生物法制备2,3-丁二醇的最新进展

2,3-丁二醇及其衍生物作为重要的液体燃料和化工原料,具有广阔的工业应用前景。高效、经济的2,3-丁二醇生物制备方法,对我国低碳经济和循环经济的建设具有重要的促进作用。针对近三年间生物法制备2,3-丁二醇领域的最新研究成果,本文综述了当前国内外学者在该领域研究的热点,即关键基因和酶的鉴定、新菌种的开发和代谢工程改造、同步糖化和共培养等发酵条件的优化、耦合工艺等分离纯化技术改进等。使用非致病的高产单一2,3-丁二醇手性异构体的代谢工程菌株,作为细胞炼制工厂,利用廉价的非粮原料作底物,采用经济、简单、环保的分离纯化方式,是2,3-丁二醇产业化发展的可靠保障。     

沸石咪唑酯骨架结构材料ZIF-71用于低浓度生物基2，3-丁二醇/1，3-丙二醇的吸附分离性能

1,3-丙二醇是一种重要的化工原料,生物发酵法生产1,3-丙二醇往往会产生副产物2,3-丁二醇,限制了生物基1,3-丙二醇的进一步工业化应用。1,3-丙二醇与2,3-丁二醇亲水性强,导致其在低浓度发酵液中分离困难。基于2,3-丁二醇比1,3-丙二醇具有长的碳链和大的极化率,本文采用含有―Cl基团（憎水且具有大的极化率）的ZIF-71吸附分离水中低浓度的2,3-丁二醇/1,3-丙二醇。结果表明,ZIF-71对双组分2,3-丁二醇/1,3-丙二醇（50 g/L,50 g/L）中2,3-丁二醇的静态竞争吸附容量为123.6 mg/g,对2,3-丁二醇/1,3-丙二醇分离选择性高达7.6,分离效果优于沸石材料Beta。在3次循环吸附-解吸实验中ZIF-71依旧保持着稳定的结构和对2,3-丁二醇的选择性吸附能力。通过分子模拟,揭示了ZIF-71对1,3-丙二醇和2,3-丁二醇的吸附分离机制。ZIF-71与1,3-丙二醇之间主要通过弱的范德华力作用;而ZIF-71与2,3-丁二醇之间则是通过强的范德华力与弱的氢键协同作用,从而对2,3-丁二醇产生选择性吸附。可以看出, ZIFs材料有望成为选择性吸附分离低浓度副产物2,3-丁二醇的吸附剂,推动生物法制1,3-丙二醇的工业化发展。     

几种多元醇的半微量分析法

乙醇,2,3-丁二醇,乙二醇,丙三醇,異戊四醇和己六醇在高分子化學工業上是比較重要的原料。作者在研究乙醇和2,3-丁二醇的發酵,以及研究簡單酯化反應,聚酯化反應和三向聚酯化反應的動力學時,用重鉻酸鉀氧化法分析乙醇,乙二醇和丙三醇的原理和手續改為半微量分析法,並推廣用來分析2,3-丁二醇,丙三醇,異戊四醇和己六醇等等。經過几年來的應用,並用其他的經典方法,如醋酸酐法作對比,結果頗为满意,不僅分析手續簡便,迅速,且分析結果的重現性很好,茲將分析手續介绍如下:     

离子排斥色谱法同时测定2,3-丁二醇发酵液中的葡萄糖和木糖及各种代谢产物

针对2,3-丁二醇发酵体系,以高交联度磺化苯乙烯-二乙烯基苯共聚物多孔微球为固定相的Aminex HPX-87H离子色谱柱为分析柱,利用示差折光检测器对该体系中的6种代谢产物(2,3-丁二醇、3-羟基丁酮、乙醇、乙酸、甲酸和乳酸)以及2种残留底物葡萄糖和木糖进行了分离.在65 ℃柱温下,以5 mmol/L H2SO4作为流动相,发酵液样品中底物葡萄糖和木糖及2,3-丁二醇等各种代谢产物的线性相关系数均在0.9990～0.9999之间,回收率为98.8%～103.2%,精密度为0.3%～2.1%.在最佳色谱条件下,能够同时测定2,3-丁二醇发酵体系中的残留底物和各种代谢产物的含量,适合于实时定量监测2,3-丁二醇发酵过程.     

产酸克氏杆菌1,3-丙二醇发酵液中2,3-丁二醇的定性和定量分析

产酸克氏杆菌(Klebsiella oxytoca)在厌氧和微好氧条件下均可以发酵甘油产生1,3-丙二醇。相对于厌氧发酵液,在微好氧发酵液的高效液相色谱图中出现两个未知物峰。对微好氧发酵液进行离心,脱盐和蒸馏处理,以两未知物质为主要成分的馏分通过气相色谱-质谱联机分析显示两种未知物质均为2,3-丁二醇,通过气相色谱和高效液相色谱分析确定两未知物质分别为meso-2,3-丁二醇和L-( )-2,3-丁二醇。建立了用HPLC法对meso-2,3-丁二醇和L-( )-2,3-丁二醇进行外标定量的测定方法,在标准品浓度100~1200mg/L范围内,meso-2,3-丁二醇线性方程为y=7×10-6x,r=0.9991;L-( )-2,3-丁二醇线性方程为y=7×10-6x,r=0.9998。在发酵液样品中meso-2,3-丁二醇的回收率为99.67%;相对标准偏差RSD为0.35%,L-( )-2,3-丁二醇的回收率为99.89%;相对标准偏差RSD为0.09%。     

基于甲苯模板合成的ZIF-93及其对1,3-丙二醇和2,3-丁二醇的吸附分离性能

生物基1,3-丙二醇原液预处理后主要是由低浓度水溶液、1,3-丙二醇和2,3-丁二醇组成。1,3-丙二醇和2,3-丁二醇均是二元醇，含有2个羟基能与水形成强的氢键，增加了分离的难度。然而仅具有范德华作用的传统疏水吸附剂通过动态柱吸附无法实现有效分离二元醇。因此，选择具有范德华作用基团—CH3和氢键作用基团—CHO的ZIF-93研究其对低浓度2,3-丁二醇/1,3-丙二醇的静态和动态柱吸附分离性能。首先，在ZIF-93合成中引入甲苯作为溶剂和模板剂，利用甲苯与咪唑基配体以及甲苯分子之间的π-π相互作用模板支撑ZIF-93的结构单元lta笼，有效提高ZIF-93的BET比表面积和微孔孔容。结果表明，ZIF-93对2,3-丁二醇(50 g/L)/1,3-丙二醇(50 g/L)的动态柱吸附量为69.9和17.3 mg/g，对2,3-丁二醇/1,3-丙二醇的选择性为4.0。相对于传统疏水吸附剂，具有氢键作用基团的ZIF-93穿透曲线斜率增大，传质区间缩短，穿透时间提高，从而提高吸附床层的有效利用率，利于工业上连续分离操作。通过模拟揭示了ZIF-93的-CHO与2,3-丁二醇的―OH和―CH     

生物制造不同立体构型2,3-丁二醇:合成机理与实现方法

总结了不同2,3-丁二醇立体异构体的生物合成机制,以及有利于这些立体异构体高效合成的一些策略,包括构建全细胞催化剂及利用合成生物学技术重建代谢途径等先进方法;同时指出,未来的研究重点是进一步利用合成生物学的方法,以提高不同立体构型2,3-丁二醇的生物合成能力,并建立这些异构体高效可行的分离方法.     

1,4-二哌啶基-2,3-二(4-甲基苯基)-2,3-丁二醇的结构研究

测定了1,4-二哌啶基-2,3-二(4-甲基苯基)-2,3-丁二醇(dl)的晶体结构,并在此基础上用半经验分子轨道理论方法研究了该分子的电子结构,讨论了分子结构的一些特征。     

2,3-位稠杂环喹唑啉酮类化合物的合成研究进展

2,3-位稠环喹唑啉酮类化合物由于具有多种优良的生物和生理活性而广泛应用于药物领域,其合成方法是目前药物研究的热点领域之一.本文主要介绍了包括以2-氨基苯甲酸类化合物、2-氨基苯甲酸甲酯类化合物、靛红酸酐类化合物、喹唑啉酮类化合物等为原料合成2,3-位稠环喹唑啉酮类化合物的方法,并对这些方法进行了简单的评述.     

气相色谱法快速测定产酸克雷伯氏杆菌发酵液中的代谢产物

利用气相色谱内标法,以正丁醇为内标,快速定量分析产酸克雷伯氏杆菌突变株发酵液中的主要代谢产物2,3-丁二醇、3-羟基丁酮和乙醇。实验结果表明:2,3-丁二醇、3-羟基丁酮及乙醇的回收率均在96%~102%之间,相对标准偏差在0.8%~4.2%之间,该法操作简捷,对发酵液的主要成分分析效果较好。     

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.