酸碱解聚玉米秸秆分子结构的实验研究

以玉米秸秆为研究对象,分别采用5%H2SO4和5%NaOH溶液对秸秆进行解聚处理,并对解聚前后秸秆结构、化学组成、热稳定性等进行分析和表征。结果表明,与未处理前相比,经酸或碱解聚处理后,秸秆纤维结晶度由51.8%分别提高到63.5%和67.0%,秸秆中大部分半纤维素和部分木质素组分被脱除,半纤维素由29.10%分别降至7.02%和6.86%,木质素由38.12%分别降至32.21%和16.52%,而纤维素则由31.54%分别升至60.54%和76.15%。经酸碱处理后,秸秆表面形态结构变得疏松,出现小孔和裂缝,降解温度达到350℃,热稳定性能增加。上述结果说明,稀酸或稀碱均对玉米秸秆分子结构有一定程度的解聚作用,但就解聚溶出木质素而言,稀碱的解聚溶出效果要优于稀酸的。     

催化加氢不同预处理玉米秸秆制取多元醇的研究

以玉米秸秆为研究对象,采用5%硫酸和5%氢氧化钠对其进行预处理,通过对解聚前后玉米秸秆官能团表征和成分分析,发现酸、碱处理后秸秆中大部分半纤维素和木质素被脱除,其中先碱后酸、先酸后碱处理后秸秆的木质素含量由28.04%分别下降至11.54%和12.14%,而纤维素相对含量由42.02%分别增加到75.12%和77.68%。通过浸渍法制备的非贵金属5%Ni-15%W/MCM-41催化剂用于催化转化预处理秸秆制取多元醇,结果表明:与未经处理的玉米秸秆多元醇得率21.00%相比,先碱后酸、先酸后碱处理的玉米秸秆催化转化多元醇得率分别达到60.72%和61.40%。α-葡萄糖和β-葡萄糖的加氢结果显示乙二醇(EG)和1,2-丙二醇(1,2-PG)得率均相近,说明葡萄糖的旋光构型对催化加氢没有影响。与C6糖加氢产物分布比较,C5糖的产物中除了有EG和1,2-PG,同时还有丙三醇的生成,提出了糖加氢制取多元醇的可能机理。     

不同方法预处理的玉米秸秆结构与酶解分析

在利用秸秆进行工业转化时,因为秸秆结构复杂,导致转化效率低,所以需对秸秆进行预处理,破坏秸秆复杂结构,提高转化效率。采用扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)和X射线衍射技术分析不同预处理方式对玉米秸秆微观结构的影响,并利用纤维素酶对不同预处理秸秆进行酶解,评价预处理效果。扫描电镜结果表明,不同预处理方式对秸秆表面形态和秸秆整体结构造成不同程度的破坏,其中NaOH预处理后的秸秆表面结构坍塌明显,表明木质纤维素结构被有效打破。利用傅里叶变换红外光谱对不同预处理方式的秸秆进行分析,其中1600和1510cm~(-1)为木质素的特征峰,NaOH预处理后的秸秆在此处的特征峰基本消失,表明NaOH预处理对秸秆木质素的去除效率比较明显。1744~1734 cm~(-1)为C=O伸缩振动特征峰,此峰的强度与木质素和半纤维素的含量有关,采用不同方法预处理后,此峰的吸收强度不同程度地减少,表明各种预处理方法不同程度地去除了秸秆的木质素和半纤维素。X-射线衍射分析表明,不同预处理后秸秆的结晶度均发生不同程度的改变,其中H_2SO_4预处理后秸秆的结晶度提高最大,达到43.4%。其中NaOH预处理秸秆后,用纤维素酶酶解60h,使其酶解产糖量达到33.32g/L。本研究分析了不同秸秆预处理方法的效果,为利用玉米秸秆生产生物化工产品提供了理论依据。     

亚麻的化学组成和微观结构对染色性能的影响

本文通过X衍射法、纤维化学成分分析法测试了亚麻纤维的微观结构、化学成分，通过对亚麻进行液氨整理改变其结晶度和取向度，从而测得亚麻的结晶度和取向度对染色性能的影响，利用碱煮、H2O2和NaOCl漂白处理降低了亚麻中木质素和半纤维素的含量，从而测量得木质素和半纤维素含量对亚麻上染率的影响。结果表明亚麻的上染率随着结晶度的降低呈线性上升，随着取向度的降低而上升；随着木质素和半纤维素含量的降低而呈上升趋势。     

超高效聚合物凝胶色谱法快速研究酸催化木质素解聚产物

该文以温和酸催化条件下的木质素磺酸盐解聚产物为研究对象，建立系统分离和分析测试木质素磺酸盐解聚后获得的低分子酚类产物的方法。选用4根油溶性的ACQUITY APC XT小孔径刚性填料色谱柱串联，在高分辨紫外检测器条件下，采用超高效凝胶渗透色谱（APC）对解聚产物实现了高效分离，获得了高灵敏度的木质素基酚类产物的相对分子质量及其分布色谱信息。探讨了反应温度、时间和催化剂浓度等对酸催化木质素磺酸盐解聚行为的影响，结果表明，对于木酚比（木质素：苯酚）为25%（质量分数）的木质素磺酸盐解聚体系，在催化剂和木质素物质的量比为2.334、130℃酸催化反应60 min时，获得了解聚效率高达80%以上的木质素基酚类产物，解聚获得的产物相对峰高分子质量（M_p）组成均分布在720、490和260 Da 3个低聚物区间，均具有很窄的分子质量分布指数（接近1）。由此可以初步推断，木质素磺酸盐在该研究采用的温和酸催化条件下，催化反应机理不受反应时间、温度以及催化剂浓度的影响，具有特定的解聚途径。     

NREL法测定木质纤维素原料组分的含量

对美国国家可再生能源实验室(NREL)方法定量木质纤维素原料中纤维素、半纤维素及木质素的实验条件进行了研究。72%浓硫酸水解1h、4%稀硫酸水解45min可将玉米秸秆中的纤维素、半纤维素降解为可用HPLC定量的单糖,适宜的样品添加量为0.5g。同时,将NREL法与国标法进行了比对,两种方法的测定结果基本一致。NREL法测定玉米秸秆中纤维素、半纤维素及木质素的含量分别为33.90%、23.89%和15.84%。     

木质素氧化还原解聚研究现状

木质素是自然界中含量巨大的天然酚类聚合物,其总量仅次于纤维素。由于其结构复杂性,仅有不到2%的木质素用于工业生产,因此实现木质素的高效综合利用是目前该领域的难题,而木质素的氧化还原转化为芳香化合物是目前一个重要且有前景的手段:木质素氧化解聚能显著降低其主要化学键键能,促进木质素转化为香草醛、紫丁香醛和高香草醛等高度官能化的单体;而木质素还原解聚可将其结构中含氧官能团脱除,转化为低氧/无氧木质素生物油,可作为高热值生物燃油,且在反应中能显著抑制缩合反应的进行。本文简要介绍了木质素的结构单元以及联接方式,同时从反应条件和催化剂等方面全面综述了国内外木质素氧化还原解聚的最新研究进展,并对其反应机理进行了详细探讨。在此基础上,针对当前木质素解聚过程中的难题提出了未来该领域的研究重点和方向。     

麦秸酸解聚产物的形成机制研究

以麦秸为研究对象,硫酸为解聚剂,对解聚前后固体残渣的结构特性以及液体产物的种类进行分析。结果表明:与未处理麦秸相比,解聚后麦秸内部结构在一定程度上被破坏,大部分半纤维素被有效的脱除,但纤维素结晶度仍较高;解聚后的产物种类有较大差异,主要受反应时间、温度和酸浓度等因素的影响,但主要产物有葡萄糖、木糖、阿拉伯糖、乙酸、糠醛和5-羟甲基糠醛。并进一步探索H+与半纤维素、纤维素以及木质素相关结构官能团的作用机制,提出了酸解聚麦秸产物的形成过程。     

微波辐射下秸秆纤维微观结构的变化

利用原子力显微镜(AFM)对微波处理前后秸秆纤维表面的变化进行了研究,并结合XRD和FTIR研究了处理前后其化学结构及结晶形态的变化情况。结果表明,未经微波处理的秸秆纤维表面比较光滑,平均粗糙度(Ra)为(86.7±6.335)nm,均方根粗糙度(Rq)为(141.1±9.055)nm;经微波处理的秸秆纤维表面比较粗糙,并出现许多细小孔洞,其Ra为(445.0±28.14)nm,Rq为(558.9±33.458)nm,微波辐射处理前后秸秆纤维的表面形态差异较大。经微波辐射处理后,秸秆纤维在2θ=22.3°处的衍射峰移至21.8°,且峰宽稍有增加,在38.1°、44.3°、64.6°、78.9°处出现的4个衍射峰,除强度稍有增强,其峰形和位置与未经处理秸秆纤维的衍射峰基本一致,表明微波处理没有改变纤维的结晶形态。FTIR光谱表明,微波处理样中未产生新的官能团,但分子间氢键及分子内氢键发生变化。微波作用未引起秸秆纤维化学结构的变化。     

氧化锌催化木质素选择性解聚制备对香豆酸甲酯

木质素是自然界中含量最丰富的芳香族可再生碳资源,具有极高的利用价值。针对当前木质素解聚技术存在反应条件苛刻、产物选择性低等难题,构建了一种廉价的金属氧化物催化剂体系,研究了草本木质素选择性解聚制备对香豆酸甲酯的性能。考察了不同金属氧化物、反应温度、反应时间以及溶剂等因素对于对香豆酸酯收率和选择性的影响。研究结果表明,金属氧化物ZnO对于草本木质素选择性解聚制备对香豆酸甲酯的过程具有最佳的催化活性。在优化的反应条件下,可获得9.8%的对香豆酸甲酯收率和61.6%的选择性;通过对木质素解聚产物的分析并结合反应前后木质素的傅里叶红外光谱（FT-IR）和二维核磁（2D HSQC NMR）表征结果发现,木质素分子中H结构单元的选择性断裂是其催化解聚过程中对香豆酸甲酯收率和选择性高的主要原因。     

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.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

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.