三叉仙菜中4种化学成分的分离鉴定

为了进一步提取三叉仙菜(Ceramium rubrum)生物活性成分的化学物质,对其进行了较为系统的化学成分研究。从三叉仙菜的乙醇提取物中,运用硅胶柱色谱和SephadexLH20凝胶柱色谱层析分离得到4个化合物,经1H NMR,13C NMR和MS波谱分析,确定其结构分别为(1)3,7,11,15-tetramethyl-hexadec-2-en-1-ol;(2)cholest-5-en-3-βol;(3)3-palmitoyloxy-propane-1,2-diol;(4)adenosine,这4个化合物均为首次从该科植物中分离得到。     

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)。     

圆形短指软珊瑚化学成分的研究

从中国海南岛三亚附近海域采集的圆形短指软珊瑚Sinularia gyrosa中分离得到4个化合物，经IR，^1H NMR和^13C NMR谱分析确定它闪的化学结构分别是孕甾烯醇酮（Ⅰ），24-亚甲基胆甾醇（Ⅱ），神经酰胺（Ⅱ），鲨肝醇（Ⅳ）。其中（Ⅰ）是首次从该种软珊瑚中分离得到。     

海筒螅中3种化学成分的分离鉴定

海筒螅（Tubuaria marina)的94%乙醇提取物，在水中混悬后，用石油醚萃取，石油醚相中的提取物经反复硅胶柱色谱分离和SephadexLH-20凝胶柱色谱分离，得到三个纯净的化合物。经^1HNMR,^13CNMR和DEPT谱鉴定，分别确定为二十一碳一烯，胆甾-5-烯-3β-醇和1-壬基-甘油醚。     

北美洲东南近海布莱克海岭中气体水合物赋存沉积区域内自生碳酸盐矿物的分带特点

自生碳酸盐矿物的分布特点，是体现孔隙水地球化学特征的一个侧面。在布莱克海岭气体水合物赋存的沉积区域里(ODP994#、995#、997#)就利用这点来评价成岩作用。碳酸盐矿物的分布特点揭示了三个独特的成岩分带：(1)在上部20mbsf (bsf：below seafloor，海底以下深度)处的碳酸盐矿物主要是生物成因的，没有显示成岩作用的存在。这个区域的方解石FOC和8180值(PDB)反映了海相碳酸盐的特点，是与海水平衡的条件下沉淀形成的；(2)在20mbsf和100mbsf深度，方解石的FOC值明显呈现负数(低至-7．0‰)，自生白云石较普遍可见(2—40wt％)，δ^13C值在3．6‰～13．7‰之间；(3)在，100mbsf以下，白云石从含量丰富减低至微量分布，而分散状的菱铁矿成为主要出现的矿物。菱铁矿的δ^1C和δ^18O值分别在5．0‰～10．9‰、2．9‰～7．6‰之间变化。把溶解无机碳(DIC)的δ^1C剖面分布特点和孔隙水的浓集梯度趋势与自生碳酸盐矿物的δ^13C和δ^18O值对比，我们发现，自生碳酸盐矿物在一个独特的深度区域里形成，呈带状分布。在20mbsf深度及以下，无机碳的δ^13C DIC出现最小负值(≤-38‰)、方解石白云石出现δ^13C负值，这种现象的出现是伴随着孔隙水碱度的增加、硫酸盐的亏损和孔隙间Ca^ 2 、Mg^ 2 离子的减少一起发生的，这表明自生方解石和自生白云石的形成是在硫酸盐还原带的底部开始(21mbsf左右)而在100mbsf附近深处大量出现。菱铁矿的形成很显然是在120～450mbsf之间发生，这个区间在气体水合物赋存的沉积物区域内和上部(赋存区域200—450mbsf)。菱铁矿的δ^13C和δ^18O值从它们出现的薄层一直到沉积物底部都几乎一致。然而，现在孔隙水中的δ^13C DIC仅仅与120～450mbsf间的菱铁矿的δ^13C值相似。此外，从菱铁矿中计算出来的与之平衡的δ^18O值与120～450mbsf区段处菱铁矿的δ^18O测量值很好地匹配起来。该区段以高碱度(40-120mm)、低Ca^ 2 、Mg^ 2 浓集度为特征，这符合菱铁矿的形成条件。     

太湖沉积物碳氮同位素组成特征与环境意义

对太湖不同湖区沉积物有机质δ^13C、δ^15N分析表明，草型湖区沉积物有机质δ^13C、δ^15N总体比藻型湖区高。湖泊从贫-中营养水体向中-富营养演化过程中，沉积物有机质δ^13C、δ^15N表现为逐渐上升的趋势，沉积物TP、TN则因受多种因素影响在各湖区表现出差异。湖泊演化到富营养阶段，沉积物有机质δ^13C、δ^15N表现为明显的偏负。近50年来不同湖区沉积物有机质δ^13C、δ^15N反映的湖泊环境演化过程与实际环境检测结果有较好的一致性，20世纪太湖水环境存在50年代及90年代两次较明显转化过程。     

液相色谱法测定鱼肌肉中孔雀石绿、结晶紫及其代谢物

孔雀石绿(MG)和结晶紫(GV)曾作为渔药使用,在鱼体内可分别代谢为无色孔雀石绿(LMG)及无色结晶紫(LGV),具有潜在的致癌性,已被许多国家禁用。本文研究了同时检测孔雀石绿、结晶紫及其代谢物无色孔雀石绿和无色结晶紫的液相色谱方法,建立了检测前处理方法及色谱条件。经过液液萃取和丙基磺酸阳离子树脂纯化,采用C18分离柱后串联二氧化铅柱氧化衍生的方法,同时检测母体药物及其代谢物,回收率>70%,重复性的相对标准偏差<15%,定量限分别为2μg/kg及1μg/kg。经样品实测,在一份鲈鱼样品中检测到无色孔雀石绿残留97μg/kg。     

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。     

印度南部热带泥炭晚第四纪气候变化的δ^13C记录

利用稳定碳同位索比值作为古气候的指示剂．取决于C3和C4植物型对生态环境的不同要求，它们的^13C／^12C之比差异较大．C3和C4植物按照各自固碳的光合作用途径，二者分别具有-26‰--28‰和-11‰--13‰的δ^13C值．这也说明它们对生态环境的不同选择．     

南沙海区表层沉积物放射性核素分布特征

用HPGeγ能谱方法测定了南沙海域表层沉积物，探测到的核素有^40K,^137Cs,^210Pb,^226Ra,^228Ra,^228Th,^238U.整体趋势为：^40K,^228Ra,^228Th,^238U4核素比活度为海盆＞陆坡＞陆架，^210Pb,^226Ra为陆坡＞海盆＞陆架，在陆坡区未探测到^137Cs，海盆的^137Cs高于陆架，波折沉积物中核素含量表现了与陆架和陆坡区不同的特征，而坡区^40K,^228Th,^238U4种核素的比活度中帽西向东逐渐降低，整个海区^228Ra,^228Th两种核素由南北向逐渐增大。     

卡拉胶及其结构研究进展

本文概述了卡拉胶的类型、命名、卡拉胶结构特征及卡拉胶在藻体中的存在情况，介绍了卡拉胶的一些分析方法。     

基于核磁共振的褐牙鲆幼鱼组织代谢组学分析

基于核磁共振的代谢组学技术是系统生物学研究的重要组成部分,近年来已被广泛应用于海洋生物学中。由于海洋环境具有高盐度的特点,海洋生物与其他生物相比,体内代谢物浓度差异极大。通常来说,海洋生物为应对高盐度的海水环境,其体内的渗透调节物,例如牛磺酸、甜菜碱、氮氧三甲胺等的浓度往往是其他代谢物的数百倍,造成体内代谢物所占代谢组权重的极不均衡。因此,选择合适的代谢组数据预处理方法,是准确分析海洋生物代谢组差异的关键。本研究以褐牙鲆(Paralichthys olivaceus)幼鱼为研究对象,经低盐胁迫48小时后,利用一维核磁共振氢谱,分析了褐牙鲆幼鱼全组织在低盐胁迫后的代谢组变化,比较了三种不同预处理方法 (单位方差换算、帕莱托换算与对数化-中心化处理)对于低盐胁迫诱导的代谢响应分析的差异。结果表明,褐牙鲆幼鱼体内的渗透调节物-氮氧三甲胺浓度是其他代谢物浓度的200倍以上,而低盐胁迫可诱导褐牙鲆幼鱼体内显著的代谢响应。其中,对数化-中心化处理的代谢组数据,经正交偏最小二乘判别分析后,能发现8个低盐胁迫诱导的差异代谢物(不含1个未知代谢物),与代谢物定量结果一致,多于其他两种预处理方法 (单位方差换算、帕莱托换算)的代谢组分析结果,适合用于褐牙鲆代谢组学分析。以上研究结果为褐牙鲆代谢组数据的准确分析提供了方法学依据。     

GC-MS联合二维核磁对文蛤多糖Fr.2A组分结构的解析

采用GC-MS联合二维核磁的方法,对文蛤均多糖结构进行解析。运用双酶辅助水提的方法,提取文蛤粗多糖(MMPX),分离纯化得到文蛤均多糖,并通过气质联用技术(GC-MS)和核磁共振波谱(1D,2D NMR),对文蛤均多糖的结构进行了分析。结果表明,从文蛤中提取得到文蛤粗多糖(MMPX),经分离纯化得到高纯度文蛤均多糖Fr.2A,其单糖组成为葡萄糖(Glc)。GC-MS分析发现,Fr.2A存在三种残基单元1,4-Glcp、T-Glcp和1,4,6-Glcp,摩尔比为5.58︰1.26︰1.0;核磁共振波谱分析表明,Fr.2A是以α-(1→4)与少量α-(1→6)连接为主链,并存在少量的α-(1→6)和β-(1→4)支链的新型水溶性D型吡喃葡聚糖。     

Extending NMR data for permeability estimation in fine-grained sediments

We combine nuclear magnetic resonance (NMR) transverse relaxation time data and gamma ray data to estimate lithology-dependent permeability in silt- and clay-rich sediments. This approach extends the utility of the Schlumberger-Doll Research (SDR) permeability equation from reservoirs to aquicludes and seals, and thus improves the value and robustness of NMR data. Data from Keathley Canyon, northern Gulf of Mexico show that NMR data can be used to define permeability from 10⁻¹⁸ to 10⁻¹⁴ m² (0.001–10 millidarcies) as calibrated and tested by direct measurements on core samples. We performed uniaxial, constant rate-of-strain consolidation experiments on sediments from Keathley Canyon to determine core-scale permeability. Permeabilities from these experiments were compared to permeabilities calculated from logging-while-drilling data. A better fit between log-derived permeability and laboratory-measured permeability was obtained using the SDR equation with a variable coefficient A, rather than a constant A as is typically used. We show how A is a function of lithology and can be modeled from gamma ray data. The relationship between A and gamma ray values suggests that variations in A are caused by platy clay minerals and the effect they have on the pore system. Our results provide improved means for permeability estimation for application in basin flow modeling, hydrocarbon migration modeling, and well completion design.     

不饱和古罗糖醛酸三糖和甘露糖醛酸三糖的结构表征

以双功能褐藻胶裂解酶 (Pseudoalteromonas sp.strain No. 2 72 )分别降解均聚古罗糖醛酸(PG)和均聚甘露糖醛酸 (PM) ,经 Bio- Gel- P6和 POROS- HQ2 0分离得到 2种三糖纯品 ,经 ESI- MS,1 H- NMR,1 3 C- NMR,1 H- 1 H COSY,1 H- 1 3 C HMQC确定其结构为 Δ4,5-古罗糖醛酸 - α(1→ 4 ) - L-古罗糖醛酸 -α(1→ 4 ) - L -古罗糖醛酸 (简写为Δ GG)和Δ4,5-甘露糖醛酸 -β (1→ 4 ) - D-甘露糖醛酸 -β (1→ 4 ) - D-甘露糖醛酸 (ΔMM) ,为进一步从事构效关系研究提供结构信息。     

Permeability in Rotliegend gas sandstones to gas and brine as predicted from NMR,mercury injection and image analysis

Permeability characterisation of low permeability, clay-rich gas sandstones is part of production forecasting and reservoir management. The physically based Kozeny (1927) equation linking permeability with porosity and pore size is derived for a porous medium with a homogeneous pore size, whereas the pore sizes in tight sandstones can range from nm to μm. Nuclear magnetic resonance (NMR) transverse relaxation was used to estimate a pore size distribution for 63 samples of Rotliegend sandstone. The surface relaxation parameter required to relate NMR to pore size is estimated by combination of NMR and mercury injection data. To estimate which pores control permeability to gas, gas permeability was calculated for each pore size increment by using the Kozeny equation. Permeability to brine is modelled by assuming a bound water layer on the mineral pore interface. The measured brine permeabilities are lower than predicted based on bound water alone for these illite rich samples. Based on the fibrous textures of illite as visible in electron microscopy we speculate that these may contribute to a lower brine permeability.     

Study of macroaggregate composition using FT-IR and H-NMR spectroscopy

Mucous macroaggregates, recently observed in the northern Adriatic in summer of 1997 and late spring of 2000, are primarily the product of phytoplankton (diatom) exudates during favourable environmental conditions in late spring, and can be viewed as macrogels. The FT-IR and ¹H-NMR spectra of macroaggregate samples from the northern Adriatic, collected in different formation stages in July 1997, August 1997, September 1997 and June 2000, as well as of cultured diatom Skeletonema costatum, showed that they are similar and composed of aliphatic components and polysaccharides bonded through carboxylic and amide groups, and organosilicon compounds. The stability of macrogels of macroaggregates is, according to FT-IR and X-ray analyses, most probably enhanced by interactions with entrapped particles of calcite, quartz and clay minerals. These organic-mineral associations seem to be important for mucous phenomena. According to ¹H-NMR spectra, the temporal differences in macroaggregate composition show a relative increasing percentage of organosilicon compounds and aliphatic components bonded to carbohydrates through ester and amide groups, and an increasing ratio between aliphatic structures and carbohydrates. This indicates that aliphatic chains bonded to Si and carbohydrates may contribute to the persistence and stability of macroaggregates in the summer stratified waters in the northern Adriatic, while the temporal decrease of carbohydrate content is most probably due to microbial and photochemical degradation of algal reserve polysaccharides.     

不同取代位置羧甲基壳聚糖的核磁共振波谱和电位滴定分析

本文制备了O-羧甲基壳聚糖、N-羧甲基壳聚糖和N,O-羧甲基壳聚糖,并采用核磁共振波谱以及电位滴定方法对不同取代位置羧甲基壳聚糖取代度进行了分析。结果表明,核磁共振碳谱及DEPT谱可以确定羧甲基壳聚糖中羧甲基的取代位置,电位滴定法可以确定O-位羧甲基、N-位羧甲基以及总羧甲基的取代度,是一种简单易行的方法。     

固相萃取法提取典型海水溶解有机质及其红外光谱和固态13C核磁共振表征

由于海水盐度大、有机质含量低,从海水中提取和纯化克级溶解性有机质(dissolved organic matter,DOM)一直十分困难。基于Bond Elut PPL固相萃取小柱法进行海水DOM固体样品提取的放大试验,建立DOM自动化调酸、PPL树脂吸附技术,最后形成提纯、冷冻干燥PPL-DOM(通过PPL树脂提取的DOM)完整工艺。采用元素分析、三维荧光光谱、红外光谱和固态¹³C核磁共振(NMR)波谱法进行样品表征。结果表明:(1)该方法对近海表层海水DOM回收率稳定在50%以上,搭建的提取装置DOM日吸附量可达230mg;(2)鳌山湾四个季节批次PPL-DOM整体分析结果表明,样品的元素组成和光谱特征相似,表明方法适用性和稳定性较好;(3)三种水生态环境的PPL-DOM¹³C NMR谱图显示样品的基本特征相似,以烷基碳、碳水化合物碳、芳香碳和羧基碳/酰胺碳为主,其中偶极去相(dipolar dephasing)谱显示了DOM前体化合物来源的差异。多种结果表明放大后的PPL固相萃取法可稳定提取克级DOM样品。     

Investigation on the pore structure and multifractal characteristics of tight oil reservoirs using NMR measurements: Permian Lucaogou Formation in Jimusaer Sag,Junggar Basin

Pore structure is a critical parameter to estimate the reservoir quality and evaluate the resource potential. However, the pore structure and heterogeneity of the unconventional tight oil reservoirs of Permian Lucaogou Formation of Jimusaer Sag, Junggar Basin are not studied well. In this paper, the multifractal analysis based on the NMR T₂ distributions was applied to investigate the pore structure and heterogeneity. The reservoir quality index (RQI) and flow zone indicator (FZI) were calculated using porosity and permeability. Two parameters T₃₅ and T₅₀ were newly defined as relaxation times corresponding to the 35% and 50% saturation on the T₂ reverse accumulative curve, respectively. The results showed that the RQI, and FZI values were extremely low, and that the NMR T₂ distributions of water saturated samples had much short relaxation components with no or little long relaxation components, indicating a complex and poor microscopic pore structure of tight oil rocks. The typical multifractal characteristics, such as the large values of singularity strength range (Δα), revealed that the pore structures of samples were strongly heterogeneous. It was also found that the clay contents have an obvious influence on the multifractal parameters, and the FZI and new defined T₃₅ are two good indicators for heterogeneity of pore structure. In addition, the feasibility and applicability of calculating the multifractal parameters from NMR and other well logs were discussed.