生物质半纤维素稀酸水解反应*

半纤维素是木质纤维素类生物质中第二大组分,半纤维素的高效、低成本转化是实现木质纤维素类生物质转化工艺实用化的一个技术关键。稀酸水解技术被广泛应用于水解生物质半纤维素,其对半纤维素糖的转化率高,得到的糖可进一步发酵生产燃料乙醇等。半纤维素还可直接水解制低聚糖等功能性食品和糠醛等化工产品。本文综述了半纤维素稀酸水解反应的研究进展。介绍了半纤维素的基本结构特征,解析了稀酸催化半纤维素水解的反应机理及反应网络,评述了半纤维素水解过程中反应条件等对目标产物的影响,并总结了半纤维素稀酸水解动力学模型。在此基础上,对今后半纤维素稀酸水解反应的研究方向与水解产物的利用进行了展望。     

木质纤维素酶解糖化*

纤维素水解转化为可发酵糖工艺是纤维素乙醇炼制过程中至关重要的环节。酶法水解工艺具有条件温和、副产物少、环境友好等特点,因而受到广泛重视。目前许多学者已针对如何提高木质纤维素酶解效率、降低纤维素酶成本等问题,开展了多种化学、生物技术及工艺耦合的研究。本文综述了近几年木质纤维素酶解领域取得的最新工艺进展和理论研究成果,对原料预处理、多酶复配优化、酶脱附与重复利用、工艺耦合、高固液比反应等方面的研究情况进行了总结,同时展望了木质纤维素酶解工艺的未来发展方向。     

木质纤维素的预处理及其酶解

从木质纤维素制取燃料乙醇,主要包括原料预处理、酶水解糖化及酒精发酵三个部分.通过前二步获得较高还原糖总量是提高乙醇得率的关键.预处理技术及工艺直接影响酶解效果,而酶水解是一个涉及多因素变化的复杂异相动力学过程.本文主要针对这两部分的国内外研究现状作一论述,并提出该领域目前所面临的问题及发展前景.     

纤维素直接催化转化制乙二醇及其他化学品:从基础研究发现到潜在工业应用(英)

纤维素直接催化转化制乙二醇是一条极具吸引力的生物质转化途径,有助于减轻化石能源资源的消耗。综述了从该反应途径的发现到获得高效、高稳定性催化剂的快速发展过程。基于对钨基催化剂的大量研究结果,本文讨论了反应机制,明确了反应路径、催化剂状态、钨物种及加氢催化活性中心各自在串联反应中的作用。围绕该反应过程的工业化应用需要,讨论了有关原生木质纤维素生物质催化转化以及高效反应过程的发展策略。在此基础上,将纤维素催化转化制乙二醇过程与生物质发酵制丙酮-丁醇-乙醇的生物炼制路线进行整合,构建出一个理想的反应过程潜在应用范例。最后,对纤维素催化转化制乙二醇反应过程进行了总结和前景展望.     

非离子型表面活性剂对木质纤维素酶催化水解的影响及机理

木质纤维素的酶解糖化过程是纤维素生物质转化中的关键步骤,也是限制纤维素生物转化生产燃料和化学品的主要瓶颈。大量的研究表明,非离子型表面活性剂能够强化木质纤维素酶解过程,显著提高纤维素的酶催化水解效率。本文综述了非离子型表面活性剂对纯纤维素和木质纤维素底物酶解的影响,分析了底物结构特性、水解条件、纤维素酶组成等诸多因素与表面活性剂作用效果之间的关联,并从纤维素酶的吸附特性、纤维素酶组分间的协同作用等方面对非离子表面活性剂的作用机理进行了总结。结合已有的研究进展和存在的问题,提出了今后表面活性剂对于木质纤维素酶催化水解影响的研究重点方向,即系统分析底物结构、水解条件等因素对表面活性剂作用的宏观影响,以及分析这种作用的热力学和动力学特性,而微观上需要从原子和分子层面上解析表面活性剂与底物和纤维素酶之间的相互作用特性。     

基于木质生物质分级利用的组分优先分离策略

木质生物质是地球上最丰富的一类生物质资源,主要由碳水化合物高分子(纤维素、半纤维素)和芳族聚合物(木质素)组成。木质纤维组分的清洁高效分离,是实现多元化、高值化生物精炼的重要基础。本文首先讨论了基于分级利用的组分分离技术与基于制备纤维素乙醇的预处理技术的不同之处;其次,梳理归纳了五种木质纤维组分优先分级分离策略:纤维素优先分离,木质素优先分离,半纤维素优先分离,木质素和半纤维素优先分离以及纤维素和半纤维素优先分离;再次,基于半纤维素优先分离策略,对国内相关的产业化应用进行了评述;最后,对木质生物质组分分离技术的当下定位和发展前景进行了总结与展望,以期对木质生物质的三大组分有较全面的价值观念和利用思路,并对木质生物质精炼技术的发展提供借鉴与参考。     

纤维素在新型绿色溶剂离子液体中的溶解及其应用*

近年来,离子液体作为一种极具应用前景的绿色溶剂受到越来越多的关注。纤维素是自然界中含量最丰富的可再生资源,必将成为未来最重要的工业原料之一。离子液体在纤维素化学领域的应用遵循了绿色化学中开发环境友好溶剂和利用生物可再生资源为原料这两个基本原则,大大拓展了纤维素的工业应用前景,为纤维素资源的绿色应用提供了一个崭新的平台。本文对纤维素在离子液体中溶解的研究进展及其在制备再生纤维素材料、纤维素衍生物及生物乙醇等方面的应用进行了综述。纤维素大分子的降解机理及其控制途径、纤维素晶态结构变化规律及其调控途径、纤维素与固体反应试剂的均相衍生化体系的建立及提高衍生化效率的途径等基础问题仍需要进一步深入研究。     

左旋葡聚糖的制备与在生物技术领域的应用

左旋葡聚糖(LGA)作为一种极具潜力的新糖源,既可以加酸水解为葡萄糖后间接用于微生物发酵,也可以被真菌或细菌甚至构造的基因工程菌直接代谢,目前已经在发酵上展现出良好的应用前景。此外,LGA还可作为碳源,生产生物乙醇、丁二酸等。目前制备LGA普遍采用生物质热解法,该方法存在能耗高、产率低、产物难以提取等缺点,应努力发展在溶剂体系中分解纤维素制备LGA的方法以提高产率。今后的研究应致力于开发微生物代谢LGA的新过程、新方法、新菌种,为LGA的高效利用提供坚实基础。     

低共熔溶剂在高分子合成中的应用

低共熔溶剂(DES)是由两种或多种物质按一定比例混合而成的低熔点混合溶剂,其熔点显著低于每一个单纯组分的熔点,可被视为一种新的离子液体。与传统有机溶剂相比,DES具有来源广泛、成本低廉、易于制备、毒性低、生物可降解等优点,并已作为一种新型的绿色反应介质被广泛用于萃取分离、无机合成、有机合成和离子凝胶等领域。近年来,DES在高分子合成中的应用也吸引了广泛的研究兴趣。本综述从简述DES及其在有机合成中的应用出发,重点介绍它们用于缩合聚合、自由基聚合、阴离子聚合、电化学聚合、开环聚合和氧化聚合等高分子合成领域的研究进展,并对其发展趋势进行展望。     

甜高粱茎秆生产燃料乙醇

本文对甜高粱茎秆原料的贮藏、汁液液态发酵、茎秆直接粉碎固态发酵以及榨汁后剩余的秆渣预处理同步糖化发酵4个方面的研究情况进行了综述,重点论述了甜高粱茎秆生产燃料乙醇的瓶颈问题即原料的贮藏和秆渣木质纤维素预处理技术。提出了一种更经济合理的甜高粱茎秆生产燃料乙醇工艺流程。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.