nutrients were added into the solid fermentation of woody biomass, Populus tomentosa, to improve pretreatment by a white rot fungus, Trametes velutina. Fungal pretreatment supplemented with trace elements resulted in large amount of lignin loss but low degradation of carbohydrate. Only 12.6?% of Klason lignin was left in the residues pretreated by T. velutina for 8?weeks supplemented with 1?% trace elements (TE group). When fungal-pretreated residues were subjected to enzymatic hydrolysis for 96?h, a maximum reducing sugar yield of 44?% was obtained from the TE group at the 8th week, 2.3 times higher than that of untreated samples. In addition, the highest ethanol yield of 22?% was observed by the fermentation of 8-week pretreated residues from the basic medium plus trace element group, which was five times more than that of untreated samples.     

Improved Sugar Conversion and Ethanol Yield for Forage Sorghum (Sorghum bicolor L. Moench) Lines with Reduced Lignin Contents

Lignin is known to impede conversion of lignocellulose into ethanol. In this study, forage sorghum plants carrying brown midrib (bmr) mutations, which reduce lignin contents, were evaluated as bioenergy feedstocks. The near-isogenic lines evaluated were: wild type, bmr-6, bmr-12, and bmr-6 bmr-12 double mutant. The bmr-6 and bmr-12 mutations were equally efficient at reducing lignin contents (by 13% and 15%, respectively), and the effects were additive (27%) for the double mutant. Reducing lignin content was highly beneficial for improving biomass conversion yields. Sorghum biomass samples were pretreated with dilute acid and recovered solids washed and hydrolyzed with cellulase to liberate glucose. Glucose yields for the sorghum biomass were improved by 27%, 23%, and 34% for bmr-6, bmr-12, and the double mutant, respectively, compared to wild type. Sorghum biomass was also pretreated with dilute acid followed by co-treatment with cellulases and Saccharomyces cerevisiae for simultaneous saccharification and fermentation (SSF) into ethanol. Conversion of cellulose to ethanol for dilute-acid pretreated sorghum biomass was improved by 22%, 21%, and 43% for bmr-6, bmr-12, and the double mutant compared to wild type, respectively. Electron microscopy of dilute-acid treated samples showed an increased number of lignin globules in double-mutant tissues as compared to the wild-type, suggesting the lignin had become more pliable. The mutations were also effective for improving ethanol yields when the (degrained) sorghum was pretreated with dilute alkali instead of dilute acid. Following pretreatment with dilute ammonium hydroxide and SSF, ethanol conversion yields were 116 and 130 mg ethanol/g dry biomass for the double-mutant samples and 98 and 113 mg/g for the wild-type samples.     

The pretreatment of corn stover with Gloeophyllum trabeum KU-41 for enzymatic hydrolysis

Background

Pretreatment is an essential step in the enzymatic hydrolysis of biomass for bio-ethanol production. The dominant concern in this step is how to decrease the high cost of pretreatment while achieving a high sugar yield. Fungal pretreatment of biomass was previously reported to be effective, with the advantage of having a low energy requirement and requiring no application of additional chemicals. In this work, Gloeophyllum trabeum KU-41 was chosen for corn stover pretreatment through screening with 40 strains of wood-rot fungi. The objective of the current work is to find out which characteristics of corn stover pretreated with G. trabeum KU-41 determine the pretreatment method to be successful and worthwhile to apply. This will be done by determining the lignin content, structural carbohydrate, cellulose crystallinity, initial adsorption capacity of cellulase and specific surface area of pretreated corn stover.

Results

The content of xylan in pretreated corn stover was decreased by 43% in comparison to the untreated corn stover. The initial cellulase adsorption capacity and the specific surface area of corn stover pretreated with G. trabeum were increased by 7.0- and 2.5-fold, respectively. Also there was little increase in the cellulose crystallinity of pretreated corn stover.

Conclusion

G. trabeum has an efficient degradation system, and the results indicated that the conversion of cellulose to glucose increases as the accessibility of cellulose increases due to the partial removal of xylan and the structure breakage of the cell wall. This pretreatment method can be further explored as an alternative to the thermochemical pretreatment method.     

Routes to Potential Bioproducts from Lignocellulosic Biomass Lignin and Hemicelluloses

An essential feature of proposed fermentation-based lignocellulose to biofuel conversion processes will be the co-production of higher value chemicals from lignin and hemicellulose components. Over the years, many routes for chemical conversion of lignin and hemicelluloses have been developed by the pulp and paper industry and we propose that some of these can be applied for bioproducts manufacturing. For lignin products, thermochemical, chemical pulping, and bleaching methods for production of polymeric and monomeric chemicals are reviewed. We conclude that peroxyacid chemistry for phenol and ring-opened products looks most interesting. For hemicellulose products, preextraction of hemicelluloses from woody biomass is important and influences the mixture of solubilized material obtained. Furfural, xylitol, acetic acid, and lactic acid are possible targets for commercialization, and the latter can be further converted to acrylic acid. Pre-extraction of hemicelluloses can be integrated into most biomass-to-biofuel conversion processes.     

Short time ionic liquids pretreatment on lignocellulosic biomass to enhance enzymatic saccharification

The potential of 1-buthyl-3-methylpyridinium chloride, [Bmpy][Cl], as a pretreatment solvent for lignocellulosic biomasses, Bagasse and Eucalyptus, was investigated. The yields of regenerated biomasses ranged between 35% and 96%, and varied according to the pretreatment time, type of ionic liquid (IL) and biomass. The pretreatment of the biomass with [Bmpy][Cl] resulted in up to 8-fold increase in the cellulose conversion when compared with the untreated biomass. For a short pretreatment period (i.e., 10 min), [Bmpy][Cl] showed better performance than 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) with respect to the initial enzymatic saccharification rates. The increase in the reaction rates with [Emim][OAc] treatment was because of a reduction in the cellulose crystallinity. In contrast, a decrease in the crystallinity index was not clearly observed for the biomass pretreated with [Bmpy][Cl], and the enhancement of the enzymatic saccharification rates using this IL is presumably due to a reduction in the degree of polymerization of cellulose in the biomass.     

Lignin Structural Alterations in Thermochemical Pretreatments with Limited Delignification

Lignocellulosic biomass has a complex and rigid cell wall structure that makes biomass recalcitrant to biological and chemical degradation. Among the three major structural biopolymers (i.e., cellulose, hemicellulose, and lignin) in plant cell walls, lignin is considered the most recalcitrant component and generally plays a negative role in the biochemical conversion of biomass to biofuels. The conversion of biomass to biofuels through a biochemical platform usually requires a pretreatment stage to reduce the recalcitrance. Pretreatment renders compositional and structural changes of biomass with these changes ultimately governing the efficiency of the subsequent enzymatic hydrolysis. Dilute acid, hot water, steam explosion, and ammonia fiber expansion pretreatments are among the leading thermochemical pretreatments with a limited delignification that can reduce biomass recalcitrance. Practical applications of these pretreatment are rapidly developing as illustrated by recent commercial scale cellulosic ethanol plants. While these thermochemical pretreatments generally lead to only a limited delignification and no significant change of lignin content in the pretreated biomass, the lignin transformations that occur during these pretreatments and the roles they play in recalcitrance reduction are important research aspects. This review highlights recent advances in our understanding of lignin alterations during these limited delignification thermochemical pretreatments, with emphasis on lignin chemical structures, molecular weights, and redistributions in the pretreated biomass.