Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS

A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355?nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones.     

类氢氖基态电离势随等离子体温度密度的变化

采用自洽场离子球模型,研究类氢氖基态1s的电离势随等离子体电子温度及电子密度的变化规律,计算得到基态电离势的百分偏移量随等离子体电子密度的变化关系,拟合结果表明两者的对数值满足很好的线性关系.该结果对计算等离子体电离态分布及光谱模拟具有一定意义.     

9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions

The most common secondary-ionization mechanism in positive ion matrix-assisted laser desorption/ionization (MALDI) involves a proton transfer reaction to ionize the analyte. Peptides and proteins are molecules that have basic (and acidic) sites that make them susceptible to proton transfer. However, non-polar, aprotic compounds that lack basic sites are more difficult to protonate, and creating charged forms of this type of analyte can pose a problem when conventional MALDI matrices are employed. In this case, forming a radical molecular ion through electron transfer is a viable alternative, and certain matrices may facilitate the process. In this work, we investigate the performance of a newly developed electron-transfer secondary reaction matrix: 9,10-diphenylanthracene (9,10-DPA). The use of 9,10-DPA as matrix for MALDI analysis has been tested using several model compounds. It appears to promote ionization through electron transfer in a highly efficient manner as compared to other potential matrices. Thermodynamic aspects of the observed electron transfers in secondary-ionization reactions were also considered, as was the possibility for kinetically controlled/endothermic, electron-transfer reactions in the MALDI plume. Copyright ? 2012 John Wiley & Sons, Ltd.     

Mass Spectrometry,Review of the Basics: Ionization

Abstract: Mass spectrometry (MS) has become an integral tool in life sciences. The first step in MS analysis is ion formation (ionization). Many ionization methods currently exist; electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) are the most commonly used. ESI relies on the formation of charged droplets releasing ions from the surface (ion evaporation model) or via complete solvent evaporation (charge residual model). MALDI ionization, however, is facilitated via laser energy and the use of a matrix. Despite wide use, ESI cannot efficiently ionize nonpolar compounds. Atmospheric pressure chemical ionization (APCI) and atmospheric pressure photo ionization (APPI) are better suited for such tasks. APPI requires photon energy and a dopant, whereas APCI is similar to chemical ionization. In 2004, ambient MS was introduced in which ionization occurs at the sample in its native form. Desorption electrospray ionization (DESI) and direct analysis in real time (DART) are the most widely used methods. In this mini-review, we provide an overview of the main ionization methods and the mechanisms of ion formation. This article is educational and intended for students/researchers who are not very familiar with MS and would like to learn the basics; it is not for MS experts.     

Exploration of gold nanoparticle beams for matter wave interferometry

We investigate molecular beam methods for gold nanoparticles. They are based on electrospray, matrix assisted laser desorption and thermal laser desorption in combination with mass spectroscopy and multi-photon ionization. These techniques are analyzed with respect to their potential for coherent matter wave experiments.     

Determination of the charge state distribution of a highly ionized coronal Au plasma

We present the first definitive measurement of the charge state distribution of a highly ionized gold plasma in coronal equilibrium. The experiment utilized the Livermore electron beam ion trap EBIT-II in a novel configuration to create a plasma with a Maxwellian temperature of 2.5 keV. The charge balance in the plasma was inferred from spectral line emission measurements which accounted for charge exchange effects. The measured average ionization state was 46.8+/-0.75. This differs from the predictions of two modeling codes by up to four charge states.     

金等离子体平均离化度随电子温度变化关系的研究

用Cowan的原子结构从头算程序和自旋轨道劈裂阵模型计算各阶电离的金离子能级和跃迁， 在碰撞辐射模型下求解能级布居数方程，计算给定等离子体密度和电子温度下等离子体中离子的分布，给出了平均离化度随电子温度的变化关系.发现稀薄的金等离子体中，在一定的电子温度范围内电子温度的升高平均电离度反而下降的反常现象.讨论了电离势对平均离化度的影响. 关键词： 金等离子体 碰撞辐射模型 布居数 平均电离度     

Probing the mechanisms of ambient ionization by laser-induced fluorescence spectroscopy

The ionization mechanisms of several atmospheric pressure ion sources based on desorption and ionization of samples deposited on a surface were studied. Home-built desorption electrospray ionization (DESI), laserspray ionization (LSI), and atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) sources were characterized using low-molecular-weight compounds, in particular fluorescent dyes. Detection of the desorbed and ionized species was performed by laser-induced fluorescence and ion cyclotron resonance mass spectrometry. The dependences of the signal intensities on various experimental parameters were studied. The data obtained reveals common features, such as formation of solvated species and clusters in the ionization processes, in all of the techniques considered.     

Non-equilibrium plasma production by pulsed laser ablation of gold

A gold target has been irradiated with a Q-switched Nd:Yag laser having 1064\,\hbox{nm} wavelength, 9\,\hbox{ns} pulse width, 900\,\hbox{mJ} maximum pulse energy and a maximum power density of the order of 10^{10}\,\hbox{W}/\hbox{cm}^2 . The laser-target interaction produces a strong gold etching with a production of a plasma in front of the target. The plasma contains neutrals and ions having high charge state. Time-of-flight measurements are presented for the analysis of the ion production and ion velocity. A cylindrical electrostatic deflection ion analyzer permits to measure the yield of the emitted ions, their charge state and their ion energy distribution. Measurements indicate that the ion charge state reaches 6^+ and 10^+ at a laser fluence of 100\,\rm{J/cm}^2 and 160\,\rm{J/cm}^2 , respectively. The maximum ion energy reaches about 2\,\hbox{keV} and 8\,\hbox{keV} at these low and at high laser fluence, respectively. Experimental ion energy distributions are given as a function of the ion charge state. Obtained results indicate that electrical fields, produced in the plume, along the normal to the plane of the target surface, exist in the unstable plasma. The electrical fields induce ion acceleration away from the target with a final velocity dependent on the ion charge state. The ion velocity distributions follow a "shifted Maxwellian distribution", which the authors have corrected for the Coulomb interactions occurring inside the plasma.     

Ionisierung von Atom- und Molekularstrahlen mit einer Plasma-Ionenquelle

A method for ionizing atomic and molecular beams is described, in which use is made of a space charge compensated plasma ion source of the Duoplasmatron type. In such a device the ionization yield (ionization and extraction efficiency) can be increased considerably as compared to that in conventional electron bombardment ionizers. The maximum yield of H ₂ ⁺ -ions from a H₂-molecular beam was 3.7%. Further results are contained in the Table.     

Conductivities in Hot Aluminium Plasma

We perform model calculations for the electrical and thermal conductivity of aluminium plasma within the generalized linear response method of Zubarev for temperatures of (5–25) eV and densities of (0.01–10) g/cm³. The composition in the expanded plasma region is determined by considering higher ionization states up to 5+ and solving the respective system of coupled mass action laws. Besides this chemical picture, a generalized Thomas‐Fermi model is applied to calculate the equation of state and the average charge state of the ions for densities near and above solid state density. Interactions between the various species are treated on T matrix level. Numerical results for the electrical and thermal conductivity of aluminium plasma are compared with experimental data and, for high densities, also with results of a Born approximation with respect to a weak electron‐ion pseudopotential.     

Revisiting the sodium and calcium matrix effects in inductively coupled plasma optical emission spectrometry. Excitation mechanisms by inelastic collisions

Abstract

The dependence of calcium and sodium matrix effects on the total excitation energy of analyte emission signals was used as a tool for the study of excitation mechanisms in radial view mode inductively coupled plasma optical emission spectroscopy. A total of 95 atomic and 66 ionic emission signals of aluminum, cobalt, chromium, iron, magnesium, manganese, nickel, and silicon in the 3.0–17.59?eV energy range were measured at the non-robust plasma operating conditions to facilitate the matrix effect study. Different matrix effects versus total excitation energy relationships were observed regarding the energy interval. The change of sign from negative to positive of the both matrix effect versus total excitation energy relationship observed around 14?eV, in the 12.06–17.59?eV energy range, is interpreted as experimental evidence of the action of two non-thermic excitation mechanisms: Penning ionization from approximately 12 to 14?eV and charge transfer from 14 to 17?eV. Based on the energy resonance principle and total spin conservation Wigner’s Theorem, possible reactions between excited ionic argon and ground state analyte ions were proposed.     

Charge transfer activation energy for alkali atoms on Re and Ta

Ion and atom desorption energies for five alkali metals on Re and Ta were determined using the ion thermal emission noise method. The activation energies for the charge transfer process in the adsorbed state were calculated using a special energetic balance equation, which describes the surface ionization and thermal desorption effect. Energies for desorption of Li, Na, K, Rb and Cs from Re and Ta surfaces were determined by measuring the time autocorrelation function of the ion thermoemission current fluctuations.     

Nucleus-electron model for states changing from a liquid metal to a plasma and the Saha equation

We extend the quantal hypernetted-chain (QHNC) method, which has been proved to yield accurate results for liquid metals, to treat a partially ionized plasma. In a plasma, the electrons change from a quantum to a classical fluid gradually with increasing temperature; the QHNC method applied to the electron gas is in fact able to provide the electron-electron correlation at an arbitrary temperature. As an illustrating example of this approach, we investigate how liquid rubidium becomes a plasma by increasing the temperature from 0 to 30 eV at a fixed normal ion density 1.03x10(22)/cm(3). The electron-ion radial distribution function (RDF) in liquid Rb has distinct inner-core and outer-core parts. Even at a temperature of 1 eV, this clear distinction remains as a characteristic of a liquid metal. At a temperature of 3 eV, this distinction disappears, and rubidium becomes a plasma with the ionization 1.21. The temperature variations of bound levels in each ion and the average ionization are calculated in Rb plasmas at the same time. Using the density-functional theory, we also derive the Saha equation applicable even to a high-density plasma at low temperatures. The QHNC method provides a procedure to solve this Saha equation with ease by using a recursive formula; the charge population of differently ionized species are obtained in Rb plasmas at several temperatures. In this way, it is shown that, with the atomic number as the only input, the QHNC method produces the average ionization, the electron-ion and ion-ion RDF's, and the charge population that are consistent with the atomic structure of each ion for a partially ionized plasma.     

Advanced targets,diagnostics and applications of laser-generated plasmas

High-intensity sub-nanosecond-pulsed lasers irradiating thin targets in vacuum permit generation of electrons and ion acceleration and high photon yield emission in non-equilibrium plasmas. At intensities higher than 10¹⁵?W/cm² thin foils can be irradiated in the target-normal sheath acceleration regime driving ion acceleration in the forward direction above 1?MeV per charge state. The distributions of emitted ions in terms of energy, charge state and angular emission are controlled by laser parameters, irradiation conditions, target geometry and composition. Advanced targets can be employed to increase the laser absorption in thin foils and to enhance the energy and the yield of the ion acceleration process. Semiconductor detectors, Thomson parabola spectrometer and streak camera can be employed as online plasma diagnostics to monitor the plasma parameters, shot by shot. Some applications in the field of the multiple ion implantation, hadrontherapy and nuclear physics are reported.     

Tungsten ions produced by infrared pulsed laser irradiation

Energetic ions have been obtained irradiating a tungsten target with a Q-switched Nd:Yag laser, 1064?nm wavelength, 9?ns pulse width, 900?mJ maximum pulse energy and power density of the order of 10¹⁰?W/cm². The laser-target interaction induces a strong metal etching with production of plasma in front of the target. The plasma contains neutrals and ions with high charge state. Time-of-flight measurements are presented for qualitative analysis of the ion production. A cylindrical electrostatic ion analyzer permits measuring of the yield of emitted ions, the charge state of detected ions and the ion energy distribution. Measurements indicate that, at a laser fluence of the order of 100?J/cm², the charge state may reach 9+ and the ion energy reaches about 5?keV. The ion energy distribution is given as a function of the charge state. Experimental results indicate that an electrical field is developed along the normal to the plane of the target surface, which accelerates the ions up to high velocity. The ion velocity distributions follow a “shifted Maxwellian distribution”, which the author has corrected for the Coulomb interactions occurring inside the plasma.     

Carbon-plasma produced in vacuum by 532 nm-3 ns laser pulses ablation

A study of VIS laser ablation of graphite, in vacuum, by using 3 ns Nd:YAG laser radiation is reported. Nanosecond pulsed ablation gives an emission mass spectrum attributable to C_n neutral and charged particles. Mass quadrupole spectroscopy, associated to electrostatic ion deflection, allows estimation of the velocity distributions of several of these emitting species within the plume as a function of the incident laser fluence. Time gated plume imaging and microscopy measurements have been used to study the plasma composition and the deposition of thin carbon films. The multi-component structure of the plume emission is rationalized in terms of charge state, ions temperature and neutrals temperature. A special regard is given to the ion acceleration process occurring inside the plasma due to the high electrical field generated in the non-equilibrium plasma conditions. The use of nanosecond laser pulses, at fluences below 10 J/cm², produces interesting C-atomic emission effects, as a high ablation yield, a high fractional ionization of the plasma and presence of nanostructures deposited on near substrates.     

Non-equilibrium plasma production by pulsed laser ablation of gold

A gold target has been irradiated with a Q-switched Nd:Yag laser having 1064?nm wavelength, 9?ns pulse width, 900?mJ maximum pulse energy and a maximum power density of the order of 10¹⁰?W/cm². The laser–target interaction produces a strong gold etching with production of a plasma in front of the target. The plasma contains neutrals and ions having a high charge state. Time-of-flight (TOF) measurements are presented for the analysis of the ion production and ion velocity. A cylindrical electrostatic deflection ion analyzer permits measurement of the yield of the emitted ions, their charge state and their ion energy distribution. Measurements indicate that the ion charge state reaches 6⁺ and 10⁺ at a laser fluence of 100?J/cm² and 160?J/cm², respectively. The maximum ion energy reaches about 2?keV and 8?keV at these low and high laser fluences, respectively. Experimental ion energy distributions are given as a function of the ion charge state. Obtained results indicate that electrical fields, produced in the plume, along the normal to the plane of the target surface, exist in the unstable plasma. The electrical fields induce ion acceleration away from the target with a final velocity dependent on the ion charge state. The ion velocity distributions follow a “shifted Maxwellian distribution”, which the authors have corrected for the Coulomb interactions occurring inside the plasma.     

Charge-state distribution and Doppler effect in an expanding photoionized plasma

The charge state distributions of Fe, Na, and F are determined in a photoionized laboratory plasma using high resolution x-ray spectroscopy. Independent measurements of the density and radiation flux indicate unprecedented values for the ionization parameter xi=20-25 erg cm s(-1) under near steady-state conditions. Line opacities are well fitted by a curve-of-growth analysis which includes the effects of velocity gradients in a one-dimensional expanding plasma. First comparisons of the measured charge state distributions with x-ray photoionization models show reasonable agreement.     

Relative Distribution of Au^48＋～Au^52＋ in Au Plasma by Ionization Dynamics

The present work proposes a theoretical method called ionization dynamics to derive the ionic charge state distribution. Using relativistic quantum mechanics to calculate the energy level lifetime and average ionic lifetime of each ion, the first-order ionization rate constant can be obtained. Based on these data, from the solution of differential equations for consecutive-irreversible ionization reactions, one will be able to derive the ionic charge state distribution.The calculated average positive charge 49.24 of Au^48 ～ Au^52 and their relative distribution are in good agreement with the results of Lawrence Livermore National Laboratory.