环戊酮光电离解离的实验和理论研究（英文）

本文介绍了真空紫外光电离质谱结合理论计算研究环戊酮单分子的光电离解离过程,在9.0～15.5 eV能量范围内,测量了环戊酮离子及其碎片离子的光电离效率曲线.通过光电离效率曲线,将环戊酮分子的电离能确定为9.23±0.03eV,并确认碎片离子为:C_5H_7O~+,C_4H_5O~+,C_4H_8~+,C_3H_3O~+,C_4H_6~+,C_2H_4O~+,C_3H_6~+, C_3H_5~+,C_3H_4~+, C_3H_3~+, C_2H_5~+,C_2H-4~+.利用量子化学计算方法,在ωB97X-D/6-31+G(d,p)理论水平基础上,提出了C_5H_8O~+的解离机制.通过对环戊酮解离路径的分析,发现开环和氢迁移过程为环戊酮离子解离的主要路径.     

环戊酮C_5H_8O的同步辐射真空紫外光电离解离研究

利用同步辐射光源,研究了环戊酮(C5H8O)在真空紫外105～140 nm波段的光电离和光解离过程.通过质谱测量各离子的光电离效率曲线,得到了该分子的垂直电离能及主要碎片离子的出现势.从理论上利用G3方法,计算了母体和中性及离子碎片的结构和能量,估算了各解离通道所需的解离能.结合实验测量值和理论计算值,指认出环戊酮分子可能的光电离解离通.     

酮类有机物放电离子淌度谱研究

离子淌度谱是一种快速检测痕量挥发性有机物的高灵敏方法。在放电离子源离子淌度谱装置上,研究了八种酮类有机物的离子淌度谱。实验测量了各种离子的约化迁移率,其中丙酮、正丁酮、1-甲基-2-吡咯烷酮、环己酮、苯乙酮的实验结果与前人63Ni放射源离子淌度谱相一致,而甲基异丙基酮、4-甲基-2-戊酮、环戊酮单体和二聚体离子的约化迁移率则是首次报道。实验测量的约化迁移率与离子质量线性相关,获得的对酮类有机物检测灵敏度在ng·L-1量级。     

甲基异戊酮的离子迁移谱

在自行研制的离子迁移谱仪器上,制备了反应离子质子化水团蔟离子[H＋（H2O）n],并研究了甲基异戊酮的迁移谱。甲基异戊酮的产物离子峰的个数由浓度决定,当浓度在0.004μg/L时出现一个产物离子峰,当浓度达到0.1μg/L时出现两个产物离子峰,当浓度达到1μg/L时出现一个产物离子峰。甲基异戊酮与反应离子发生反应,生成单体团簇离子和二聚体团簇离子。实验测量了各种离子的约化迁移率。     

环戊酮光电离解离的实验和理论研究

本文介绍了真空紫外光电离质谱结合理论计算研究环戊酮单分子的光电离解离过程. 在9.0∽15.5 eV能量范围内,测量了环戊酮离子及其碎片离子的光电离效率曲线. 通过光电离效率曲线,将环戊酮分子的电离能确定为9.23±0.03 eV,并确认碎片离子为：C₅H₇O⁺,C₄H₅O⁺,C₄H₈⁺,C₃H₃O⁺,C₄H₆⁺,C₂H₄O⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺,C₂H₅⁺, C₂H₄⁺. 利用量子化学计算方法,在ωB97X-D/6-31+G(d,p)理论水平基础上,提出了C₅H₈O⁺的解离机制. 通过对环戊酮解离路径的分析,发现开环和氢迁移过程为环戊酮离子解离的主要路径.     

飞秒激光作用下3-甲基吡啶的多光子电离质谱研究

利用800 nm的飞秒激光作为光源对3-甲基吡啶分子进行了多光子电离解离过程和机制的研究,发现3-甲基吡啶为先电离后解离,并分析了可能的解离通道.在B3LYP/6-311G++(d,p)水平下,计算了各个解离通道所需的能量,与我们实验所得的各离子的光强指数符合较好.     

飞秒激光作用下3-甲基吡啶的多光子电离质谱研究

利用800 nm的飞秒激光作为光源对3-甲基吡啶分子进行了多光子电离解离过程和机制的研究,发现3-甲基吡啶为先电离后解离,并分析了可能的解离通道.在B3LYP/6-311G++(d,p)水平下,计算了各个解离通道所需的能量,与我们实验所得的各离子的光强指数符合较好.     

荧光猝灭法研究单羰基姜黄素衍生物与酪氨酸酶间的相互作用

用二烯酮结构代替不稳定的二烯二酮结构合成了3个结构稳定的单羰基姜黄素衍生物1,5-双(4-羟基)-1,4-戊二烯-3-酮(1a)、2,5-双(4-羟基-苯亚甲基)环戊酮(1b)和2,6-双(4-羟基-苯亚甲基)环己酮(1c).运用荧光光谱法研究了化合物与酪氨酸酶间的相互作用.实验结果表明,酪氨酸酶可致使合成化合物的荧光...     

2-甲基-2-丙烯-1-醇的光电离解离研究

利用可调谐真空紫外同步辐射和分子束实验装置在8.0～15.5 eV的光子能量范围内,研究2-甲基-2-内烯-1-醇的光电离解离.测出母体离子和碎片离子:C_4H_8O~+、C_4H_7O~+、C_3H_5O~+、C_4H_7~+、C_4H_6~+、C_4H_5~+、C_2H_4O~+、C_2H_3O~+、C_3H_6~+、C_3H_5~+、C_3H_3~+、CH_3O~+和CHO~+的光电离效率曲线,并获得母体分子的电离能和碎片离子的实验出现势.在B3LYP/6-31+G(d,p)理论水平上,计算光电离过程中母体分子、过渡态和中间体的稳定结构.采用CCSD(T)/cc-pVTZ耦合簇方法计算零点能,得到母体电离能和碎片离子的出现势.通过实验和理论研究,提出2-甲基-2-丙烯-1-醇的光解离路径,分子内氢转移是其中大部分解离途径中的主要过程.     

2-甲基-2-丙烯-1-醇的光电离解离研究（英文）

利用可调谐真空紫外同步辐射和分子束实验装置在8.0～15.5 eV的光子能量范围内,研究2-甲基-2-内烯-1-醇的光电离解离.测出母体离子和碎片离子:C_4H_8O~+、C_4H_7O~+、C_3H_5O~+、C_4H_7~+、C_4H_6~+、C_4H_5~+、C_2H_4O~+、C_2H_3O~+、C_3H_6~+、C_3H_5~+、C_3H_3~+、CH_3O~+和CHO~+的光电离效率曲线,并获得母体分子的电离能和碎片离子的实验出现势.在B3LYP/6-31+G(d,p)理论水平上,计算光电离过程中母体分子、过渡态和中间体的稳定结构.采用CCSD(T)/cc-pVTZ耦合簇方法计算零点能,得到母体电离能和碎片离子的出现势.通过实验和理论研究,提出2-甲基-2-丙烯-1-醇的光解离路径,分子内氢转移是其中大部分解离途径中的主要过程.     

Dissociation energies of molecular hydrogen and the hydrogen molecular ion

We have obtained improved values for the dissociation energies of molecular hydrogen and its ion by using a high-resolution pulse-amplified laser to probe the second dissociation limit. The onset of the vibrational continuum is observed by state-selective detection of the atomic products of dissociation, and several auxiliary measurements link the results to the ground state. The dissociation energies are accurate to 0.010-0.026 cm(-1), improving previous measurements by a factor of 3-7. Agreement with ab initio calculations is good for H2, D2, and their ions, but not for HD and HD+.     

Complexation of divalent metal ions with diols in the presence of anion auxiliary ligands: zinc-induced oxidation of ethylene glycol to glycolaldehyde by consecutive hydride ion and proton shifts

Ternary complexes of the type AH???M(2+)???L(-) (AH?=?diol, including diethylene and triethylene glycol, M?=?Ca, Mn, Fe, Co, Ni, Cu and Zn and auxiliary anion ligand L(-) =?CH(3)COO(-), HCOO(-) and Cl(-)) have been generated in the gas phase by MALDI and ESI, and their dissociation characteristics have been obtained. Use of the auxiliary ligands enables the complexation of AH with the divalent metal ion without AH becoming deprotonated, although A(-)???M(2+) is often also generated in the ion source or after MS/MS. For M?=?Ca, dissociation occurs to AH?+?M(2+)???L(-) and/or to A(-)???M(2+) + LH, the latter being produced from the H-shifted isomer A(-) ???M(2+)???LH. For a given ligand L(-), the intensity ratio of these processes can be interpreted (barring reverse energy barriers) in terms of the quantity PA(A(-)) - Ca(aff) (A(-)), where PA is the proton affinity and Ca(aff) is the calcium ion affinity. Deuterium labeling shows that the complex ion HOCH(2)CH(2) OH???Zn(2+)???(-)OOCCH(3), in addition to losing acetic acid (60 Da), also eliminates glycolaldehyde (HOCH(2)CH=O, also 60 Da); it is proposed that these reactions commence with a hydride ion shift to produce the ion-dipole complex HOCH(2)CHOH(+)??? HZnOOCCH(3), which then undergoes proton transfer and dissociation to HOCH(2)CH=O?+?HZn(+)???O?=?C(OH)CH(3). In this reaction, ethylene glycol is oxidized by consecutive hydride ion and proton shifts. A minor process leads to loss of the isomeric species HOCH=CHOH.     

Muonic molecules in superintense laser fields

We study theoretically the ionization and dissociation of muonic molecular ions (e.g., dd mu) in superintense laser fields. We predict that the bond breaks by tunneling of the lightest ion through a bond-softened barrier at intensity I > or =10(21) W/cm(2). Ionization of the muonic atomic fragment occurs at much higher intensity I > or =6 x 10(22) W/cm(2). Since the field controls the ion trajectory after dissociation, it forces recollision of a approximately 10(5)-10(6) eV ion with the muonic atom. Recollision can trigger a nuclear reaction with sub-laser-cycle precision. In general, molecules can serve as precursors for laser control of nuclear processes.     

Gas phase activation energy for unimolecular dissociation of biomolecular ions determined by focused RAdiation for gaseous multiphoton ENergy transfer (FRAGMENT)

We present a novel approach for the determination of activation energy for the unimolecular dissociation of a large (>50 atoms) ion, based on measurement of the unimolecular dissociation rate constant as a function of continuous-wave CO(2) laser intensity. Following a short ( approximately 1 s) induction period, CO(2) laser irradiation produces an essentially blackbody internal energy distribution, whose 'temperature' varies inversely with laser intensity. The only currently available method for measuring such activation energies is blackbody infrared radiative dissociation (BIRD). Compared with BIRD, FRAGMENT: (a) eliminates the need to heat the surrounding ion trap and vacuum chamber to each of several temperatures (each requiring hours for temperature equilibration); (b) offers a three-fold wider range of effective blackbody temperature; and (c) extends the range of applications to include initially cold ions (e.g., gas-phase H/D exchange). Our FRAGMENT-determined activation energy for dissociation of protonated bradykinin, 1.2 +/- 0.1 eV, agrees within experimental error to the value, 1.3 +/- 0.1 eV, previously reported by Williams et al. from BIRD experiments. Copyright 1999 John Wiley & Sons, Ltd.     

Structure and stability of the negative hydrogen molecular ion

We present the results of a Coulomb explosion experiment that allows for the imaging of the rovibrational wave function of the metastable H2- ion. Our measurements confirm the predicted large internuclear separation of 6 a.u., and they show that the ion decays by autodetachment rather than by spontaneous dissociation. Imaging of the resulting H2 products reveals a large angular momentum of J = 25 ± 2, quantifying the rotation that leads to the metastability of this most fundamental molecular anion.     

利用时间切片离子速度成像技术对AlO在193 nm的光解反应动力学研究

本文利用时间切片离子速度成像技术对AlO分子在193 nm下的光解反应动力学进行了研究. 实验通过产物Al⁺的离子速度和角度分布分析,发现了两个光解离反应通道,分别为中性AlO分子的单光子解离生成产物Al(²P_u)+O(³P_g)的通道,和AlO分子吸收两个光子电离产生AlO⁺进而解离生成产物为Al⁺(¹S_g)+O(³P_g)的反应通道. 每一个解离通道包括了AlO(v=0∽2)振动态的贡献,其中中性解离反应通道与离子解离反应通道相比,产物的各向异性参数对AlO的振动态依赖更大.     

Observation of accurate ion dissociation thresholds in pulsed field ionization-photoelectron studies

We report the first observation, together with a mechanism for such an observation, of a steplike feature in the pulsed field ionization photoelectron measurement of CH4(C2H2), marking the 0 K dissociation threshold for the formation of CH3(+) + H(C2H(+) + H) from CH4(C2H2). The nonexistence of a step in the spectrum for C 2H4 at its dissociation threshold for C2H2(+) formation provides strong support for the proposed mechanism. This experiment shows that, for a range of molecules, where the ion dissociation lifetimes near the dissociation thresholds are <10(-7) s, pulsed field ionization photoelectron measurements will yield not only highly accurate ionization energies, but also 0 K dissociation thresholds.     

荧光光谱法研究蒜头果蛋白与金属离子的相互作用

蒜头果蛋白(malanin)是从云南、广西特有植物蒜头果中分离纯化出的一种新的、具有抗肿瘤活性的糖蛋白。用荧光光谱法研究了Cu2+,Ag+和Ca2+对malanin和apo-malanin溶液(经EDTA透析脱去金属离子后的脱金属蛋白)荧光强度的影响。结果表明,Cu2+对malanin和apo-malanin荧光均有明显的静态猝灭现象,其离解常数K_d分别为2.37×10-4和2.66×10-4 mol·L-1;Ag+对malanin的荧光强度变化不大,但对apo-malanin荧光强度却有明显的静态猝灭现象,其离解常数K_d为2.37×10-4 mol·L-1;而Ca2+对malanin和apo-malanin荧光强度均无明显变化,说明Ca2+对维持malanin分子天然构象具有重要作用。     

振动波包法模拟氢溴酸光解离动力学

研究了在零度和非零度时的双原子分子离子HBr⁺在不同包络函数的超快激光脉冲作用下的光解离动力学. 主要计算了HBr⁺电子基态时的参数. 利用从头算理论在CCSD/6-311++G(3df,2pd)水平计算了HBr+的势能值,用Morse参数模拟后,与非依时傅立叶格点哈密顿方法获得的束缚态振动能量本征值进行比较. 另外,探索了温度、脉冲包络函数和光强度对光解离过程的影响.     

Collision-induced dissociation of oligonucleotide anions fully modified at the 2'-position of the ribose: 2'-F/-H and 2'-F/-H/-OMe mix-mers

Gas-phase dissociation of various 2'-position modified oligonucleotide anions has been studied as a function of precursor ion charge state using ion trap and low energy beam-type collision-induced dissociation (CID). For a completely 2'-O-methyl modified 6-mer, all possible dissociation channels along the phosphodiester linkage, generating complementary (a-B)/w-, b/x-, c/y-, d/z-ion series, were observed with no single dominant type of dissociation pathway. Full sequence information was generated from each charge state via ion trap CID. More sequential fragmentation was noted under beam-type CID conditions. Comparison with model DNA, in which all 2'-OH groups are converted to 2'-H, and RNA anions suggests that the 2'-OMe substitution stabilizes the phosphodiester linkage with respect to fragmentation relative to both DNA and RNA oligomers. For modified mix-mer anions, comprised of DNA nucleotides and 2'-F substituted nucleotides or a mixture of DNA nucleotides and 2'-O-methyl (2'-OMe) and 2'-F substituted nucleotides, 3'-side backbone cleavage was found to be inhibited by the 2'-OMe or 2'-F modification on the nucleotides under ion trap CID conditions. Thus, the sequence information was limited to the a-Base/w-fragments from the cleavage of the 3' C-O bond of the 2'-H (DNA) nucleotides. Under beam-type CID conditions, limited additional cleavage adjacent to 2'-OMe substituted nucleotides was noted but 2'-F modified residues remained resistant to cleavage.