Kurilosides A1, A2, C1, D,E and F—Triterpene Glycosides from the Far Eastern Sea Cucumber Thyonidium (= Duasmodactyla) kurilensis (Levin): Structures with Unusual Non-Holostane Aglycones and Cytotoxicities

Six new monosulfated triterpene tetra-, penta- and hexaosides, namely, the kurilosides A₁ (1), A₂ (2), C₁ (3), D (4), E (5) and F (6), as well as the known earlier kuriloside A (7), having unusual non-holostane aglycones without lactone, have been isolated from the sea cucumber Thyonidium (= Duasmodactyla) kurilensis (Levin) (Cucumariidae, Dendrochirotida), collected in the Sea of Okhotsk near Onekotan Island from a depth of 100 m. Structures of the glycosides were established by 2D NMR spectroscopy and HR-ESI mass spectrometry. Kurilosides of the groups A and E contain carbohydrate moieties with a rare architecture (a pentasaccharide branched by C(4) Xyl1), differing from each other in the second monosaccharide residue (quinovose or glucose, correspondingly); kurilosides of the group C are characterized by a unique tetrasaccharide branched by a C(4) Xyl1 sugar chain; and kurilosides of the groups D and F are hexaosides differing from each other in the presence of an O-methyl group in the fourth (terminal) sugar unit. All these glycosides contain a sulfate group at C-6 of the glucose residue attached to C-4 Xyl1 and the non-holostane aglycones have a 9(11) double bond and lack γ-lactone. The cytotoxic activities of compounds 1–7 against mouse neuroblastoma Neuro 2a, normal epithelial JB-6 cells and erythrocytes were studied. Kuriloside A₁ (1) was the most active compound in the series, demonstrating strong cytotoxicity against the erythrocytes and JB-6 cells and a moderate effect against Neuro 2a cells.     

Anti-Inflammatory Cembranoids from a Formosa Soft Coral Sarcophyton cherbonnieri

The present investigation on chemical constituents of the soft coral Sarcophyton cherbonnieri resulted in the isolation of seven new cembranoids, cherbonolides F–L (1–7). The chemical structures of 1–7 were determined by spectroscopic methods, including infrared, one- and two-dimensional (1D and 2D) NMR (COSY, HSQC, HMBC, and NOESY), MS experiments, and a chemical reduction of hydroperoxide by triphenylphosphine. The anti-inflammatory activities of 1–7 against neutrophil proinflammatory responses were evaluated by measuring their inhibitory ability toward N-formyl-methionyl-leucyl-phenylalanine/cytochalasin B (fMLF/CB)-induced superoxide anion generation and elastase release in primary human neutrophils. The results showed that all isolates exhibited moderate activities, while cherbonolide G (2) and cherbonolide H (3) displayed a more active effect than others on the inhibition of elastase release (48.2% ± 6.2%) and superoxide anion generation (44.5% ± 4.6%) at 30 µM, respectively.     

种植年限对设施蔬菜土壤养分和环境的影响

为了给设施蔬菜地合理施肥提供依据,研究了不同种植年限设施蔬菜地土壤理化性质、微生物数量及酶活性变化,以露地土壤为对照(CK),采集种植1 a(年)、3 a、5 a、7 a、9 a、11 a、13 a、15 a、17 a、20 a以及20 a以上的0~20 cm设施蔬菜土壤样品,采用常规土壤理化性质检测方法测定了土壤理化性质和酶活性,采用平板计数法,分析土壤微生物数量。结果表明,设施菜地种植年限与土壤容重呈正相关,与土壤孔隙度呈负相关;设施菜地土壤pH值随种植年限的增加逐年降低,两者呈显著的负相关性;土壤EC值、土壤有机质和速效磷含量都随种植年限的增加而逐年增高,并与种植年限呈显著的正相关性;与CK相比,种植13 a的蔬菜样地土壤全氮和速效钾含量均显著地增加;连续种植20 a以上,设施蔬菜土壤含盐量比对照土壤显著地增加了486.49%。土壤细菌和放线菌数量、过氧化氢酶和碱性磷酸酶活性呈现出先增加后减少的趋势,且都在种植年限为11~13 a时达到最大;真菌数量随着种植年限的增加而增加,而土壤脲酶活性则随种植年限的增加呈下降趋势;转化酶活性随着种植年限的增加保持不变。土壤微生物数量与酶活性之间存在一定程度的相关关系,其中土壤真菌数量与土壤酶活性之间的相关性最为显著。综上所述,种植年限不同的设施菜地,土壤养分失衡,呈现酸化趋势,盐分含量逐年增加,土传真菌病害潜在发生,对设施蔬菜生产不利。     

有机肥对酿酒葡萄土壤微生物、酶活性及产量的影响

为明确施用不同有机肥对土壤有机质、酶活性和微生物以及酿酒葡萄产量的影响,采用田间小区设计,以5 a生赤霞珠酿酒葡萄为试验材料,研究不同有机肥对土层0～20、20～40 cm和40～60 cm中土壤有机质、酶活性和微生物的影响。以不施用有机肥为对照(CK),设置沼渣(BR)、羊粪有机肥(SMOF)、牛粪有机肥(CMOF)、猪粪有机肥(PMOF)、牛粪+沼渣有机肥(CMOF+BR)5个处理进行大田试验。结果表明:不同有机肥施用后与CK相比,土壤有机质增加6.79%～44.97%,土壤微生物碳增加19.78%～91.53%,微生物氮增加2.22倍～3.93倍,碱性磷酸酶增加57.78%～512.55%,过氧化氢酶增加53.45%～240.48%,增产15.12%～46.89%。不同土层施用牛粪有机肥相对于其它有机肥处理土壤有机质含量增长8.49%～33.29%;土壤中微生物碳、氮的含量分别增加5.30%～42.46%和6.12%～49.65%;碱性磷酸酶增大8.01%～184.63%,过氧化氢酶增加5.14%～84.27%,脲酶提高25.58%～410.70%,蔗糖酶升高6.00%～107.65%;微生物总数增多5.99%～56.56%。施用牛粪有机肥相比较其它有机肥增产7.08%～27.60%。说明在宁夏地区施用有机肥可有效提高土壤有机质的含量,增加微生物的数量,增加土壤酶活性,促进酿酒葡萄的生长发育,提高产量,其中以牛粪效果最为显著。     

裸果木渗透调节物质和抗氧化酶活性对干旱的响应

裸果木(Gymnocarpos przewalskii)起源于古地中海,为荒漠区少有的第三纪孑遗植物种。本文采用2017年6月、7月和8月采集于甘肃安西自然保护区内的裸果木中龄和老龄植株叶片,分析自然干旱影响下叶片渗透调节物质及抗氧化酶活性的变化。结果表明:随着干旱程度的增加,裸果木叶片的可溶性蛋白(SP)显著积累,发挥着重要的渗透调节作用,中龄植株叶片的可溶性糖(SS)含量和老龄植株叶片的脯氨酸(Pro)含量先增加后显著降低,渗透调节作用有限。干旱加剧时,中龄植株叶片的超氧化物歧化酶(SOD)活性和抗坏血酸过氧化物酶(APX)活性呈明显的先增后降。严重干旱时,过氧化物酶(POD)活性和过氧化氢酶(CAT)活性明显增强,说明其通过4种酶的协同作用清除过剩的活性氧,减轻过氧化伤害;老龄植株叶片的CAT活性持续增强,APX活性明显的先升后降,POD活性在重度干旱时显著增强,主要通过这3种酶减轻膜系统伤害。丙二醛(MDA)含量则随干旱程度增大显著增加,膜脂过氧化程度不断加深。在相同的降雨条件下,裸果木中、老龄植株的Pro、SS、SP含量、POD和CAT活性、MDA含量对干旱的响应程度存在显著差异,隶属度函数评价法表明,老龄植株的抗旱能力大于中龄植株,表明裸果木的抗旱性随年龄的增大而提高。     

氘标记稻瘟酯的合成及其杀菌活性

氘标记农药作为探针或者内标在农药代谢、毒理研究或者农药残留分析中发挥着重要作用。由于动力学同位素效应,C-D键比C-H键更为稳定,因此氘标记农药可能具有更长的半衰期,以及对非靶标生物更小的毒性。稻瘟酯是一种对水稻恶苗病和稻瘟病有良好防治效果的农用杀菌剂。本项研究利用单电子转移还原氘化反应和氘标记中间体,成功合成了4个不同位点被选择性氘代的稻瘟酯,其中3个化合物未见文献报道,并对其进行了杀菌活性测试。离体杀菌活性测试结果显示,上述4种氘代稻瘟酯对水稻稻瘟病菌和水稻恶苗病菌均具有良好的生物活性,与未被标记的稻瘟酯无显著差异。氘标记稻瘟酯未来可作为代谢、毒理研究的探针及农药残留分析中的内标。     

天维菌素酰化衍生物的合成及杀虫杀螨活性

以天维菌素B、天维菌素B单糖苷和天维菌素B苷元为原料,经选择性C-5羟基保护,在C-13、C-4′和C-4″位引入不同酰基基团,合成了3个系列共23个天维菌素B酰化衍生物,并通过1H NMR、13C NMR和高分辨质谱对所有目标化合物的结构进行了表征。生物活性测定结果表明,所有衍生物对小菜蛾Plutella xylostella、朱砂叶螨Tetranychus cinnabarinus以及松材线虫Bursaphelenchus xylophilus均表现出不同程度的毒杀活性,其中天维菌素B C-4″位衍生物的活性优于C-4′位衍生物及13位衍生物。化合物8e对小菜蛾和松材线虫的毒杀活性最优,LC50值分别为9.2 mg/L和0.42 mg/L,化合物8b对朱砂叶螨的毒性最高,LC50值为0.0019 mg/L,均优于对照药天维菌素B。