褐藻小粘膜藻的化学成分

应用正相硅胶、生物胶Bio-Beads、凝胶Sephadex LH-20柱色谱和反相HPLC等层析方法,从小粘膜藻(Leathesia nana)中分离得到7个化合物,通过IR、MS、1D和2DNMR等波谱技术鉴定为4-羟基苯甲酸(1)、3．羟乙酰基吲哚(2)、2,3-二溴．4,5-二羟基苯甲醛(3)、3-溴-4,5-二羟基苯甲醛(4)、2,3．二溴-4,5．二羟基苯甲基乙醚(5)、双-(2,3-二溴-4,5-二羟基卞基)-醚(6)和3．溴-4．(2,3-二溴-4,5-二羟基苯甲基)-5-甲氧甲基苯二酚(7)。     

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。     

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)。     

坛紫菜(Porphyra haitanensis)化学成分的研究

利用硅胶色谱、Sephadex LH-20凝胶色谱、HPLC等技术,从坛紫菜(Porphyra haitanensis)乙醇提取物首次分离纯化得到了7个化合物,通过质谱(MS)及核磁共振波谱(1H NMR、13C NMR)等现代波谱技术鉴定为：1,8-二羟基-9,10-蒽醌(1)、邻苯二甲酸二正丁酯(2)、邻苯二甲酸二异丁酯(3)、β-谷甾醇(4)、鲨肝醇(5)、(E)-N-2(1,3-二羟基-4-十八烯基)-十六酰胺(6)、胆甾醇(7)。其中,化合物1对金黄色葡萄球菌(Staphyloccocus aureus)的最低抑菌浓度(MIC)为80μg/mL。     

海洋褐藻叉开网翼藻中的单萜成分研究

为了研究中国沿海海藻中的活性化学成分, 利用正相硅胶柱色谱、Sephadex LH-20 柱色谱、反相HPLC 及重结晶等手段, 从采自青岛的褐藻叉开网翼藻(Dictyopteris divaricata Okam.)中首次分离得到了6 个单萜类化合物, 经红外波谱(IR), 质谱(MS)及核磁共振波谱(¹H NMR、¹³C NMR)等现代波谱技术鉴定为loliolide (1), isololiolide (2), 3β-hydroxy-5α,6α-epoxy-7-megastigmen-9-one (3), dehydrovomifoliol(4), (3R)-4-[(2R,4S)-2-hydroxy-2,6,6-trimethylcyclohexylidene]-3-buten-2-oneiol (5), (3R)-4-[(2R,4S)-4-acetoxy-2-hydroxy-2,6,6-trimethylcyclohexylidene]-3-buten-2-one (6)。并通过MTT 法对所得化合物进行细胞毒活性筛选, 通过比色法进行乙酰胆碱酯酶抑制活性筛选。     

瘤状软骨凹顶藻化学成分研究

采用硅胶柱色谱以及Sephadex LH-20凝胶色谱手段,对海洋红藻瘤状软骨凹顶藻(Chondrophycus papillous Garbary et Harper)进行化学成分研究,分离得到5个化合物.通过MS、NMR等方法对得到的化合物进行结构确证,分别鉴定为邻苯二甲酸二丁酯(Ⅰ),邻苯二甲酸二异辛酯(Ⅱ),胆甾醇(Ⅲ),植醇(Ⅳ)和4-羟基苯甲醛(Ⅴ).所有化合物均为首次从该种海藻中分离得到.通过MTT法对得到的单体化合物进行细胞毒活性筛选,结果显示所有化合物在10 mg/L浓度下均无明显活性.     

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。     

海洋链霉菌L211 次生代谢产物分离和结构鉴定

利用硅胶柱、凝胶柱及制备薄层色谱等色谱方法对海洋链霉菌Streptomyces sp.L211发酵液的乙酸乙酯相浸膏进行了分离,通过1H-NMR、13C-NMR、EIMS等方法鉴定了10个化合物:Kalamycin(1),Medermycin(2),Menoxymycin-B(3),spatozoate(4),邻氨基苯甲酸(5),3-吲哚乙醇(6),1-乙酰基咔啉(7),对羟基苯基乙醇(8),吲哚-3-乙酸(9),吲哚-3-甲酸(10)。     

海绵共附生放线菌SH6004菌株中抗肿瘤活性成分的研究

研究共附生微生物,采用活性追踪的方法从1株海绵共附生放线菌SH6004的乙酸乙酯提取物中分离得到7个化合物,根据化合物的光谱特征和理化性质分别鉴定为N-甲基苯甲酰胺(1),2-苯甲酰氧基乙酸(2),对羟基苯乙酰胺(3),N-[2-(4-羟基苯基)乙基]乙酰胺(4),环-(丙-异亮)(5),尿嘧啶-2′-脱氧核苷(6)和胸腺嘧啶-2′-脱氧核苷(7).并利用SRB(丽丝胺罗丹明B)法,对7个单体化合物的体外抗肿瘤活性进行了初步评价,其中化合物3、6和7显示了弱的抗肿瘤活性.     

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.     

南海礁栖海藻共附生真菌Pestalotiopsis neglecta SCSIO41 403次级代谢产物研究

研究南海礁栖腔节藻Coelarthrum sp.共附生真菌Pestalotiopsis neglecta SCSIO41403的次级代谢产物。采用中压正相柱层析色谱法和半制备高效液相色谱法, 对真菌发酵产物进行分离纯化, 制备获得6个次级代谢产物单体化合物, 使用核磁共振、质谱等波谱学方法, 结合其理化性质以及文献数据对比, 分别鉴定为: gamahorin (1)、microsporaline C (2)、7-hydroxy-5-methoxy-4,6-dimethylphthalidc (3)、demethyl nectriapyrone A (4)、4-hydroxybenzaldehyde (5)和4-hydroxyphenethyl acetate (6)。这6个化合物均为首次从该菌株发现, 其中化合物1、2、5和6是首次从海洋动植物共附生真菌中发现。抗菌活性筛选显示其中化合物3对白色念珠菌有明显抑制活性。     

产自两株海洋真菌的三种鞘脂类的结构测定

3种鞘脂类代谢产物N-2’-羟基十六碳酰基-1-O-β-D-吡喃葡萄糖基-9-甲基-4E,8E-十八碳二烯-1-醇(A)、N-2’-羟基-3’E-十八碳烯酰基-1-O-β-D-吡喃葡萄糖基-9-甲基-4E,8E-十八碳二烯-1-醇(B)和N-十六碳酰基二氢鞘氨醇(C)分别产生于来源于中国南海的2株海洋真菌(菌株编号为1924和3893),通过2DNMR、MS等方法测定了它们的结构。这是首次从南海红树内生真菌分离得到的3种鞘脂类代谢产物。     

深海冷泉来源真菌Talaromyces helicus SCSIO41311中聚酮类化学成分研究

文章旨在研究南海冷泉来源真菌Talaromyces helicus SCSIO41311中聚酮类次生代谢产物。主要采用正相硅胶柱层析、反相硅胶柱层析、Sephadex LH-20、高效液相色谱(high performance liquid chromatography, HPLC)及薄层色谱(thin layer chromatography, TLC)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)等现代波谱分析方法及理化性质进行结构鉴定。从中分离得到7个聚酮类化合物, 分别为: desmethylsulochrin (1)、sulochrin (2)、monomethylsulochrin (3)、circinophoric acid (4)、dimethyl 2,3-dimethylosoate (5)、endocrocin (6)和1-methyl emodin (7)。所有化合物均为首次从深海冷泉微生物中得到, 其中化合物1为首次报道其核磁数据。     

Dissolved Vanillin as Tracer for Estuarine Lignin Conversion

Lignin is produced only by vascular plants and therefore can be used as a tracer for terrestrial organic carbon input to the estuarine and marine environments. Lignin measurements have been done by analyses of the oxidation products such as vanillin or 4-hydroxybenzaldehyde.In the Elbe Estuary, free dissolved vanillin was analysed in order to test whether such measurements yield information on terrestrial carbon inputs into the Estuary and on the vanillin derived from lignin oxidation. In the period 1990–1992, concentrations of dissolved vanillin in the Elbe ranged from 0 to 60 μg l⁻¹(mean: 8 μg l⁻¹). Higher values were found in areas of increased microbial activity such as the turbidity zone and the river mouth where the water chemistry is influenced by large tidal flats. No correlation was found between dissolved vanillin and suspended matter concentrations, although lignin is normally associated with suspended particulate matter, nor was a covariance seen between dissolved vanillin and the terrestrial carbon inputs into the Estuary. Apparently, biological conversion of lignin was faster than the transport processes, and local sources were more dominant for the vanillin concentration than riverine sources. The dissolved vanillin turnover was fast and, consequently, a significant amount of lignin may be converted within an estuary. In sediments from the Estuary, the concentrations of dissolved vanillin were similar to those found in the water phase and showed no clear vertical profile. The sediment is unlikely to be the source for vanillin.     

Investigation of the carrageenans extracted from Solieria filiformis and Agardhiella subulata from Mar Piccolo, Taranto

Dried samples of the red algae Solieria filiformis and Agardhiella subulata from Mar Piccolo, Taranto, were extracted by stirring in water at 25 (Cold), 85 (Hot) and 120 (pressure) °C. For each species, six successive cold, three hot and two pressure extractions were performed and analyzed separately. Water-soluble polysaccharides were isolated after treatment with amylase, alcohol precipitation, dialysis and freeze drying. The total, starch-free yields were 27 and 24% of the dry weight for S. filiformis (SF) and A. subulata (AS), respectively. FTIR and NMR spectroscopic analysis showed that the different cold and hot water extracts had a similar structural backbone, which can be characteristic of gelling type carrageenans with a dominant iota repeating structure (DA2S-G4S). However, some irregularities were detected by NMR, which may be attributed to 6-sulphated 4-linked precursor units. The occurrence of such and other irregularities was more frequent in the SF samples, giving a possible explanation for the enhanced extractability in cold water of carrageenan polymers from this species.     

老鼠簕植物内生真菌Aspergillus terreus (W-8)抗肿瘤活性成分的研究

对红树林植物的枝干、枝叶样品进行微生物分离,以P388细胞为模型进行活性评价得到14株具有抗肿瘤活性的真菌。采用溶剂萃取、柱色谱及半制备HPLC等分离手段对来源于红树林植物老鼠簕Acanthus ilicifolius Linn.的菌株Aspergillus terreus(W-8)发酵产物进行了活性追踪分离,共得到5个化合物。通过理化性质及波谱技术,结合文献,鉴定其结构分别为aspulvinone H1(1)、aspulvinone H(2)b、utyrolactone I(3)t、errein(4)和3-propylbenzene-1,2-diol(5),其中化合物1的核磁数据为首次报道。采用MTT法初步评价了单体化合物的抗肿瘤活性,结果表明化合物4、5对A549、K562和Hela细胞均具有中等强度的细胞毒活性。     

海绵来源真菌Aspergillus sp BH4次级代谢产物的初步研究

研究1株来源于海绵的真菌Aspergillus sp BH4的次级代谢产物，该菌的发酵产物具有细胞毒活性。采用硅胶柱色谱、制备薄层色谱及重结晶方法，对其活性组分一乙酸乙酯提取物的化学成分进行分离纯化，结合文献及NMR，MS波谱数据确定了4个单体化合物的结构。     

鸭毛藻内生真菌Hypocreales sp.的化学成分研究

从采自大连近海的红藻鸭毛藻（Symphyocladia latiuscula）中分离到一株肉座菌目真菌（Hypocreales sp．），对其发酵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，并通过一维、二维核磁共振技术、质谱技术等从该菌发酵液中分离鉴定了10个化舍物：双酚A（1）；邻羟基苯甲酸（2）；吲哚甲酸（3）；吲哚乙酸（4）；N-乙酰色胺（5）；（22E，24R）-麦角甾-7，9，22三烯-3β-醇（6）；过氧化麦角甾醇（7）；（22E，24R）-5α，6α-环氧麦角甾-8，22-二烯-3β，7α-二醇（8）；（22E，24R）-麦角甾-7，22-二烯-6β-甲氧基-3β，5α-二醇（9）；啤酒甾醇（10）。这些化合物均为首次从该菌中分离得到，其中化合物1为首次作为天然产物分离得到。     

中国南海短指软珊瑚中化学成分的研究

运用硅胶柱层析、Sephadex LH-20凝胶柱层析和HPLC等技术,采用活性追踪分离的方法,对南海短指软珊瑚Sinularia sp.的化学成分进行了研究.从乙醇提取物中分离获得单体化合物,运用NMR,MS等波谱技术鉴定了8个化合物的结构,分别为:3β-羟基-24-亚甲基胆甾-5-烯-7-酮(1),孕甾烯醇酮(2),cembrene A(3),epoxycembrane A(4),4,8,12-trimethyl-1-(1-methylethenyl)-3,7-cyclotetradecadien-10-one(5),(3E,7E,11E)-11,12-dihydroxy-1-isopropyl-4,8,12-trimethyicyclotetradeca-1,3,7-triene(6),邻苯二甲酸二丁酯(7)和十九烷-2-酮(8).化合物5和8为首次从珊瑚动物中分离得到,6为首次从短指软珊瑚属中分离得到.化合物3和4显示较强的卤虫致死活性.西松烷二萜类化合物是该短指软珊瑚中的重要活性成分.     

New insight into the microtexture of chalks from NMR analysis

An integrated petrographical and petrophysical study was carried out on a set of 35 outcrop chalk samples, covering a wide range of lithologies and textures. In this study various chalk rock-types have been characterized, in terms of microtextures and porous network, by integrating both geological, sediment-petrological and petrophysical data, including porosity, permeability, low-field NMR (Nuclear Magnetic Resonance), MICP and specific surface area (BET) measurements. The data allow an in depth understanding of the NMR signal of chalks, with a focus on tight chalks, including all low reservoir quality chalks independently of their sedimentological and/or diagenetic history. The study aims to develop an NMR-based approach to characterize a broad range of chalk samples. The provided laboratory low-field NMR chalk classification can be used as a guide to interpret NMR logging data.Based on the petrographical and petrophysical analysis, 6 groups of samples were identified, each of them characterized by a unique NMR signature: (1) micritic chalks, (2) grainy chalks, (3) cemented chalks, (4) marl-seam chalks, (5) argillaceous chalks and (6) silicified chalk. NMR T₂ distributions were linked to pore body size and T₂ logarithmic (T_2lm) was calculated. It is apparent that tight chalks, whether their characteristics are sedimentological or diagenetic, yield smaller pore body sizes (T_2lm < 20 ms), as well as narrower pore throats (average radius < 150 nm) and lower permeability values (typically below 0.2 mD). Grainy chalks possess T₂ distributions reflecting larger pore sizes (T_2lm > 60 ms) and pore throats (average radius > 290 nm) and higher permeabilities (up to 13 mD). The marl-seam chalk samples yield bimodal T₂ distributions, with a first peak related to the micritic matrix pores and a second peak related to intraparticle pores within fossils. For all samples, permeability was inferred from NMR spectra using SDR (Schlumberger Doll Research) model.