发射光谱研究多针对板正电晕放电形貌

利用光学发射光谱(OES)法检测N₂发射光谱,研究了常压下多针对板正电晕放电中辉光放电和击穿流光放电的高能电子分布,并与相同电极结构下负电晕放电进行了比较。根据N₂第二正态激发谱峰I_SPB在空间的分布,较精确地确定了辉光放电电离区形貌和击穿流光放电电通道形貌,体积分辉光放电中I_SPB获知I_SPB与放电电流I之间的关系。辉光放电中,电离区范围和I_SPB比负电晕放电小,电子雪崩沿针径向比沿轴向发展范围大;随着U升高,电离区范围只沿针轴向小幅度增大;I_SPB的积分值与I近似成二阶线性关系。击穿流光放电中,针板之间形成放电通道;针尖周围I_SPB较强的区域成“子弹状”,距离针尖较远的放电通道内高能电子密度沿针轴向分布比较均匀,沿针径向先略有增大后减小。     

Restoration of coherence effects in high-power excitation of an intramolecular quasicontinuum

Three theoretical models were advanced for the dynamics of molecular multiphoton excitation: (i) The zero-order optically active mode connected by intramolecular random anharmonic couplings to a background manifold. (ii) Molecular eigenstates coupled by random radiative transition dipole moments. (iii) The kinetic master equation approach. It is demonstrated that in the Markoffian limit, as long as the intramolecular vibrational relaxation width is small relative to the Rabi frequency, these three approaches are equivalent. In the case of high-field excitation, coherent quantum effects are exhibited even in a randomly coupled system. Resurrection of the quantum oscillations and coherent pumping can be exhibited in intense field excitation on the time scale of intramolecular vibrational relaxation.     

Proton dissociation constants of benzoylacetone and isonitrosobenzoylacetone in aqueous dioxane media

Thermodynamic proton dissociation constants,TpKa of benzoylacetone(HBA) as well as isonitrosobenzoylacetone (HINBA) have been determinedpH-metrically in 10–50% (v/v) dioxane-water mixtures at 25 and 35±0.01°C applying an empiricalpH correction for mixed aqueous media. ThepKa's in aqueous medium (at 0% dioxane) are obtained following the method of extrapolation and least-squares. BothHBA andHINBA are very weak monoprotic acids withTpKa between 7.0 and 10.0.TpKa's do not vary linearly with the reciprocal of the dielectric constant of the medium, but a plot ofTpKa vs. the mole fraction of dioxane is linear at a given temperature. The true constantKa' and solvation number,n, in the expression (H⁺)(A ^–)/(HA)=Ka' (S) ⁿ =Ka* for these reagents have been evaluated by analysing the experimental data mathematically. Values of G ⁰, H ⁰, and S ⁰ are also computed. Temperature and medium effects are briefly discussed.

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Protonen-Dissoziationskonstanten von Benzoylaceton und Isonitrosobenzoylaceton in wäßrigem Dioxan

Zusammenfassung Es wurden die thermodynamischen Protonen-Dissoziationskonstanten (TpKa) von Benzoylaceton (HBA) und Isonitrosobenzoylaceton (HINBA)pH-metrisch in 10–50% (v/v) Dioxan-Wasser-Mischungen bei 25 und 35 ± 0.01°C bestimmt, wobei eine empirischepH-Korrektur für das gemischt-wäßrige Medium angewendet wurde. DiepKa-Werte in wäßrigem Medium (0% Dioxan) folgen aus der Extrapolation und der Methode kleinster Fehlerquadrate. SowohlHBA als auchHINBA sind sehr schwache monoprotische Säuren mitTpKa zwischen 7.0 und 10.0. DieTpKa's variieren nicht linear mit der reziproken Dielektrizitätskonstante des Mediums, ein DiagrammTpKa gegen Molenbruch Dioxan ergibt jedoch für eine konstante Temperatur eine Gerade. Die wahre KonstanteKa' und die Solvatationszahln des Ausdrucks (H⁺)(A ^–)/(HA)=Ka'(S) ⁿ =Ka* wurde aus den experimentellen Daten für beide Reagentien errechnet. Die thermodynamischen Parameter G°, H° und S° wurden ebenfalls bestimmt, Temperatur- und Lösungsmitteleffekte werden diskutiert.

     

氨/乙醇混合团簇多光子电离质谱

用多光子电离技术结合飞行时间质谱仪对氨与乙醇混合团簇进行了研究。在脉冲激光波长分别为266,355nm和532nm条件下,仅在355nm作用下观测到团簇离子。主要的电离产物为质子化的（C2H5OH）n（NH3）mH＋（n=0—3,m=0—4）混合团簇离子,且各个序列的离子强度随m的增大而减小。经分析,氨与乙醇混合团簇电离后团簇离子发生内部质子化转移反应是形成质子化团簇离子的主要原因。不同尺寸团簇离子信号强度随电离激光光强变化的光强指数曲线显示,团簇均发生四光子电离过程。通过理论计算得到其中性和离子团簇的稳定结构,解离能,解离通道。并证实团簇发生电离解离时发生了团簇内质子转移反应。     

Electron impact ionization and excitation rate coefficients in the negative glow region of a glow discharge

Some easy to use reasonable approximations for electron impact rate coefficients have been considered. The most important rate coefficients for electron collisions in noble gases are electron-neutral ionization and electron impact excitation. Electron-neutral ionization besides electron impact excitation of some states of the argon and helium atom in direct current (dc) glow discharge plasma has been calculated. The plasma parameters of electron are significant factors for computing the rate coefficients. We present first results of probe diagnostic that includes the double probe measurements of the plasma parameters, namely, electron temperature (T_e) and electron density (n_e). Electron properties obtained from the double probe characteristic curves including T_e and n_e as well as the calculated rate coefficients (ionization and excitation) were studied as a function of the axial distance from the cathode while the discharge operating parameters of voltage and pressure were varied. Two regions of the glow discharge were investigated: cathode fall region and negative glow. Particular emphasis was placed on the negative glow region.     

超冷里德堡原子的产生以及探测

利用激光冷却与俘获技术获得冷原子,由双光子激发产生超冷里德堡原子,利用场电离法得到了里德堡原子ns和nd态的离子谱图;再将激光波长固定在6p3/2-34d态的共振跃迁线上,得到了离子和里德堡原子的TOF(Time of Flight)图,并对实验结果做了分析.     

异核双原子和三原子分子在红外强激光场中的电离抑制

Ionization is the fundamental process in interaction of atoms/molecules with femtosecond strong laser fields. Comparing to atoms, molecules exhibit peculiar behaviors in strong-field ionization because of their diverse geometric structures, molecular electronic orbitals as well as extra nuclear degrees of freedom. In this study, we investigate strong field single and double ionization of carbon monoxide (CO) and carbon dioxide (CO₂) in linearly polarized 50-fs, 800-nm laser fields with peak intensity in the range of 2×10¹³ W/cm² to 2×10¹⁴ W/cm² using time-of-flight mass spectrometer. By comparing the ionization yields with that of the companion atom krypton (Kr), which has similar ionization potential to the molecules, we investigate the effect of molecular electronic orbitals on the strong-field ionization. The results show that comparing to Kr, no significant suppression is observed in single ionization of both molecules and in non-sequential double ionization (NSDI) of CO, while the NSDI probability of CO₂ is strongly suppressed. Based on our results and previous studies on homonuclear diatomic molecules (N₂ and O₂), the mechanism of different suppression effect is discussed. It is indicated that the different structure of the highest occupied molecular orbitals of CO and CO₂ leads to distinct behaviors in two-center interference by the electronic wave-packet and angular distributions of the ionized electrons, resulting in different suppression effect in strong-field ionization.     

Integration of metabolomics and network pharmacology to validate the mechanism of Schisandra chinensis（Turcz.）Baill - Acorus tatarinowii Schott ameliorating the Alzheimer's disease by regulating the aromatase activity to affect local estrogen in brain of AD model rats

Alzheimer's disease (AD) is a latent and progressive neurodegenerative disease. Schisandra chinensis（Turcz.）Baill - Acorus tatarinowii Schott (Sc-At) are effective in treating neurological disorders.Purpose of this study is to explore the mechanism of Sc-At in AD treatment. First, untargeted ultra-performance liquid chromatography quadrupole-time of flight/mass spectrometer (UPLC-QTOF/MS) metabolomics was employed to detect the rat brain metabolism. Then, network pharmacology was used to determine the potential anti-AD targets. Bioinformatics, and molecular docking were conducted for further analysis. A MetScape study examined the association between differential metabolites and potential targets. Finally, the targeted ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) metabolomics and the potential protein activity studies were carried out to elucidate the mechanisms. The results showed that Sc-At improved the neuronal cell alignment disorder in hippocampal CA1 region of AD rats. In brain metabolomics, 30 differential metabolites were screened in the study model versus blank group. The network pharmacology analyzed 54 targets of Sc-At anti-AD where, 14 were correlated with amyloid β-protein (Aβ). Aromatase was selected as an important hub target having the best binding power in molecular docking simulation predictions and also correlated with Aβ. Further tests showed that the brain aromatase activity, and the downstream product 17β-Estradiol levels were elevated in AD rats treated with Sc-At. This work may provide new perspectives for the pharmacological effects and the action mechanisms of natural compounds extracts in treating AD progression.     

酪胺和多巴胺VUV光电离/解离的实验和理论研究

利用同步辐射真空紫外光电离质谱和理论计算对中性酪胺和多巴胺分子的光诱导解离过程进行研究．在较低光子能量下,通过近阈光电离仅得到母体离子信号．当增加光子能量到11.7 eV甚至更高时,从酪胺和多巴胺分别得到四个清晰可辨的碎片离子信号．另外通过测量母体离子的光电离效率曲线,酪胺和多巴胺分子的电离能分别为7.98和7.67 eV(实验误差为±0.05 eV)．结合理论计算建立这两个分子的详细碎裂路径,包括相似的胺乙基消除路径．其中碎片C₇H₈O₂^+·(m/z=124)和C₇H₈O^+·(m/z=108)的生成认为来自McLafferty重排,该过程经历分子内的γ氢迁移诱导的β开裂反应． 另外,C7-C8键直接开裂可以生成CH₂NH₂⁺(m/z=30)碎片离子,并且该过程和McLafferty重排为主要的裂解路径.     

430-490nm激光作用下CH_3I分子的多光子电离离解研究

利用飞行时间质谱仪研究了CH3I分子在 4 30～ 4 90nm激光作用下的多光子电离 (MPI)离解过程和机制。得到了分子的飞行时间质谱 ,从整个实验波段 4 30～ 4 90nm的MPI离子谱发现 ,短波的MPI离子谱峰相对较高 ,长波的MPI离子谱峰相对较宽而弥散。对MPI离子谱中的一些共振峰标识为分子的 ( 5pπ ,8s) ,( 5pπ ,6p)以及 ( 5pπ ,7s)里德堡态共振吸收峰。还标识了 ( 5pπ ,7s)里德堡态的系列振动模。在短波段CH3I分子为 ( 3+1)多光子过程 ,长波段为 ( 2+2 )多光过程。