Electron transfer ion/ion reactions in a three-dimensional quadrupole ion trap: reactions of doubly and triply protonated peptides with SO2*-

Ion-ion reactions between a variety of peptide cations (doubly and triply charged) and SO2 anions have been studied in a 3-D quadrupole ion trap, resulting in proton and electron transfer. Electron transfer dissociation (ETD) gives many c- and z-type fragments, resulting in extensive sequence coverage in the case of triply protonated peptides with SO2*-. For triply charged neurotensin, in which a direct comparison can be made between 3-D and linear ion trap results, abundances of ETD fragments relative to one another appear to be similar. Reactions of doubly protonated peptides with SO2*- give much less structural information from ETD than triply protonated peptides. Collision-induced dissociation (CID) of singly charged ions formed in reactions with SO2*- shows a combination of proton and electron transfer products. CID of the singly charged species gives more structural information than ETD of the doubly protonated peptide, but not as much information as ETD of the triply protonated peptide.     

Statistical characterization of ion trap tandem mass spectra from doubly charged tryptic peptides

Collision-induced dissociation (CID) is a common ion activation technique used to energize mass-selected peptide ions during tandem mass spectrometry. Characteristic fragment ions form from the cleavage of amide bonds within a peptide undergoing CID, allowing the inference of its amino acid sequence. The statistical characterization of these fragment ions is essential for improving peptide identification algorithms and for understanding the complex reactions taking place during CID. An examination of 1465 ion trap spectra from doubly charged tryptic peptides reveals several trends important to understanding this fragmentation process. While less abundant than y ions, b ions are present in sufficient numbers to aid sequencing algorithms. Fragment ions exhibit a characteristic series-specific relationship between their masses and intensities. Each residue influences fragmentation at adjacent amide bonds, with Pro quantifiably enhancing cleavage at its N-terminal amide bond and His increasing the formation of b ions at its C-terminal amide bond. Fragment ions corresponding to a formal loss of ammonia appear preferentially in peptides containing Gln and Asn. These trends are partially responsible for the complexity of peptide tandem mass spectra.     

Charge determination of product ions formed from collision-induced dissociation of multiply protonated molecules via ion/molecule reactions.

The use of ion/molecule reactions involving multiply protonated ions derived from electrospray for the determination of the charges of product ions formed from collision-induced dissociation is described. The experiments are carried out with a quadrupole ion trap capable of multiple stages of mass spectrometry. The approach is illustrated with proton transfer from a product ion from quadruply protonated melittin, and from a product ion from the (M + 20H)20+ ion from horse myoglobin, to 1,6-diaminohexane. The major product ion from quadruply protonated bovine insulin is used to illustrate the use of a clustering reaction with 1,6-diaminohexane. The ion trap is shown to be a particularly useful tool for employing both collisional activation and low-energy ion/molecule reactions in the same experiment to determine product ion charge.     

N等离子体基注渗方法研究

等离子体基注渗技术在材料表面改性中具有极为重要的应用，本文报道了一种实现恒温条件的N等离子体基注渗的工艺方法，利用该方法可以根据工艺研究需要，实现注渗剂量、注渗能量(加速电压)和注渗温度单一参数调节，为等离子体体基注渗工艺的优化提供了一种切实可行的研究方法。利用本文提出的工艺方法，对纯铁进行了各种温度下的N离子注渗。结果表明，处理过程中，可依据工艺设计，单参数大范围改变注渗电压或注渗恒温温度，温度波动很小，离子注入层厚度得到明显提高。     

Relative dissociation energies of protonated peptides by electrospray ionization/surface-induced dissociation

Relative dissociation energies (RDEs) are obtained for the major fragment ions produced by electrospray ionization/surface-induced dissociation of singly protonated triglycine, tetraglycine, leucine enkephalin, and leucine enkephalin arginine. A previously described data analysis method (Lim, H.; et al. J. Phys. Chem. B 1998, 102, 4753) is employed to analyze the energy-resolved mass spectra by subtracting out the distribution of energy transferred to the surface, integrating over the distribution of the incident ion energy, and taking into account the precursor ion initial internal energy and kinetic energy distributions. These variables are optimized by anchoring the RDE for the lowest energy fragment of a given precursor ion to its literature values and then using these optimized parameters to obtain the other RDEs. The RDEs of the four major fragments of triglycine vary from 2.4 eV for the b(2) fragment ion to 6.0 eV for the a(2) ion. The RDEs of the four major fragments of tetraglycine vary from 3.2 eV for the y(2) ion to 5.7 eV for the a(2) ion. The leucine enkephalin RDEs range from 1.1 eV for the b(4) ion to 2.1 eV for the b(2) ion. The leucine enkephalin arginine RDEs all lay between 2.5 and 3.5 eV. The overall trend of fragmentation order for all peptides is (y(n), b(n)) < a(n) and is consistent with the results from other experiments. The peptide RDEs presented here are only as accurate as the literature values to which they are anchored. Determination of absolute dissociation energies from SID data will require further refinement of the data analysis method.     

Surface-induced dissociation of protonated peptides: implications of initial kinetic energy spread.

Surface-induced dissociation (SID) has been used to produce daughter ion spectra of small protonated peptides generated by fast atom bombardment (FAB). The relative abundances of daughter ions depends critically upon the energy of the ion/surface collision. A wide array of decomposition processes may be observed using ELAB collision energies in the range 10-20 eV. At approximately 13-eV collision energy, the variety of decomposition processes is maximized for the small peptides studied; hence, maximum structural information may be deduced. Collisionally-activated dissociations (CAD) using argon gas and the identical protonated peptides could not produce as large an array of daughter ions in a constant condition experiment. An apparent contradiction is thereby posed because SID is known to produce a narrow distribution of ion internal energies relative to CAD. This apparent contradiction is resolved by considering the rather large kinetic energy spread of ions leaving the FAB source. For the SID process, this large initial kinetic energy distribution is converted into a significantly wider spread in center-of-mass collision energy, leading to a broader variety of decomposition processes (high and low energy) compared to CAD.     

Implementation of ion/ion reactions in a quadrupole/time-of-flight tandem mass spectrometer

A commercial quadrupole/time-of-flight (QqTOF) tandem mass spectrometer has been adapted for ion/ion reaction studies. To enable mutual storage of oppositely charged ions in a linear ion trap, the oscillating quadrupole field of the second quadrupole of the system (Q2) serves to store ions in the radial dimension while auxiliary radio frequency is superposed on the end lenses of Q2 during the reaction period to create barriers in the axial dimension. A pulsed dual electrospray (ESI) source is directly coupled to the instrument interface for the purpose of proton transfer reactions. Singly and doubly charged protein ions as high in mass as 66 kDa are readily formed and observed after proton-transfer reactions. For the modified instrument, the mass resolving power is approximately 8000 for a wide m/z range, and the mass accuracy is approximately 20 ppm for external calibration and approximately 5 ppm for internal calibration after ion/ion reactions. Parallel ion parking is demonstrated with a six-component protein mixture, which shows the potential application of reducing spectral complexity and concentrating certain charge states. The current system has high flexibility with respect to defining MS(n) experiments involving collision-induced dissociation (CID) and ion/ion reactions. Protein precursor and CID product masses can be determined with good accuracy, providing an attractive platform for top-down proteomics. Electron transfer dissociation ion/ion reactions are implemented by using a pulsed nano-ESI/atmospheric pressure chemical ionization dual source for ionization. The reaction between protonated peptide ions and radical anions of 1,3-dinitrobenzene formed exclusively c- and z-type fragment ions.     

Phase morphology effect on elevated temperature mechanical behavior of nanostructures

A devitrification procedure by annealing was applied to a multicomponent Fe-based metallic glass in order to obtain nanocrystalline materials. Phase composition and phase morphology were strongly dependent on the annealing conditions. An elevated temperature mechanical behavior of nanostructures was evaluated by tensile testing. A strong effect of phase morphology on the mechanical response of the material was revealed. A most attractive combination of strength and plasticity was observed in the nanostructure with approximately equal grain sizes of crystallized phases.     

Enantiomeric analysis of pharmaceutical compounds by ion/molecule reactions

Protonated complexes involving cyclodextrin hosts and guest compounds that are pharmacologically important are produced in the gas phase and reacted with a gaseous amine. The guest is exchanged to produce a new protonated complex with the amine. The reaction is enantioselective and is used to develop a method for determining enantiomeric excess using only mass spectrometry. The pharmaceutical compounds include DOPA, amphetamine, ephedrine, and penicillamine. The presence of more than one reacting species is observed with DOPA and penicillamine. Molecular dynamics calculations are used to understand the nature of the interactions and the possible source of the variations in the reactivities.     

Hold-time effect of a single overload on crack retardation at elevated temperature

Many studies have shown that the application of a single overload cycle during constant amplitude load cycling will produce crack retardation or delay. At elevated temperature, the delay effect is time-dependent due to creep that occurs during the overload cycle. A simple method is described to estimate the number of delay cycles as a function of hold time. The reduced crack growth rate following an overload is modelled by a modified constant-amplitude crack propagation relationship. The modification consists in the replacement of the crack rate term by a fractional derivative; the order of the derivative being related to the overload ratio. Delay is assumed to be equal to the number of constant amplitude cycles required by the crack tip to traverse the creep-damage zone created by the overload. A simple notch-type analysis is developed to estimate the creep-damage zone. Predictions compared very favorably with experimental results obtained with a side-grooved DCB specimen with a constant-K characteristic for a fine-grain superalloy IN-100 at 1200°F. The applicability of LEFM for crack growth under creep/fatigue conditions is discussed together with the extension of the results to spectrum loading.     

A quadrupole ion trap mass spectrometer with three independent ion sources for the study of gas-phase ion/ion reactions

An instrument for the study of gas-phase ion/ion reactions in which three independent sources of ions, namely, two electrospray ionization sources and one atmospheric sampling glow discharge ionization source, are interfaced to a quadrupole ion trap mass analyzer is described. This instrument expands the scope of gas-phase ion/ion reaction studies by allowing for manipulation of the charge states of multiply charged reactant and product ions. Examples are provided involving the formation of protein-protein complexes in the gas phase. Complexes with charge states that cannot be formed from reactant ion charge states present in the normal electrospray charge state distributions can be formed in the new apparatus. Strategies that rely on both reactant ion charge state manipulation and product ion charge state manipulation are demonstrated. In addition, simplification of product ion spectra generated from dissociation of complexes formed via ion/ion reactions can be effected by using the discharge source to reduce the charge state of the product ions to primarily 1+.     

Effects of carbon readsorption on tungsten under high-flux, low-energy Ar ion irradiation at elevated temperature

The erosion kinetics under irradiation by Ar ions extracted from plasma by 300 V negative bias voltage of 2 μm-thick W film contaminated by redeposited carbon atoms was investigated in dependence on the Ar-working gas pressure in the range 0.2-10 Pa at 410 K. The erosion and deposition parameters were deduced from the dependence of the sample's weight change on irradiation time. Two regimes were distinguished which contributed differently to the carbon transport efficiency from the surface towards the bulk, namely, the weight-decrease regime, when sputtering prevailed redeposition, and the weight-increase regime, when redeposition prevailed sputtering. Carbon distribution profiles measured by the SIMS technique showed that carbon was efficiently transported into the W film when its surface was not covered by a continuous amorphous C layer. The C transport efficiency decreased when W was covered by a continuous amorphous C film.These results were qualitatively explained by dynamic mixing of atoms on the surface. It was assumed that surface chemical potential increased under irradiation and that C adatoms were driven into grain boundaries of nanocrystalline W film. The continuous amorphous C film on tungsten blocked the access of activated C atoms to the grain boundaries.     

Separation of isomeric peptides using electrospray ionization/high-resolution ion mobility spectrometry

In this paper, the first examples of baseline separation of isomeric macromolecules by electrospray ionization/ion mobility spectrometry (ESI/IMS) at atmospheric pressure are presented. The behavior of a number of different isomeric peptides in the IMS was investigated using nitrogen as a drift gas. The IMS was coupled to a quadrupole mass spectrometer, which was used for identification and selective detection of the electrosprayed ions. The mobility data were used to determine their average collision cross sections. The gas-phase ions of isomeric peptides were found to have different collision cross sections. In all cases, doubly charged ions exhibited significantly (8-20%) larger collision cross sections than the respective singly charged species. The analysis of mixtures of the isomeric peptides clearly demonstrated the capability of IMS to separate gas-phase peptide ions due to small differences in their conformational structures, which cannot be determined by mass spectrometry. An actual resolving power of 80 was achieved for two doubly charged reversed sequenced pentapeptides. Baseline separation was provided for ions differing by only 2.5% in their measured collision cross sections; partial separation was shown for isomeric ions exhibiting differences as small as 1.1%.     

Control of ion distortion in field asymmetric waveform ion mobility spectrometry via variation of dispersion field and gas temperature

Field asymmetric waveform ion mobility spectrometry (FAIMS) has emerged as an analytical tool of broad utility, especially in conjunction with mass spectrometry. Of particular promise is the use of FAIMS and 2-D ion mobility methods that combine FAIMS with conventional IMS to resolve and characterize protein and other macromolecular conformers. However, FAIMS operation requires a strong electric field, and ions are inevitably heated by energetic collisions with buffer gas molecules. This may induce ion isomerization or dissociation, which distort the separation properties of FAIMS (and subsequent stages) or reduce instrumental sensitivity. As FAIMS employs a periodic waveform, whether those processes are controlled by ion temperature at maximum or average field intensity has been debated. Here we address this issue by measuring the unfolding of compact ubiquitin ion geometries as a function of waveform amplitude (dispersion field, E(D)) and gas temperature, T. The field heating is quantified by matching the dependences of structural transitions on E(D) and T: increasing E(D) from 12 to 16 or from 16 to 20 kV/cm is equivalent to heating the (N2) gas by approximately 15-25 degrees C. The magnitude of field heating for any E(D) can be estimated using the two-temperature theory, and raising E(D) by 4 kV/cm augments heating by approximately 15-30 degrees C for maximum and approximately 4-8 degrees C for average field in the FAIMS cycle. Hence, isomerization of ions in FAIMS appears to be determined by the excitation at waveform peaks.     

Fabrication of excimer laser annealed poly-Si thin film transistor by using an elevated temperature ion shower doping

We have investigated the effect of an ion shower doping of laser annealed poly-Si films at elevated substrate temperatures. The substrate temperature was varied from room temperature to 300°C when the poly-Si film was doped with phosphorus by a non-mass-separated ion shower. Optical, structural, and electrical characterizations have been performed in order to study the effect of the ion shower doping. The sheet resistance of the doped poly-Si films was decreased from 7 × 10⁶ Ω/sq to 700 Ω/sq when the substrate temperature was increased from room temperature to 300°C. This large change in sheet resistance is due to the fact that the doped films do not become amorphous but remain in the polycrystallinephase. The mildly elevated substrate heating appears to contribute mainly to reduction of ion damages incurred in the poly-Si films in addition to the activation of dopants during the ion shower doping. From the fabricated n-channel poly-Si TFTs, the current crowding effect do not occur because of the low contact source-drain resistance and the field effect mobility of 120 cm²/(V s) has been obtained.     

Relative information content and top-down proteomics by mass spectrometry: utility of ion/ion proton-transfer reactions in electrospray-based approaches

Computer simulations of electrospray ionization (ESI) and collision-induced dissociation (CID) experiments were employed to examine the informing power associated with "top-down" proteomics implemented with some commonly used mass analyzers, i.e., the quadrupole ion trap (QIT), the Fourier transform-ion cyclotron resonance mass spectrometer (FT-ICRMS), and the time-of-flight (TOF) mass spectrometer. Using a ratio of the separated (or resolved) peaks to the total number of predicted peaks as a measure of informing power, the ESI-MS simulation of a mixture of proteins showed that the FT-ICRMS exhibited the highest informing power among the three instruments being studied, with the QIT giving the lowest informing power, which was expected from the analysis of the "component capacity" of the three approaches. Also as expected on the basis of resolving elements per component, a dramatic increase in the informing power of the approach was obtained when ion/ion proton-transfer reactions were used to reduce the number of peaks and to minimize overlap between ions of different mass and charge but similar mass-to-charge ratio. With the assumptions made in this study, the informing power of the TOF + ion/ion approach rivaled or even exceeded that of the FT-ICRMS approach, despite significantly lower mass resolution. This result stemmed from both a reduction in the number of peaks and their dispersion over a much wider range of mass-to-charge ratios. Similar results were obtained from the CID simulation, where the informing power of different approaches was evaluated on the basis of the ratio of the number of ions for which a mass could be determined unambiguously to the total number of ions in the spectra.     

温度对离子束溅射生长Ge/Si量子点的形貌影响

采用离子束溅射技术,在不同温度的Si(100)衬底上生长了一系列Ge量子点样品,利用AFM和Raman光谱对样品表面形貌和结构进行表征,结果表明,随着温度升高,量子点密度增大(750℃生长的量子点密度达到1.85×1010cm-2),均匀性变好及结晶性增强;但随生长温度升高,Si-Ge互混程度也同时加剧。     

Activation of intact electron-transfer products of polypeptides and proteins in cation transmission mode ion/ion reactions

Cationic peptide electron-transfer products that do not fragment spontaneously are exposed to ion trap collisional activation immediately upon formation while they pass through a high-pressure collision cell (Q2), where the electron-transfer reagent anions are stored. Radial ion acceleration, which is normal to the ion flow, is implemented by applying an auxiliary dipolar alternating current to a pair of opposing rods of the Q2 quadrupole array at a frequency in resonance with the surviving electron-transfer products. Collisional cooling of cations in the pressurized Q2 ensures efficient overlap of the positive and negative ions for ion/ion reactions and also gives rise to relatively long residence times (milliseconds) for ions in Q2, making it possible to fragment ions via radial excitation during their axial transmission. The radial activation for transmission mode electron-transfer ion/ion reactions has been demonstrated with a doubly protonated tryptic peptide, a triply protonated phosphopeptide, and [M + 7H]7+ ions of ubiquitin. In all cases, significant increases in fragment ion yields and structural information from electron-transfer dissociation (ETD) were observed, suggesting the utility of this method for improving transmission mode ETD performance for relatively low charge states of peptides and proteins.     

The effect of elevated temperature and silicon addition on a cobalt-based wear resistant superalloy

The effects of an elevated temperature and a 5 wt% silicon addition on the resultant microstructure and inherent phases of Stellite 6 were investigated by using room and high temperature optical microscopy, X-ray diffraction, scanning electron microscopy (SEM) and also bulk hardness and microhardness measurements. It has been observed that exposing Stellite 6 to heat treatments at 1000°C results in a characteristic textured structure and coarsening of interdendritic regions due to bulk diffusion. In addition, both dendritic and interdendritic hardness values increase due to texture formation and increased amounts of carbide and intermetallic phases, respectively. On the other hand, silicon addition to Stellite 6 causes the transformation of the original spongy dendritic microstructure in as-cast Stellite 6 to a eutectic dendritic and skeleton interdendritic structure. Also, when silicon added Stellite 6 was heat treated at 1000°C, particulates emanating from the interdendritic skeleton become irregularly dispersed in the dendritic region. In addition, similarly to Stellite 6; a high temperature heat treatment results in an increase in hardness values of silicon added Stellite 6 due to the presence of an Co₂ Si intermetallic phase.