普鲁洛尼克型非离子表面活性剂的结构分檄及其同系物分子量分布…

以ＦＡＢＭＳ、ＥＩＭＳ、ＦＴＩＲ等手段鉴定了从工业产品中分离得到的一种未知表面活性剂的化学结构为聚氧丙烯／聚氧乙烯共聚物，其商品名称为普鲁洛尼克型非离子表面活性剂。用ＦＡＢＭＳ谱观察到该表面活性剂系物的各种准分子离子峰呈近似的高斯分布，根据各种准分子离子峰的相对强度得出该表面活剂同系物的分子量分布及平均分子量。     

铝与溴代二甲氨基苯基荧光酮的多元配合物的光度研究

本文研究了在表面活性剂存在性，铝与溴代二甲氨基苯基荧光酮的显色反应。在弱酸性介质中，Ａｌ＾３＋ＢＤＭＡＦ－ＣＴＭＡＢ三元配合物在水浴加热至７０℃－８０℃时形成，其最大吸收波长为５７７ｎｍ，Ａｌ＾３＋：ＢＤＭＡＦ＝１：２，表观摩尔吸光系数为１．３４×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，表观稳定常数为７．４×１０＾５。在ＰＨ９．５－１０．５的氨性缓冲介质中，Ａｌ＾３＋－Ｆ＾－－ＢＤＭＡＦ－非离子表面     

一些含锗有机酸的快原子轰击质谱

本文报道了一系列含锗有机酸在甘油中的快原子轰击质谱（ＦＡＢＭＳ）及共在间硝基苄醇（ＮＢＡ）中的正、负离子ＦＡＢＭＳ。这些含锗有机酸在不同的底物中的ＦＡＢＭＳ显示了不同的特征。负离子谱提供了分子量信息，正、负离子谱可为这类化合物的结构鉴定提供互相补充的信息。讨论了底物和取代基对ＦＡＢＭＳ的影响，正、负离子的产生机制及离子的亚稳分解途径。     

PNPAR－CTMAB光度法测定水中痕量阴离子表面活性剂

本文研究了对硝基偶氮间苯二酚（ＰＮＰＡＲ）与溴化十六烷基三甲铵（ＣＴＭＡＢ）形成的离子缔合物ＰＮＰＡＲ－ＣＴＭＡＢ作显色剂与阴离子表面活性剂（ＡＳ）的显色反应。发现在ｐＨ１３．０的ＮａＯＨ介质中，ＡＳ能定量置换出ＰＮＰＡＲ－ＣＴＭＡＢ中的ＰＮＰＡＲ，而使其最大吸收波长６３０ｎｍ处吸光度下降。阴离子表面活性剂十二烷基苯磺酸钠（ＳＤＢＳ）和十二烷基磺酸钠（ＳＤＳ）的ε值分别为３．５×１０￣４，５．８×１０￣４Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），浓度分别在０～８７μｇ／２５ｍＬ，０～６８μｇ／２５ｍＬ范围内符合比尔定律。此法应用于环境水中痕量阴离子表面活性剂测定，结果满意。     

PNPAR—CTMAB光度法测定水中痕量阴离子表面活性剂

本文研究了对硝基偶氮间苯二酚（ＰＮＰＡＲ）与溴化十六烷基三甲铵（ＣＴＭＡＢ）形成的离子缔合物ＰＮＰＡＲ－ＣＴＭＡＢ作显色剂与阴离子表面活性剂（ＡＳ）的显色反应，发现在ｐＨ１３．０的ＮａＯＨ介质中，ＡＳ能定量置换出ＰＮＰＡＲ－ＣＴＭＡＢ中的ＰＮＰＡＲ，而使其最大吸收波长６３０ｎｍ处吸光度下降，阴离子表面活性十二烷基苯磺酸钠（ＳＤＢＳ）和十二烷基磺酸钠（ＳＤＳ）的ε值分别为３．５×１０＾４，５．８×１     

次卟啉及其金属配合物的FAB和APCI质谱

本文报道一些次卟啉及其金属配合物的ＦＡＢ和ＡＰＣＩ质谱，比较两种电离方式所测得的谱图表明，所有化合物的ＡＰＣＩ和ＦＡＢ谱都显示有特征的质子化分子离子峰ＭＨ＋。在ＡＰＣＩＭＳ上的主要碎片离子是脱掉金属离子并加两个氢原子生成ｍ／ｚ５１１离子〔ＭＨ－Ｍｅｔ＋２Ｈ〕＋。而ＦＡＢ谱却形成一系列由边链断裂的碎片离子峰，由羰基的β断裂生成的离子较特征（底物为间－硝基苄醇）。当用二乙醇胺做底物时，观察到分子离子与底物的加成离子。     

酞菁锰—表面活性剂薄膜电极的电化学表征及其对三氯乙酸的电化学催 …

将酞菁锰（ＭｎＰｃ）掺入阳离子表面活性剂双十二烷基二甲基溴化铵（ＤＤＡＢ）的氯仿溶液，并涂布于热解石墨电极表面，待氯仿挥发后即制得ＭｎＰｃ－ＤＤＡＢ薄膜电极，循环伏安实验表明，在ＫＢｒ溶液中，该薄膜电极有两对还原氧化峰，第一对峰的Ｅｐｃｔ＝－０．２７Ｖ，Ｅｐａ１＝０．０１Ｖ；第二对峰的Ｅｐｃ２＝－０．７６Ｖ，Ｅｐａ２＝－０．６２Ｖ（ｖｓ．ＳＣＥ）。本文着重探讨了第二对峰的电化学行为，估计了该体系电     

酞菁锰-表面活性剂薄膜电极的电化学表征及其对三氯乙酸的电化学催化作用的研究

将酞菁锰（ＭｎＰｃ）掺入阳离子表面活性剂双十二烷基二甲基溴化铵（ＤＤＡＢ）的氯仿溶液，并涂布于热解石墨电极表面，待氯仿挥发后即制得ＭｎＰｃ－ＤＤＡＢ薄膜电极。循环伏安实验表明，在ＫＢｒ溶液中，该薄膜电极有两对还原氧化峰，第一对峰的Ｅｐｃ１＝－０．２７Ｖ，Ｅｐａ１＝０．０１Ｖ；第二对峰的Ｅｐｃ２＝－０．７６Ｖ，Ｅｐａ２＝－０．６２Ｖ（ｖｓ．ＳＣＥ）。本文着重探讨了第二对峰的电化学行为，估计了该体系的电荷传递扩散系数Ｄｃｔ和表观非均相电极反应速率常数Ｋ０′等电化学参数，并可将该薄膜电极用于催化三氯乙酸的电化学还原。     

质谱法鉴定两种化学添加剂中阴离子表面活性剂

本文提出用ＦＡＢ－ＭＳ和ＤＣＩ－ＭＳ法对两种工业化学添加剂中阴离子表面活性剂成份的鉴定方案，方法简便，并对类似未知物的鉴定有参考价值。所得结果为其它方法和应用试验进一步证实。     

流动注射光度法测定铁的研究：Ⅱ.Fe（Ⅲ）—CAS—SAS胶束体系

用自行组装的ＦＩＡ装置，对Ｆｅ（Ⅲ）－ＣＡＳ－表面活性剂体系进行了系统研究。着重考察了表面活性剂的影响，选择了Ｆｅ（Ⅲ）－ＣＡＳ－ＴｒｉｔｏｎＸ－１００－ＨＤＭＡＡ混合胶束体系，拟定了Ｆｅ（Ⅲ）的ＦＩＡ光度法，用于总铁量的测定，方法的线性范围，检测限及采样速度分别为０～０．６ｍｇ．Ｌ＾－１，０．００２ｍｇ．Ｌ＾－１和９０样次ｈ＾－１，该法用于天然水或某些工业用水总铁量的测定，结果满意。     

甘草次酸及其衍生物的质谱研究

本文通过应用ＥＩ质谱和高分辨质谱对甘草次酸及其衍生物进行研究，阐明了分子离子的各种裂解、重排机理，讨论了主要离子的形成过程以及不同取代基对分子离子峰强度的影响。并用软电离手段──快原子轰击正、负离子（ＰＦＡＢ和ＮＦＡＢ）质谱，使ＥＩ谱上不出现分子离子峰的两个化合物而获得满意结果。     

有机磷化合物的快原子轰击质谱研究 Ⅶ.N-对甲苯磺酰基-N''''-异丙基-N-取代-S-丙基磷酰二胺酯

本文讨论一类新合成的磷酰二胺酯的质谱特征。其电子轰击质谱(EIMS)分子离子峰很弱(<1%),我们采用快原子轰击质谱(FABMS),讨论其PFABMS与NFABMS的区别、取代基的影响,PFABMS与NFABMS的主要离子产生机理。     

Ni2＋的引入对离子液体烷基化催化性能的影响

Thealkylationofisobutanewithbuteneisanim portantprocessforthe productionofhigh qualitypetroleum .In placeofconcentratedsulfuricacid ,Et3NHCl/AlCl3ionicliquidhasbeenusedinthereac tionwithfairlygoodeffect[1] ,butthereisstillabigdifferencecomparedwiththeresultsofconcentratedsulfuricacid .TheC8contentinthealkylatesobtainedwithconcentratedsulfuricacidwas 72 1% [2 ] ,butitwasonly 5 6 %withtheionicliquid .ThekeyreactioninthealkylationishydrogentransferfromC+8toC08[3] ,andthisisthemainreasonforth…     

Structure of pluronic F-127 and its tetraphenylporphyrin complexes: X-ray diffraction study

The structure of pluronic F-127 and its complexes with tetraphenylporphyrin has been studied by SAXS and WAXS techniques. It has been shown that the samples prepared via evaporation of chloroform and aqueous solutions of pluronic and its mixtures with tetraphenylporphyrin have a semicrystalline layered structure with the crystalline phase composed of poly(ethylene oxide). The identity period of layers in the samples prepared from the aqueous solution of pluronic has been found to be larger than that in the samples prepared from chloroform solutions of the polymer. This result may apparently be explained by a more pronounced hydration of the samples prepared by the former method. The presence of tetraphenylporphyrin in the samples has an insignificant effect on the parameters of the crystalline and layered structures of pluronic. When the tetraphenylporphyrin content is not larger than its solubilization limit with pluronic, tetraphenylporphyrin concentrates in the amorphous layers of pluronic in the noncrystalline finely dispersed state.     

Characterization of the mycotoxin fumonisin B1: comparison of thermospray, fast-atom bombardment and electrospray mass spectrometry.

The utility of thermospray mass spectrometry (TSMS), fast-atom bombardment mass spectrometry (FABMS), and electrospray mass spectrometry (ESMS) for the analysis of Fumonisin B1 is investigated. In addition, the analysis of two different standards of Fumonisin B1 as well as an inoculated corn culture extract that contained Fumonisin B1 is reported. The results of these efforts show that ESMS, as well as FABMS and a combination of FAB and tandem mass spectrometry (FABMS/MS), provide useful data for the characterization of Fumonisin B1. The detection limit was 50 pg for Fumonisin B1 when analyzed by full scan FABMS, and 5 pg when analyzed by single-reaction monitoring FABMS/MS.     

Method for the derivatization of organic compounds at the sub-nanomole level with reagent vapor

Summary A method for the micro-derivatization of organic compounds has been developed especially adapted for gas chromatography mass spectrometry (GCMS) or fast atom bombardment mass spectrometry (FABMS). Single or multistep reactions can be carried out at the sub-nanomole level using the necessary reagents in the vapor phase. Examples are the per-trifluoroacetylation of a mixture of glucose, mannose and galactose, for GCMS and the conversion of a pentapeptide (Leu-enkephalin) to a derivative with a quaternary ammonium group attached to the C-terminal amino acid for FABMS. The collision induced mass spectrum of the cation generated by FABMS is significantly different from that of the protonated molecular ion of the underivatized peptide. The major advantages of the procedure are the elimination of losses by surface adsorption, of contamination of the sample and ability to transfer all of the product into the mass spectrometer.

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Verfahren zur Derivatisierung organischer Verbindungen im Sub-Nanomol-Bereich mit Reagensdampf

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Dedicated to Prof. Dr. W. Fresenius on the occasion of his 75th birthday     

一元弱酸(碱)溶液稀释过程中离子浓度递变幅度的相对非均等性

对一元弱酸（碱）溶液稀释过程中各种离子浓度递变幅度的相对非均等进行研究,推出了离子浓度递变幅度的大小次序排列及其相关概念,这一研究,有助于从整体上把握离子浓度递变规律,为正确判断离子浓度的变化结果提供了理论依据。     

Structure determination of phosphoinositol oligosaccharides from parasitic protozoa using fast atom bombardment mass spectrometry

Glycosylphosphatidylinositols (GPIs) are widely distributed membrane constituents of protozoa and higher eukaryotes, where they anchor proteins and other macromolecules to the cell surface. Free glycosylinositol phospholipids (i.e. not attached to protein or polysaccharide) have also been detected in some parasitic protozoa, and are thought play a role in the interaction of parasite and host. This paper describes the fast atom bombardment mass spectrometry (FABMS) of glycosylinositol phospholipids from the Trypanosomatid parasites Leptomonas samueli, Endotrypanum schaudinni and Leishmania adleri. FABMS in the positive-and negative-ion modes in conjunction with collisional activation permits the rapid determination of the monosaccharide composition, the sequence of residues, the branching pattern and the nature and location of non-carbohydrate substituents. When supplemented by high-field NMR, FABMS provides a highly efficient route to the complete structure elucidation of these materials.     

Interactional and aggregation behavior of twin tail cationic surfactants with pluronic L64 in aqueous solution

The aqueous mixed systems of twin tail cationic surfactants didodecyldimethylammonium bromide, ditetradecyldimethylammonium bromide, and dihexadecyldimethylammonium bromide with pluronic L64 have been studied to determine the bulk aggregation and interactional behavior. Various experimental techniques, namely small-angle neutron scattering (SANS), fluorescence, conductivity, and surface tension, have been employed to investigate the mixed micellization. The SANS data analysis has been employed to determine the shapes of different aggregates formed. Pure twin tail cationic surfactants form vesicles whereas the micelles of pure pluronic L64 are spherical. The mixed systems (surfactant + L64) also form spherical micelles, and the spherical shape of mixed micelles is predominantly controlled by pluronic L64. Various interfacial parameters such as surface excess (Γ _max), minimum area per molecule (A _min), and thermodynamic parameters such as the standard Gibbs free energy of micellization (DG_mic⁰ \Delta G_{{mic}}^{{0}} ), Gibbs free energy of adsorption (DG_ads⁰ \Delta G_{{ads}}^{{0}} ), and effective Gibbs free energy (DG_eff⁰ \Delta G_{{eff}}^{{0}} ) have been determined from the surface tension measurements. The results were interpreted on the basis of pseudophase separation model and regular solution theory. The interactions of each surfactant with pluronic L64 are found to be nonideal and antagonistic. The repulsive nature of the interaction is explained on the basis of the changes in the microenvironment of micelles of pluronic L64. Micelles of pluronic L64 are less hydrophobic and contains significant amount of water, and inclusion of hydrophobic alkyl chains of twin tail cationic surfactants disturbs this microenvironment of pluronic L64 micelle.