花烯及其衍生物的合成研究进展

碗型多环芳烃类化合物(π bowls)被认为是全碳非平面π堆积体系的核心材料,呈C_(3v)对称的花烯(sumanene)是此类化合物的典型代表。花烯由于其特殊的结构,直到2003年才被首次合成出来,本文对花烯及其衍生物的合成方法进行了综述。

高蜡原油及其生油岩中新生物标志物——α雪松烯和花侧柏烯

作者在我国典型的高蜡-特高蜡原油盆地大民屯凹陷下第三系上始新统一渐新统沙河街组的生油岩,及高蜡原油中检出了两个新型的、代表陆源高等植物输入的生物标志物——α雪松烯和花侧柏烯。这两个化合物是裸子植物门(Gymnospermae)松柏目(Coniferales)柏科(Cupressaceae),和两个杉科属(Taxodiaceae)针叶植物精油中的特征组分。在地质样品中,仅Grantham和Douglas(1980)报道从英国巴维(Bovey)盆地渐新统褐煤层中的一个化石树脂酸和一个褐煤蜡以及美国加利福尼亚艾奥尼(Ione)谷的上新统富硅高岭石中发现这两个化合物。近期,我们在原油及其生油岩中检出这两个化合物尚属首次报道。由于它们在大民屯生油岩抽提物中含量高且分布广,初步研究发现这类化合物在特高蜡原油中含量高于低含蜡原油,其检出为沉积盆地的古植物输入及特高蜡原油的形成机制提供了新的线索。化合物的确认是通过GC保留时间,GC-Ms谱图对比以及标样共注完成的。

Esterification of cyclohexene with formic acid over a peanut shell-derived carbon solid acid catalyst

A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and elemental analysis, which showed that it was an amorphous carbon material composed of aromatic carbon sheets in random orientations. Sulfonic acid groups were present on the surface at a density of 0.81 mmol/g. The carbon solid acid catalyst showed better performance than HZSM‐5 for the esterification of cyclohexene with formic acid. At a3：1 molar ratio of formic acid to cyclohexene, catalyst loading of 0.07 g/mL of cyclohexene, and reaction time of 1 h at 413 K, the cyclohexene conversion was 88.4% with 97.3% selectivity to cyclohexyl formate. The carbon solid acid catalyst showed better reusability than HZSM‐5 because its large pores were minimally affected by the accumulation of oligomerized cyclohexene, which deactivated HZSM‐5. The activity of the carbon solid acid catalyst decreased somewhat in the first two recycles due to the leaching of polycyclic aromatic hydrocarbon containing –SO3H groups and then it remained constant in the following reuse.

Effects of Ethephon on Flowering of Ornamental Pineapple in Guzmania

[Objective] This study aimed to establish the technical system for forcing ornamental pineapple in Guzmania to flower and further provide technical parameters for large-scale cultivation.[Method] The effect of different concentrations of ethephon solution on flowering in Guzmania ornamental pineapple was studied by using randomized block design.[Results] All the different concentrations of ethephon solution were capable to force the four mainly-cultivated ornamental pineapple varieties to flower to varying degrees.After the flower forcing,it took about 180 d for the pineapple to stay in the ornamentation period,and there were no significant differences in inflorescence shape,inflorescence height,inflorescence diameter and bract number among different treatment pineapples.[Conclusion] All the four varieties have shown high sensitivity to ethephon.The optimal ethephon concentration is 400 mg/L for treating G.lingulata,G.remembrance and G.denise and 500 mg/L for treating G.conifera.After treatment,their major ornamentation traits are were able to satisfy the requirements for commercial production of pineapple.

Expression of Ethylene Biosynthetic Genes Regulated by Pollination associated Factors in Doritaenopsis hybrida Flowers

Pollination of flowers initiates postpollination development in orchid (Doritaenopsis hybrida Hort.) flowers, including perianth senescence, stigma closure, and ovary development. Because ethylene is thought to play a key role in coordinating these developmental changes, the authors studied the temporal and spatial patterns of expression of genes encoding 1 aminocyclopropane 1 carboxylic acid (ACC) synthase and ACC oxidase following pollination associated factor treatments in orchid flowers. Both ACC synthase and ACC oxidase mRNA accumulation in the various parts of the flowers is induced by auxin, and ethylene, but not by emasculation. The patterns of both ACC synthase and ACC oxidase mRNA accumulation are similar in all floral organs following auxin and ethylene treatments. Further, in situ hybridization analysis indicates that the ACC oxidase mRNA is localized in epidermal and parenchyma cells of the stigma after auxin and ethylene treatments. The putative roles of auxin, ethylene and emasculation are discussed in terms of the regulation of ACC synthase and ACC oxidase gene expression in flowers.

RESPONSES TO ETHYLENE AND PROTEIN SYNTHESIS OF CARNATION FLOWERS

The symptoms of petal response to ethylene, including petal in-rolling and increase in ion leakage through cell membrane, were completely inhibited by treatment of transcription inhibitor a-amanitin as well as protein synthesis inhibitor--cycloheximide. It was observed in Dianthus caryophyllus L. cv. White Sim that protein synthesis in flowers declined and the responsiveness to ethylene increased as the flowers became matured. However, when the flowers were pre-treated with aminooxyacetic acid (AOA), an inhibitor of ethylene synthesis, the observed responsiveness to ethylene in flowers declined with age. These results suggested that responsiveness to ethylene in flowers may be due to a declination in the capacity of protein synthesis in flowers.

非平面芳烃的碳氢活化研究进展

碳氢(C—H)活化反应作为现代分子拼接的重要手段,具有原子经济性高、合成路线简单等优点,因此通过C—H活化对非平面芳烃进行衍生,逐渐成为有机化学研究的热点之一。该文系统归纳了近年来典型的非平面芳烃——环仿、螺烯、碗烯、花烯和富勒烯的C—H键活化反应,并对未来潜在的研究方向进行展望,以期获得更多优秀的非平面碳基材料。

A Research Overview on Arachidonic Acid:Fermentation Regulation and Purification

Arachidonic acid （ARA or AA）, one of the most important polyunsaturated fatty acids （PUFAs）, has various physiological activities and positive effects on human health. ARA production by Mortierella alpina has become a hot topic in recent years, owing to that it is effective, safe and easy to control. How to improve ARA yield and purification efficiency is important to ARA production in M. alpina. Therefore, in this review, we summarized some methods to improve ARA yield： optimization of culture conditions, mycelium aging technologies and metabolic regulation, and the commonly used methods for ARA isolation and purification, to provide a theoretical basis for ARA production by M. alpina fermentation.

ent-Kaurene Diterpenoids from Isodon adenanthus

Three new ent-kaurene diterpenoids, adenanthins N, 0 and P (1-3), and four known diterpenoids, leucophyllin E (4), glabcensin C (5), adenanthin A (6), leucophyllin B (7), together with a highly unsaturated fatty acid, 9,16-dioxo-10,1 2,14-octadeca-trienoic acid (8), were isolated from Isodon adenanthus (Diels) Kudo. The structure of compound 4 was revised accordingly. Compound I showed significant cytotoxic activity against K562 cells with IC50 = 0.45 mug/mL.

Hepatitis B virus X protein promotes liver cell proliferation via a positive cascade loop involving arachidonic acid metabolism and p-ERK1/2

Hepatitis B virus X protein （HBx） plays a crucial role in the development of hepatocellular carcinoma. Here, we sought to identify the mechanisms by which HBx mediates liver cell proliferation. We found that HBx upregulated the levels of cyclooxygenase-2 （COX-2）, 5-1ipoxygenase （5-LOX） and phosphorylated extracellular signal-regulated protein kinases 1/2 （p-ERK1/2） in liver cells. HBx-induced p-ERK1/2 was abolished by inhibition of Gi/o proteins, COX or LOX. In addition, HBx increased the amounts of prostaglandin E2 （PGE2） and leukotriene B4 （LTB4） released from cell lines derived from hepatocytes. Moreover, these released arachidonic acid metabolites were able to activate ERK1/2. Interestingly, activated ERK1/2 could upregulate the expression of COX-2 and 5-LOX in a positive feedback manner. In conclusion, HBx enhances and maintains liver cell proliferation via a positive feedback loop involving COX-2, 5-LOX, released arachidonic acid metabolites, Gi/o proteins and p-ERK1/2.

FATTY ACIDS PROFILE IN A HIGH CELL DENSITY CULTURE OF ARACHIDONIC ACID-RICH PARIETOCHLORIS INCISA (TREBOUXIOPHYCEAE,CHLOROPHYTA) EXPOSED TO HIGH PFD

The changes in arachidonic acid (AA) and fatty acids profiles along the growth curve of Parietochloris incisa, a coccoid snow green alga, were studied in a 2.8 cm light-path flat photobioreactor, exposed to strong photon flux density [PFD, 2400 μEmol/(m 2·s)]. Sixteen fatty acids were identified by gas chromatography showing that AA was the dominant fatty acid (33%-41%) followed by linoleic acid (17%-21%). AA content was closely investigated with respect to total fatty acids (TFA), ash free dry weight (AFDW) of cell mass as well as total culture content. These parameters were influenced significantly in a similar manner by culture growth phase, i.e., slightly decreasing in the lag period, gradually increasing in the logarithmic phase, becoming maximal at the early stationary phase, starting to decrease at the late stationary phase, sharply dropping at the decline phase. The increase in AA per culture volume during the logarithmic phase was not only associated with the increase in AFDW but also connected with a corresponding increase in AA/TFA, TFA/AFDW as well as AA/AFDW. The sharp decrease in AA content of the culture during the decline phase was mainly due to the decrease in AA/TFA, TFA/AFDW and AA/AFDW, although AFDW declined only a small extent. Maximal AA concentration, obtained at the early stationary phase, was 900 mg/L culture volume, and the average daily net increase of AA during 9 days logarithmic growth was 1.7 g/(m 2·day). Therefore, harvesting prior to the decline phase in a batch culture, or at steady state in continuous culture mode seems best for high AA production. The latter possibility was also further confirmed by continuous culture with 5 gradients of harvesting rate.

Docosahexaenoic acid suppresses arachidonic acid-induced proliferation of LS-174T human colon carcinoma cells

AIM： To investigate the impact of arachidonic acid （AA） and docosahexaenoic acid （DHA） and their combination on colon cancer cell growth. METHODS： The LS-174T colon cancer cell line was used to study the role of the prostaglandin precursor AA and the omega-3 polyunsaturated fatty acid DHA on cell growth. Cell viability was assessed in XTT assays. For analysis of cell cycle and cell death, flow cytometry and DAPI staining were applied. Expression of cyclooxygenase-2 （COX-2）, p21 and bcl-2 in ceils incubated with AA or DHA was examined by real-time RT-PCR. Prostaglandin E2 （PGE2） generation in the presence of AA and DHA was measured using a PGE2- ELISA. RESULTS： AA increased cell growth, whereas DHA reduced viability of LS 174T cells in a time- and dosedependent manner. Furthermore, DHA down- regulated mRNA of bcl-2 and up-regulated p21. Interestingly, DHA was able to suppress AA-induced cell proliferation and significantly lowered AA-derived PGE2 formation. DHA also down-regulated COX-2 expression. In addition to the effect on PGE2 formation, DHA directly reduced PGE2-induced cell proliferation in a dosedependent manner. CONCLUSION： These results suggest that DHA can inhibit the pro-proliferative effect of abundant AA or PGE2.

Cytosolic Phospholipase A2 and Its Role in Cancer

Cytosolic phospholipase A2α （cPLA2α） catalyzes the release of arachidonic acid （AA） and lysophosphoglyceride from membrane phospholipids. Although the roles of AA and eicosanoids in cellular viability, the processes of inflammation and cancer cell development have been extensively studied, the function of cPLA2α in the processes of inflammation and cancer cell development is not clear. This review summarizes published evidences for the biochemical properties and regulatory mechanisms of cPLA2α. The potential for use of cPLA2α as a novel diagnostic target and predictive biomarker for tumors is also discussed.

The effects of season on fatty acid composition and ω3/ω6 ratios of northern pike(Esox lucius L.,1758) muscle lipids

In the present study, the effects of season on fatty acid composition, total lipids, and ω3/ω6 ratios of northern pike muscle lipids in Klzlhrmak River （Klrlkkale, Turkey） were investigated. A total of 35 different fatty acids were determined in gas chromatography. Among these, palmitic, oleic, and palmitoleic acids had the highest proportion. The main polyunsaturated fatty acids （PUFAs） were found to be docosahexaenoic acid, eicosapentaenoic acid, and arachidonic acid. There were more PUFAs than monounsaturated fatty acids （MUFA） in all seasons. Similarly, the percentages of ω3 fatty acids were higher than those of total ω6 fatty acids in the fatty acid composition. ω3/ω6 ratios were calculated as 1.53, 1.32, 1.97, and 1.71 in spring, summer, autumn and winter, respectively. Overall, we found that the fatty acid composition and ω3/ω6 fatty acid ratio in the muscle of northern pike were significantly influenced by season.

3D MoS_(2)/graphene nanoflowers as anode for advanced lithium-ion batteries

Vertical MoS2nanosheets were controllably patterned onto graphene as nanoflowers through a two-step hydrothermal method. The interconnected network and intimate contact between MoS2nanosheets and graphene by vertical channels enabled a high mechanical integrity of electrode and cycling stability. In particular, MoS2/graphene nanoflowers anode delivered an ultrahigh specific capacity of 901.8 mA·h/g after 700 stable cycles at 1000 mA/g and a corresponding capacity retention as 98.9% from the second cycle onwards.

Lipid characterization of an arachidonic acid-rich oil producing fungus Mortierella alpina

Mortierella alpina has been considered as the most effective producer of arachidonic acid(ARA)-rich oil. It was found that several methods could improve the percentage of ARA in total lipids successfully, as they activated the desaturation system on the endoplasmic reticulum. Additionally, in M. alpina the ARA exists in several forms, such as triacylglycerol(TAG), and diacylglycerol(DAG). These forms are caused by different acyltransferases and they determine the nutrient value of the microbial oil. However, few works revealed detailed fatty acid distribution among lipid classes, which to some extent impeded the accurate regulation in ARA accumulation. Herein, this paper gives information on the accumulation process of main lipid classes and the changes of fatty acid composition in these lipids during ARA accumulation period in M. alpina. The result demonstrates that TAG was the dominant component of the total lipids, and it is the main form for ARA storage. The ARA enrichment stage occurred during 168–192 h when the amount of total lipids maintained steady. Further analysis indicated that the newly formed ARA-TAG might come from the incorporation and modi fication of saturated and monounsaturated fatty acids in other lipid classes. This work could be helpful for further optimization of ARA-rich TAG production.

In Vivo Anti-Inflammatory Assessment of Quillaja saponaria Mol. Extracts

Aqueous extracts from the native Chilean Quillaja saponaria tree are used orally and topically to treat lung inflammatory problems and toothache. This study aimed to corroborate their presumed anti-inflammatory activity, identify their active ingredients and validate their use. The topical anti-inflammatory activity of a commercial partially purified Quillaja saponin aqueous extract （Ultra Dry 100Q, UD）, the crude acid hydrolysate （H-100Q） of this material, its two most abundant sapogenins QA （quillaic acid） and PA （phytolaccagenic acid）, and two formulations containing QA were subjected to topical assays for the inhibition ofmurine ear inflammation elicited by AA （arachidonic acid） or TPA （phorbol ester）. The dose-dependent anti-inflammatory activity of QA was confirmed in both AA （maximal effect 92.1%） and TPA （maximal effect 62.2%） assays, and PA showed significant anti-inflammatory activity against AA （46.5%）. Two dermo pharmaceutical formulations containing 8% w/v QA as the active ingredient--a cream and a gel--also exhibited significant anti-inflammatory effects in the TPA （50.8%） and AA （39.5%） assays.

Anti-Inflammatory Activity of Ferruginol from Prumnupitys andina

Ferruginol, a phenolic diterpenoid, was isolated from Prumnupitys andina, a Chilean native plant, as the main compound. Ferruginol has displayed an interesting range of biological activities such as in vitro anti-inflammatory activity. Aim of this research is to evaluate the dermal anti-inflammatory activity of ferruginol, using in vivo models at first time. Ferruginol was subjected to topical assays for the inhibition of inflammation elicited by AA （arachidonic acid） or TPA （phorbol ester） in the murine model. The topical anti-inflammatory activity was evaluated in vivo using groups of 8 animals were treated with a single dose of ferruginol, equimolar doses with regard to the reference drugs, indomethacin and nimesulide. We showed a chemical data were consistent with a type-abietane diterpenoid known as ferruginol. Ferruginol showed topical anti-inflammatory activity at 21.0% and 20.5% in AA and TPA models, respectively. Our results provide data to support further investigations about ferruginol, a type-abietane diterpenoid, as a potential anti-inflammatory agent.

留萼木叶中2个新的萜类化合物

目的研究留萼木Blachia pentzii叶中的化学成分及其体外抗肿瘤活性。方法利用硅胶柱色谱、MCI柱色谱、ODS柱色谱和半制备HPLC等柱色谱分离技术进行分离纯化,并综合应用HR-ESI-MS、NMR和ECD等多种波谱方法鉴定化合物结构,采用CCK-8或MTT法筛选了部位浸膏和新化合物对几种肿瘤细胞的增殖抑制作用。结果从留萼木叶的95%乙醇提取物中分离得到2个萜类化合物,分别鉴定为(R)-5-methyl-5-((S)-4-methyl-2-oxocyclohex-3-en-1-yl)dihydrofuran-2(3H)-one(1)和3β-乙酰基多花独尾草-8-烯-17-酸(2);醋酸乙酯萃取部位对人肺癌A549细胞、人宫颈癌He La细胞、人肝癌HepG2细胞3种肿瘤细胞系的半数抑制浓度(half inhibitory concentration,IC50)分别为(21.37±1.98)、(22.91±0.33)、(22.14±4.95)μg/mL。化合物2在80μmol/L对2种胃癌细胞HGC-27、AGS抑制率分别达到81.9%和89.2%。结论化合物1为降倍半萜类,2为三萜类,1和2均为新化合物,分别命名为留萼木素A和3β-乙酰基多花独尾草-8-烯-17-酸;化合物2对胃癌细胞具有一定的增殖抑制作用。

芪参益气滴丸及其挥发性成分降香油的GC指纹图谱研究

目的建立芪参益气滴丸（QYDP）及其主要挥发性成分降香油的GC指纹图谱,并采用GC-MS对主要共有峰进行指认。方法采用HP-INNOWax（30 m×0.25 mm,0.25μm）毛细管柱进行分离。程序升温,初始温度100℃,保持2 min,以3℃/min升至160℃,以1℃/min升至190℃,以5℃/min升至220℃,以10℃/min升至250℃;载气为高纯氮气,体积流量0.5 mL/min;进样口温度230℃,分流比5∶1;检测器为FID,检测温度300℃;EI离子源温度230℃,电离电压70 eV,全离子扫描,扫描质量范围m/z 35~600,溶剂延迟8 min。结果标定了QYDP GC指纹图谱中33个共有峰,降香油GC指纹图谱中25个共有峰,并推测出反式橙花叔醇、氧化橙花叔醇异构体、法尼醇异构体、檀香花烯、降莰烷、β-没药烯、反式-β-檀香醇等23个共有峰成分。各批制剂及降香油指纹图谱相似度均在0.979以上。结论该方法简单、可靠,可为QYDP及降香油的质量评价与控制提供依据。