利用光谱、质谱和色谱研究中国辽河油田西斜坡原油卟啉生物标志物的特征

在石油和含油岩石中存在着多种类型的生物标志化合物,石油卟啉就是其中的一种.近 年来,生物标志化合物的研究已构成石油勘探工作中的一个极为活跃的研究领域.通过各种 生物标志物类型、组成、分布以及相互关系等的探讨,可为石油的成因、原始有机质的来源、油源对比、运移路线以及沉积古地理环境等方面研究提供具有理论意义的重要信息.在多种类型生物标志物基础上作出的结论要比基于单独一类标志物得到的认识更有说服力.对于辽河原油来说,烷烃类型的生物标志物研究较多,而卟啉类生物标志物由于化学操作过程繁、难,因此研究的较少,至今尚未见到有关报道.本文在完成对石油卟啉标志物的提取、分离研究的基础上,利用紫外-可见光谱、质谱及高效液相色谱对辽河油田西斜坡原油中卟啉生物标志物的特征进行了研究.     

石油卟啉在反相─CN／C_（18）组合柱高效液相色谱中的分离与分析

石油卟啉是原油和含油沉积物中的一种地质化学标记物，由于卟啉族是一种极其复杂的混合物，且含量甚微，因此，给分离和鉴定工作带来相当大的困难。采用─ＣＮ／Ｃ＿（１８）组合柱、甲醇－水梯度淋洗的反相高效液相色谱和高灵敏度鉴定的质谱对卟啉族进行研究，结果表明，在所建立的色谱系统中，卟啉的类型和同系物都得到较好的分离，色谱图有较好的重现性，在分离的基础上对有地质信息的卟啉标记物进行了质谱分析。     

N-错位卟啉的研究进展

N-错位卟啉既是卟啉的同分异构体又是异卟啉的典型代表,也是一类非常重要的卟啉类化合物.因其独特的化学结构及反应活性,近年来引起化学工作者的广泛关注.介绍了N-错位卟啉研究的意义、N-错位卟啉的结构和性质.重点综述了N-错位卟啉的合成及其在催化化学、生物化学和材料化学领域的应用进展.同时对N-错位扩展卟啉和其它错位异卟啉的发展现状作了简要概述,并对N-错位卟啉化学的发展进行了展望.     

石油卟啉在反相─CN／C_（18）组合柱高效液相色谱中的分离与分析

 石油卟啉是原油和含油沉积物中的一种地质化学标记物，由于卟啉族是一种极其复杂的混合物，且含量甚微，因此，给分离和鉴定工作带来相当大的困难。采用─ＣＮ／Ｃ＿（１８）组合柱、甲醇－水梯度淋洗的反相高效液相色谱和高灵敏度鉴定的质谱对卟啉族进行研究，结果表明，在所建立的色谱系统中，卟啉的类型和同系物都得到较好的分离，色谱图有较好的重现性，在分离的基础上对有地质信息的卟啉标记物进行了质谱分析。     

关于meso—四苯基卟啉在冰醋酸中的存在形式

前言卟啉在生物化学、分析化学、药物化学等领域有着广泛研究和重要应用［１～３］。近年来虽然对卟啉类化合物的研究报道很多［４～６］，但对卟啉在酸性介质中的研究很少。较早期的研究工作认为卟啉类化合物在酸性介质中仅以其二酸形式存在［７］。本文实验结果显示ｍｅ...     

双重作用机制卟啉靶向给药体系的研究进展

近年来卟啉化学研究的一个新热点是,依据卟啉类化合物在肿瘤细胞优先集聚的特点,将其作为携带剂介导现有抗癌药物,实现靶向给药,同时利用卟啉的光敏性,实现分子内加和增效,合成具有化学杀伤和光动力杀伤双重活性的卟啉-抗癌药物体系。本文主要就双重作用机制卟啉靶向给药体系的研究进展进行综述。     

塔里木塔河原油中钒卟啉的分离和鉴定

石油卟啉的存在是石油有机成因说的重要证据之一，并且根据石油卟啉的类型和分布可以推测石油的沉积环境及成熟程度。另一方面，石油中的卟啉主要是镍卟啉和钒卟啉，镍和钒是石油加工过程中裂化催化剂失活的主要原因，对石油卟啉的认识将有助于脱金属工艺的开发，从而降低镍和钒对加工过程的不利影响。     

卟啉衍生物的合成与性能研究进展（英文）

卟啉化学是有机化学研究中不可或缺的一个方向。由于卟啉在结构上具有一个大的共轭体系,从而具有典型的芳香性。其具有优异的光电性能、独特的光动力治疗作用、高效的催化活性,并且广泛存在于血红素、叶绿素、维生素B_(12)、过氧化氢酶等有机生物分子中,所有这一切都吸引着科学家们进行深入研究。本文从取代卟啉、缩合卟啉以及扩环卟啉三个方面分别讨论了卟啉的研究进展,通过列举一系列经典的反应以及卟啉衍生物,总结了卟啉衍生物的合成方法及其发展方向。另外,文中还对于卟啉的一些特殊物理、化学和光电性质,做了重点介绍。本文旨在为卟啉的研究者们提供参考。     

卟啉衍生物的合成与性能研究进展

卟啉化学是有机化学研究中不可或缺的一个方向。由于卟啉在结构上具有一个大的共轭体系,从而具有典型的芳香性。其具有优异的光电性能、独特的光动力治疗作用、高效的催化活性,并且广泛存在于血红素、叶绿素、维生素B_(12)、过氧化氢酶等有机生物分子中,所有这一切都吸引着科学家们进行深入研究。本文从取代卟啉、缩合卟啉以及扩环卟啉三个方面分别讨论了卟啉的研究进展,通过列举一系列经典的反应以及卟啉衍生物,总结了卟啉衍生物的合成方法及其发展方向。另外,文中还对于卟啉的一些特殊物理、化学和光电性质,做了重点介绍。本文旨在为卟啉的研究者们提供参考。     

卟啉类化合物与人血清白蛋白相互作用的研究进展

卟啉类化合物与人血清白蛋白的相互作用研究可以为制备新型金属卟啉与蛋白质的结合体及卟啉类化合物的功能开发研究提供重要的理论基础,是当前仿生化学、生物有机、医药化学等领域中的热门研究课题。本文综述了近几年来具有不同结构特点的卟啉类化合物与人血清白蛋白间的相互作用,并展望了该研究方向的发展趋势和应用前景。     

Synthesis and origins of the methylpropanoporphyrins from Serpiano Oil Shale

A new synthesis of the methylpropanoporphyrins from Serpiano Oil Shale using the tripyrrene-a,c-biladiene approach is reported; a plausible pathway for the geochemical genesis of these unusual petroporphyrins is presented.     

Biocatalytic removal of nickel and vanadium from petroporphyrins and asphaltenes

Asphaltenes from a crude oil rich in heavy metals (Castilla crude oil) were fractionated and partially characterized. Biocatalytic modifications of these fractionated asphaltenes by three different hemoproteins: chloro-peroxidase (CPO), cytochrome C peroxidase (Cit-C), and lignin peroxi-dase (LPO) were evaluated in both aqueous buffer and organic solvents. The reactions were carried out in aqueous buffers, ternary systems of toluene: isopropanol: water, and aqueous-miscible organic solvent solutions with petroporphyrins as substrate. The petroporphyrins were more soluble in the ternary systems and aqueous miscible-organic solvent systems than in the aqueous buffer systems. However, only the CPO-mediated reactions were effective in eliminating the Soret peak in both aqueous and organic solvent systems. The effects of CPO-mediated reactions on the release of the metals complexed with the porphyrins and asphaltenes were also determined. Chloroperoxidase was able to alter components in the heavy fractions of petroleum and remove 53 and 27% of total heavy metals (Ni and V, respectively) from petroporphyrin-rich fractions and asphaltenes     

Nuclear magnetic resonance spectroscopy of petroporphyrins : Self-aggregation effects, nuclear overhauser enhancements, and spin-lattice relaxation used in structural elucidation

The substitution pattern of the two major petroporphyrins of Marl Slate, the ETIO III and the C₃₂ DPEP, is determined by NMR spectroscopy alone, using self-aggregation effects, nuclear Overhauser enhancements and spin-lattice relaxation times. Protoporphyrin IX dimethyl ester was used as a model compound.     

Fingerprinting of Crude Oils for Pollution Control

Abstract

Total, demetallated porphyrins from selected “export” and “weathered” crude oils were analyzed by high performance liquid chromatography (HPLC). The aim was to study the effect, if any, of oil weathering processes on the type and distribution of these compounds and hence, assess the applicability of their HPLC fingerprints in the area of pollution control. The results revealed that petroporphyrins are not readily susceptible to natural weathering processes and that their HPLC fingerprints may be applied to crude oil classification and could supplement other techniques of identifying oil pollutants.     

Fingerprinting Petroporphyrin Structures with Vibrational Spectroscopy. 4. Resonance Raman Spectra of Nickel(II) Cycloalkanoporphyrins: Structural Effects Due To Exocyclic Ring Size

Nickel(II) complexes of cycloalkanoporphyrins (CAPs) bearing a saturated carbon ring of varying size between pyrrole C(beta) and methine bridge carbon atoms are widespread in crude oil and related organic rich sediments. We have synthesized a series of NiCAPs containing meso,beta-ethano (NiCAP5), meso,beta-propano (NiCAP6), and meso,beta-butano (NiCAP7) groups and applied UV-visible absorption and resonance Raman (RR) spectroscopies to investigate the effects of the exocyclic ring size on the porphyrin structure and to establish vibrational CAP marker frequencies for petroporphyrins in fossil fuels. The RR spectra of NiCAPs, excited at or near porphyrin Soret ( approximately 400 nm) and Q (510-580 nm) bands are informative and display a rich array of skeletal and alkyl substituent modes. High-frequency (1300-1700 cm(-)(1)) structure-sensitive RR bands shift down considerably (up to 24 cm(-)(1)) with increasing size of the exocyclic ring, implicating increased nonplanar distortions of the tetrapyrrole macrocycle. Unlike in other petroporphyrins studied thus far, etio- and tetrahydrobenzoporphyrins, out-of-plane distortions of the porphyrin imposed by the meso,beta-cycloalkano ring are also sufficient to destroy the center of symmetry of the porphyrin pi-system and produce significant enhancement of the IR-active E(u) skeletal modes in the Q-band-excited RR spectra. The UV-visible absorption spectra also vary with the size of the exocyclic ring; both the Soret and Q bands progressively red shift as the cycloalkano chain becomes longer, implying a destabilization of the two highest occupied pi orbitals in NiCAP6 and NiCAP7. In addition, the size of the exocyclic ring in NiCAPs can be readily determined from the frequency of the approximately 900 cm(-)(1) marker band and the characteristic patterns of skeletal and substituent bands in the 700-1200 and nu(4) ( approximately 1380 cm(-)(1)) regions.     

Porphyrins with exocyclic rings. Part 22: Synthesis of deoxophylloerythroetioporphyrin (DPEP), three ring homologues, and five related nonpolar bacteriopetroporphyrins using a western ring closure and an improved b-bilene methodology

Dipyrrolic intermediates incorporating five-membered carbocyclic rings are easily prepared from cyclopenta[b]pyrroles, and this unit represents the southern half of the DPEP-type geoporphyrins found in organic-rich sediments such as oil shales and petroleum. Related dipyrroles with six-, seven- or eight-membered carbocyclic rings were shown to give b-bilenes when reacted with dipyrrylmethane carbaldehydes under mildly acidic conditions. Following deprotection of the terminal ester groups, cyclization with TFA-CH(OMe)₃ gave a series of ring homologues of deoxophylloerythroetioporphyrin (DPEP). The b-bilenes generated from the five-membered ring dipyrroles proved to be rather unstable and had to be used directly without purification. Cyclization gave DPEP contaminated with an etioporphyrin by-product, but these could be separated as the nickel(II) derivatives by flash chromatography. This approach gave superior yields of DPEP compared to previously reported methods. In addition, the methodology could be extended to the synthesis of related petroporphyrins, and a series of five molecular fossils derived from bacteriochlorophylls d were synthesized by this approach.     

Schistes bitumineux de Timahdit (Maroc) : composition et propriétés physicochimiques

The oil shales of Timahdit (Morocco) constitute an important resource in energy. Indeed, the total organic matter is mainly constituted by kerogen. The elementary analysis gives atomic ratios H/C and O/C that are characteristic of a type II kerogen, poorly evolved, constituent of a good mother-rock. The different constituents separated from extractible organic matter by column or thin layer chromatography have been characterized. The analysis of saturated and aromatic hydrocarbons by gas chromatography has proved that the organic matter of the shales of Timahdit is immature, resulting essentially from a phytoplanctonic biomass (marine origin) with a small continental influence. These results have been confirmed by the spectroscopic study of vanadyl and nickel petroporphyrins (DPEP and Etio) isolated from the organic matter of the Timahdit shales.     

Petroporphyrins—III: Characterisation of a c32 aetioporphyrin from gilsonite as the bis[porphyrinato-mercury(II) acetato]mercury(II) complex. Origin and significance

A C₃₂ aetio porphyrin isolated from Gilsonite bitumen (ca. 60 × 10⁶yr) was assigned unambiguously as aetioporphyrin—III by ¹H NMR analysis of its bis[porphyrinato-mercury(II) acetato]mercury(II) complex and by comparison with an authentic sample. The occurrence of this compound provides the first direct evidence that the petroporphyrins of Gilsonite are the product of reductive degradation of naturally-occurring chlorophylls, and conversion of the chlorin to the porphyrin system.     

Chemistry of Vanadyl Porphyrins

The chemistry of vanadyl porphyrins has been explored using vanadyl octaethylporphyrin as the type substance, and with special reference to the occurrence of such substances in petroporphyrins. Spectroscopic properties (electronic spectra, IR spectra, mass spectra) are described, and electronic spectra are employed to detect the occupation of the vacant axial coordination site. Direct substitution of vanadyl octaethylporphyrin furnishes meso-substituted products: various nitro, chloro and benzoyloxy derivatives are characterised. Trans alkylation is observed when vanadyl octaethylporphyrin is heated in vacuo on various supports, including clay minerals: the reaction provides a model for the generation of the homologous series of vanadyl polyalkylporphyrins found in crude oils and bitumens.