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。     

傅里叶变换离子回旋共振质谱的地球化学意义及其在油气勘探中的应用前景

NSO杂原子化合物在烃源岩和原油中通常只占很小的一部分,但其包含重要的地质地球化学信息。由于组成复杂且难以分离,对该类化合物的组成研究相对薄弱。电喷雾电离源（ESI）结合傅里叶变换离子回旋共振质谱（FT-ICR MS）是一种新型检测石油组分的手段,具有选择性电离、超高质谱分辨率和质量精度等特征,非常适合检测石油复杂基质中微量NSO极性杂原子化合物分子组成,近年来开始应用于油气勘探领域。结合对塔里木盆地海相油与陆相油、辽河稠油等样品的FT-ICR MS分析,发现原油中NSO化合物受母源岩与油气成因类型、成熟度、油气运移示踪及硫酸盐热化学还原反应（TSR）控制,可提供相关的识别与评价信息,显示FT-ICR MS在油气地球化学理论研究和油气勘探中具有潜在的应用价值。     

Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

ESI高影响论文揭示的北极自然科学研究特点

在全球气候持续变暖背景下,北极地区冻土退化、冰川退缩、海冰减少等导致了一系列的生态环境问题,同时也使得资源勘探开发与国际新航道开通成为可能,北极地区的重要性日益凸显.依据2009—2019年6月期间有关北极研究的408篇ESI高影响论文,对发文量、主要作者、研究机构、国家、研究方向等字段进行分析,从自然科学角度,宏观而...     

Integrated assessment for establishing an oil environmental vulnerability map: Case study for the Santos Basin region,Brazil

The growth of maritime transport and oil exploitation activities may increase the risk of oil spills. Thus, plans and actions to prevent or mitigate impacts are needed to minimize the effects caused by oil. However, tools used worldwide to support contingency plans have not been integrated, thus leading to failure in establishing priority areas. This investigation aimed to develop indices of environmental vulnerability to oil (IEVO), by combining information about environmental sensibility to oil and results of numerical modeling of spilled oil. To achieve that, a case study concerning to oil spills scenarios in a subtropical coastal area was designed, and IEVOs were calculated and presented in maps, in order to make the information about the areas’ vulnerability more easily visualized. For summer, the extension of coastline potentially affected by oil was approximately 150 km, and most of the coastline presented medium to high vulnerability. For winter, 230 km coastline would be affected, from which 75% were classified as medium to high vulnerability. Thus, IEVO maps allowed a rapid and clearer interpretation of the vulnerability of the mapped region, facilitating the planning process and the actions in response to an oil spill.     

ESI计量分析数据库的功能与科学评价——以中国地学研究机构的科学评价为例

ESI是国际著名的学术信息机构ISI建设的衡量科学研究绩效、跟踪科学发展趋势的计量分析数据库。在介绍ESI功能的基础上,利用ESI中10年来中国地球科学论文被引情况对国家评价、研究机构评价、科学家评价、期刊评价、论文评价等方面进行了分析。从发表论文数量看,中国已经进入地学大国的行列,但与地学强国还相距甚远。地学科学家应该在提高论文质量、提升论文引用率方面更加努力,为我国乃至世界地球科学的发展做出更大的贡献。     

Quantification of Diclofenac in Hospital Effluent and Identification of Metabolites and Degradation Products

In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10^?3 mol L^?1, and phase B was methanol (5 × 10^?3 mol L^?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L^?1, the LQs, 8.3 and 0.05 µg L^?1, and the linear range from 10 up to 2000 µg L^?1 and 0.05 up to 10 µg L^?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.     

Bioassay‐directed fractionation for analyzing estrogens in surface waters of the German Baltic Sea

A reversed‐phase fractionation method with subsequent biological and chemical analysis has been developed to estimate the contributions of the most potent estrogens to observed estrogenic effect potentials. Surface water samples were taken in the German Baltic Sea (Inner Wismar Bay and Darss Peninsula, sampling campaign July 2003) and were separated into seven individual fractions. Three fractions showed significant estrogenic activities and clear dose‐dependant responses were obtained in the yeast estrogen screen (YES). In the 2nd fractions liquid chromatographic‐electrospray‐tandem mass spectrometric (LC‐ESI‐MS‐MS) analyses showed the presence of bisphenol A (Inner Wismar Bay: 4.8 ng L^–1 and 6 ng L^–1; Darss Peninsula: 0.91 ng L^–1 and 1.7 ng L^–1) and ethinylestradiol (Inner Wismar Bay: 2.0 ng L^–1 and 6.0 ng L^–1; Darss Peninsula: < MDL and 1.7 ng L^–1), whereas estrogenic activities in the YES were only around 10% of the positive control E2. Although not identified prior in the total extract the natural hormones estradiol (Inner Wismar Bay: 0.13 ng L^–1 and 0.19 ng L^–1; Darss Peninsula: 0.12 ng L^–1 and 0.16 ng L^–1) and estriol (Inner Wismar Bay: < MDL and 0.33 ng L^–1; Darss Peninsula: < MDL) could be detected in the 3rd fractions, where high estrogenic potentials could be observed. The 4th fractions showed high responses as well and estrone were herein quantified with concentrations of 0.16 ng L^–1 and 0.18 ng L^–1 (Darss Peninsula) up to 0.37 ng L^–1 (Inner Wismar Bay). Measured and calculated estradiol equivalents for individual fractions correlated very well (R² = 0.78), when disregarding results of the 2nd fraction, where high deviations occurred.     

乍得Bongor强反转裂谷盆地高酸值原油成因

乍得Bongor盆地是受中非剪切带影响发育起来的中、新生代陆内强反转裂谷盆地,反转和走滑构造是盆地最显著的构造特征。所发现的原油主要为中质油(重度为20°～34°API),其次为重质油(重度小于20°API),普遍高含沥青质、高含蜡、高酸值、低含硫。为了探讨高酸值原油的成因,作者选择了该盆地15个不同酸值的原油样品,尝试应用高分辨率质谱分析原油有机酸的组成。分析结果表明,高酸值原油的有机酸主要由环烷酸组成;环烷酸碳原子数分布范围较宽,且以一环、二环、三环环烷酸为主。生物降解作用是形成高酸值原油的主要原因,而构造反转造成盆地抬升,则加速了生物降解作用的发生。     

Effect of secondary oil migration distance on composition of acidic NSO compounds in crude oils determined by negative-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry

The acidic and neutral NSO compounds in a series of Duvernay-sourced oils in Canada, which are believed to have migrated extensively over relatively long distances such as along the Rimbey-Meadowbrook reef trends, were characterized by negative-ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Heteroatomic compounds were characterized according to their class (number of nitrogen, oxygen and sulfur heteroatoms), degree of aromaticity [rings plus double bonds (DBE)] and carbon number distribution. The N₁, N₁O₁, N₁O₂, N₁S₁, O₁ and O₂ classes were identified in Duvernay-sourced oils. With increasing migration distance, the relative abundance of O₂, N₁O₁ and N₁O₂ showed a significant decrease, while the O₁ class increased from < 10% to nearly 30% of the total. With increasing migration along the Rimbey-Meadowbrook reef trend, pyrrolic nitrogen compounds (N₁ class) shows an enrichment of alkylcarbazoles (DBE = 9) relative to alkylbenzocarbazoles (DBE = 12), and of higher homologous relative to the lower homologous. O₁ compounds show a relative enrichment of those with low DBE values. Additionally, the N₁O₁ and N₁S₁ compounds show a relative enrichment of those with high DBE values, and of higher homologues compared to the lower homologues, indicating great potential for developing new migration indices.