固体无机样品的激光等离子体质谱分析

激光等离子体质谱是一种新颖的质谱分析手段，具有灵敏度高，分析速度快，分析范围广，分析结果准确性高等优点。本文介绍了在自制的激光离子体源飞行时间质谱计上，有关催化剂，铝箔，活性碳，岩石等固体无机样品的质谱分析结果，显示了激光等离子体质谱的优越性与广泛的应用价值。     

激光作用氮化铝产生的铝原子簇正负离子

为了继续关于ⅣA与ⅤA族元素二元原子簇的研究,我们最近选取了AlN为样品,在自制的装置上记录了其激光等离子体中正负离子的质谱.该装置的原理与构造已有另文介绍.实验时的激光波长是532nm,作用在样品上的激光功率密度有10~7W·cm~(-2).仪器可以同时记录正负离子的飞行时间质谱.图1所示的正负离子的质谱由连续200次采集的数据叠加而成。     

温度限制串联相关神经网络及其在细菌辨识中的应用

蛋白质在微生物研究中可用作生物标记物,故在生物技术中其表征工作很重要．各种质谱技术已被用于细菌的表征[‘－’j．1994年,Cain等[‘]首先报道了将色谱和基体辅助激光解离/电离飞行时间质谱(M     

2,5-二芳基噁二唑的研究(Ⅲ)──反式-2-｛4-[2-(4-取代苯基)乙烯基]苯基｝-5-(4-联苯基)噁二唑的合成、电子光谱与光性能

2，5-二芳基二唑是具有较高的化学稳定性和激光转换效率的有机闪烁剂和紫外波段的激光染料．为了进一步研究该类化合物结构与光性能的关系，探寻吸收波长接近可见光区的激光染料，我们合成了8种具有较大的共扼体系的化合物I一Vlll：三结果与讨论正．1红外光谱与质谱化合物l－W的IR谱均在1080和730cm－’附近出现了与哈二吐环有关的较强红外吸收峰，而在966cm－‘处的C一H面外弯曲振动吸收峰则证明本文化合物具有反式结构．化合物l－Wb为芳香共扼分子，化学稳定性较高，因而其质谱图中分子离子峰均为基峰，其它碎片峰则相对较弱（表1）．…     

稀土富勒烯生成的影响因素初探

采用某些特殊的放电和提取方法，如反向放电和甲苯高温高压提取等可以有效地提高稀土富勒烯的生成效率［‘，‘’，并已先后成功高效地合成了许多含稀土富勒烯「‘’．对其提纯、表征、衍生和应用也进行了研究［‘－’j．但对影响稀土富勒烯生成的因素研究较少．在石墨律中同时填入La，Y，Sc的稀土氧化物，对其稀土富勒烯生成效率的情况进行了研究，认为稀土元素的第一电离能是影响稀土富勒烯生成的主要因素‘’，’‘．Moro等采用激光和热解吸质谱对稀土富勒烯的研究结果表明，稀土元素的氧化态是影响稀土富勒烯生成的决定性因素”’．本…     

样品化学环境对激光质谱的影响

本文从三个方面研究了样品化学环境对激光解吸质谱行为的影响，利用ＮＣ膜对水溶液的吸附作用并以此为基底，研究了水溶液中中性分子Ｎ，Ｎ，Ｎ’，Ｎ’－四甲基－１，４苯二胺（ＴＭＰＤ）（电子供体）与苯醌（ＢＱ）（电子受体）之间的电荷转移对质谱图分子离子峰强度的影响；并用此法对４－氨基－ｎ－丁酸和２－萘酚的ＰＫ值进行测定；同时也研究了镁、铜和钴四苯基卟啉化合物在弱酸性的固相基体中激光质谱行为。研究结果说明了化学环境对激光质谱行为的密切关联。     

纳米金刚石球晶的激光溅射产生与透射电镜表征

在高温高压合成金刚石技术日趋成熟的同时，气相沉积（CVD）条件下实现常压金刚石膜的合成已倍受人们的关注．利用脉冲激光溅射石墨，发现可在一定的基底上获得一类具有某些金刚石特征的薄膜，即类金刚石碳膜（DLC）［‘－‘j．这为在常规条件下合成金刚石带来了新的希望．但DLC只具有金刚石的某些特征，而基本上不具备晶体的有序结构［”’j．我们曾报道了在激光液相溅射的产物中观察到众多的碳球D‘，并通过高分辨透射电镜（HREM）、选区衍射（SAED）及其它相关实验，确定了其具有金刚石结构．且实验部分实验所用的激光是Q开关Nd…     

基体辅助激光解吸电离飞行时间质谱法测定钙调素的分子量

近几年来，由于各种“软”电离技术的发展和应用「‘，’‘，为利用质谱分析生物大分子提供了一条十分有效的途径［‘j，其中基体辅助激光解吸电离飞行时间质谱法（MALDI－TOF－MS）是最有前途的技术之一D‘．钙调素（CaM）是动植物中普遍存在的多功能的胞内钙受体蛋白，参与调控许多生理反应［”．最近几年也在细胞外区域发现了钙调素及其功能［”．钙调素分子量的准确、快速测定是钙调素性质、结构和功能研究的首要问题．目前CaM分子量的测定大多采用SDS－PAGE、凝胶过滤和沉淀平衡等方法，例如对牛脑CaM分子量的SDS－PAGE测…     

近场激光热透镜光谱法测定催化反应动力学参数的研究

激光热透镜光谱法(LTLS)是一种高灵敏光热光谱分析技术,可测定10－’~10－’吸光度[‘j．LTLS既可     

对硝基甲苯的同步辐射光电离研究

光电离对硝基甲苯（PNT）可获得其电离势及碎片离子的出现势，并由此推断出离子产生的可能通道．目前尚未见到有关PNT光电离研究的报道，仅George等［‘j使用电子轰击电离质谱测得过它的电离势．我们使用同步辐射光电离质谱测得了PNT的电离势和8种碎片离子的出现势，给出了飞行时间（TOF）质谱图，归属了质谱中的主要离子峰，初步分析了光解离电离通道．1实验部分实验装置由阈值光电子一光离子符合（TPEPICO）装置改造而成［’，’］，光电离室上方的四极质谱计由TOF质谱计代替，下方的四极质谱计由盛固体样品的小炉取代．样品蒸…     

Reactivity and infrared spectroscopy of gaseous hydrated trivalent metal ions

Hydrated trivalent rare earth metal ions containing yttrium and all naturally abundant lanthanide metals are formed using electrospray ionization, and the structures and reactivities of these ions containing 17-21 water molecules are probed using blackbody infrared radiative dissociation (BIRD) and infrared action spectroscopy. With the low-energy activation conditions of BIRD, there is an abrupt transition in the dissociation pathway from the exclusive loss of a single neutral water molecule to the exclusive loss of a small protonated water cluster via a charge-separation process. This transition occurs over a narrow range of cluster sizes that differs by only a few water molecules for each metal ion. The effective turnover size at which these two dissociation rates become equal depends on metal ion identity and is poorly correlated with the third ionization energies of the isolated metals but is well correlated with the hydrolysis constants of the trivalent metal ions in bulk aqueous solution. Infrared action spectra of these ions at cluster sizes near the turnover size are largely independent of the specific identity of the trivalent metal ion, suggesting that any differences in the structures of the ions present in our experiment are subtle.     

Decomposition channels for multiply charged ammonia clusters

Multiply charged ammonia cluster ions are produced by adiabatic nozzle expansion and subsequent ionization by electron impact. They are analyzed in a double focussing sector field mass spectrometer (reversed geometry). Doubly charged clusters are only detected above a critical size of 51 and triply charged clusters above 121. Some of these multiply charged ions decay via metastable dissociation processes in the experimental time window accessible. Doubly charged ammonia clusters with sizes ofn≧51 lose one neutral monomer or, roughly ten times less probable, two neutral monomers. Conversely, triply charged ammonia clusters with sizes 110≦n≦120 show an extremely asymmetric Coulomb dissociation resulting in doubly charged cluster ions of about 90% of the initial mass     

Reactions of Laser Ablation-magnesium Plasma with Methanol Clusters

IntroductionReactions of metal ions with neutral molecules orclusters produce a variety of metal complex ions andother new series of cluster ions including cations andanions.The laser ablation-molecular beam(LA-MB)method has marked its relevance in the st…     

Multiply charged cluster ions of Ar,Kr, Xe,N2, O2, CO2, SO2 and NH3: Production mechanism,appearance size and appearance energy

Clusters of Ar, Kr, Xe, N₂, O₂, CO₂, SO₂ and NH₃ formed by supersonic nozzle expansion have been studied by electron impact ionization mass spectrometry (up to 15000 amu). Besides mass spectra of singly charged ions showing the characteristic anomalous distributions, we have in particular investigated the properties of multiply charged cluster ions. Critical appearance sizes of doubly and triply charged cluster ions, n₂ and n₃ respectively, found in the present study confirm recent theoretical predictions about n₃/n₂ and their dependence on the properties of the cluster constituents. The appearance energies of multiply charged cluster ions determined are shifted way below the appearance energies of the respective monomer ions. These huge red shifts together with the observed linear threshold laws and large maximum ionization efficiencies indicate that multiply charged cluster ions are produced by sequential single ionization events of one incoming electron at different cluster sites. Furthermore, we have also obtained for the first time clear evidence that (for electron energies above the appearance energy of doubly charged ions) an appreciable amount of singly charged (also fragment) ions is produced via Coulomb explosion of unstable doubly charged ions in the ion source.     

Evaluation of different implementations of the Thomson liquid drop model: comparison to monovalent and divalent cluster ion experimental data

The Thomson model, used for calculating thermodynamic properties of cluster ions from macroscopic properties, and variations of this model were compared to each other and to experimental data for both hydrated mono- and divalent ions. Previous models that used the Thomson equation to calculate sequential binding thermodynamic values of hydrated ions, either continuously or discretely including an ion-dipole interaction term, were compared to a discrete model that includes the excluded volume of an impurity ion. All models, given their limitations, provided reasonable agreement to data for monovalent ions. For divalent cluster ions, the continuous model, and a discrete model that includes the ion-exclusion volume provide significantly better agreement to both the binding enthalpy and the binding entropy data as compared to the model that includes an ion-dipole term. A systematic deviation in the continuous model resulted in significantly lower binding enthalpies than the discrete model for clusters with fewer than about nine and 19 water molecules for mono- and divalent ions, respectively, but this difference became negligible for larger clusters. Previous investigations of the various Thomson model implementations used parameters for bulk water at 313 K. Using parameters at 298 K has a negligible effect at small cluster sizes, but at larger sizes, the binding enthalpies are 0.2 kcal/mol higher than with the 313 K parameters. Although small, the effect is significant for ion nanocalorimetry experiments in which thermochemical information is obtained from the number of water molecules lost upon activating large clusters.     

Measurement of cluster ions and residue nanoparticles from water samples with an electrospray/differential mobility analyzer.

Cluster ions and residue nanoparticles with sizes below 30 nm were generated by electrospraying (ES) and drying droplets of pure water, tap water, and aqueous solutions of salts. The mobility spectra of the cluster ions between 9.1 and 9.3 x 10(-5) m2/(V s) were measured using a differential mobility analyzer (DMA) operated at room temperature and atmospheric pressure. A modified Faraday cup and a condensation nucleus counter were used for detection. The concentrations of total residue/contaminants in the water were determined as a function of sizes of measured aerosol particles and of the initial droplets. Method detection limits were at sub-ppb level for pure water and sub-ppm level for tap water. ES/DMA is capable of simultaneously measuring the mobility distribution of cluster ions and concentration of total residue present in water samples.     

碳原子簇的结构与质谱关联

在自制的仪器上以脉冲激光蒸发和电离单质碳样品,可以产生各种大小的碳原子簇正负离子。这些原子簇的飞行时间质谱可以直接与Hückel规则、Euler定理等相关联。而由此分析得出,随着碳原子簇的增大,它们所经历的各种基本几何构型的转化。     

Serine-phosphoric acid cluster ions studied by electrospray ionization and tandem mass spectrometry

More than 310 kinds of cluster ions of S(m) P(n) H(k) (k+) are observed in a single ESI mass spectrum of a mixed solution of serine and phosphoric acid. Some typical cluster ions are selected, activated by collision in a FT ICR cell, and the dissociation pathways were deduced in detail. For large singly protonated ions, the collisions cause the ejection of subunits of serine or phosphoric acid subsequently producing the ions of S(2) P(4) H(1) (1+) , which can be further dissociated by the loss of phosphoric acid molecules in turn and form the protonated serine dimer and monomer. However, for the doubly protonated ions, the dissociation pathways change from the loss of a protonated serine dimer for the ions of S(7) P(9) H(2) (2+) to the neutral loss of H(3) PO(4) for the ions of S(7) P(12) H(2) (2+) or the neutral loss of serine or H(3) PO(4) for the larger clusters, indicating the effect of cluster sizes on the process of dissociation. The structure of S(2) P(4) H(1) (1+) is suggested based on B3LYP/6-31G(d,p) calculations. The diversity and structural orderliness of the hetero-cluster ions are mainly attributed to the network of hydrogen bonds inside the cluster ions and the extraordinary amphotericity of the components.     

Single photon ionization of van der Waals clusters with a soft x-ray laser: (SO2)n and (SO2)n(H2O)m

van der Waals cluster (SO2)n is investigated by using single photon ionization of a 26.5 eV soft x-ray laser. During the ionization process, neutral clusters suffer a small fragmentation because almost all energy is taken away by the photoelectron and a small part of the photon energy is deposited into the (SO2)n cluster. The distribution of (SO2)n clusters decreases roughly exponentially with increasing cluster size. The photoionization dissociation fraction of I[(SO2)(n-1)SO+] / I[(SO2)n+] decreases with increasing cluster size due to the formation of cluster. The metastable dissociation rate constants of (SO2)n+ are measured in the range of (0.6-1.5) x 10(4) s(-1) for cluster sizes 5< or =n< or =16. Mixed SO2-H2O clusters are studied at different experimental conditions. At the condition of high SO2 concentration (20% SO2 partial pressure), (SO2)n+ cluster ions dominate the mass spectrum, and the unprotonated mixed cluster ions (SO2)nH2O+ (1< or =n< or =5) are observed. At the condition of low SO2 concentration (5% SO2 partial pressure) (H2O)nH+ cluster ions are the dominant signals, and protonated cluster ions (SO2)(H2O)nH+ are observed. The mixed clusters, containing only one SO2 or H2O molecule, SO2(H2O)nH+ and (SO2)nH2O+ are observed, respectively.     

Studies in cluster ion formation. Part IV. Characterization of cluster ions formed during the fast atom bombardment of solutions of mixed tetraalkylammionium salts. A. Concentration effects and the influence of ionic size

Cluster ion formation by fast atom bombardment mass spectrometry of 15 binary mixtures of tetraalkylammonium halide salts in liquid matrices has been studied. In some instances the replacement of even one of the cations in the pure cluster ion by a different cation to yield mixed cation cluster ions has a destabilizing effect on the clusters, and results in the disappearance of the ion intensity anomalies. The effect of the anion and cation sizes and also the matrix composition on the stability of mixed cluster ions is discussed.