N2分子在强激光场中的场致电离

研究了在强激光脉冲中各种不同取向的N2分子发生场致电离的电离几率和表观电离效率.用量子化学方法计算了N2+分子离子在各种不同取向上的势能曲线,然后用传递矩阵方法得到了N2分子在不同方向上的电离几率,经过角度平均之后得到了各种取向的所有N2分子的总电离几率,并对计算结果进行了激光时间和空间修正.用800nm和70fs的激光脉冲对N2分子进行了在强激光场中的电离实验,得到了N2分子电离后产生的电子的角度分布图和电离几率随激光功率密度变化的关系曲线.实验结果和理论计算结果符合得很好.     

多组态含时自旋非限制HartreeFock理论

基于自旋非限制HartreeFock理论,发展了自旋非限制多组态含时HartreeFock理论方法来研究激光场中的多电子相关动力学．自旋向上和自旋向下的自旋轨道分别在他们各自的子空间内传播;并通过约化密度矩阵和平均场算符相互作用．分别利用了自旋限制和非限制的多组态含时HartreeFock方法虚时和实时传播计算氦原子基态能量和电离几率．自旋非限制的计算结果与其他报道相吻合．     

Matrix-assisted laser desorption/ionization (MALDI) mechanism revisited

Although matrix-assisted laser desorption/ionization (MALDI) was developed more than a decade ago and broad applications have been successfully demonstrated, detailed mechanism of MALDI is still not well understood. Two major models; namely photochemical ionization (PI) and cluster ionization (CI) mechanisms have been proposed to explain many of experimental results. With the photochemical ionization model, analyte ions are considered to be produced from a protonation or deprotonation process involving an analyte molecule colliding with a matrix ion in the gas phase. With the cluster ionization model, charged particles are desorbed with a strong photoabsorption by matrix molecules. Analyte ions are subsequently produced by desolvation of matrix from cluster ions. Nevertheless, many observations still cannot be explained by these two models. In this work, we consider a pseudo proton transfer process during crystallization as a primary mechanism for producing analyte ions in MALDI. We propose an energy transfer induced disproportionation (ETID) model to explain the observation of an equal amount of positive and negative ions produced in MALDI for large biomolecules. Some experimental results are used for comparisons of various models.     

Separations based on the mechanical forces of light

A photon as a particle has an energy and a momentum. In a matter-photon interaction, the matter and photons may exchange their momenta observing the momentum conservation law. The consequence of the momentum transfer from a photon to a matter particle is a mechanical force exerted on the particle. Several separation methods based on this force of light are reviewed. Photophoresis separations for micron-sized particles and optical force chromatography for chemical-sized molecules are discussed.     

Model of Confined Atoms in Arbitrary Static Electric Fields: Relevance to Non-degenerate Plasmas

Abstract

The inhomogeneous electron cloud in atomic ions ‘confined’ in hot plasmas and subjected to high static electric fields is studied, because of a body of experimental data on multiphoton ionization. In particular, the canonical (Bloch) density matrix is obtained in closed form for independent electrons moving in a static electric field of arbitrary strength and confined by a harmonic oscillator potential. To bring the model into contact with atoms in plasmas, the oscillator force constant is connected with the plasma density. For non-degenerate electrons an ‘atomic’ potential is included, by means of the Thomas—Fermi (TF) method. In an Appendix, a fully non-local theory is then developed which transcends this TF approximation. Simple numerical examples are presented for realistic values of field, temperature and plasma density.     

单分子结的构筑及分子电导性质的测试

分子电子学已成为21世纪研究的热点. 通过将具有特定功能的分子连接在纳米尺度金属电极之间从而构筑包括分子导线、开关、整流器在内的各种分子尺度电子器件, 这引起了科学家们广泛的研究兴趣. 在分子电子学研究中, 构筑金属/分子/金属(MMM)分子结是研究分子器件中电子传输性质的关键. 尽管已经取得了很大的进展, 目前在纳米尺度下构筑稳定可靠的MMM分子结并测试单个分子的电学性质仍然面临很多挑战. 本文着重对单分子电学性质的测试技术和相关理论研究的最新进展以及存在的挑战做了概述.     

Medium effects on the ionization constants of some quinoline derivatives

Summary The deprotonation and acid ionization constants of some quinoline derivatives in aqueous organic solvents were determined. The organic solvents used include methanol and ethanol as amphiprotic solvents andDMF andDMSO as dipolar aprotic solvents. The obtainedpK ₁ andpK ₂ values are discussed with respect to the nature and the amount of the organic component. The high stabilization of the non-protonated form by dispersion forces and of the proton by its interaction with the solvent are the main factors responsible for the increase in the ionization constants of the protonated forms of the quinolines under investigation. On the other hand, H-bonding interactions (in addition to the electrostatic effect) seem to play the major role in determining the second acid-base equilibrium of 8-hydroxyquinoline. The deprotonation constants of the examined quinolines are correlated with their experimentally determined lone-pair ionization potential values.

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Lösungsmitteleffekte auf die Ionisationskonstanten einiger Chinolinderivate

Zusammenfassung Die Deprotonierungs- und Ionisationskonstanten einiger Chinolinderivate wurden in wäßrigen organischen Medien, darunter Methanol und Ethanol als amphiprotische undDMF undDMSO als dipolare aprotische Lösungsmittel, bestimmt. Die gemessenenpK ₁- undpK ₂-Werte werden im Hinblick auf die Art und Menge der organische Komponente diskutiert. Die hohe Stabilisierung der nichtprotonierten Form durch Dispersionskräfte und des Protons durch Wechselwirkungen mit dem Lösungsmittel sind die wesentlichen Faktoren, die für den Anstieg der Ionisationskonstanten der protonierten Formen der untersuchten Chinoline verantwortlich sind. Andererseits scheinen Wasserstoffbrückenbindungen — zusätzlich zum elektrostatischen Effekt — das zweite Säure-Basen-Gleichgewicht von 8-Hydroxychinolin entscheidend zu beeinflussen. Die Deprotonierungskonstanten aller untersuchten Chinoline werden mit ihren experimentell bestimmtenlone-pair-Ionisationspotentialen korreliert.

     

强双光子吸收引发的聚合反应

近年来 ,具有强双光子吸收性能的有机材料[1] 在双光子荧光显微术[2 ] 、光限幅[3] 和激光转换[4 ] 等领域中的应用引起了各国学者的广泛关注 ,强双光子吸收引发的聚合反应[5～ 8] 及其应用尤其令人瞩目 .与传统的紫外光引发的聚合反应相比 ,强双光子吸收引发的聚合反应有两个明显特征 :(1 )双光子吸收的强度与入射光强的平方成正比 ,因而在入射激光光束密聚焦的情况下 ,聚合反应只发生在入射光波长立方 (λ3)范围的微小体积内 ;(2 )聚合反应的辐照光源为可见 -近红外激光 ,长波长使得入射光的损耗较小 ,因此在介质中的穿透性好 .同时由于双…     

The multiconfigurational spin tensor electron propagator method (MCSTEP): Comparison with extended Koopmans' theorem results

Summary We applied the multiconfigurational spin tensor electron propagator method (MCSTEP) for determining the lowest few (in energy) vertical ionization potentials (IPs) of HF, H₂O, NH₃, CH₄, N₂, CO, HNC, HCN, C₂H₂, H₂CO, and B₂H₆. We chose these molecules so that we could compare MCSTEP IPs with recently reported extended Koopmans' theorem (EKT) IPs on the same molecules. Using standard Dunning core-valence basis sets with relatively small complete active spaces, MCSTEP results are in very good to excellent agreement with experiment. These MCSTEP IPs are obtained using matrices no larger than 400 × 400. EKT matrices are even smaller; however, to obtain similar but generally slightly worse agreement with experiment, fairly large active spaces are required with EKT.     

Capillary electrophoretic separation and fractionation of hydrophobic peptides onto a pre-structured matrix assisted laser desorption/ ionization target for mass spectrometric analysis

A CE separation of hydrophobic peptides followed by fractionation onto a prestructured MALDI target and off-line MS analysis was performed. An improved and partially automated manufacturing procedure of the previously described MALDI target is presented. This target is structurally coated with silicone and especially developed for hydrophobic peptides and proteins. Here, the target plate was designed specifically for the CE fraction collection. Different solvents were evaluated to meet the requirements of peptide solubility and compatibility to both the CE and MALDI methods and to the fractionation procedure. CE-MALDI-MS analysis of nine highly hydrophobic peptides from cyanogen bromide-digested bacteriorhodopsin is demonstrated.     

酸性染料分子表面印迹材料的设计与制备及其分子识别特性研究

本文使用\"接枝交联聚合与印迹过程同步进行\"的分子表面印迹方法,以阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)为功能单体,以活性艳红X-3B(RBR)为模板分子,制备了酸性染料分子表面印迹材料,并考察了印迹材料的分子识别性能。在水溶液中,凭籍强静电相互作用与阳离子-π相互作用,阳离子单体DAC自动地结合在模板RBR分子周围,在氨基/过硫酸盐表面引发体系作用下,DAC及交联剂N,N'-亚甲基双丙烯酰胺(MBA)在硅胶微粒表面发生接枝交联聚合,制得了酸性染料分子表面印迹材料MIP-PDAC/SiO2。该分子表面印迹材料对RBR分子具有高度的识别选择性,相对于结构与RBR相似的活性黄X-RG和活性嫩黄X-6G两种酸性染料,MIP-PDAC/SiO2对RBR的识别选择性系数分别为8.1和8.9。     

The conformational dynamics of humic polyanions in model organic and organo-mineral aggregates

Molecular mechanics calculations and simulated annealing were applied to model humic polyanions originating from lignin. The dynamic behavior of such oxidized lignins in model soil organic complexes, such as an oxidized lignin-carbohydrate complex (LCC) and humic (oxidized LCC)-clay aggregates, was analyzed. Neither ionization nor hydrogen bonding bring significant changes in the conformational properties of oxidized lignin and LCC. Oxidized lignin and LCC oligomers (humic substances in soil) bind to the mineral surfaces, a process that was exemplified in computational experiments on complexes with muscovite. Upon ionization, a lignin-derived oligomer develops strong attractive organo-mineral interactions through cation bridges. Without metal cations, electrostatic repulsion between negatively charged anions and the oxygen-mineral surface prevails, and the two parts of the organo-mineral complex drift apart. This tendency is typical of an oxidized lignin oligomer but not of a topological oxidized LCC.     

飞秒强激光场中一氧化碳分子隧穿电离产生阳离子的振动态分布

本文通过实验研究了强激光场照射CO分子后阳离子的振动态布居.观察到振动分辨的荧光光谱,且这些光谱可以很好地归属于CO+阳离子的A2∏(v'=0～3)→X2∑(v\"=0～3)跃迁,表明CO分子的内层轨道发生了强场电离.根据测得的光谱和Franck-Condon因子获得了CO+的A2∏(v'=0～3)振动态的相对布居.研究发现,CO分子强场电离的振动态分布明显偏离了Franck-Condon因子的预期,但与包含电离率和中性态与阳离子态振动波函数重叠的计算结果非常一致.CO+(A2∏,v')的布居强烈依赖于激光强度,但对激光椭偏率的依赖性较小.分析表明,核间距依赖的电离在CO分子强场电离诱导的振动态布居中起到了重要作用.     

分子影像探针

分子影像是近年出现并迅速发展的一个生物医学领域,在疾病的治疗与诊断中发挥着重要作用。同时它又是一门交叉学科,涉及化学、医学、生物、计算机科学、放射科学、材料科学等。分子影像的发展除了需要先进的成像设备外,最关键的是合成新型而高效的成像探针。目前,分子影像探针广泛应用于科学研究和临床,并且也取得了巨大进步。本文主要综述了5种常见的分子影像探针:超声成像探针、X-射线计算机断层成像探针、光学成像探针、核磁共振成像探针、正电子发射计算机断层扫描成像探针,并对分子影像探针的应用进行了概述,最后对分子影像探针的发展进行了展望。     

单分子器件中的新颖静电场效应

分子电子学旨在利用单个分子作为结构单元组装出功能电路以实现器件微型化。随着分子电子学的发展,各种功能器件被开发出来,很多独特的量子现象也被研究者所发现。这些突破得益于各种调控分子器件中电荷传输的刺激响应手段(例如静电场、磁场、光照、机械力和化学刺激)的运用。在众多调控方法中,利用静电场的调控方法以其独特的优势而备受关注,并且带来了许多新颖的发现。首先,和在所有电子器件中一样,静电场以非侵入的方式作用于单分子器件中。其次,不同于传统电子器件,在尺寸极小的单分子器件中施加电压可以产生极大的静电场,为调控电荷输运和催化单分子尺度化学反应等提供了必要条件。本文从常用的断裂结构筑技术展开介绍,总结静电场在调控分子-电极接触界面、分子构型和分子构象、单分子尺度化学反应、分子自旋态、分子氧化还原态、分子能级与电极能级等方面的应用。并对静电场调控在分子电子学领域内存在的一些挑战和潜在应用做了总结和展望。     

Survey of ligand field parameters of strong field d complexes obtained from the g matrix

Using a newly proposed approach involving an internally consistent set of equations, the ligand field parameters Δ/ξ, V/ξ and k are obtained from literature values of the g matrix for strong field d⁵ systems of various conformations in which |Δ/ξ|≤10. Qualitative analysis of the observed results is done using the Angular Overlap Model, AOM.