Time-of-flight mass spectrometry with an electrospray ion beam.

An electrospray ionization source has been coupled to a reflection time-of-flight mass spectrometer. By orienting the ion source perpendicular to the field-free drift region, the longitudinal energy spread of the ion packet has been substantially reduced, allowing a mass resolving power of over 1000 to be achieved for both low-mass and high-mass ions of biological interest. In addition, instrument sensitivity allows the routine detection of low-picomole and subpicomole quantities of large multiply charged species such as cytochrome c (MW = 12,360.9). The potential utility of this instrument for conducting rapid screening of chromatographic effluents is discussed in light of its simplicity, rapid scanning speed, and high sensitivity.     

Using focused ion beam for nanosized structure formation in microfluidic chips

Microfluidic chips (MFCs) provide a basis for modern compact analytical systems possessing unique performance characteristics. Using nanosized functional structures in MFCs opens new possibilities in this field. Results of the formation of nanosized structures used as traps for microscopic particles in MFC channels are presented and discussed. Micron-sized channels in MFC structures on glass substrates were formed by photolithography and acid etching, while nanosized structures were obtained using focused ion and electron beams. The proposed MFC structures can be used for studying biological objects by high-resolution microscopy techniques.     

Metal cluster complex primary ion beam source for secondary ion mass spectrometry (SIMS)

To develop a solution-type ion beam source utilizing a wide variety of metal cluster complexes that are stable only in organic solvents, we have investigated an electrospray method for transferring ions from solutions to gas phase. As initial experiments, we have studied electrospray characteristics of ethanol solutions containing a room-temperature molten salt (i.e., an ionic liquid) and acetic acid as alternatives to solutions of metal cluster complexes. In electrospray experiments, we used a stainless-steel capillary with an inner diameter of 30 μm. Experimental results showed that electrosprayed currents increased with applied voltage in both positive-ion and negative-ion modes. In addition to positive currents, stable negative currents were also confirmed to be produced. Current exceeding 250 nA was produced at 2 kV with a flow rate of 2 μL/min at a concentration of 1 × 10⁻³ mol/L. It was confirmed that several nA out of electrosprayed currents were delivered through an orifice (120 μm internal diameter) into a vacuum chamber. Experimental results indicate that the electrospray method seems to be applicable to an ion beam source for utilizing massive metal cluster complexes in solutions.     

Fourier transform time-of-flight mass spectrometry in an electrostatic ion beam trap

We report on the application of an electrostatic ion beam trap as a mass spectrometer. The instrument is analogous to an optical resonator; ions are trapped between focusing mirrors. The storage time is limited by the residual gas pressure and reaches up to several seconds, resulting in long ion flight paths. The oscillation of ion bunches between the mirrors is monitored by nondestructive image charge detection in a field-free region and mass spectra are obtained via Fourier transform. The principle of operation is demonstrated by measuring the mass spectrum of trapped Ar+ and Xe+ particles, produced by a standard electron impact ion source. Also, mass spectra of heavier PEGnNa+ and bradykinin ions from a pulsed MALDI ion source were obtained. The long ion flight path, combined with mass-independent charge detection, makes this system particularly interesting for the investigation of large molecules.     

Glow discharge ionization source for liquid chromatography/particle beam mass spectrometry

A detailed evaluation of the analytical characteristics of a liquid chromatography/particle beam-glow discharge mass spectrometry (LC/PB-GDMS) system is described for applications in the area of inorganic (free metals in solution) and organic compound analysis. A highly efficient particle beam interface is used to introduce analyte species into a glow discharge source for subsequent vaporization and ionization. The GD operating current and gas pressure were optimized, with the general responses found to be similar to those obtained previously for particulate matter analysis by this PB-GDMS system. The mass spectra obtained for inorganic species are comprised exclusively of the respective elements' isotopic patterns, with no evidence of appreciable oxide species formation. Organic species introduced into the discharge through the particle beam interface yield mass spectra that are virtually identical to those from standard electron impact (70 eV) ionization. An analytical response curve for caffeine, using 200-microL (H2O/MeOH) injection volumes, showed less than 5% RSD for replicate injections over a concentration range of 10-500 ppm, with a detection limit of 13 ppb (2.7 ng) obtained for the caffeine molecular ion. Similarly, detection limits for Fe, Ag, and Cs ranged from 5.8 to 6.1 ppb (approximately 1 ng, each) in the injected volume. As an example of the feasibility of the PB-GDMS system as a detector for liquid chromatography, the separation and identification of the organic constituents in diet soda was performed.     

Quantitative analysis of low molecular weight polar compounds by continuous flow liquid secondary ion tandem mass spectrometry

Quantitative analyses of low molecular weight (100-200) polar compounds [1-methyl-4-phenylpyridine (MPP+), 2-amino-3-(methylamino)propanoic acid (synonyms, beta-(methyl-amino)-L-alanine or BMAA), and tryptophan] were conducted on a triple-stage quadrupole mass spectrometer configured for continuous flow liquid secondary ion mass spectrometry ionization (CF L-SIMS). It is shown that quantification by CF L-SIMS at subnanogram sensitivity can be precise (correlation coefficients greater than 0.99), accurate, specific, and routine for compounds not measurable by static L-SIMS. Successful analyses, however, are strongly dependent upon the stability of the film formed by the mobile phase on the probe tip. In our system, film stability is affected by mobile phase composition and flow rate, ion source and probe tip temperature, probe-tip and capillary alignment, film thickness, and sample composition.     

Metal salts for molecular ion yield enhancement in organic secondary ion mass spectrometry: a critical assessment

In a search for molecular ion signal enhancement in organic SIMS, the efficiency of a series of organic and inorganic salts for molecular cationization has been tested using a panel of nonvolatile molecules with very different chemical characteristics (leucine enkephalin, Irganox 1010, tetraphenylnaphthalene, polystyrene). The compounds used for cationization include alkali bromide and group Ib metal salts (XBr with X = Li, Na, K; CF3CO2Ag; AgNO3; [CH3COCH=C(O-)CH3]2Cu; AuCl3). Alkali ions, very good for polar molecule cationization, prove to be of limited interest for nonpolar molecules such as polystyrene. Silver trifluoroacetate displays excellent results for all the considered molecules, except for leucine enkephalin (which might be due to the use of different solvents for the analyte and the salt). Instead, silver nitrate mixed with leucine enkephalin in an ethanol solution provides intense molecular signals. The influence of the respective concentrations of analyte and salt in solution, of the silver trifluoroacetate solution stability, and of the sample microstructure on the secondary ion intensities are also investigated. The results of other combinations of analyte and salts are reported. Finally, the use of salts is critically compared to other sample preparation procedures previously proposed for SIMS analysis of large organic molecules.     

Application of molecular beam deflection time-of-flight mass spectrometry to peptide analysis

The application of molecular beam deflection time-of-flight mass spectrometry (MBD-TOFMS) to peptide identification is described. The technique permits a simultaneous measurement of molecular mass and electric dipole susceptibility. The mass and susceptibility are not strongly correlated, and the results can be presented as a two-dimensional map. The susceptibility provides a useful way to disperse isobaric and isomeric peptides, and at least for small peptides, the susceptibility is significantly different for different amino acid sequences. Results for peptides in the mass range 1000-2300 Da show that the mass and susceptibility lead to a higher identification score than mass spectra alone.     

Corona discharge ion mobility spectrometry with orthogonal acceleration time of flight mass spectrometry for monitoring of volatile organic compounds

We demonstrate the application of corona discharge ion mobility spectrometry with orthogonal acceleration time of flight mass spectrometry (CD IMS-oaTOF) for volatile organic compounds (VOCs) monitoring. Two-dimensional (2D) IMS-oaTOF spectra of VOCs were recorded in nearly real time. The corona discharge atmospheric pressure chemical ionization (APCI) source was operated in positive mode in nitrogen and air. The CD ion source generates in air H(3)O(+)(H(2)O)(n) and NO(+). The NO(+) offers additional possibility for selective ionization and for an increase of the sensitivity of monoaromatic compounds. In addition to H(3)O(+)(H(2)O)(n) and NO(+), we have carried out ionization of VOCs using acetone as dopant gas ((CH(3))(2)COH(+)). Sixteen model VOCs (tetrahydrofuran, butanol, n-propanol, iso-propano, acetone, methanol, ethanol, toluene, benzene, amomnia, dioxan, triethylamine, acetonitrile, formaldehyde, m-xylene, 2,2,2-trifluoroethylamine) were tested using these ionization techniques.     

Dynamic range expansion applied to mass spectrometry based on data-dependent selective ion ejection in capillary liquid chromatography fourier transform ion cyclotron resonance for enhanced proteome characterization.

The characterization of cellular proteomes is important for understanding biochemical processes ranging from cell differentiation to cancer development. In one highly promising approach, whole protein extracts or fractions are digested (e.g., with trypsin) and injected into a packed capillary column for subsequent separation. The separated peptides are then introduced on-line to an electrospray ionization source of a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer for the detection of peptide accurate mass tags that serve as biomarkers for their parent proteins. In this work, we report the use of data-dependent selective external ion ejection in conjunction with FTICR and on-line capillary LC separations for the enhanced characterization of peptide mixtures and a yeast extract proteome. The number of peptides identified in an LC-FTICR analysis of a yeast proteome digest employing data-dependent rf-only dipolar ejection of the most abundant ion species prior to ion accumulation was 40% higher than that detected in a separate LC-FTICR analysis using conventional nonselective ion accumulation.     

Modeling and analysis of the induced signal detected in electrostatic ion beam trap for mass spectrometry

The induced image charge and image current acquired by a detector tube for mass analysis are simulated using a numerical electrostatic model in the context of the electrostatic ion beam trap (EIBT). With the simulation results, the principle of mass analysis using the induced signal is demonstrated and studied systematically. The results show that the intensity of the detected signal is significantly influenced by the size and configuration of the detector, and also impacted by ion velocity, the number of ions in the ion group, and the ion beam length. The simulation results could not only be used to optimize the size and configuration of the detector and thus to improve the detected signal, but also to support the signal analysis (such as FFT) at an EIBT for mass spectrometry.     

液相色谱串联质谱测定鳗鱼中硝基呋喃的含量

硝基呋喃类药物及其代谢产物可使实验动物发生癌变、基因突变,同时具有生殖毒性,可能对人体产生危害。因此,硝基呋喃含量的检测在食品安全中是至关重要的,本文采用液相色谱串联质谱技术检测四种硝基呋喃类代谢物。硝基呋喃类代谢物在酸性条件下经过2-硝基苯甲醛衍生化,用乙酸乙酯提取纯化,电喷雾离子化,液相色谱-串联质谱检测。结果表明,四种硝基呋喃类药物的色谱峰面积与浓度在0.1～10.0 ng/mL范围内均呈现很好的线性关系,该方法具有操作简便、灵敏、准确等优点。     

Instrumental aspects of secondary ion mass spectrometry and secondary ion imaging mass spectrometry

A short survey of the varieties of the Secondary Ion Mass Spectrometry (SIMS) known at present is given. The principle of quantitative analysis with respect to thin film analysis is discussed. The properties of SIMS and SIIMS (Secondary Ion Imaging Mass Spectrometry) are compared with those of Electron Microprobe Analysis. Results of an analysis of a thin film of titanium oxide and of an FeMn ferrite by means of SIMS and SIIMS are given.