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1.
采用汇聚式合成策略高效完成了天然产物薯蓣皂苷的合成。在PhCF_3/~t BuCN/CH_2Cl_2溶剂中,以HB(C_6F_5)_4作为催化剂,-20℃条件下马铃薯三糖三氯亚胺酯供体与薯蓣皂苷元反应,以β/α=11.8/1的立体选择性和97%的产率得到糖苷化产物,然后脱除保护基得到薯蓣皂苷。  相似文献   

2.
完成呋喃甾烷型甾体皂苷甲基Funlioside B的合成。在三氟化硼乙醚促进下,薯蓣皂苷元与乙酸酐反应以55%的产率得到3,16-二-氧-乙酰基-22-羟基-胆甾烷13。以三甲基硅基三氟甲磺酸酯为促进剂,化合物13与葡萄糖三氯亚胺酯给体11进行糖苷化反应以83%的产率得到单糖苷15。最后,在甲醇中,用氢氧化锂脱除酰基保护基团后并在无水甲醇中回流反应,以95%的产率得到甲基Funlioside B。  相似文献   

3.
首次完成天然胆甾烷型皂苷11-deoxyheloside A的合成。在相转移催化的条件下,葡萄糖溴苷1与膦酸单乙酯2反应以69%的收率得到葡萄糖膦酸酯供体3;以胆甾烷苷元4为原料,经Luche还原和乙酰化反应以及三氟甲磺酸负载硅胶脱除TBDPS基团得到胆甾烷二醇10;在金催化剂的作用下,胆甾二醇10与葡萄糖膦酸酯供体3进行糖苷化反应,然后脱除酰基保护基以97%的产率完成11-deoxyheloside A的合成。  相似文献   

4.
研究了半枝莲Scutellaria barbata D.Don的化学成分。利用硅胶色谱、Sephadex LH-20凝胶色谱、HPLC等手段对化学成分进行分离纯化;通过理化性质、波谱分析方法结合文献对照,鉴定了化合物的结构。从半枝莲甲醇提取物中,共分离鉴定了10个单体化合物:齐墩果酸(1)、熊果酸(2)、反式-4-甲基肉桂酸(3)、金色酰胺醇酯(4)、对羟基苯甲醛(5)、对羟基苯乙酮(6)、5-羟基-7,3′,4′,5′-四甲氧基黄酮(7)、芹菜素(8)、5,7,4′-三羟基-8-甲氧基黄酮(9)、5,7,4′-三羟基-6-甲氧基黄酮(10)。化合物1、3、7为首次从该植物中分离得到。  相似文献   

5.
本文发展了一种对薯蓣皂苷元官能团化的新型方法。在催化量的(PhO)3PAuCl和AgB(C6F5)4的协同作用下,薯蓣皂苷元邻炔基苯甲酸酯与亲核试剂反应,在薯蓣皂苷元的3位/6位形成碳氧键、碳氮键、碳硫键和碳碳键,得到多种薯蓣皂苷元衍生物/异甾体衍生物,为薯蓣皂苷元的结构改造提供了新的合成方法。  相似文献   

6.
合成了一种二糖薯蓣皂苷。本文在实现6′-O-Piv-β-D-半乳糖薯蓣皂苷4制备的基础上,通过与葡萄糖给体9进行区域选择性糖苷化反应和乙酰化反应得到化合物7,通过解析7的1 H NMR,13 C NMR,1 H-1 H COSY,HMQC,HM-BC谱图,确定了化合物4选择性糖苷化的位点是其2′-OH,最后经脱除保护基得到二糖皂苷8。  相似文献   

7.
以灰树花发酵菌丝体水不溶性多糖GF4A为原料,以三氧化硫三甲胺盐(SO3·Me3N)为酯化试剂,探讨了GF4A的硫酸酯化工艺.实验结果表明,当三氧化硫与GF4A中单糖摩尔比为5.8∶1、反应温度为80 ℃、反应时间6 h时,所得酯化产物(SGF4A)水溶性好、产率高.该产物硫酸酯取代度为1.6, 相对分子质量为88 kD.通过红外光谱及核磁共振碳谱分析表明,糖残基中所有C-6羟基以及部分C-4和C-2位羟基被酯化.体外实验表明,SGF4A具有较好的抗凝活性.  相似文献   

8.
3-(3′-羟基)丁基苯酞是丁苯酞在体内的代谢产物,具有多种药理作用,可以作为一种新的活性成分应用于药物开发中。本文以甘氨酸、甲硫氨酸和亮氨酸为起始原料,经过Boc保护,再与3-(3′-羟基)丁基苯酞进行缩合,脱保护3步反应合成了3-(3′-羟基)丁基苯酞的氨基酸酯。以期提高水溶性和改善药代动力学性质,获得3-(3′-羟基)丁基苯酞的前药。  相似文献   

9.
中性糖对古糖酯含量测定的影响   总被引:2,自引:0,他引:2  
采用硫酸-苯酚法、硫酸-咔唑法和硫酸-间羟联苯3种方法分别对古糖酯的含量测定进行了研究,并考察了3种方法中加入8种单糖即阿拉伯糖(Ara)、半乳糖(Gal)、葡萄糖(Glc)、果糖(Fru)、木糖(Xyl)、甘露糖(Man)、鼠李糖(Rha)和岩藻糖(Fuc)后对古糖酯含量测定的影响。结果表明3种方法测定古糖酯含量时,其吸收值与古糖酯浓度(在0.1~0.5mg/mL范围内)都呈良好的线性关系,不同的中性糖对3种测定方法影响不同。样品回收率亦不相同。  相似文献   

10.
表没食子儿茶素没食子酸酯(EGCG)经甲基化后在抗过敏、降血脂等方面具有更高的生物活性。但茶叶中甲基化EGCG含量较低,为进一步研究其生物活性,本文对其半合成路线进行了优化。先以EGCG为原料制得五苄基化的表没食子儿茶素(EGC),然后将没食子酸丙酯经4-甲氧基苯甲醛二甲缩醛保护,甲基化,脱保护,苄基化,水解得到3,4-二苄氧基-5-甲氧基苯甲酸,再与苄基化EGC酯化和脱苄基得到表没食子儿茶素3-O-甲基没食子酸酯(3″-Me-EGCG);同样将没食子酸丙酯经全乙酰化、选择性甲基化、脱除乙酰基、苄基化、水解得到3,5-二苄氧基-4-甲氧基苯甲酸,再与苄基化EGC酯化和脱苄基得到表没食子儿茶素4-O-甲基没食子酸酯(4″-Me-EGCG);总产率分别为53%和57%。  相似文献   

11.
In order to assess the impact of deep-sea mining on the in situ benthic life, we measured the microbial standing stock and concentration of organic nutrients in the deep-sea sediments of the Central Indian Ocean Basin in the Indian pioneer area. Sediments were collected using box core and grab samples during September 1996. The total bacterial numbers ranged from 10 10 -10 11 cells per g -1 dry weight sediment. There was a marginal decrease in the number of bacteria from surface to 30 cm depth, though the subsurface section registered a higher number than did the surface. The highest numbers were encountered at depths of 4-8 cm. The retrievable number of bacteria were two orders less in comparison with the direct total counts of bacteria. An almost homogeneous distribution of bacteria, total organic carbon, living biomass, and lipids throughout the depth of cores indicates active microbial and benthic processes in the deep sea sediments. On the other hand, a uniform distribution of total counts of bacteria, carbohydrates, and total organic carbon in all the cores indicates their stable nature and suggests that they can serve as useful parameters for long-term monitoring of the area after the benthic disturbance. Further studies on temporal variability in this region would not only verify the observed norms of distribution of these variables but would also help to understand restabilization processes after the simulated benthic disturbance.  相似文献   

12.
The interdependence between the seismo-acoustic properties of a marine sediment and its geotechnical/physical parameters has been known for many years, and it has been postulated that this should allow the extraction of geotechnical information from seismic data. Though in the literature many correlations have been published for the surficial layer, there is a lack of information for greater sediment depths. In this article, a desktop study on a synthetic seafloor model illustrates how the application of published near-surface prediction equations to subsurface sediments (up to several tens of meters burial depth) can lead to spurious predictions. To test this further, acoustic and geotechnical properties were measured on a number of sediment core samples, some of which were subjected to loading in acoustically-equipped consolidation cells (oedometers) to simulate greater burial depth conditions. For low effective pressures (representing small burial depths extending to around 10 meters subsurface), the general applicability of established relationships was confirmed: the prediction of porosity, bulk density, and mean grain size from acoustic velocity and impedance appears generally possible for the investigated sedimentary environments. As effective pressure increases through, the observed relationships deviate more and more from the established ones for the near-surface area. For the samples tested in this study, in some instances increasing pressure even resulted in decreasing velocities. There are several possible explanations for this abnormal behavior, including the presence of gas, overconsolidation, or bimodal grain size distribution. The results indicate that an appropriate depth correction must be introduced into the published prediction equations in order to obtain reliable estimates of physical sediment properties for greater subsurface depths.  相似文献   

13.
海上大直径钢管桩打桩过程中,桩周土体受到强烈扰动而发生强度弱化,掌握桩周土体强度弱化规律对于准确预测打桩过程、保证工程安全具有重要意义。为研究土体强度弱化规律,开展了环剪试验模拟打桩对桩周土体的扰动,测试土体强度随剪切速率的变化规律,建立了描述土体强度弱化规律的拟合公式,引入到打桩分析软件中。研究结果表明:土体的强度折减程度不仅与土体本身的性质有关还受到土体的埋深和剪切速率的影响,埋深越深土体强度折减程度越低,剪切速率越高土体强度折减越高,在打桩分析中可采用这里推荐的线性折减方法来模拟不同深度处土体强度的折减规律。  相似文献   

14.
An acoustic inversion method using a wide-band signal and two near field receivers is proposed and applied to multiple layered seabed models including a manganese sediment. The inversion problem can be formulated into a probabilistic model comprised of signals, a forward model, and additive noise. The forward model simulates wide-band signals, such as chirp signals, and is chosen to be the source-waveletconvolution plane wave modeling method. The wavelet matching technique, using weighted least-squares fitting, estimates the sediment sound-speed and thickness on which determination of the possible numerical ranges for a priori uniform distribution is based. The genetic algorithm is applied to a global optimization problem to find a maximum a posteriori solution for determined a priori search space. Here the object function is defined by an L 2 norm of the difference between measured and modeled signals. Not only the marginal pdf but also its statistics are calculated by numerical evaluation of integrals using the samples selected during importance sampling process of the genetic algorithm.  相似文献   

15.
Specific properties of the interannual sea level variations and annual tides in the Northwestern Pacific were studied. Several tide stations were monitored. The monthly mean sea level for the year of 1995 was analyzed at each tide station. A seismic event in 1995, some tectonic activity around the subject area, and the Kuroshio (the oceanic western boundary current) may possibly contaminate results which would have occurred from the astronomical annual tide alone.  相似文献   

16.
17.
Oedometer tests have been carried out on 70 undisturbed surficial clays (at approximately 250 mm below the mudline), mostly collected by free-fall corers from sites widely scattered throughout the deep-sea North Atlantic. Acoustic measurements were also made, initially on contiguous samples and ultimately on the same sample using a geophysically instrumented oedometer which also collected electrical resistivity data. Apart from those quiescent areas below the carbonate compensation depth, such as north of the West Indies where very fine clays exist, most of the samples are silty clays whose geotechnical-geophysical properties are dependent on the type of clay minerals present (and their ability to take in moisture), the sand-size fraction, and the quantity of carbonate present. Thus the pure clays have high compressibilities which decrease on the addition of coarse particles, while the converse is true for the acoustic parameters, these increasing with the sand fraction. Using the notion of the intrinsic compression line for all samples, and comparison to it of the measured compression curves, it is clear that, contrary to some previously held ideas, most deep-sea clays are normally consolidated; the addition of carbonate has the effect of creating an open, stronger sediment skeleton. Interestingly, where information is available, the variation with depth of a sample's acoustic velocity follows the void ratio pressure relationship of the compression curve. This allows the construction of an in-situ sediment compression curve using the in-situ geophysical observations.  相似文献   

18.
19.
A set of 27 marine planktonic bacteria isolated from the polar regions was characterized by 16S rDNA sequencing and physiological and biochemical testing. More than half of these bacteria were positive for caseinase, gelatinase and 13-glucosidase, and could utilize glucose, maltose or malic acid as carbon source for cell growth. Twelve isolates expressed nitrate reduction activities. Except for one antarctic isolate BSwlO175 belonging to Actinobacteria phylum, these isolates were classified as γ-Proteobacteria, suggesting that γ-Proteobacteria dominated in cultivable marine bacterioplankton at both poles. Genus Pseudoalteromonas was the predominant group in the Chukchi Sea and the Bering Sea, and genus ShewaneUa dominated in cultivable bacterioplankton in the Prydz Bay. With sequence similarities above 97%, genus Psychrobacter was found at both poles. These 27 isolates were psychrotolerant, and significant 16S rDNA sequence similarities were found not only between arctic and antarctic marine bacteria ( 〉 99% ), but also between polar marine bacteria and bacteria from other aquatic environments ( ≥ 98.8% ), including temperate ocean, deep sea, pond and lake, suggesting that in the polar oceans less temperature-sensitive bacteria may be cosmopolitan and have a bipolar, even global, distribution at the species level.  相似文献   

20.
The effect of different fixation and storage protocols on the flow cytometric (FCM) simultaneous analysis of bacterioplankton and phytoplankton in coastal seawater samples (Mediterranean coastal lagoons) was investigated. FCM measurements (cell number, fluorescence and scatter characteristics) were obtained through DAPI staining. Three fixatives [glutaraldehyde (GA), formaldehyde (FA) and paraformaldehyde (PFA)] and two storage (3 months duration) methods (5 °C and −196 °C) were tested. Two dominant populations were detected in studied samples: bacteria and eukaryotic picophytoplankton. Adding fixatives (2% final concentration) appears necessary to obtain FCM exhaustive counts of all the bacteria and phytoplanktonic cells. This was related to the permeation effect of fixatives which allowed a better DAPI staining of the cells. Maximum fluorescence, i.e. optimal staining of the cells was obtained with FA or PFA, and significant lower fluorescences with GA. Fixed samples stored at 5 °C induced rapid cell loss. Only storage in liquid nitrogen of samples fixed with FA or PFA, allows mid-term (≥4 months) preservation of bacteria or picophytoplankton cell numbers, and limited evolution of DAPI-induced fluorescence and scatter characteristics.  相似文献   

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