Biosynthesis of a syringyl 8-O-4′ neolignan in Eucommia ulmoides: formation of syringylglycerol-8-O-4′-(sinapyl alcohol) ether from sinapyl alcohol

To investigate the biosynthesis and stereochemistry of syringylglycerol-8-O-4′-(sinapyl alcohol) ether (SGSE), a syringyl 8-O-4′ neolignan, feeding experiments and enzyme assays using Eucommia ulmoides were carried out. Diastereoselective formation of erythro-SGSE was found. When [8-¹⁴C]sinapyl alcohol was administered to excised shoots of E. ulmoides, ¹⁴C was incorporated into free SGSE and SGSE glucosides. In stems, incorporation into (+)-erythro-[¹⁴C]SGSE (0.037%) with 9.1% enantiomeric excess (% e.e.) was found; incorporation into the threo isomer was not detectable. Erythro-[¹⁴C]SGSE glucosides (0.047%) dominated over threo forms (0.007%) with 74.0% diastereomeric excess (% d.e.); both diastereomers were levorotatory with 32.0% e.e. and 18.3% e.e., respectively. In leaves, higher incorporation into (−)-erythro-[¹⁴C]SGSE (0.500%, 15.9% e.e.) than into the threo isomer (0.206%, 7.4% e.e.) was observed (41.6% d.e.). (−)-Erythro-[¹⁴C]SGSE glucosides (1.692%, 25.0% e.e.) were produced at higher rates than threo isomers (0.177%, 16.4% e.e.) with 81.0% d.e. In incubations of a mixture of [8-¹⁴C]sinapyl and [8-¹⁴C]coniferyl alcohols with an insoluble enzyme preparation from stems of E. ulmoides, erythro-SGSE was preferentially produced. The highest % d.e. (82.8) was observed at 60 min with the (+)-erythro isomer (21.4% e.e.) and the (−)-threo form (4.3% e.e.).Part of this report was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002, and the 47th Lignin Symposium, Fukuoka, October 2002     

Stereochemistry and biosynthesis of 8-O-4′ neolignans in Eucommia ulmoides: diastereoselective formation of guaiacylglycerol-8-O-4′-(sinapyl alcohol) ether

Stereochemistry and biosynthesis of guaiacylglycerol-8-O-4′-(sinapyl alcohol) ether (GGSE), an 8-O-4′ neolignan, which consists of coniferyl and sinapyl alcohol moieties, in Eucommia ulmoides were investigated. Four 8-O-4′ neolignans, GGSE, syringylglycerol-8-O-4′-(coniferyl alcohol) ether (SGCE), guaiacylglycerol-8-O-4′-(coniferyl alcohol) ether (GGCE), and syringylglycerol-8-O-4′-(sinapyl alcohol) ether (SGSE), were synthesized. Their erythro and threo diastereomers were separated through acetonide derivatives, intermediates of the synthesis, and identified by means of nuclear magnetic resonance (NMR) spectroscopy. All of the erythro-acetonide derivatives have larger coupling constants (ca 9 Hz) for the C₇-H resonances than those of the threo ones (1.5–2 Hz). In the case of the four 8-O-4′ neolignans, the C₇-H coupling constants of the threo-isomers are not smaller than those of the erythro ones. GGSE isolated previously from this plant was identified as the erythro isomer by comparison of the ¹³C-NMR data with synthetic erythro-GGSE and threo-GGSE and the other 8-O-4′ neolignans mentioned as above. Administration of a mixture of [8-¹⁴C]coniferyl alcohol and [8-¹⁴C]sinapyl alcohol to excised shoots of E. ulmoides was carried out and the incorporation of ¹⁴C into erythro-[¹⁴C]GGSE was found to be higher than that in threo-[¹⁴C]GGSE. The occurrence of diastereoselective formation of erythro-GGSE by cross coupling of coniferyl and sinapyl alcohols is suggested.Part of this paper was presented at the 47th Lignin Symposium, Fukuoka, October 2002 and the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, April 2003     

水稻颖花自然开放过程中茉莉酸(JA)生物合成的变化

外源茉莉酸(JA)及其甲酯(MeJA)对水稻、小麦、黑麦和高粱等禾本科植物颖花开放具有强烈的诱导效应，然而内源JA是否参与颖花开放的调控目前还缺乏充分的证据。本研究应用高效液相色谱-串联质谱(HPLC-MS/MS)系统检测了粳稻武运粳7号和籼稻明恢63颖花自然开放过程中JA水平变化，并以实时定量反转录PCR (real-time RT-PCR)技术分析了武运粳7号颖花开放过程中JA生物合成途径关键基因表达变化。结果发现，水稻颖花JA水平的变化与开颖进程相一致。JA水平在上午颖花开颖前较平稳，开颖时急剧上升至峰值，闭颖后又下降。开颖时JA水平的峰值比开颖前1 h提高4~5倍。与JA水平变化相对应，催化JA生物合成途径关键步骤同工酶的编码基因OsDAD1-3、OsLOX-RCI1、OsAOS1、OsAOC和OsOPR7的表达在开颖时会有不同程度的上调，闭颖后又下调。同一稻穗上正在开放的颖花JA含量及上述JA生物合成途径基因的表达水平也比已开放和未开放的颖花高。颖花开放时JA水平及其生物合成基因表达的上升和闭颖后的下降有力地表明内源JA参与水稻颖花开放的调控。     

花香基因工程研究进展

综述了花香物质生物合成途径及其相关酶和基因的研究进展;探讨了基因工程调控及改良植物花香的策略;同时简要评述了花香基因工程研究中存在的问题并展望了其应用前景.     

基因工程调控木质素生物合成研究现状及在竹子上改良的应用前景

利用基因工程手段调控木质素合成途径中关键酶基因能降低木质素含量,改变木质素组成,提高造纸工业中纸浆的得率,减少能源的消耗和降低成本,有利于环境保护。对木质素生物合成中涉及的几种重要酶类及这些酶的基因工程概况进行了综述,总结了现阶段木质素研究中存在的一些问题,提出了一些更有效地利用基因工程改良植物的对策和建议,展望了生物技术手段在竹子改良上的应用前景。     

木质素生物合成及其基因调控研究进展

介绍了木质素的组成、生物合成途径、涉及的酶类,综述了近年来基因工程技术调控木质素生物合成的研究进展,并对今后的研究进行了展望。     

Wheat arabinoxylans: Exploiting variation in amount and composition to develop enhanced varieties

Arabinoxylans (AX) are the major polymers of wheat grain cell walls. The content and the structure of AX polymers show large differences between tissues and between wheat cultivars that affect the end-use properties and nutritional quality of the grain. The development of new wheat cultivars with enhanced quality, therefore, requires methods to exploit this variation and it is essential to understand and modulate the mechanisms controlling the key events of cell-wall polymer synthesis.This paper summarises recent knowledge on the structure and physicochemical properties of AX including variation between cultivars and tissues, methods for analysis and screening, biosynthetic mechanisms and approaches to identifying key genes. This knowledge is essential to understand AX properties and defined possible targets for plant breeding.     

Recent advances in caffeine and theobromine toxicities: a review

Caffeine and theobromine are purine alkaloids widely consumed as stimulants and snacks in coffee and cocoa based foods and most often as part of ingredients in drugs. Man has enjoyed a long history of consumption of caffeine and theobromine. Recent interest in these two alkoloids, however, is centered on their potential reproductive toxicities. Caffeine and theobromine are now known to cross the placental and blood brain barrier thus potentially inducing fetal malformation by affecting the expression of genes vital in development. The developing fetus may not have developed enzymes for detoxification of these methylxanthine alkaloids via demethylation. There is a need, therefore, to protect the conceptus against insults from teratogens of this nature. Apart from its reproductive toxicity, the presence of caffeine and theobromine in cocoa could limit its potentials as a nourishing food. This is an issue that needs to be addressed by nutritionists and the food industry at large. This paper discusses the natural sources, consumption and uses, toxicity and the major advances in the reproductive toxicology of caffeine and theobromine. The biosynthesis of these compounds in plants, metabolism in mammalian systems and the involvement of cytochrome P450 are reviewed and summarized. Evidence in favor of the toxicity of these compounds in experimental animals is presented with emphasis on the implications of these findings in humans. The paper concludes with a call for caution in the use of caffeine and theobromine pending further and more elaborate investigations.     

Pseudopterosin Biosynthesis: Aromatization of the Diterpene Cyclase Product,Elisabethatriene

Putative precursors in pseudopterosin biosynthesis, the hydrocarbons isoelisabethatriene (10) and erogorgiaene (11), have been identified from an extract of Pseudopterogorgia elisabethae collected in the Florida Keys. Biosynthetic experiments designed to test the utilization of these compounds in pseudopterosin production revealed that erogorgiaene is transformed to pseudopterosins A–D. Together with our previous data, it is now apparent that early steps in pseudopterosin biosynthesis involve the cyclization of geranylgeranyl diphosphate to elisabethatriene followed by the dehydrogenation and aromatization to erogorgiaene.