The analysis of alkyl-capped alcohol ethoxylates and alcohol ethoxycarboxylates from alcohol ethoxylates by atmospheric pressure chemical ionization mass spectrometry

Alcohol ethoxylates (AEs) are nonionic surfactants. They are industrially important compounds that have historically been difficult to analyze, with the best results to date achieved through derivatization (e.g., silylation) followed by analysis by gas chromatography/mass spectrometry (GC/MS). Recently, mass spectrometric techniques such as field desorption (FD), time-of-flight secondary ion mass spectrometry (TOF-SIMS), fast atom bombardment (FAB), electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) have been employed to analyze surfynol(R) 4xx. In an effort to produce low-cost alkyl-capped AEs and anionic detergents from AEs, a fast and reliable measure of the product yields and conversions from AEs is required in research. We found that the product yields and conversions from reactions of AEs, obtained by the employment of atmospheric pressure chemical ionization (APCI), were in good agreement with those obtained from proton nuclear magnetic resonance spectroscopy ((1)H-NMR). Therefore, APCI can be used as a validated tool for studying AE reactions. Mixtures that contain either silylated or unsilylated ethoxylates and/or carboxylates yield the same APCI mass spectra. Copyright -Copyright 1999 John Wiley & Sons, Ltd.     

Molecular imaging by Mid-IR laser ablation mass spectrometry

Mid-IR laser ablation at atmospheric pressure (AP) produces a mixture of ions, neutrals, clusters, and particles with a size distribution extending into the nanoparticle range. Using external electric fields the ions can be extracted and sampled by a mass spectrometer. In AP infrared (IR) matrix-assisted laser desorption ionization (MALDI) experiments, the plume was shown to contain an appreciable proportion of ionic components that reflected the composition of the ablated target and enabled mass spectrometric analysis. The detected ion intensities rapidly declined with increasing distance of sampling from the ablated surface to ∼4 mm. This was rationalized in terms of ion recombination and the stopping of the plume expansion by the background gas. In laser ablation electrospray ionization (LAESI) experiments, the ablation plume was intercepted by an electrospray. The neutral particles in the plume were ionized by the charged droplets in the spray and enabled the detection of large molecules (up to 66 kDa). Maximum ion production in LAESI was observed at large (∼15 mm) spray axis to ablated surface distance indicating a radically different ion formation mechanism compared to AP IR-MALDI. The feasibility of molecular imaging by both AP IR-MALDI and LAESI was demonstrated on targets with mock patterns. Presented at the 9-th International Conference on Laser Ablation, 2007 Tenerife, Canary Islands, Spain     

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.     

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。     

On-plate deposition of oxidized proteins to facilitate protein footprinting studies by radical probe mass spectrometry

The on-plate deposition of oxidized proteins is described to advance footprinting applications by radical probe mass spectrometry (RP-MS). An electrospray ionization (ESI) needle assembly mounted vertically over a 384-target matrix-assisted laser desorption/ionization (MALDI) plate enabled the limited oxidation of proteins as they were released in the charged droplets ahead of their deposition on the plate. This method combined with on-plate proteolytic digestion protocols expedites the analysis of proteins oxidized by RP-MS, and avoids the need to collect and reconstitute samples prior to analysis by MALDI mass spectrometry. Oxidation of peptides from solutions in water as well as an ammonium bicarbonate solution was investigated to test the optimal conditions required for on-plate oxidation of proteins. These comprised of peptides with a wide range of reactive amino acids including Phe, Tyr, Pro, His, Leu, Met and Lys that were previously shown to oxidize in both electrospray discharge and synchrotron radiolysis based footprinting experiments. The on-plate deposition of lysozyme oxidized at electrospray needle voltages of 6 and 9 kV were carried out to demonstrate conditions suitable for footprinting experiments as well as those that induce the onset of protein damage. Copyright ? 2012 John Wiley & Sons, Ltd.     

On-line matrix addition for detecting aerosol particles

Single aerosol particles were measured by matrix-assisted laser desorption/ionization (MALDI) with an aerosol time-of-flight mass spectrometer (ATOFMS). The inlet to the ATOFMS was coupled with an evaporation/condensation flow cell that allowed matrix addition by condensation onto the particles. The coated particles entered the ion source through three-stage differentially pumped capillary inlet and were then ionized by a focused 266 nm Nd:YAG laser. The mass spectra and aerodynamic size of the single particles can be obtained simultaneously. The on-line matrix addition technique makes it possible to identify biological aerosols in real-time.     

气相过渡金属钽碳链团簇的研究

Nd:YAG产生的二倍频532nm激光消融金属靶表面,同时含有3%乙炔的氦载气喷向旋转的金属靶,通过等离子体反应形成中性的气相碳链-金属团簇分子。然后经过超声膨胀后,由skimmer形成准直的分子束,进入飞行时间质谱仪的电离区,被电离激光电离。当电离激光波长为248nm时,只观察到了TaCy+（y = 0-10）的碳链团簇离子信号,实验发现奇数碳链的过渡金属钽团簇离子信号比较小,而偶数碳链的团簇离子信号较大。当电离激光波长为266nm时,观察到了TaxCy+（x = 1-4,y = 0-4）的碳链团簇离子信号。     

MALDI-MS detection of noncovalent interactions of single stranded DNA with Escherichia coli single-stranded DNA-binding protein

The Escherichia coli single-stranded DNA binding protein (SSB) selectively binds single-stranded (ss) DNA and participates in the process of DNA replication, recombination and repair. Different binding modes have previously been observed in SSB?ssDNA complexes, due to the four potential binding sites of SSB. Here, chemical cross-linking, combined with high-mass matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS), is used to determine the stoichiometry of the SSB?ssDNA complex. SSB forms a stable homotetramer in solution, but only the monomeric species (m/z 19,100) can be detected with standard MALDI-MS. With chemical cross-linking, the quaternary structure of SSB is conserved, and the tetramer (m/z 79,500) was observed. We found that ssDNA also functions as a stabilizer to conserve the quaternary structure of SSB, as evidenced by the detection of a SSB?ssDNA complex at m/z 94,200 even in the absence of chemical cross-linking. The stability of the SSB?ssDNA complex with MALDI strongly depends on the length and strand of oligonucleotides and the stoichiometry of the SSB?ssDNA complex, which could be attributed to electrostatic interactions that are enhanced in the gas phase. The key factor affecting the stoichiometry of the SSB?ssDNA complex is how ssDNA binds to SSB, rather than the protein-to-DNA ratio. This further suggests that detection of the complex by MALDI is a result of specific binding, and not due to non-specific aggregation in the MALDI plume.     

延时提取正交发射MALDI技术研究

在反射式飞行时间质谱仪上,采用脉冲电场延时提取技术及离子正交发射采样方式,进行了基质辅助激光解吸附电离技术(MALDI)的研究.实验所用激光波长为266nm,基质为2,5二羟基苯甲酸,样品为孔雀石绿和多肽.得到了上述样品在MALDI条件下离子的质谱图和初速度分布.质谱测量的分辨率达到4000,质量测量的线性相关度好于0.9999,平均误差小于0.0075%.     

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.     

1-萘酚团簇的紫外光电离质谱研究

用飞行时间质谱仪和超声速脉冲分子束技术研究了紫外激光对1-萘酚(1HN)团簇的电离质谱.观测到(1HN)_n~+系列的团簇离子,且离子强度随团簇尺寸的增大而减小.电离激光的强度(在5μJ/pulse～100μJ/pulse范围内)对团簇离子强度的相对分布影响较小,说明软电离为产生团簇离子的主要过程,团簇离子的强度分布反映出电离前中性团簇的分布特征.增大电离区的进样气压可以产生更大尺寸的团簇离子,同时在(1HN)_n~+后面观测到新系列的团簇离子.这些新生离子与(H_2O)_m有关,考虑到1-萘酚团簇可以通过OH形成H键,推测该新生团簇离子通过团簇内的反应而产生.     

Multiple peak formation in laser ionization mass spectrometry

Molecules in the source region of a time of flight mass spectrometer are ionized by ultraviolet laser radiation. Under certain conditions mass spectra consisting of a remarkably periodic set of ion peaks are generated. It is demonstrated that these result from spatially periodic ionization within the mass spectrometer which is a consequence of the development of standing electromagnetic waves.     

甲醇/水混合团簇的多光子电离质谱研究

利用多光子电离技术结合飞行时间质谱仪对甲醇/水混合团簇进行了研究.在脉冲激光波长为355 nm条件下观测到团簇离子.主要的电离产物为质子化的(CH3OH)n(H2O)H+(n=l-13)混合团簇离子与(CH3OH)nH+团簇离子,经分析(CH3OH)1o(H2O) H+和(CH3OH)3H+为幻数结构.甲醇水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.     

Analysis of t-butylphenol acetylene condensed resin with methyl-methine linkages in vulcanized rubber by pyrolysis-gas chromatography/mass spectrometry

Methyl-methine linkages of Novolac, a commercially available t-butylphenol acetylene condensed (TBPA) resin, have been identified by recognition of pyrolysis pathways using pyrolysis-gas chromatography/mass spectrometry (Py-GC/mS) in vulcanized rubber. The diagnostic mass spectrum of t-butylphenol with methyl-methine linkages between phenolic rings was observed at m/z 192, corresponding to 4-t-butyl-2-ethyl-6-methylphenol. Other molecular ions were observed at m/z 178, 164, and 150 in the characteristic pyrolyzates. The ion at m/z 192 in the TBPA resin was observed to be characteristic for methyl-methine linkages between the phenolic groups, and the analytical pyrolysis-GC/mS method was thus able to identify the resin at low levels in vulcanized rubber. Copyright 1999 John Wiley & Sons, Ltd.     

532nm及355nm丁酮多光子电离质谱研究

利用激光质谱法,采用355 nm及532 nm激光作为光源对丁酮分子进行了多光子电离解离研究,得到了2种波长下丁酮的多光子电离飞行时间质谱图主要有质荷比为1(H ),15(CH3 ),43(CH3CO )的质谱峰.532 nm质谱比较丰富,有较强的质荷比为45的信号,可以认为这是丁酮异构体电离解离得到的产物;同时探测到了质荷比为4,6,8的信号,可能是高价离子.355 nm质谱图相对简单.根据信号比例随激光能量的变化及主要的离子信号,得出了2种波长下主要的解离电离通道.     

The ionization potentials of clustered sodium atoms

Small clusters of sodium atoms have been produced by the isentropic flow of high pressure vapour through a small orifice. These clusters have been ionized by ultra-violet light and detected using a mass spectrometer. Clusters of up to eight sodium atoms have been observed and their ionization potentials have been measured. The ionization potentials of Na₃ and Na_s are 3.9 v and 4.0 v respectively, showing that even the smallest clusters tend to the value expected for a continuous drop of metal of the same size.     

532 nm及355 nm丁酮多光子电离质谱研究

利用激光质谱法,采用355 nm及532 nm激光作为光源对丁酮分子进行了多光子电离解离研究,得到了2种波长下丁酮的多光子电离飞行时间质谱图主要有质荷比为1(H ),15(CH3 ),43(CH3CO )的质谱峰.532 nm质谱比较丰富,有较强的质荷比为45的信号,可以认为这是丁酮异构体电离解离得到的产物;同时探测到了质荷比为4,6,8的信号,可能是高价离子.355 nm质谱图相对简单.根据信号比例随激光能量的变化及主要的离子信号,得出了2种波长下主要的解离电离通道.     

Determination and analysis of opiates in complex mixtures by surface-ionization mass spectrometry

The results of studies of the analytical opportunities of surface-ionization mass spectrometry (SIMS) for high-sensitivity and selective detection and analysis of opiate mixtures—natural opium, crude heroin, and narcotic analgesic omnopon—are presented. The experiments were carried out using an MX-1320 chemical mass spectrometer modernized for studying surface ionization (SI). It was ascertained that the opiate mixtures are ionized by highly efficient surface ionization. The bands of M⁺ (for papaverine), (M-H)⁺, (M-H-2nH)⁺, (M-R)⁺, and (M-R-2nH)⁺ ions, where M is a molecule, H is a hydrogen atom, R is a radical, are observed in the mass spectra; they are the sum of the SI mass spectra of components of the mixtures. The series of bands of ions with m/z of 144 and 146 that is characteristic of SI-morphinelike molecules is the main one in the mass spectrum of crude heroin, while for omnopon and natural opium this series is the main at low temperatures of a thermionic emitter (up to ∼900 K). At high temperatures of the thermionic emitter, the band series with m/z of 218 and 220 is the main series. Studies of natural opium, crude heroin, and omnopon have shown that the SIMS method allows analyzing mixtures without preliminary chromatographic separation thereof. The study also contains the results of comparative analyses of opiate mixtures by SIMS and chromate- and mass spectrometry (HP-6890) with electronic ionization.     

Multiphoton ionization and dissociation of CH3I at 266 and 355 nm

The mechanisms of multiphoton ionization (MPI) and dissociation of CH3I have been studied using timeof-flight (TOF) mass spectrometer at 266 and 355 nm. MPI mass spectrum at 266 nm consists mostly of fragment ions. This is consistent with a neutral-fragment photoionization mechanism in which rapid one-photon dissociation occurs from the repulsive potential energy surface followed by MPI of neutral photofragments. The observation of parent ions at 355-nm excitation is indicative of parent-ionic ladder mechanism in which the parent ions are produced directly by two-photon excitation resonantly excited to Rydberg C state and then ionized through additional one-photon absorption to produce CH3I+. Fragment ions are produced by dissociation of CH3I+.     

532 nm激光作用下CH3I分子的多光子电离

利用飞行时间质谱仪在超声射流冷却条件下探讨了532 nm激光作用下CH3I分子的多光子电离(MPI)解离过程和机制,得到了分子的飞行时间质谱,质谱中包含较强的I 、CH3 离子信号和较弱的CH3I 、CHn (n≤2)、C 、H 离子信号.不同激光能量下的质谱信号在排布上相似,但在强度上有差别.在532 nm激光作用下CH3I分子的多光子电离包括两个过程:一是CH3I分子由双光子激发到A带解离,生成I原子和CH3基团,然后再吸收光子实现中性碎片电离;另一通道是CH3I分子由三光子共振激发到里德堡C态,处于激发态的母体分子继续吸收两个光子电离形成母体离子,碎片离子可由母体离子解离形成.