四种卤代PTP1B抑制剂的化学合成及其活性研究

从松节藻中分离的含卤素化合物表现出显著PTP1B抑制活性。其中BPN效果最佳。为研究BPN侧链基团极性对其抑制活性的影响,本文以香兰素(1)为起始原料,经过溴代、氧化、还原、傅克烷基化以及酯化等反应,成功合成了新化合物2,3-二溴-1-(2-溴-3,4-二甲氧基-6-((4-硝基苯氧基)甲基)苯甲基)-4,5-二甲氧基苯(10)、4-((3-溴-2-(2,3-二溴-4,5-二甲氧基苄基)-4,5-二甲氧基苄基)醚)苯胺(11)、4-((3-溴-2-(2,3-二溴-4,5-二甲氧基苄基)-4,5-二甲氧基苄基)醚)-4-乙酰乙酸(12)和3-溴-2-(2,3-二溴-4,5-二甲氧基苄基)-4,5-二甲氧基苯甲醛肟(14)。通过1 H-NMR,13C-NMR等方法对目标产物进行了结构表征。并对化合物进行了PTP1B酶抑制活性的测定,结果表明化合物侧链极性对PTP1B酶抑制活性有显著影响。     

3-溴-2-(2′,3′-二溴-4′,5′-二甲氧基苯甲基)-4,5-二甲氧基苯甲酸甲酯的合成及其PTP1B 酶抑制活性研究

为了研究海洋溴系列化合物的生物活性,以香兰素(1)为起始原料,经过溴代、还原、氧化、傅克酰基化及酯化等反应,成功的合成了新化合物3-溴-2-(2′,3′-二溴-4′,5′-二甲氧基苯甲基)-4,5-二甲氧基苯甲酸甲酯(9),总收率为19.6%。通过1H-NMR,13C-NMR等方法对目标产物进行了结构表征。通过比色法对目标化合物进行了PTP1B酶抑制活性测定,结果显示化合物浓度为20 mg/L时,PTP1B酶抑制率为55.84%,表明该化合物有一定的PTP1B酶抑制活性。     

多管藻内生真菌Chaetomium globosum.苯甲醛类次生代谢成分研究

从采自青岛近海的红藻多管藻(Polysiphonia urceolata)中分离到一株毛壳霉属真菌球毛壳菌(Chaetomium globosum.),对其发酵代谢产物的化学成分进行了研究。采用溶剂提取、分配,硅胶柱层析、葡聚糖凝胶柱层析以及制备薄层层析等技术已分离获得6个单体化合物,通过一维、二维超导核磁共振技术、质谱技术等鉴定了其中4个化合物的结构,均为苯甲醛类衍生物,分别为2-(1-庚烯基)-3、6-二羟基-5-(3-甲基-2-丁烯基)苯甲醛(Ⅰ)、2-庚基-3、6-二羟基-5-(3-甲基-2-丁烯基)苯甲醛(Ⅱ)、2-(3、5-庚二烯基)-3、6-二羟基-5-(3-甲基-2-丁烯基)苯甲醛(Ⅲ)、2-(1、3、5-庚三烯基)-3、6-二羟基-5-(3-甲基-2-丁烯基)苯甲醛(Ⅳ)。     

粗枝软骨藻化学成分研究

为了研究中国沿海海藻中的抗肿瘤活性成分,利用正相硅胶柱色谱和凝胶Sephadex LH-20色谱,从采自青岛的粗枝软骨藻(Chondria crasscaulis)中分离得到了5个化合物,经红外光谱(IR)、核磁共振光谱(1H NMR、13C NMR)以及质谱(MS)等现代波谱技术鉴定为loliolide(1),2-羟基苯甲醛(2),4-羟基苯甲醛(3),4-羟基-3-甲氧基苯甲醛(4)和4-羟基苯甲酸(5)。     

双苯甲酰胺类辣素结构化合物的合成、抑菌及防污性能

以N-羟甲基苯甲酰胺和取代芳烃为原料,合成了N-(3-苯甲酰胺甲基-2-羟基-4,5-二甲基苄基)苯甲酰胺(A)、N-(3-苯甲酰胺甲基-2-羟基-4,6-二甲基苄基)苯甲酰胺(B)、N-(4-苯甲酰胺甲基-2-羟基-3,6-二甲基苄基)苯甲酰胺(C)、N-(3-甲基-5-苯甲酰胺甲基-2-羟基苄基)苯甲酰胺(D)、N-(4-甲基-5-苯甲酰胺甲基-2-羟基苄基)苯甲酰胺(E)、N-(5-苯甲酰胺甲基-2-羟基-3-甲氧基苄基)苯甲酰胺(F)和N-(5-苯甲酰胺甲基-2-甲氧基-4-甲基苄基)苯甲酰胺(G)共7种双苯甲酰胺基取代的类辣素结构化合物。通过红外光谱(IR)和核磁氢谱(1 H NMR)对其结构进行了表征。抑菌试验结果表明化合物F和化合物G对2种受试菌金黄色葡萄球菌和大肠杆菌的抑制活性最高,最小抑菌浓度均可达到0.125mg/mL。以该7种化合物为辅助防污剂,复合氧化亚铜制备海洋防污涂料,实海挂板120天后,除含D试片外其余6个试片均表面光洁无污损生物附着,表现出优良的防污性能。     

耐盐真菌Aspergillus variecolor B-17产生的烃基苯甲醛衍生物及其细胞毒活性

为从极端环境微生物中获得抗肿瘤药物先导化合物,作者从采自内蒙古盐湖的沉积物中分离了96株耐盐真菌.采用小鼠乳腺癌细胞株tsFT210和海虾(Artemia salina Leach)筛选抗肿瘤活性微生物,1株耐盐真菌Aspergillus variecolor B-17表现出明显的细胞毒活性和海虾致死活性.采用活性跟踪的分离方法,从该菌株的大量发酵产物的石油醚层提取物中分离得到了3个单体化合物.通过一维、二维超导核磁共振、质谱等波谱方法确定其结构分别为:2-(E-1-庚烯基)-3,6-二羟基-5-(3-甲基-2-丁烯基)苯甲醛(1)、2-庚基-3,6-二羟基-5-(3-甲基-2-丁烯基)苯甲醛(2)、2-(E,E-3,5-庚二烯基)-3,6-二羟基-5-(3-甲基-2-丁烯基)苯甲醛(3).化合物1、2和3对P388、A549、HL-60和BEL-7402肿瘤细胞表现弱的细胞增殖抑制活性,IC50值分别为88,68,66,65 μmol/L,9,99,110,84 μmol/L以及77,147,93,203 μmol/L.     

南海软珊瑚共附生真菌Aspergillus sp.EGF15-0-3苯甲醛类化合物研究

本文研究了具有克服肿瘤耐药活性的软珊瑚共附生真菌Aspergillus sp. EGF 15-0-3苯甲醛类化学成分。采用硅胶柱层析、十八烷基硅烷键合硅胶层析、Sephadex LH-20层析、高效液相色谱(high performance liquid chromatography, HPLC)等多种方法进行分离纯化; 通过核磁共振波谱(nuclear magnetic resonance, NMR)、质谱(mass spectrometry, MS)等现代波谱分析及物理常数对照等方法进行结构鉴定; 采用MTT法对苯甲醛部位和单体化合物进行克服肿瘤耐药活性研究。从EGF15-0-3的苯甲醛部位共得到9个苯甲醛类化合物, 结构依次为flavoglaucin (1)、tetrahydroauroglaucin (2)、isoaspergin (3)、 isotetrahydroauro-glaucin (4)、dihydroauroglaucin (5)、isodihydroauroglaucin (6)、2-(1',5'-heptadienyl)-3, 6-dihydroxy-5-(3'-methyl-2'-butenyl) benzaldehyde (7)、auro-glaucin (8)和2-(2',3-epoxy-1'-heptenyl)-6-hydroxy-5- (3'methyl-2'-butenyl) benzaldehyde (9)。体外克服肿瘤耐药活性研究表明, 苯甲醛类化合物9具有较强的克服肿瘤耐药活性, 可能是由于其结构2位烷基侧链与3羟基形成吡喃环所致。     

海洋红藻多管藻内生真菌EN-22 的化学成分研究

对采自广西涠州岛近海多管藻(Poiysiphonia urceolata)分离到的一株内生真菌EN-22的次生代谢产物的化学成分进行了研究.利用正相硅胶柱层析、葡聚糖凝胶Sephadex LH-20柱层析、制备薄层层析(PTLC)以及重结晶等分离手段从该菌发酵液中分离得到15个化合物,通过一维、二维核磁共振技术、质谱技术等鉴定了所有化合物的结构,分别为:4-(4-喹啉)-4-羟基-2-丁酮(1),3-羟基-3-(2-氧丙基)吲哚-2-酮(2),3-吲哚乙醇(3),3-吲哚甲酸(4),2-羟基-3-吲哚丙酸(5),2-酮-3-吲哚乙醇(6),3,3-二吲哚-2-羟基-丙醇(7),β-咔啉(8),尿嘧啶(9),环-(S-脯氨酸-S-异亮氨酸)(10),(22E,24R)-3β,5α,9α-三羟基麦角甾-7,22-二烯-6-酮(11),(22E,24R)-5α,6α-环氧麦角甾-8,22-二烯-3β,7α-二醇(12),5α,6α-环氧-24(R)-甲基胆甾-7,22-二烯-3β-醇(13),胡萝卜苷(14),过氧化麦角甾醇(15);其中化合物1和2为新天然产物,并首次报道化合物1的碳谱数据.     

常山酮的合成方法研究

本文对常山酮(halofuginone)的合成方法进行了研究和改进,以2-甲基-3-羟基吡啶为起始原料,其甲基化产物与乙腈加成后经Rh/Al2O3选择性还原得(3-甲氧基-2-哌啶基)-丙酮,再经溴代、N-保护后与6-氯-7-溴-4(3H)-喹唑啉酮偶联,产物经水解脱保护得目标化合物6-氯-7-溴-3-(3-(3-羟基-2-哌啶基)-丙酮基)-4(3H)-喹唑啉酮氢溴酸盐,通过6步反应制得了常山酮,总收率为11.6%,为常山酮的工业化生产提供了可能。目标产物和各步中间体结构经MS1、H NMR和13CNMR确证。     

3株海洋来源微生物代谢产物及其抗肿瘤活性

从3株海洋微生物发酵物的抗肿瘤活性部位分离鉴定了放线菌内酯素(1)、2-吡咯酸(2)、5,7,4'-三羟基异黄酮(3)、7,4'-二羟基异黄酮(4)、环(脯-甘)二肽(5)、N-甲酰基-星形孢菌素(6)、过氧化麦角甾醇(7)、6,9-环氧麦角甾-7,22-二烯-3-醇(8)等8个化合物。这些化合物分别产自2株放线菌L39-3(1和2)、L20-1d1(3~6)和1株真菌LJW-110(7和8)。抗肿瘤活性初步测试结果表明,除2和5以外对K562细胞均有不同程度抑制作用,在100μg/mL浓度下的抑制率约在32%~66%范围之内。     

Microbial Biomass and Organic Nutrients in the Deep-Sea Sediments of the Central Indian Ocean Basin

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.     

海上大直径钢管桩打桩过程中桩周土强度弱化研究

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。     

Geoacoustic Inversion via Genetic Algorithm and Its Application to Manganese Sediment Identification

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.     

Phylogenetic diversity and phenotypic characterization of cultivable bacterioplankton isolated from polar oceans

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.     

Deep-Sea Sediment Compression Curves: Some Controlling Factors, Spurious Overconsolidation, Predictions, and Geophysical Reproduction

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.     

INFORMATION FOR AUTHORS

<正>Acta Oceanologica Sinica(AOS)is a comprehensive academic journal edited by the Editorial Committee of Acta Oceanologica Sinica and is designed to provide a forum for important research papers of the marine scientific community which reflect the information on a worldwide basis.The journal publishes scholarly papers on marine science and technology,including physics,chemistry,biology,     

Estimation of Sediment Properties during Benthic Impact Experiments

Sediment properties, such as water content and density, have been used to estimate the dry and wet weights, as well as the volume of sediment recovered and discharged, during benthic impact experiments conducted in the Pacific and Indian Oceans. The estimates show that the weights of dry (355-1332 t) and wet sediment (1651-4888 t) recovered during the experiments, are not only a function of the total duration and distance covered during the experiment, but also depend on water content and density of the sediment. Estimation of dry sediment and its volumetric ratio in the discharge, are key parameters for calculating the discharged volume. The estimated volume of wet sediment recovered (1427-4049 m 3 ) as well as discharged (2693-6951 m 3 ) during the experiments, provide important inputs to evaluate the sediment resettlement and migration. Using these estimates, the average depth of excavation on the seafloor, can also been calculated. However, the stages of sediment recovery and discharge are expressed differently in some of the experiments. In order to standardize these, different stages have been identified, and definitions of certain terms have been suggested, for use in the future. The methods of calculating different properties, as well as weight and volume of discharged sediment are described in the paper for use in other applications concerning deep-sea discharges.