Absolute configuration of arylglycerol-β-aryl ethers obtained by asymmetric reduction of the correspondingα-ketonic compound with intactFusarium solani cells

When (±)--oxo-guaiacylglycerol--(vanillic acid) ether (1) is degraded byFusarium solani M-13-1, the-ketone is initially reduced to giveerythro andthreo guaiacylglycerol--(vanillic acid) ethers (2), arylglycerol--aryl ethers, both of which are enantiomerically pure. The absolute configuration in each2 was determined by Mosher's method; the products were converted to,-di-(R)--methoxy--trifluoromethylphenylacetates (MTPA esters) (3) oferythro (-)- andthreo (+)-veratrylglycerol--(methyl vanillate) ethers (3), whose¹H nuclear magnetic resonance (NMR) spectra were examined and compared with those of four di-(R)-MTPA ester (3) diastereomers from chemically synthesizederythro (±)-3 andthreo (±)-3. To assign the- and-MTPA-OCH₃ peaks, the¹H NMR scans of several compounds that have substructures of 3 and their 3,4,5-trimethoxyphenyl analogues were examined. When a racemic alcohol reacts with (R)-MTPA to give a pair of (R)-MTPA ester diastereomers, the value was defined as the absolute value of the difference in the¹H chemical shifts of the peak between the diastereomers. It was found that the values of-MTPA-OCH₃ were larger than those of-MTPA-OCH₃ owing to a shielding effect of the veratryl ring located on the-MTPA-OCH₃, and that the-MTPA-OCH₃ peaks in the 3,4,5-trimethoxyphenyl compounds shifted downfield relative to those in the veratryl compounds. On the basis of the¹h NMR data of (R)-MTPA esters, the absolute configuration of the four chemically prepared diastereomers (3) were determined. The catabolicerythro 3 [fromerythro (-)-3] andthreo 3 [fromthreo (+)-3] were identical to (R, S, R)-erythro 3 and (R, S, S)- threo 3, respectively. An hydrogen species in the fungal reduction would attack the-ketone fromre-face of both (R)-1 and (S)-1, givingerythro (S, R)-2 andthreo (S, S)-2, respectively.Part of this paper was presented at the 33rd Lignin Symposium, Tsukuba, November 1988     

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。     

豆油乙二醇乙醚酯生物柴油燃料特性研究

以乙二醇乙醚和精制大豆油在金属钠催化下合成出了豆油乙二醇乙醚酯生物柴油,考察了该生物柴油作为替代燃料在性能方面与柴油的差别;研究了作为柴油添加剂,其加入量对混合燃料性能的影响。结果表明,豆油乙二醇乙醚酯生物柴油的燃料特性达到了国外生物柴油生产标准,可以直接作为柴油使用,也可与矿物柴油掺合使用,提高了柴油的使用性能。     

乙醇、乙二醇二甲醚与柴油混合燃料排放特性研究

提出了将乙二醇二甲醚作为乙醇柴油燃料的一种组成成分,利用乙二醇二甲醚好的发火性来改善乙醇柴油燃料差的发火性。试验表明乙二醇二甲醚与乙醇、柴油互溶,具有较好的稳定性。对三种比例混合燃料测试了柴油机在主要工况下的性能与排放特性,得出乙二醇二甲醚加入量以E20为最佳,此时,烟度降低了约80%,NOx略有增加,燃油消耗率略有下降。此外考察了随着十六烷值的变化对混合燃料的排放特性的影响,得出随着十六烷值的增加,NOx排放逐渐增加,对烟度和经济性存在一个最佳值。     

二甲醚发动机的研究与开发

介绍了二甲醚作为代用燃料的性能优势,二甲醚发动机的结构、原理和排放应对措施     

不同氮磷钾配施对烤烟石油醚提取物和中性致香物质的影响

田间试验以烤烟(Nicotiana tabacum L.)品种中烟100为材料,研究了N、P、K肥配施对烤烟石油醚提取物和致香物质含量的影响.结果表明:不施肥处理烟叶石油醚提取物含量和致香物质总量及不同种类致香物质含量都较低:N、P、K任意两种肥料配施均可以不同程度提高烤烟石油醚提取物和不同种类致香物质的含量;NPK的配施,随着施肥量的增加,烤烟石油醚提取物含量也随着增加,而致香物质含量呈现先增后减的抛物线现象.因此,N、P、K的合理配施是提高烤烟石油醚提取物和致香物质的重要措施.由田间试验结果获取的推荐施肥方案为N:P_2O_5:K_2O=1:2:3,其用量分别为75 kg/hm~2、150kg/hm~2和225kg/hm~2.     

纳米CuI催化偶联反应合成二苯醚类农药中间体

二苯醚是一种重要的农药中间体,通过W/O微乳法,制备出形貌均一的球状纳米CuI,并应用于催化C-O交叉偶联反应中,在温和的反应条件下,合成了具有优良产率的二苯醚类化合物,该方法可在今后的农药合成中应用。     

New clues concerning pigment biosynthesis in green colored fiber provided by proteomics-based analysis

To separate the proteins related to pigment synthesis in green colored fiber (GCF), we performed a comparative proteomic analysis to identify the differentially expressed proteins between green cotton fiber and a white near-isogenic line (NIL). One differential spot identified as phenylocumaran benzylic ether redutase-like protein (PCBER) was expressed only in GCF, but was not found in white colored fiber (WCF) at any time points. Since PCBER was a key enzyme in lignans biosynthesis, total lignans were extracted from GCF and WCF and their content was determined by using a chromotropic acid spectrophotometric method. The results showed that total lignans content in GCF was significantly higher than that in WCF. The qPCR analysis for two PLR genes associated with lignans biosynthesis showed that the expression level of two genes was much higher in GCF than that in WCF at 24 and 27 days post anthesis (DPA), which may be responsible for the higher lignans content in GCF. Our study suggested that PCBER and lignans may be responsible for the color difference between GCF and WCF. Additionally, p-dimethylaminocinnamaldehyde (DMACA) staining demonstrated that the pigment in GCF was not proanthocyanidins, and was different from that in brown colored fiber (BCF). This study provided new clues for uncovering the molecular mechanisms related to pigment biosynthesis in GCF.     

N-苯氧苯基取代的α-氨基酸衍生物的合成及生物活性

 【目的】合成N-苯氧苯基取代的α-氨基酸衍生物,并测定化合物的生物活性及其在植物体内的传导性。【方法】通过氨基二苯醚类化合物分别与乙醛酸乙酯和丙酮酸乙酯缩合,形成2个希夫碱化合物（Ia-Ib）,并经NaBH4还原,合成了5个N-苯氧苯基取代的α-氨基酸衍生物,以二苯醚类除草剂三氟羧草醚为对照药剂,测定化合物对水稻幼苗根、芽的室内生物活性;以空心莲子草为试验材料,以苯氧苯基甘氨酸乙酯（IIa）为试验药剂,喷雾处理空心莲子草后采用HPLC法测定该化合物在植株根中的含量来判断其传导性。【结果】化合物Ⅰa和Ⅱa对水稻幼苗的根、芽的生长均具有一定的抑制作用,化合物Ⅱb在低浓度下对水稻芽具有促进生长的作用,化合物Ⅱc和Ⅱd在低浓度下对水稻幼苗的根具有促进生长的作用;供试化合物在光照条件下的生物活性均比在黑暗条件下高;利用化合物Ⅱa 300 mg•L-1的药液喷雾处理空心莲子草地上部分12 h后,在其根部检测到目标化合物(IIa)含量为8.67 mg•kg-1 FW。【结论】二苯醚类化合物衍生出氨基酸基团后,所得衍生物既保留了二苯醚类除草剂的需光性除草活性特点,又增加了经由植物韧皮部向根部的传导性。     

快速测定烟草及烟草制品中石油醚提取物总量

为提高烟草石油醚提取物含量的测定效率,介绍了一种快速测定烟草及烟草制品中石油醚提取物总量的方法。利用设计加工的直接萃取装置来提取烤烟、白肋烟和香料烟等3种烟叶11个样品中的石油醚提取物总量,与行业标准中的方法进行比较。结果表明:①旧方法测定1个样品需要14h以上,而新方法只需5.5h;②新方法的RSD小于或略大于1%;③新方法与标准方法的测定结果的相对偏差小于2.13%。该方法适合烟草石油醚提取物的快速测定。