A data analysis method for isochronous mass spectrometry using two time-of-flight detectors at CSRe

The concept of isochronous mass spectrometry(IMS) applying two time-of-flight(TOF) detectors originated many years ago at GSI. However, the corresponding method for data analysis has never been discussed in detail. Recently, two TOF detectors have been installed at CSRe and the new working mode of the ring is under test. In this paper, a data analysis method for this mode is introduced and tested with a series of simulations. The results show that the new IMS method can significantly improve mass resolving power via the additional velocity information of stored ions. This improvement is especially important for nuclides with Lorentz factor γ-value far away from the transition point γt of the storage ring CSRe.     

Improvement of sensitivity using principal component analysis by dual focused ion beam time-of-flight secondary ion mass spectrometry

It is important to develop and to practically use the method to analyze a micro-nanometer order area. Especially, three-dimensional microanalysis for minute structure that consists of the organic compounds and the polymer is difficult. We developed a novel three-dimensional microanalysis method by means of focused ion beam (FIB) for section processing and ToF-SIMS for mapping method. For the purpose of realization of three-dimensional microanalysis and a chemical and structural analysis of the organic matter, the sensitivity improvement of ToF-SIMS in the three-dimensional analysis device and the method of the spectral analysis are examined. To improve the sensitivity of ToF-SIMS, the sample stage was modified to arrange perpendicularly with the ToF optical axis, and the distortion of electric field was corrected. And, by analyzing the fragment ions by using the principal component analysis (PCA) to raise the efficiency of the spectrum analysis, spatial resolution has improved. As a result, the resolution of the device improved to sub micrometer order, and advanced to the achievement of the three-dimensional microanalysis.     

Femtosecond laser-induced fragmentation and cluster formation studies of solid phase trinitrotoluene using time-of-flight mass spectrometry

We use surface-femtosecond laser mass spectrometry to study the fragments/products formed when trinitrotoluene (TNT) is subjected to femtosecond laser pulse irradiation and to study the conditions under which TNT is removed from a solid surface. In surface-femtosecond laser mass spectrometry a compound is deposited on a solid substrate and is desorbed into vacuum by femtosecond irradiation forming a plume of ionized and neutral species. The positive or negative ions are then accelerated by an electric potential and allowed to drift in the field-free region of a time-of-flight mass spectrometer. The mass-to-charge ratio of each ion is obtained using the value of the accelerating field and the ion flight time. In this paper we report femtosecond laser mass spectra for the positive ions formed by desorbing TNT with 130 fs pulses centered at 800 nm for fluences ranging from 7 to 1.4 × 10⁵ J/m². The conditions under which TNT removal and ionization occur are also discussed.     

膜进样/飞行时间质谱实时分析水源水中挥发性有机污染物

为建立饮用水源地污染事故监控预警系统,采用膜进样/飞行时间质谱技术,对苯系物、取代苯、卤代烷等典型挥发性有机物模拟事故状况下的污染水体进行了在线监测.研究结果表明,该技术对目标有机污染物的响应时间短,对苯系物为30～70 s、对卤代烷为30 s,线性检测范围达到3～4个数量级,苯系物和氯苯的检测限小于10 μg·L-1...     

Protein quantification on dendrimer-activated surfaces by using time-of-flight secondary ion mass spectrometry and principal component regression

Interaction between streptavidin and biotin on poly(amidoamine) (PAMAM) dendrimer-activated surfaces and on self-assembled monolayers (SAMs) was quantitatively studied by using time-of-flight secondary ion mass spectrometry (ToF-SIMS). The surface protein density was systematically varied as a function of protein concentration and independently quantified using the ellipsometry technique. Principal component analysis (PCA) and principal component regression (PCR) were used to identify a correlation between the intensities of the secondary ion peaks and the surface protein densities. From the ToF-SIMS and ellipsometry results, a good linear correlation of protein density was found. Our study shows that surface protein densities are higher on dendrimer-activated surfaces than on SAMs surfaces due to the spherical property of the dendrimer, and that these surface protein densities can be easily quantified with high sensitivity in a label-free manner by ToF-SIMS.     

Imaging of aerosols using time of flight secondary ion mass spectrometry

Interest in environmental aerosol chemistry has grown over the last decade as a result of its role in both climate change and troposheric pollution. In this work, the combination of ToF-SIMS and SEM/EDX was employed to explore the surface chemistry of aerosols. The capabilities and limitations of ToF-SIMS were investigated using particles of known composition and size produced by a vibrating orifice aerosol generator (VOAG). Principal component analysis (PCA) proved to help in the distinction of particles of different types by consolidating the information generated by ToF-SIMS.     

Molecular distribution of some commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Nonylphenol ethoxylates (NPEs) belong to a group of nonionic surfactants that are collectively referred to as alkylphenol ethoxylates (APEs). APEs find widespread use in heavy-duty commercial and household cleaning formulations, shampoos, and industrial processing, i.e. textile manufacture. Their environmental impact depends on the molecular distribution and the extent of their biodegradation in municipal sewage systems, waterways and rivers. We have established two sample preparation methods that have enabled the determination of the molecular distributions of six commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). In both methods, alpha-cyano-4-hydroxycinnamic acid, dissolved in acetonitrile/tetrahydrofuran, was used as the matrix. In one set of experiments, the NPEs were dissolved in an acetonitrile/tetrahydrofuran solvent system prior to mixing with the matrix solution, and the resulting MALDI-TOF mass spectra produced mostly sodiated molecules [M + Na](+). The NPEs, all having the formula 4-(C(9)H(19))-C(6)H(4)-(OCH(2)CH(2))(n)-OH, are Surfonic (R)N-95, N-100, N-102, N-120, N-150 and N-300. Surfonic N-95 and N-100 gave n values of 5-20; Surfonic N-102, N-120, N-150, and N-300 gave n values of 5-21, 5-22, 8-25 and 15-40, respectively. In order to develop a sample preparation method that could be used with less polar NPEs, we dissolved the NPEs (except N-300) in pentane prior to mixing with the matrix solution, and found that the MALDI spectral quality was unaffected by the solvent systems. Copyright 1999 John Wiley & Sons, Ltd.     

Analysis of intensities of positive and negative ion species from silicon dioxide films using time-of-flight secondary ion mass spectrometry and electronegativity of fragments

Intensities of positive and negative ion species emitted from thermally oxidized and plasma-enhanced chemical vapor deposited (PECVD) SiO₂ films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the Saha-Boltzmann equation. Intensities of positive and negative secondary ion species were normalized to those of ²⁸Si⁺ and ²⁸Si⁻ ions, respectively, and an effective temperature of approximately (7.2 ± 0.1) × 10³ K of the sputtered region bombarded with pulsed 22 kV Au₃⁺ primary ions was determined. Intensity spectra showed polarity dependence on both n and m values of Si_nO_m fragments, and a slight shift to negative polarity for PECVD SiO₂ compared to thermally oxidized SiO₂ films. By dividing the intensity ratios of negative-to-positive ions for PECVD SiO₂ by those for thermally oxidized SiO₂ films to cancel statistical factors, the difference in absolute electronegativity (half the sum of ionization potential and electron affinity of fragments) between both films was obtained. An increase in electronegativity for SiO_m (m = 1, 2) and Si₂O_m (m = 1-4) fragments for PECVD SiO₂ films compared to thermally oxidized films was obtained to be 0.1-0.2 Pauling units, indicating a more covalent nature of Si-O bonds for PECVD SiO₂ films compared to the thermally oxidized SiO₂ films.     

Identification and quantification of amyloid beta-related peptides in human plasma using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Proteolytic processing of the amyloid precursor protein (APP) by β-secretase and γ-secretase leads to the generation and deposition of amyloid β (Aβ) in Alzheimer’s disease (AD). N-terminally or C-terminally truncated Aβ variants have been found in human cerebrospinal fluid and cultured cell media using immunoprecipitation and mass spectrometry. Unfortunately, the profile of plasma Aβ variants has not been revealed due to the difficulty of isolating Aβ from plasma. We present here for the first time studies of Aβ and related peptides in human plasma. Twenty-two Aβ-related peptides including novel peptides truncated before the β-secretase site were detected in human plasma and 20 of the peptides were identified by tandem mass spectrometry. Using an internal standard, we developed a quantitative assay for the Aβ-related peptides and demonstrated plasma dilution linearity and the precision required for their quantitation. The present method should enhance the understanding of APP processing and clearance in AD progression.     

Identification of wheat varieties using matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry and an artificial neural network

A novel tool for variety identification of wheat (Triticum aestivum L.) has been developed: an artificial neural network (ANN) is used to classify the gliadin fraction analysed by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS). The robustness of this novel method with respect to various experimental parameters has been tested. The results can be summarised: (i) With this approach 97% of the wheat varieties can be classified correctly with a corresponding correlation coefficient of 1.0, (ii) The method is fast since the time of extracting gliadins from flour can be reduced to 20 min without significant decrease in overall performance, (iii) The storage of flour or extracts under standard conditions does not influence the classification ability (i. e. the generalisation ability) of the method, and (iv) The classification obtained is not influenced by the identity of the operator making the analysis. This study demonstrates that a combination of an ANN and MALDI-TOFMS analysis of the gliadin fraction provides a fast and reliable tool for the variety identification of wheat. Copyright 1999 John Wiley & Sons, Ltd.     

Imaging subcellular features of a sectioned rat brain using time-of-flight secondary ion mass spectrometry and scanning probe microscopy

Coronal sections of unfixed rat brain samples were prepared on a flat substrate in order to reveal hippocampal formation (CA1-4 pyramidal neurons) and adjacent neocortical white matter. We demonstrate the feasibility of using surface sensitive techniques such as time-of-flight secondary ion mass spectrometry (ToF-SIMS) and scanning probe microscopy (SPM) to probe lipid distribution, as well as the subcellular features of neurons. In the same anatomical areas, the phase shift image in SPM is especially useful in revealing the cross-section of subcellular structures. We show that the phase shift images reveal distinctive subcellular features and ion images of CN⁻ and PO₂⁻ fragments from ToF-SIMS appear to define some of the subcellular features.     

Using time-of-flight secondary ion mass spectrometry and multivariate statistical analysis to detect and image octabenzyl-polyhedral oligomeric silsesquioxane in polycarbonate

Silsesquioxane, with an empirical formula of RSiO_3/2, has the potential to combine the mechanical properties of plastics with the oxidative stability of ceramics in one material [D.W. Scott, J. Am. Chem. Soc. 68 (1946) 356; K.J. Shea, D.A. Loy, Acc. Chem. Res. 34 (2001) 707; K.-M. Kim, D.-K. Keum, Y. Chujo, Macromolecules 36 (2003) 867; M.J. Abad, L. Barral, D.P. Fasce, R.J.J. William, Macromolecules 36 (2003) 3128]. The high sensitivity, surface specificity, and ability to detect and image high mass additives make time-of-flight secondary ion mass spectrometry (ToF-SIMS) a powerful surface analytical instrument for the characterization of polymer composite surfaces in an analytical laboratory [J.C. Vickerman, D. Briggs (Eds.), ToF-SIMS Surface Analysis by Mass Spectrometry, Surface Spectra/IMPublications, UK, 2001; X. Vanden Eynde, P. Bertand, Surf. Interface Anal. 27 (1999) 157; P.M. Thompson, Anal. Chem. 63 (1991) 2447; S.J. Simko, S.R. Bryan, D.P. Griffis, R.W. Murray, R.W. Linton, Anal. Chem. 57 (1985) 1198; S. Affrossman, S.A. O’Neill, M. Stamm, Macromolecules 31 (1998) 6280]. In this paper, we compare ToF-SIMS spectra of control samples with spectra generated from polymer nano-composites based on octabenzyl-polyhedral oligomeric silsesquioxane (BnPOSS) as well as spectra (and images) generated from multivariate statistical analysis (MVSA) of the entire spectral image. We will demonstrate that ToF-SIMS is able to detect and image low concentrations of BnPOSS in polycarbonate. We emphasize the use of MVSA tools for converting the massive amount of data contained in a ToF-SIMS spectral image into a smaller number of useful chemical components (spectra and images) that fully describe the ToF-SIMS measurement.