用RIMS研究低能He2+与Ar碰撞的多电子过程

用反冲离子动量谱仪研究了低能He2+与Ar碰撞的多电子交换过程。该技术的独特优势是对反冲离子末态动量的完全测量。实验上鉴别了单电子俘获SC，双电子俘获DC和转移电离TI各子过程，并得到了末态量子态布居信息，首次测量了该体系各反应道的角微分截面及直接与碰撞参数相关的信息。实验发现电子主要俘获到入射离子基态或单激发态，反冲离子处于单激发态或多激发态，并有较大几率形成空心离子。研究表明电荷交换过程中存在较强的电子-电子关联作用。角分布随反冲离子电荷态增加而变宽，并向大角度方向移动，表明碰撞参数减小，相互作用加剧。SC和DC与MCBM理论角微分截面符合很好，说明在大碰撞参数时经典近似有一定合理性。不同碰撞参数范围内反冲纵向动量分布表明，SC在碰撞参数7.2a.u.≥b≥3.6a.u.时发生机率最大，随碰撞参数减小，靶离子有不断向更高激发态过渡的趋势

三体核力对核物质中基态关联效应和中子星物质中1S0态质子超流性的影响

本论文介绍了极端条件下核物质性质研究的现状以及目前常用的几种微观核多体方法，系统描述了核物质中的基态关联效应、温度效应对单核子势的影响和同位旋非对称核物质 态中子、质子超流性，重点考虑了利用介子交换流方法建立的微观三体核力所产生的影响。利用BHF和BCS的理论方法,计算了同位旋非对称核物质中 态中子和质子的对关联能隙，着重讨论了三体核力的影响。结果表明，三体核力对同位旋非对称核物质中 态的中子超流性影响相对较小，但是对 态的质子超流性具有重要影响，其效应随总核子数密度的增大而迅速增强。随着同位旋非对称度 的增加，中子能隙向低密移动，能隙峰值逐渐增大，并且这种效果随着 的增加而逐渐减弱，而质子的情况刚好相反。另外还参与了 稳定中子星物质中超流性的研究。利用质量算子空穴线展开，通过计算不同温度和密度下的核物质中单核子势和核子有效质量，重点研究和讨论了基态关联效应和三体核力贡献对热核物质中单核子势的影响，研究表明：基态关联效应提供了一个排斥效应，温度和三体核力都削弱了基态关联效应

中子及中子星物质中的3PF2态超流性和微观三体核力效力效应

本论文介绍了当前中子及中子星物质中超流性研究的背景及现状、核多体理论Brueckner-Hartree-Fock及同位旋相关的Brueckner-Hartree-Fock方法，以及利用BHF和BCS理论计算中子及中子星物质中的对关联能隙方法。系统计算并描述了中子及中子星物质中子的3PF2态超流性，并重点考虑了利用介子交换流方法建立的微观三体核力所产生的影响。 我们的研究结果表明：三体核力对中子物质中3PF2态中子超流性有强烈的增强效应。 当在BCS能隙方程中采用自由粒子能谱近似时，三体核力使相应的对关联能隙峰值增加了77%(由0.64MeV增大到1.13MeV)；当采用自洽BHF单粒子能谱时，三体核力导致相应的对关联能隙峰值由0.22MeV增大到0.50MeV，增加了约127%。 三体核力使中子星物质中3PF2态中子超流能隙随着密度的增大而单调递增。当采用自洽BHF单粒子能谱时不考虑三体核力时，对关联能隙峰值在密度约1.9fm-3时有峰值0.19MeV。而在这个两体力导致的能隙的峰值密度，三体核力导致相应的对关联能隙由0.19MeV增大到0.36MeV

三体核力影响下的核物质状态方程及中子星物质中的中子质子超流性

本论文介绍了极端条件下核物质研究的现状以及目前常用的几种核多体方法，系统描述了冷、热非对称核物质的状态方程和刀稳定中子星物质中的15。态中子和质子超流性，特别是微观三体核力对此所产生的影响。通过引入微观三体核力，扩展了有限温度的BI．tleclcller-Hal'tree-Fock（FTBHF）理论。利用这一扩展的理沦，详细研究了同位旋非对称热核物质的状态方程、液气相变临界现象以及三体核力对此所产生的影响。在不同的中质比条件下，重点讨论了热核物质液气相变的临界温度和动力学不稳定区域的温度、同位旋相关性。由此表明，三体核力的引入在一定程度上降低了液气相变的临界温度值，在固定的温度和密度下，非对称核物质的压弧随同位旋非对称度的增加而单调的增力日，而且随着核物质温度的升高和非对称度的增加，动力学不稳定区域逐渐缩小。通过与其它理论模型（特别是Di1'ac-BHF方法）所预言的结果相比较，就目前扩展的包含三体核力修正的FTBHF理论与Dilac-BHF方法所计算的临界温度的差异问题，文中给出一种可能的解释。通过计算热核物质的单粒子结合能，给出了有限温度条件下对称能的计算方式，并且细致研究了不同温度、密度下的对称能以及三体核力在高密度区域对对称能的影响。结果表明，微观三体核力强烈影响着高密度区域的对称能，使其对温度的变化更加明显。此外，其它重要物理量（例如中子和质子的单粒子势能、有效质量等）的同位旋依赖性和温度、密度相关性在文中也被详细的讨论。利用质量算子的空穴线展井，表明了在基态关联所导致的对单核子势的重排修正项影响下的HLlgenholtz-VanHove(HVH)定理的恢复程度，并且进一步计算了中子和质子化学势。并且以包含兰体核力的FTBI-方法为基础，研究了热核物质中重排项的密度和温度依赖性并讨论了三体核力对重排项的影响。通过计算不同温度和密度下的核物质中单核子势和核子有效质量，特别是研究和讨论了基态关联效应和三体核力贡献对热核物质中单核子势的影响，表明了基态关联和三体核力对单核子势修正的重要性。利用BHF和BCS的理论方法，计算了β稳定中子星物质中处于150态的中子和质子的对关联能隙，着重研究和讨论了三体核力的影响。结果表明，三体核力对刀稳定物质中｛s0态中子超流性的影响相对较小，但是对，S0态质子超流性具有重要影响，其效应随核子数密度的增大而迅速增强。三体核力的主要作用是强烈地抑制了高密度区刀稳定中子星物质中的150态质子超流性，而且三体核力对中子星物质中，So态超流相的抑制效应主要是通过质子或中子的有效对相互作用而起作用的。

Studies on the Biotransformation of Arctigenin Using Electrospray Ionization Mass Spectrometry

To study the biotransformation of arctigenin, arctigenin was anaerobically incubated with Eubacterium sp. ARC-2 of human intestinal bacteria in vitro. Arctigenin formed a molecular ion [M-H](-) in negative ion mode. The arctigenin and its metabolites were investigated directly by the electrospray ionization tandem mass spectrometry ion trap and Fourier transform ion cyclotron resonance. Arctigenin was transformed to 4',4 ''-dihydroxylenterolactone by E sp. ARC-2 through 3 types of demethylation products.

A polymorph of diaquabis(pyrazine-2-carboxylato-kappa N-2(1),O)copper(II)

The title compound, [Cu(C5H3N2O2)(2)(H2O)(2)], is a new polymorph of the previously reported compound [Klein et al. (1982). Inorg. Chem. 21, 1891-1897]. The Cu-II atom, lying on an inversion center, is coordinated by two N atoms and two O atoms from two pyrazine-2-carboxylate ligands and by two water molecules in a distorted octahedral geometry with the water molecules occupying the axial sites. Intermolecular O-H center dot center dot center dot O, O-H center dot center dot center dot N and C-H center dot center dot center dot O hydrogen bonds connect the complex molecules into a two-dimensional layer parallel to (10 (1) over bar), whereas the previously reported polymorph exhibits a three-dimensional hydrogen-bonded network.

Gas Phase Addition of Rare-earth Fullerenes with Benzene

Gas phase adduct of endohedral rare-earth fullerenes Nd@C-S2 with the ion system of benzene-[Nd@C-S2-C6H6](+) was observed for the first time by ion-molecular reaction under chemical ionization condition. The possible reaction passageway and molecular structures of this gas phase adduct were discussed and a parallel "reversed umbrella" pi-pi interaction complex of the [C6H6](+) ion reacting with the neutral rare-earth fullerenes Nd@C-S2 was considered to be much reasonable. The experimental result indicated that endohedral rare-earth fullerenes has relatively active reactivity and aromatic properties similar towards benzene molecular ion in gas phase.

ELECTROCHEMISTRY OF THE TRANSFER OF ISOPOLY AND HETEROPOLY ANIONS ACROSS THE WATER NITROBENZENE INTERFACE - ISOPOLYTUNGSTATE AND HETEROPOLYTUNGSTATE ANIONS

The transfer behavior of the heteropoly anion [H3PW11O39]4- and the isopoly anion [H2W12O39]4- across the water/nitrobenzene interface was investigated by cyclic voltammetry and chronopotentiometry with linear current scanning. The transfer processes were

LC-DAD-ESI-MS Characterization of Carbohydrates Using a New Labeling Reagent

A novel labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) coupling to liquid chromatography with electrospray ionization mass spectrometry for the detection of carbohydrates from the derivatized rape bee pollen samples is reported. Carbohydrates are derivatized to their bis-NMP-labeled derivatives. Derivatives showed an intense protonated molecular ion at m/z [M+H](+) in positive-ion detection mode. The mass-to-charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative analysis of carbohydrates. This characteristic fragment ion is from the cleavage of C2-C3 bond in carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose and glyceraldehydes and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids such as galacturonic acid and glucuronic acid (m = n - 2, n is carbon number of carbohydrate). No interferences for all aliphatic and aromatic aldehydes presented in natural environmental samples were observed due to the highly specific parent mass-to-charge ratio and the characteristic fragment ions. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed-phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose and fucose can successfully be detected.

Analysis of carbohydrates in a tibetan medicine using new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone, by HPLC with DAD detection and ESI-MS identification

A new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP), coupling with liquid chromatography (LC) with electrospray ionization mass spectrometry (ESI-MS) for the detection of carbohydrates from a famous Tibetan medicine is reported. Carbohydrates were derivatized to their bis-NMP-labeled derivatives. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose, and fucose could be successfully detected by UV and ESI-MS. Derivatives showed intense protonated molecular ion at m/z [M+H]+ in positive ion mode. The mass to charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative identification of carbohydrates; this characteristic fragment ion was from the cleavage of C2-C3 bond in the carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose, and glyceraldehydes, and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids, such as galacturonic acid and glucuronic acid (m=n-2, n is carbon atom number of carbohydrate). Compared with the traditional 1-phenyl-3-methyl-5-pyrazolone (PMP) reagent, currently synthesized NMP show the advantage of higher sensitivity to carbohydrate compounds with UV and ESI-MS detection.

Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

Determination of aliphatic amines from soil and wastewater of a paper mill by pre-column derivatization using HPLC and tandem mass spectrometry (HPLC-MS/MS)

A pre-column derivatization method for the sensitive determination of aliphatic amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by HPLC with fluorescence detection and APCI/NIS identification in positive-ion mode has been developed. The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by the 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent, BCEOC, that could easily and quickly label amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M + H](+) with APCI/MS in positive-ion mode. The collision induced dissociation of the protonated molecular ion formed characteristic fragment ions at m/z 264.1, m/z 246.0 and m/z 218.1, corresponding to the cleavages of CH2CH2O-CO, CH2CH2-OCO, and N-CH2CH2O bonds. Studies on derivatization conditions demonstrated that excellent derivatization yields close to 100% were observed with a 3 to 4-fold molar reagent excess in acetonitrile solvent, in the presence of borate buffer (pH 9.0) at 40 degrees C for 10 min. In addition, the detection responses for BCEOC derivatives were compared with those obtained with CEOC and FMOC as labeling reagents. The ratios I-BCEOC/I-CEOC and I-BCEOC/I-FMOC were, respectively, 1.40-2.76 and 1.36-2.92 for fluorescence responses (here, I was the relative fluorescence intensity). Separation of the amine derivatives had been optimized on an Eclipse XDB-C-8 column. Detection limits calculated from an 0.10 pmol injection, at a signal-to-noise ratio of 3, were 18.65-38.82 fmol (injection volume 10 mu L for fluorescence detection. The relative standard deviations for intraday determination (n = 6) of standard amine derivatives (50 pmol) were 0.0063-0.037% for retention times and 3.36-6.93% for peak areas. The mean intra-and inter-assay precision for all amines were <5.4% and 5.8%, respectively. The recoveries of amines ranged from 96 to 113%. Excellent linear responses were observed with correlation coefficients of >0.9994. The established method provided a simple and highly sensitive technique for the quantitative analysis of trace amounts of aliphatic amines from biological and natural environmental samples.

Determination of free fatty acids in soil and bryophyte plants by precolumn derivatization via HPLC with fluorescence detection and tandem mass spectrometry (HPLC-MS/MS)

A sensitive method for the determination of 30 kinds of free fatty acids (FFAs, C-1-C-30) with 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4,5-f] 9,10-phenan- threne (TSPP) as labeling reagent and using high performance liquid chromatography with fluorescence detection and identification by online postcolumn mass spectrometry with atmospheric pressure chemical ionization (APCI) source in positive-ion mode (HPLC/MS/APCI) has been developed. TSPP could easily and quickly label FFAs in the presence of K2CO3 catalyst at 90 degrees C for 30 min in N,N-dimethylformamide (DMF) solvent, and maximal labeling yields close to 100% were observed with a 5-fold excess of molar reagent. Derivatives were stable enough to be efficiently analyzed by high performance liquid chromatography. TSPP was introduced into fatty acid molecules and effectively augmented MS ionization of fatty acid derivatives and led to regular MS and MS/MS information. The collision induced cleavage of protonated molecular ions formed specific fragment ions at m/z [MH](+)(molecular ion), m/z [M'+CH2CH2](+)(M' was molecular mass of the corresponding FFA) and m/z 295.0 (the, mass of protonated molecular core structure of TSPP). Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C-8 column (4.6 x 150 mm, 5 mu m, Agilent) with a good baseline resolution in combination with a gradient elution. Linear ranges of 30 FFAs are 2.441 x 10(-3) to 20 mu mol/L, detection limits are 3.24 similar to 36.97 fmol (injection volume 10 mu L, at a signal-to-noise ratio of 3, S/N 3:1). The mean interday precision ranged from 93.4 to 106.2% with the largest mean coefficients of variation (R.S.D.) < 7,5%. The mean intraday precision for all standards was < 6.4% of the expected concentration. Excellent linear responses were observed with correlation coefficients of > 0.9991. Good compositional data could be obtained from the analysis of extracted fatty acids from as little as 200 mg of bryophyte plant samples.Therefore, the facile TSPP derivatization coupled with HPLC/MS/APCI analysis allowed the development of a highly sensitive method for the quantitation of trace levels of short and long chain fatty acids from biological and natural environmental samples.

Analysis of saturated free fatty acids from pollen by HPLC with fluorescence detection

A sensitive method for the determination of free fatty acids using 2-(2-(anthracen-10-yl)-1H-naphtho[2,3-dimidazol-1-yl) ethyl-p-toluenesuIfonate (ANITS) as tagging reagent with fluorescence detection has been developed. ANITS could easily and quickly label fatty acids in the presence of the K2CO3 catalyst at 90 degrees C for 40 min in N,N-dimethylformamide solvent. From the extracts of rape bee pollen samples, 20 free fatty acids were sensitively determined. Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C8 column by HPLC in conjunction with gradient elution. The corresponding derivatives were identified by post-column APCI/MS in positive-ion detection mode. ANITS-fatty acid derivatives gave an intense molecular ion peak at mlz [M+H](+); with MS/MS analysis, the collision-induced dissociation spectra of m/z [M+H](+) produced the specific fragment ions at mlz [M-345](+) and mlz 345.0 (here, m/z 345 is the core structural moiety of the ANITS molecule). The fluorescence excitation and emission wavelengths of the derivatives were lambda(ex) = 250 nm and lambda(em) = 512 nm, respectively. Linear correlation coefficients for all fatty acid derivatives are > 0.9999. Detection limits, at a signal-to-noise ratio of 3 : 1, are 24.76-98.79 fmol for the labeled fatty acids.

Enhancement of atmospheric pressure chemical ionization for the determination of free and glycine-conjugated bile acids in human serum

A highly sensitive and accurate method based on the precolumn derivatization of bile acids (BA) with a high ionization efficiency labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl-benzenesulfonate (BDEBS) coupled with LC/MS has been developed. After derivatization, BA molecules introduced a weak basic nitrogen atom into the molecular core structure that was readily ionized in commonly used acidic HPLC mobile phases. Derivatives were sufficiently stable to be efficiently analyzed by atmospheric pressure chemical ionization (APCI)-MS/MS in positive-ion mode. The MS/MS spectra of BA derivatives showed an intense protonated molecular ion at m/z [M + H](+). The collision-induced dissociation of the molecular ion produced fragment ions at [MH - H2O](+), [MH - 2H(2)O](+), [MH - 3H(2)O](+). The characteristic fragment ions were at m/z 320.8, 262.8, and 243.7 corresponding to a cleavage of N - CO, O - CO, and C - OCC, respectively, and bonds of derivatized molecules. The selected reaction monitoring, based on the m/z [M + H]+ -> [MH - H2O](+), [MH - H2O](+), [MH - 2H(2)O](+), [MH-3H(2)O](+), 320.8, 262.8, and 243.7 transitions, was highly specific for the BA derivatives. The LODs for APCI in a positive-ion mode, at an S/N of 5, were 44.36-153.6 fmol. The validation results showed high accuracy in the range of 93-107% and the mean interday precision for all standards was < 15% at broad linear dynamic ranges (0.0244-25nmol/mL). Good linear responses were observed with coefficients of > 0.9935 in APCI/MS detection. Therefore, the facile BDEBS derivatization coupled with mass spectrometric analysis allowed the development of a highly sensitive and specific method for the quantitation of trace levels of the free and glycine-conjugated BA from human serum samples.