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.     

Mixed alkali metal selenate proton conductors: Phase transitions and crystal structure of [Rb0.54(Nh4)0.46]3H(SeO4)2

Optical birefringence, calorimetric, thermal expansion, powder and single crystal X-ray diffraction investigations of mixed proton conductors [Rb_1-x(NH₄)_x]₃H(SeO₄)₂ were performed with the aim of studying the influence of partial substitution of cations on the superprotonic phase transition, on the atomic structure and on other characteristic features of this type of crystals.     

Determination of structure parameters in strong-field ionization models of atoms

The Ammosov–Delone–Krainov (ADK) and Perelomov–Popov–Terent’ev (PPT) ionization models were widely used in strong-field physics and attosecond science due to their many attractive advantages such as simpler analytical formula, less computational demands, and satisfied accuracy of ionization rate. Based on the density-functional theory, we systematically determine accurate structure parameters of 25 atoms, 24 positive ions and 13 negative ions and tabulate for future applications. The wave function with correct asymptotic behavior is obtained by solving the time-independent Schrödinger equation with B-spline basis sets and the accurate structure parameters are extracted from this wave function in the asymptotic region. The accuracies of structure parameters are carefully examined by comparing the ionization probabilities (or yields) calculated by PPT and ADK models with those of solving the three-dimensional time-dependent Schrödinger equation and the experimental data.     

Comparison of two cold atmospheric pressure plasma jet configurations in argon

The present study compares the operation of two cold atmospheric plasma jet (CAPJ) configurations: needle-to-cylinder electrode configuration (CAPJ I) and single high-voltage cylinder electrode around the quartz tube (CAPJ II). The CAPJs were operated in argon flowing through a quartz capillary with 0.5-mm inner diameter into the ambient air, and the plasma was generated by sinusoidal kHz frequency AC power supplies. The main emphasis of the study was on the mechanism of the initiation of ionization waves for these two configurations. For both CAPJs, there appeared several ionization waves during one half-period of the applied voltage waveform, and the number of ionization waves increased at higher voltage amplitudes. However, we discovered marked differences in the initiation of the ionization waves for two different CAPJ configuration. The applied voltage controlled the initiation of consecutive ionization waves, which propagated from the grounded electrode towards the tube orifice in CAPJ I. In the case of CAPJ II, certain time had to pass for the initiation of a new ionization wave, and subsequent ionization waves within the same half-period started at the tube orifice. In addition to the differences in the initiation of the ionization waves, we observed that the CAPJ I was ignited and sustained at lower voltages, while CAPJ II produced a longer plasma jet. The observed advantages and deficiencies of investigated CAPJ configurations point out their potential in different applications.     

Edge-enriched graphene with boron and nitrogen co-doping for enhanced oxygen reduction reaction

Carbon-based electrocatalysts for oxygen reduction reaction (ORR), especially in anion exchange membrane fuel cells (AEMFCs), have received a lot of attention because they exhibit excellent stability and are comparable to commercial Pt/C catalysts. Currently, to maximize the catalytic activity of carbon-based electrocatalysts, there are two major strategies: heteroatom doping or exposing active edge sites. However, the approach of increasing heteroatomic dopants of active edge sites has been rarely addressed. In this study, we present a simple strategy to prepare edge-enriched graphene catalysts with an increased ratio of heteroatomic dopants suitable for ORR of AEMFCs. The catalysts were prepared under harsh oxidation conditions, followed by a simple co-doping process with boron and nitrogen. The ORR activity of the catalysts was observed to be related to an increase of edge sites with heteroatomic dopants. We believe that the edge-enriched structure leads to accelerated electron transfer with enhanced oxygen adsorption.     

空间波函数的对称性对氦原子双光子双电离过程中电子关联的影响

通过数值求解含时薛定谔方程,研究了氦原子具有对称空间波函数的1s2s 1S态和具有反对称空间波函数的1s2s 3S态分别作为初态的双光子双电离过程. 结果表明,对于初态为单重态1s2s 1S的双光子双电离过程,两个电离电子的能量分布随激光脉冲持续时间的增加呈现由单峰到双峰的变化,这里的单峰和双峰分别意味着两个电离电子主要携带相等和不等的能量;然而对于初态为三重态1s2s 3S的双光子双电离过程,两个电离电子的能量分布随激光脉冲持续时间的增加总是保持双峰结构. 这些结果表明当原子的初态处于反对称空间波函数时,两电子的空间密度分布具有较少的重叠,从而导致电子在超短激光脉冲中电离时电子关联能无法平均分配.     

3d过渡金属掺杂M_2@Si_(20)(M=Sc-Zn)团簇的密度泛函理论研究

利用密度泛函理论(DFT)研究3d过渡金属掺杂硅团簇的几何结构和稳定性,计算了绝热电子亲和能和垂直电离能,内嵌双金属间距,自旋磁矩等.结果表明内嵌的Sc、Ti、V、Mn金属二聚体和十二面体硅笼构成了稳定的富勒烯结构,随着d电子数目的增加其内嵌的富勒烯构型有部分畸变,总体而言Si_(20)团簇掺杂双金属后稳定性得到了提高.     

NO的多光子电离谱及跃迁通道的研究

本文对中间共振能级为A~2∑~+、F~2⊿、H~2∑和H’~3H态的NO四光子电离谱作了转动谱线标识及研究.提出了双共振及碰撞电离模型,以解释实验中出现的强度反常谱线.     

IBr分子的多光子电离谱的分析

本文用多光子电离的方法,观察了IBr分子高电子态(E)的2光子共振跃迁,结合Franck-Condon原理,从IBr分子的振动谱分析,首次得到IBr(E)态的转动常数B’_(?)-(0.0653±0.0003)cm~(-1).     

A method for imaging of chemical shift or magnetic field distributions

A phase encoding method for imaging of chemical shift or magnetic field distributions is described. The method utilizes the spin-echo principle and the time period between signal collection and excitation is constant but the time period between excitation and the 180 degrees pulse is varied by constant steps. The method is relatively easy to apply with the Fourier or projection reconstruction methods.