木质生物质平台化合物催化转化制备长链烷烃的反应路径与催化剂研究进展

介绍了木质纤维素生物质催化转化制取长链烷烃的反应路径。主要从木质纤维素的水解制得平台化合物,中间产物通过羟醛缩合、羟化烷基化、酮化、自身缩合等途径进行加氢脱氧等多步骤合成长链烷烃。阐述了各步转化的反应机理、产物控制途径和相应的催化剂体系,并从技术角度对该领域的研究进行了展望。     

油桐LACS4基因的克隆与原核及真核表达

长链酰基辅酶A合成酶(LACS)在油脂代谢过程中发挥着重要的作用。以油桐近成熟种子为材料,在已构建的转录组数据库基础上,克隆得到一个油桐长链酰基辅酶A合成酶基因,在此基因c DNA全长序列的基础上,成功构建了油桐LACS4基因的真核表达和原核表达载体,其中,酵母表达载体p YES2-LACS4成功转入酿酒酵母菌株INVSc1中,并进行相关生长趋势分析;在大肠杆菌BL21(DE3)宿主细胞中,原核表达载体p ET30a-LACS4也成功诱导表达,并获得大约为74k Da的表观分子量的相应目的蛋白。     

囊盘菌(Ascocoryne)挥发性气体成分多样性及其产烃分析

[目的]内生真菌紫胶囊盘菌(菌株NRRL 50072)首次被发现能产生石化燃料类似成分的挥发性有机代谢产物,这为生物质能源的发展开辟了新的途径,但囊盘菌属的真菌是否都具有该类代谢属性需要进一步明确。[方法]通过组织表面消毒分离囊盘菌不同菌株,经最大似然法构建分子系统发育树明确亲缘关系,利用顶空固相微萃取方法结合气质联用技术(HSSPEM-GC-MS),进行挥发性成分测定和分析。[结果]不同囊盘菌菌株均能产生挥发性烃、醇、酯、醛、酮和酸等代谢产物,但产物存在高度的多样性,即使近缘的菌株之间其挥发性产物也存在很大差异。[结论]囊盘菌属真菌可能普遍具有产挥发性烃类的能力,但其代谢产物种类具有菌株专化性。因此,发现或遗传工程创造目标新菌株资源是深入研究和开发利用囊盘菌真菌生物柴油的重要基础。     

制备生物柴油用脂肪酶产生菌的诱变和筛选

以提高全细胞生物催化制备生物柴油的效率为目的,采用紫外诱变的方法对产脂肪酶的米根霉菌株进行诱变和筛选。筛选得到的诱变株命名为LY6,脂肪酶水解酶活(4.33 U/mL)是原始菌株的4.33倍,合成酶活(0.28 U/mL)是原始菌株的1.12倍,脂肪酶水解酶最适反应pH值为7.0。将筛选得到的菌株制备成固定化全细胞生物催化剂催化大豆油转酯化制备生物柴油,在醇油比为3∶1(物质的量之比,下同)时,脂肪酸甲酯得率比原始菌株提高了41.0%,达到87.3%;在醇油比为4∶1时,最终生物柴油的甲酯得率比原始菌株提高了16.8%,达到96.1%,故经筛选得到的菌株能作为全细胞生物催化制备生物柴油的优良菌株。     

金福菇菌株间品比试验

在相同培养条件下,对金福菇的两个菌株进行了菌丝长速、长势和生物学转化率比较实验。结果表明：2个菌株不仅在菌丝长速方面差异明显,金福菇1号长速较快,且在长势、子实体的色泽、形态和生物学效率方面均优于荆西口蘑。     

纤维素降解菌株的分离与筛选

从实验室已有的木腐菌与土壤中分离获得的菌株中筛选出具有较高纤维素降解能力的菌株。利用羧甲基纤维素钠为唯一碳源的选择培养,利用刚果红染色进行初筛,选择透明圈与菌落直径比值较大的菌落进行酶活测定再次进行复筛。同时,利用分子学手段对高效产胞外纤维素酶的菌株进行鉴定。最终,筛选出4株高效产胞外纤维素酶的菌株,其中菌株HF-3在28 ℃、180 r/min条件下发酵培养5 d后,胞外纤维素酶活性最高,高达67.772 U/mL,经鉴定为密褐褶孔菌Gloeophyllum trabeum;另外Y5、Y6、Y2共3株菌株酶活较高,分别为37.714 U/mL、30.694 U/mL、25.336 U/mL,属于链霉菌,依次鉴定为浅灰白链霉菌Streptomyces griseoloalbus、丝状链霉菌Streptomyces filamentosuss和威德摩尔链霉菌Streptomyces wedmorensis。试验筛选得到HF-3、Y5、Y6以及Y2菌株具有较高纤维素降解能力,可为复合菌系的研制提供材料。     

陕西林业科技2008年总目次

链霉菌NW136菌株发酵条件的研究……陈丽红,惠友为（1）     

从茶叶中绿色提取咖啡因的方法探讨

从茶叶中提取咖啡因的方法很多,但是主要存在产率低、耗时长等不足。笔者探讨改进从茶叶中提取咖啡因的一些途径和方法,采用了5种方法：水提法、醇提法,有机溶剂提取法、索氏抽提法和微波法。对这几种方法进行了比较,并对实验结果进行了探讨,认为微波法提取咖啡因产率较高、耗时较短,具有实用性。     

雷竹OsFCA同源基因的克隆与序列分析

分别以雷竹嫩叶的基因组DNA和幼穗的cDNA为模板,采用PCR方法扩增出长为490bp及262bp的片段。序列分析结果表明,该基因序列包含1个长为228bp的内含子。其编码区共编Ns86个氨基酸。其氨基酸序列与水稻中OsFCA、小麦中TaFCA的一致性分别为79．8％与69．9％,表明雷伢中可能存在调控开花的自主调控途径。     

油橄榄羟基酪醇的生物合成及其衍生物研究进展

介绍了传统化学合成羟基酪醇的方法,针对化学合成反应步骤多、催化剂昂贵、产率低、污染大等问题,重点总结了以橄榄苦苷和酪醇为原料生物法合成羟基酪醇的途径,同时还综述了羟基酪醇烷基醚、脂肪酸酯、糖基化等衍生物的制备方法、生物活性及其构效关系,为羟基酪醇及其衍生物批量制备及其抗肿瘤、抗癌、心脑血管疾病新药的筛选提供参考和指导作用。     

2,6-二甲基-7-辛烯-2-烷基(或羟烷基)醚的合成研究

以氢型丝光沸石为催化剂，二氢月桂烯与单醇或二醇加成反应生成2，6-二甲基-7-辛烯-2-烷基或羟烷基醚。实验结果发现，各种醇与烯生成醚化合物的趋势如下：直链伯醇易于支链伯醇；伯醇易于仲醇；低碳直链伯醇易于高碳直链伯醇，同时还发现，1，3-丁二醇、1，6-己二醇与烯的反应，只生成单醚。文中还考察了反应温度和时间对反应的影响。     

合成气制低碳混合醇单管放大试验的研究

选择生物质气化制低碳混合醇作为开发对象,在实验室完成了3 mL级低碳混合醇合成催化剂的筛选工作和寿命考察,进行了催化剂的放大制备;并将选定的催化剂应用于300 mL单管低碳醇合成装置,考察反应温度和循环比等对催化剂的CO转化率、总醇合成收率和C2+醇选择性的影响,对低碳醇合成工艺进行优化,结果表明:试验在压力5 MPa、温度280℃和进塔气流量3 000 L/h(空速10 000 h-1)条件下,CO转化率达30%,总醇和C2+醇选择性分别为50%和35%,总醇时空产率达0.215 kg/(kg.h)(相对于催化剂)。这为千吨级低碳醇合成中试奠定基础。     

Structural conversion of the lignin subunit at the cinnamyl alcohol stage in Eucalyptus camaldulensis

The lignin biosynthetic pathway in Eucalyptus camaldulensis was investigated by feeding stems with deuterium-labeled precursor. Pentadeutero[,-D₂ OCD₃] coniferyl alcohol was synthesized and supplied to shoots of E. camaldulensis, and incorporation of the labeled precursor into lignin was traced by gas chromatography-mass spectrometry. In addition to the direct incorporation of labeled precursor into the guaiacyl unit, a pentadeuterium-labeled syringyl unit was detected. This finding indicates that the -deuterium atoms in the hydroxymethyl group of labeled coniferyl alcohol remain intact during modification of the aromatic ring. The relative level of trideuterium-labeled syringyl monomer (the result of conversion via the cinnamic acid pathway) was negligible, suggesting that the pathway at the monolignol stage is used for conversion of exogenously supplied precursor. Our results provide conclusive evidence of a novel alternative pathway for generation of lignin subunits at the monolignol stage even in plants that do not accumulate coniferin in lignifying tissues.     

Substituent effects of 3,5-disubstituted p-coumaryl alcohols on their oxidation using horseradish peroxidase–H2O2 as the oxidant

The consumption rates of three monolignols (p-coumaryl, coniferyl, and sinapyl alcohols) and eight analogues using horseradish peroxidase (HRP)–H₂O₂ as an oxidant were measured and compared with the anodic peak potentials thereof measured with cyclic voltammetry. 3-Monosubstituted p-coumaryl alcohols, i.e., 3-methoxy-, 3-ethoxy-, 3-n-propoxy-, and 3-n-butoxy-p-coumaryl alcohols, had faster reaction rates than p-coumaryl alcohol. This is most probably due to the electron-donating effect of alkoxyl groups. However, the reaction rates gradually decreased with an increase in the molecular weight of the alkoxyl groups. Furthermore, t-butoxyl group, which is a very bulky substituent, caused an extreme reduction in the reaction rate, even though its electron-donating effect was almost the same as that of other alkoxyl groups. The reaction rates of 3,5-disubstituted p-coumaryl alcohols, especially 3,5-dimethyl-p-coumaryl alcohol, were very low compared with 3-monosubstituted p-coumaryl alcohols. These results suggest that there are three main factors of hindrance during the approach of monolignols to the active site of HRP. First, from the results of 3-monoalkoxy-p-coumaryl alcohols, it was suggested that the volume of substituents could decrease their oxidation rates. Second, from the results of 3,5-disubstituted p-coumaryl alcohols, it was suggested that local steric hindrance by the amino residues quite near the heme decreased the oxidation rates. Third, from the results of the substrates with hydrophobic substituents at their 3,5-positions, we suggested that hydrophilicity near heme would decrease their oxidation rates.     

Liquefaction of beech wood in various supercritical alcohols

The liquefaction of Japanese beech (Fagus crenata Blume) was studied with various straight-chain alcohols in subcritical and supercritical states using a batch-type reaction vessel to obtain liquid fuel from lignocellulosics. Under the reaction condition of 270°C, beech wood was liquefied to some extent in all alcohols with about 50%–65% insoluble residue left after treatment for 30min. Under the condition of 350°C, however, more than 90% of wood was decomposed and liquefied in all alcohols. Alcohols with longer alkyl chains liquefied lignocellulosics in shorter reaction times. Because many kinds of alcohols, such as methanol and ethanol, can be produced from biomass, 100% biomass-based liquid fuel can be prepared by supercritical alcohol technology when using such bioalcohols. This study was presented in part at the 55th Annual Meeting of the Japan Wood Research Society, Kyoto, Japan, March 16–18, 2005     

The effects of ganoderma alcohols isolated from Ganoderma lucidum on the androgen receptor binding and the growth of LNCaP cells

The effects of ganoderma alcohols isolated from ethanol extracts of Ganoderma lucidum (Fr.) Krast (Ganodermataceae) on the androgen receptor binding and the growth of LNCaP cells have been investigated. Less than two hydroxyl groups in 17β-side chain are needed for binding to androgen receptor. In the case of the ganoderma alcohols with the same number of hydroxyl groups in 17β-side chain, the one which has C-3 carbonyl group showed better binding activity to androgen receptor than that which has C-3 hydroxyl group. The unsaturation in 17β-side chain is needed for the inhibition of the cell proliferation of androgen-induced LNCaP cells growth.     

细胞色素C与植物细胞编程性死亡

目前普遍认为:细胞色素C(Cyt c)从植物线粒体内向胞浆的释放与植物细胞编程性死亡(PCD)关系密切。与动物PCD过程相似,植物线粒体内Cyt c的释放通过线粒体通透性转换孔(MPTP)或直接通过线粒体外膜的孔蛋白——电位依赖型阴离子通道进行。活性氧(ROS)诱导MPTP的形成,释放Cyt c,导致呼吸电子传递链阻断,ATP合成解偶联,产生ROS,ROS反过来再刺激Cyt c的释放;细胞浆内高水平的Ca2 会触发MPTP的形成以及Cytc的释放。作为植物PCD的早期事件,Cyt c的释放激活了特异性半胱氨酸蛋白酶类的信号级联放大途径,最后产生以核小体DNA长度为基数的DNA片段。在植物中,已经鉴定了几个具有与动物细胞凋亡蛋白酶活化因子-1相同序列的植物基因产物;Cyt c的释放对PCD的激活作为细胞凋亡的古老机制,从多细胞生物的单细胞祖先继承并进化而来。     

稻壳醋液的成分分析及抑菌、杀菌性能研究

以稻壳为原料制备稻壳醋液,采用气-质联用仪分析了稻壳醋液的主要化学成分,并研究了不同稀释比的稻壳醋液对真菌类和细菌类中有代表性菌株的抑菌和杀菌性能.试验从稻壳醋液中鉴定出39种有机组分,其主要成分为酚类、酸类、酮类、醇类、酯类、醛类及其它组分.抑菌性能测试试验表明稻壳醋液有较好的抑菌作用.在作用8 min的条件下,醋液...     

Immunohistochemical localization of enzymes related to lignin biosynthesis in the primary xylem of hybrid aspen

We have investigated the spatial regulation of the accumulation of enzymes involved in the biosynthesis of shikimate and lignin during differentiation of primary xylem from the apical meristem via procambium in hybrid aspen (Populus sieboldii x Populus grandidentata). Immuohistochemical staining revealed that, in the top part of shoots, lignification began in a single or just a few adjacent vessel elements and subsequently spread to neighboring cells. The spatial localization of 3-deoxy-D-arabino-heptulosonate 7-phosphate synthase (DAHPS), which is one of the key enzymes in the shikimate pathway, was tightly correlated with the cell-specific deposition of lignin in the primary xylem. We also found that the spatial localization of enzymes in the general phenylpropanoid pathway and in the lignin-specific pathway was closely associated with the cell-specific deposition of lignin and the accumulation of DAHPS. Our data suggest that enzymes that act in the shikimate, general phenylpropanoid, and lignin-specific pathways are initially produced and function coordinately in a single or a few adjacent elements at the start of primary xylem development.