血卟啉衍生物的色谱分离

本文拟定的纸色谱法是以苯-乙酸乙酯-甲醇-乙酸(9:2:1:1)作展开剂,将血卟啉衍生物(HPD)分离为五部份,分别测定各部份浸取液的荧光发射光谱,作为一种对血卟啉衍生物组份作对比鉴定的参考方法。采用Ward的高效液相色谱程序对比研究结果表明,国产与美国产HPD的组份近似,均以血卟啉为主要组份,而前者血卟啉的含量较高;二者还均含有羟乙基乙烯基衍生物和羟基乙酸酯,初步研究了血卟啉衍生物在甲醇-水溶剂系统中的高效液相色谱行为,进一步将血卟啉衍生物分离为九部份,有利于单一组份研究。     

来源于血液的几种卟啉的核磁共振测定

本工作测得血卟啉、血卟啉二甲酯和原卟啉二甲酯的~1H和~(13)C-NMP谱,找出血卟啉的合适溶剂,使直接测定成为可能,对于推进光敏化诊治恶性肿瘤新技术在我国的开展有一定意义。具有四吡咯共轭大环结构的卟啉化合物在络合物化学、生物化学、光谱学等方面都表现出特异性,并具有多种用途,是被广泛研究着的一类大分子化合物。近年来发现血卟啉及其醋酸衍生物可作为光敏化诊断和治疗恶性肿瘤的一种有效物质,从而引起了人们对于血卟啉的浓厚兴趣。     

芳香胺的芳香醛衍生物的负离子化学电离质谱行为

尝试了六种芳香醛作为芳香胺负离子化学电离质谱分析的衍生化剂,并讨论了衍生物的负离子化学电离质谱行为。     

自身化学电离质谱法测定(赤/苏)-2-甲基苯丙二醇胺类衍生物的准确质量

采用自身化学电离离子化／付里叶变换质谱法（ＳＣＩ／ＦＴＭＳ）测定了（赤／苏）－２－甲基苯丙二醇胺类衍生物共２４个样品的质子化分子离子的准确质量,与理论值相比,相对误差均小于５×１０－６级,结果表明ＳＣＩ／ＦＴＭＳ是测定电离过程中不稳定化合物元素组成的简便、快速、准确的方法。     

自身化学电离质谱法测定(赤/苏)-2-甲基苯丙二醇胺类衍生物的准确质量

采用自身化学电离离子化/付里叶变换质谱法(SCI/FTMS)测定了(赤/苏)-2-甲基苯丙二醇胺类衍生物共24个样品的质子化分子离子的准确质量,与理论值相比,相对误差均小于5×10^-6级,结果表明SCI/FTMS是测定电离过程中不稳定化合物元素组成的简便、快速、准确的方法。     

2-碘-3-苯亚磺酰基-2-丙烯基-1-醇类化合物自身化学电离质谱研究

四级质谱仪上采用自身化学电离的方法测定2-碘-3-苯亚磺酰基-2-丙烯基-1-醇及其6个衍生物.通过分子离子峰(MH+)和特征碎片离子峰提供的分子结构信息,确证上述化合物的结构.方法简便,迅速,准确.     

软电离质谱在烟草化学中的应用进展

综述了软电离质谱技术原理和特点,及其在烟草及烟气中有害成分分析测定、实时在线卷烟烟气测定、致香物质的分离与鉴定、农残测定等方面展望了其在烟草化学中的应用,主要包括化学电离质谱、电喷雾电离质谱、大气压化学电离质谱、激光解吸电离质谱、单光子电离质谱等技术(引用文献54篇)。     

几种血卟啉3,8-烷氧(硫)基衍生物产生单重态氧能力的研究

在“血卟啉衍生物”(HPD)^[1]肿瘤光动力疗法取得令人瞩目成就的同时,化学家们证明了临床使用的HPD制剂并非原意义上的血卟啉衍生物,而是一种复杂的卟啉混合物^[2],其中血卟啉(HP),羟乙基-乙烯基-次卟啉(HVD),原卟啉(PP)约占总量的80%,Dougherty等分离得到其余20%未知结构羧基卟啉,认为此为HPD的有效成分,经进一步分析测定其主要成分是二血卟啉醚(DHE)^[3]。     

血卟啉衍生物YHPD主要成分的核磁共振研究

本文报道国产血卟啉衍生物YHPD作为一种良好的光敏药物,已成功地用于肿瘤的光化学治疗。本文报道了对它的主要组分进行NMR结构分析的结果。将YHPD经高压液相色谱分离后,得到4个主要成分:A,B,C和D。其NMR结果表明,组分A为单乙酰基血卟啉,组分B和C为一对乙烯基次卟啉异构体,组分D通过二维同核相关、二维NOE,~(13)C谱、偏共振和快原子轰击质谱分析,证明为由C—C键相接的原卟啉二聚体。这一发现有助于从组分结构上对国产和国外血卟啉衍生物生物学活性的比较,也有助于认识临床使用的经碱处理的血卟啉衍生物(一种复杂混合物)的成分组成及有效成分。     

有机磷化合物的质谱研究(Ⅺ)——1,3,2—二氮磷杂环戊烷衍生物的化学电离质谱

本文报道了11种1,3,2-二氮磷杂环戊烷衍生物的化学电离质谱(CIMS),对热不稳定的化合物采用了解吸化学电离技术(DCI),着重探讨了三价磷和五价磷化合物质谱的差异及均三氮苯取代基的引入对质谱行为的影响;对该类化合物的CIMS和EIMS进行了比较。     

Identification of amino acid thiohydantoin derivatives by chemical ionization mass spectrometry

The chemical ionization mass spectra of 16 amino acid thiohydantoins were examined using isobutane or ammonia as reagent gases. Except for a few cases, including some aromatic amino acids, the chemical ionization spectra were much simpler than the corresponding electron impact spectra. Therefore, the major component in the amino acid thiohydantoin mixture was easily detected by chemical ionization mass spectrometry. The combination of the chemical ionization method and thiohydantoin formation was applied successfully to the sequence analysis of model peptides.     

Sites of protonation in phenothiazines: Methane and ammonia chemical ionization mass spectra

Positive ion methane and ammonia chemical ionization mass spectra for ten phenothiazine derivatives are reported. The fragmentations observed in the chemical ionization mass spectra are rationalized in terms of the location of the added proton. High-resolution measurements are used to confirm empirical formulae of the ions in the mass spectra. Changes in the mass spectra with a change in the chemical ionization reagent gas from methane to ammonia are described. A comparison with positive ion secondary ion mass spectra of the same compounds show that the amount of fragmentation is higher in the secondary ion mass spectra, but the same types of ions are observed in spectra produced by both ionization methods.     

The mass spectrometry of polychlorinated dibenzo-p-dioxins

The negative ion chemical ionization mass spectra of polychlorinated dibenzo-p-dioxins using oxygen, methane and methane/oxygen are reported together with their methane positive ion chemical ionization mass spectra and conventional electron impact spectra. The methane/oxygen negative ion chemical ionization mass spectra proved to be the most useful of the negative ion spectra for structure determination.     

Atmospheric pressure ionization mass spectrometry of the polychlorinated dibenzo-p-dioxins

The branching ratios for the reaction pathways of 39 polychlorinate dibenzo-p-dioxins (PCDDs) under oxygen negative chemical ionization/atmospheric pressure ionization mass spectrometric conditions were measured. These results demonstrated that the PCDDs could be separated into 14 groups by this technique. These results were compared with those reported previously for 14 PCDDs using oxygen negative chemical ionization mass spectrometry.     

常压热解离化学电离源的研制及表征

自行研制了常压热解离化学电离源(TDCI),与商品化LTQ XL质谱仪成功联用,进一步考察了TDCI的性能,并对其应用领域进行了初步探索.TDCI-MS/MS谱图表明,离子液体可在现有实验条件下产生特征离子碎片;升高TDCI源偏置电压和温度,可以提高离子液体的信号强度.基于优化后的实验参数,常压热解离化学电离质谱方法(...     

质谱技术在糖类结构分析中的应用

综述了电子轰击、化学电离、快原子轰击、电喷雾离子化、基质辅助激光解吸、串联质谱等质谱技术在糖类结构分析中的应用。引用文献共53篇。     

Mass spectral fragmentation pathways in RDX and HMX. A mass analyzed ion kinetic energy spectrometric/collisional induced dissociation study

A collisional induced dissociation study of 1,3,5-trinitro-1,3,5 triazacyclohexane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) was carried out using mass analyzed kinetic energy spectrometry. High resolution mass spectra and mass analyzed ion kinetic energy/collisional induced dissociation spectra of RDX and HMX were recorded in the electron impact, chemical ionization and negative ion chemical ionization modes. Fragmentation pathways of the compounds investigated were determined in all three modes of ionization. It was found that a major part of the fragment ions in RDX and HMX originate from formation of the aduct ions [M+NO]⁺ and [M+NO₂]⁺ in electron impact and chemical ionization, and from [M+NO]^? and [M+NO₂]^? in negative chemical ionization, followed by dissociation.     

Stereochemical effects in the mass spectra of 2-hydroxy-, 5-hydroxy- and 2,5-dihydroxyprotoadamantanes

Electron ionization and methane and isobutane chemical ionization mass spectra have been obtained for the four configurationally isomeric 2,5-protoadamantanediols and the corresponding model monoalcohols. Although the electron impact (both 70 and 15 eV) and methane chemical ionization mass spectra of the 2,5-protoadamantanediols are distinct, the variations are not large and in general they are difficult to rationalize in terms of specific structural features. In contrast, the isobutane chemical ionization mass spectra of these diols show significant differences which can easily be correlated with sterochemical orientations of the substituents.     

Chemical ionization and electron impact mass spectrometry of some organophosphonate compounds

The application of gas chromatography chemical ionization mass spectrometry to the determination of a variety of alkyl alkylphosphonates, phosphonofluoridates, phosphonothiolates and an amidophosphorocyanidate is described. Comparison is made between the electron ionization and chemical ionization mass spectrometry of these compounds. Chemical ionization mass spectrometry is shown to enhance the capability for identification, especially when a limited sample is available. Results indicate that methane is highly useful for obtaining protonated molecular ions and association ions (formed by the transfer of a reactant ion to a sample molecule) as well as meaningful fragment ions. Ionizing ethylene and isobutane gives protonated molecular ions as base peaks for all of the compounds studied, including those where a lower abundance of the [MH]₊ ion is found via methane chemical ionization mass spectrometry. Ethylene is superior to isobutane on the basis of its effectiveness for serving as both a carrier and a reagent gas and gives better sensitivity. Although not an intrinsic part of this present study, analytical sensitivities in the subnanogram range were found.     

Electron capture negative ion and positive ion chemical ionization mass spectrometry of polychlorinated phenoxyanisoles

Several polychlorinated phenoxyphenols with three to nine chlorine atoms were examined as their methyl ethers by electron capture negative ion and positive ion chemical ionization and electron impact mass spectrometry. In chemical ionization studies methane, hydrogen, nitrogen, helium and argon were used as reagent gases. Selected compounds were also examined with deuteriomethane, ammonia and deuterioammonia as reagent gases. Utilization of chemical ionization spectra in conjuction with electron impact spectra provides substantial structural information about these compounds. Chemical ionization spectra provide information about chlorine atom substitution. The position of phenoxy substitution can be established from electron capture negative ion and positive ion spectra.