异辛基膦酸单异辛酯稀土配合物的快原子轰击质谱(FABMS)

酸性磷酸酯金属配合物组成和结构的测定有利于阐明萃取机理,是萃取化学中令人感兴趣的课题。标题配合物由于热稳定性差、挥发性小而且分子量大(结构筒式I,简称LnL_3),常规的质谱分析(EIMS、CIMS)难以进行。本文应用FABMS成功地对此配合物作了测定,并用亚稳跃迁技术对其裂解规律进行了探讨。

Synthesis, characterization, and thermal degradation studies on group VIA derived weak-link polymers

Polymers containing group VIA derived weak links, viz. poly(styrene disulfide) (PSD), poly- (styrene tetrasulfide) (PST), and poly(styrene diselenide) (PSDSE), have been synthesized. The polymers PSD and PST were characterized by NMR, IR, UV, TGA, and fast atom bombardment m w spectrometric (FABMS) techniques. The presence of different configurational sequences in PSD and PST were identified by *3C NMR spectroscopy. PSDSE, being insoluble in common organic solvents, was characterized using solid-state lac NMR (CP-MAS) spectroscopy. Thermal degradation of polymers under direct pyrolysis-mass spectrometric (DP-MS) conditions revealed that all the polymers undergo degradation through the weaklink scission. A comparative study of the pyrolysis products of these polymers with that of poly(styrene peroxide) (PSP) revealed a smooth transformation down the group with no monomer (styrene or oxygen) formation in PSP to only styrene and selenium metal in PSDSE. This trend of group VIA is explained from the energetics of the C-X bond (X = 0, S, and Se) which also seems to be important in addition to the weak X-X bond cleavage. In PSP and PSD, the behavior is also explained from the energetics of the alkoxy and thiyl radicals. The unique exothermic degradation in PSP compared to endothermic degradation in PSD and PSDSE is explained from the nature of the producta of degradation.

金属络合物的快原子轰击质谱研究

本文应用快原子轰击质谱和亚稳跃迁研究了盐、冠醚稀土络合物、异辛基膦酸单异辛酯及其金属络合物的质谱碎裂行为。结果表明：（I）离子型盐类化合物的FABMS中的特征离子为：（1）[e·Mat+n·M-(mn-DH]~+ (2)[M+Mat-Cm-1)+n·R]~+(3)[M+e·TEA-(m-1)H+a·MXm]~+。这些离子形成于液相反应和气相碎裂；（II）冠醚稀土络合物的FABMS中存在着稀土冠醚络离子、冠醚系列离子、稀土盐系列离子及硝酸根系列负离子。气相中的离子与溶液中的离子有一定的对应关系；（III）异辛基膦酸单异辛酯的快原子轰击质谱显示丰度较大的二聚体离子，它直观地反映了该化合物液相的二聚状态。其铜盐的FABMS给出该化合物的分子离子（M~+和M~-）及准分子离子（[M+2H]~+、(M+H)~-、(M-H)~-和[M-WH~-]）。稀土络合物则得到准分子离子[M+H]~+，在高于分子离子的质量端还存在系列离子[M·（HL）_n+H]~+(n=1,2,3)这些化合物的质谱特征与溶液中的平衡有一定的对应关系。另外，本文还对络合物快原子轰击下的氧化还原过程进行了讨论。

质谱在高分子热分解及油脂分析中的应用

本论文主要包括三个部分。第一部分简单介绍了四极杆质谱仪的工作原理和所用实验技术；第二部分首先综述了质谱技术在高分子链结构和热分解机理研究中的应用，然后以直接裂解质谱（DPMS）为主要手段研究了聚对苯硫醚（PPS）、聚噻吩（PT）、聚苯胺（PAn）、聚邻甲基苯胺（POT）和聚β-羟基丁酸酯（PHB）及其共聚物的热分解行为和某些结构性质。主要讨论了电子能量、裂解温度、电离方式等对高分子裂解产物的影响，表明DPMS是研究高分子热分解机理的有效方法。几种导电聚合物的热分解均以自由基方式降解，PPS裂解形成环状和线状齐聚物，PT、PAn及POT只能形成线状齐聚物；聚β-羟基烷酸酯的热分解通过β-CH转移反应形成由羟基和烯烃结尾的齐聚物，形成的齐聚物准分子离子可进一步脱去一个分子水。第三部分用GC、GC/MS分离鉴定了山核桃油中的脂肪酸，并用FABMS测定了山核油中混合甘油三酸酯的组成。FABMS能反映不同甘油三酸酯的组成和含量，而GC、GC/MS能对各种脂肪酸进行定性和定量分析，两种方法相互补充，较全面地获得了山核桃油的组成信息。

A new method for the preparation of fullerol

Reaction of C-60 with excessive potassium in toluene at refluxing temperature results in black precipitate KaC60 with high conversion, which can completely be hydrolyzed to prepare the fullerol. Investigations including FT-IR. H-1 NMR C-13 NMR, UV-Vis and FABMS of the product were reported.

Convenient preparation and properties of C-60(OH)(x)

In this paper, we introduce a very convenient method to produce water soluble C-60 derivatives- fullerols by the reaction of C-60 with potassium in toluene solution, FT-IR, H-1 NMR and FABMS proved the multi-hydroxyl and C-60 cage structures of the products, The properties of unstability to light, heat, basicity of aqueous solution and the solubility in some common polar solvents were also described.

C_(60)的二聚合现象

C_(60)的聚合反应是一项十分有意义的研究课题。“珍珠项链”式的C_(60)聚合物将具有优良的导电和非线性光学性能,有可能成为新型功能高分子材料。自Yeretzian等人于1992年采用激光蒸发C_(60)膜率先在气相中实现C_(60)聚合以来,这一领域的研究一直方兴未艾。但总体来看,采用激光等手段尚不能得到宏观量的结构规整的聚合物。1994年瑞士科学家Pekker等人采用金属钾与C_(60)高温蒸气的反应,在特定的温区得到聚合度逾100000的C_(60)线性聚合物,表明钾对于

一些含锗有机酸的快原子轰击质谱

本文报道了—系列合锗有机酸在甘油中的快原子轰击质谱(FABMS)及其在间硝基苄醇(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.

快原子轰击质谱直接分析山核桃油中的混合甘油三酸酯

本文利用快原子轰击质谱(FABMS)直接测定山核桃油中未经任何前处理的混合甘油三酸酯,能获得其分子量和碎片结构信息,在GC和GC/MS分析的基础上。根据FABMS测得的分子量可推导出甘油三酸酯的组成和不同甘油三酸酯的含量。FABMS定量结果和GC、GC/MS测定结果及文献值相符。

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。

有机膦酸酯稀土萃取剂的快原子轰击质谱研究

本文报道了用正、负离子快原子轰击质谱法鉴定有机膦酸酯稀土萃取剂的方法。结果表明:该类化合物的FABMS比较简单,具有〔MH〕~+,〔M_2H〕~+,〔M_3H〕~+等系列离子;断裂方式简明,规律性强。主要表现为C—O,P—O,C—P键断裂;在正离子FABMS中,准分子离子经C—O键断裂,重排后形成的离子RP(OH)_3~+为基峰离子,在负离子FABMS中,准分子离子RP(O)(OR_1))O~-为基峰。

冠醚稀土络合物的快原子轰击质谱

本文报道十余个冠醚稀土络合物的快原子轰击质谱(FABMS)。通过分析FABMS的特征及亚稳离子分解讨论了溶液中的反应和络合性质。

Bromophenol derivatives from the red alga Rhodomela confervoides

Eight new bromophenol derivatives, 2,3-dibromo-4,5-dihydroxybenzyl methyl sulfoxide (1), 4-(2,3-dibromo-4,5-dihydroxyphenyl)-3-butene-2-one (2), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (3), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid methyl ester (4), 2-phenyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (5), 4'-methoxy-2",3',3"-tribromo-4",5',5"-trihydroxydiphenylacetic acid (6), and 3-bromo-5-hydroxy-4-methoxyphenylacetic acid (7) and its methyl ester (8), together with a known bromophenol, 3-bromo-5-hydroxy4-methoxybenzoic acid (9), were isolated from the red alga Rhodomela confervoides. Their structures were elucidated by spectroscopic methods including IR, EIMS, FABMS, ESIMS, HRFABMS, HRESIMS, 1D and 2D NMR, and single-crystal X-ray structure analysis. Compounds 1-4, 8, and 9 were found inactive against several human cancer cell lines and microorganisms.

A novel polyhydroxyl sterol from Asterina pectinifera

A novel polyhydroxyl sterol ( 1) along with one known polyhydroxyl sterol (2), and two known monoglycosides, asterosaponin P-1 (3) and its desulfated monoglycoside (4), have been isolated from the whole bodies of a common Pacific starfish Asterina pectinifera. The structure of the new polyhydroxyl sterol was determined as 15beta, 16beta-isopropylidenedioxy-5alpha-cholestane-3beta, 4beta, 6alpha, 7alpha, 8,26-hexaol by spectroscopic methods, including FABMS, HR-FABMS, 1D and 2D NMR techniques.

A fast atom bombardment mass spectrometry study of tris (3, 6-dioxaheptyl) amine-alkali metal halide complexes and hydrogen bonded complexes

The objective of this thesis was to demonstrate the potential of fast atom bombardment mass spectrometry (FABMS) as a probe of condensed phase systems and its possible uses for the study of hydrogen bonding. FABMS was used to study three different systems. The first study was aimed at investigating the selectivity of the ligand tris(3,6-dioxaheptyl) amine (tdoha) for the alkali metal cations. FABMS results correlated well with infrared and nmr data. Systems where a crown ether competed with tdoha for a given alkali metal cation were also investigated by fast atom bombardment. The results were found to correlate with the cation affinity of tdoha and the ability of the crown ether to bind the cation. In the second and third studies, H-bonded systems were investigated. The imidazole-electron donor complexes were investigated and FABMS results showed the expected H-bond strength of the respective complexes. The effects of concentration, liquid matrix, water content, deuterium exchange, and pre-ionization of the complex were also investigated. In the third system investigated, the abundance of the diphenyl sulfone-ammonium salt complexes (presumably H-bonded) in the FABMS spectrum were found to correlate with qualitative considerations such as steric hindrance and strength of ion pairs.