The role of ceric ion in vinyl polymerization and graft copolymerization

Six kinds of new ceric ion redox initiation systems for vinyl radical polymerization and two kinds of macromolecule graft copolymerization by ceric ion have been briefly reviewed in this paper. The initiators include ceric ion/acetanilide, ceric ion/alkyl phenylcarbamate, ceric ion/4-methoxysuccinyltoluidine, ceric ion/aliphatic aldehyde, ceric ion/aromatic aldehyde, ceric ion/diketone systems. Macromolecules such as poly(ether-urethane) and macromolecules having active pendant groups were selected for graft copolymerization with acrylamide initiated by ceric ion.     

毛细管离子色谱进展

从毛细管离子色谱柱制备和毛细管离子色谱仪器研制两方面评述了毛细管离子色谱目前的发展状况。毛细管离子色谱柱包括开管离子色谱柱，毛细管颗粒填充离子色谱柱以及最近几年发展起来的整体毛细管离子色谱柱。对毛细管离子色谱仪的总结包括微流量泵、小体积进样器、适合毛细管离子色谱系统的小体积抑制器、电导和光学检测器等。     

离子对水的17O-NMR化学位移和水结构的影响

在小于1 mol•L-1的浓度范围内,测试了碱金属、碱土金属氯化物、卤化钠及其它常见含氧酸盐溶液的17O-NMR化学位移（δ(H217O)）.发现离子对δ(H217O)的影响与离子的半径、电荷、离子外层电子结构及离子结构有关.其它离子参数相同时,离子半径越大,离子的摩尔δ(H217O)越大;在电子结构相同的情况下,离子电荷越大,离子的摩尔δ(H217O)越大;多原子离子的摩尔δ(H217O)更多地是与其离子结构相关.离子的摩尔δ(H217O)的大小反映了该离子对水的结构的影响情况,离子的摩尔δ(H217O)越大,对水的结构促进作用越强.     

Development of a SIMION-Simulated Ion Funnel Tube for Proton Transfer Reaction Mass Spectrometry

Because the optimum working pressure of ion funnel (IF) is very close to the typical operating pressure of a traditional drift tube for proton transfer reaction mass spectrometry (PTR-MS), it is possible to develop an IF drift tube for PTR-MS to improve the sensitivity. In this study, an ion funnel capable of functioning as a drift tube in a PTR-MS system was designed and studied by computer simulation. To optimize the geometrical and electrical parameters of the ion funnel, five ion funnel configurations were constructed. The merits and features of the respective ion funnels were evaluated, and the ion transmission characteristics were investigated and analyzed. An optimized ion funnel model was compared against the typical traditional drift tube that was used in PTR-MS for ion transmission, and it was found that the ion traveling trajectories in the ion funnel and traditional drift tube had different shapes and ion transmission efficiencies. Preliminary investigations revealed that this ion funnel improved the ion transmission efficiency by at least 10 times. The simulation and experiment results are helpful in guiding the design of an improved ion funnel to develop a PTR-MS system with higher sensitivity.     

磁性离子交换树脂连续化运行条件的研究

本文针对现行离子交换操作过程和离子交换树脂的不足,研制出一种新磁性离子交换树脂,并对其应用于连续化子离子交换过程的运行条件进行了较详细的研究,结果表明,磁性离子交换树脂应用于连续化操作过程,可增大操作流速或提高工作效率。     

Mutual storage mode ion/ion reactions in a hybrid linear ion trap

Ion/ion proton transfer reactions involving mutual storage of both ion polarities in a linear ion trap (LIT) that comprises part of a hybrid triple quadrupole/linear ion trap mass spectrometer have been effected. Mutual ion storage in the x- and y-dimensions arises from the normal operation of the oscillating quadrupole field of the quadrupole array, while storage in the z-dimension is enabled by applying unbalanced radio-frequency amplitudes to opposing sets of rods of the array. Efficient trapping (>90%) is achieved for thermalized ions over periods of several seconds. Reactions were demonstrated for multiply charged protein/peptide cations formed by electrospray with anions derived from glow discharge ionization of perfluoro(methyldecalin) (PMD) introduced from the side of the LIT rod array. Doubly and singly charged protein ions are readily formed via ion/ion reactions. The parameters that affect ion/ion reactions are discussed, including the degree of RF unbalance on the LIT rods, vacuum pressure, nature of the buffer gas, reaction time, anion abundance, and the low mass cutoff for ion/ion reaction. The present system has a demonstrated upper mass-to-charge ratio limit of at least 33,000. The system also has high flexibility with respect to defining MS(n) experiments involving both collision-induced dissociation (CID) and ion/ion reactions. Experiments are demonstrated involving beam-type CID in the pressurized collision quadrupole (Q2) followed by ion/ion reactions involving the product ions in the LIT. Ion parking experiments are also demonstrated using the mutual storage ion/ion reaction mode in the LIT, with a parking efficiency over 60%.     

Automatic gain control in mass spectrometry using a jet disrupter electrode in an electrodynamic ion funnel

We report on the use of a jet disrupter electrode in an electrodynamic ion funnel as an electronic valve to regulate the intensity of the ion beam transmitted through the interface of a mass spectrometer in order to perform automatic gain control (AGC). The ion flux is determined by either directly detecting the ion current on the conductance limiting orifice of the ion funnel or using a short mass spectrometry acquisition. Based upon the ion flux intensity, the voltage of the jet disrupter is adjusted to alter the transmission efficiency of the ion funnel to provide a desired ion population to the mass analyzer. Ion beam regulation by an ion funnel is shown to provide control to within a few percent of a targeted ion intensity or abundance. The utility of ion funnel AGC was evaluated using a protein tryptic digest analyzed with liquid chromatography Fourier transform ion cyclotron resonance (LC-FTICR) mass spectrometry. The ion population in the ICR cell was accurately controlled to selected levels, which improved data quality and provided better mass measurement accuracy.     

Adduction of solvent molecules by ions isolated within an ion trap mass spectrometer under atmospheric pressure ionisation conditions

Benzylpyridine and papaverine, an alkyl quinoline, both produce product ions containing an azepinium ring during atmospheric pressure chemical ionisation or electrospray multistage mass spectrometry. By controlling the trapping conditions, an isolated azepinium ion was held within the trap for an extended period of time without excitation. A subsequent analytical scan revealed a mass spectrum containing ions at two mass-to-charge (m/z) ratios, the first at the m/z of the isolated product ion and the second at an m/z ratio corresponding to the adduction of a molecule of solvent. Isolation and resonance excitation of the adduct ion remove the solvent molecule, resulting in recovery of the azepinium ion at the same signal intensity as the adduct ion. Isolating and trapping the ion for a further period allowed the solvent adduct ion to be re-formed. Modulation of the solvent flowing into the source while the ion was trapped allowed variation in the solvent molecule adducted to the trapped ion. The proportion of the ion current due to the adduct ion depends on the nature of the isolated ion, the proton affinity of the solvent and the length of time for which the ion was trapped. Adduct ion formation, deliberately maximised in this study, can occur to a significant extent under standard ion trap operating conditions, reducing the ion current of product ions of interest and, ultimately, the response in tandem mass spectrometric assays.     

Evolution of instrumentation for the study of gas-phase ion/ion chemistry via mass spectrometry

The scope of gas-phase ion/ion chemistry accessible to mass spectrometry is largely defined by the available tools. Due to the development of novel instrumentation, a wide range of reaction phenomenologies has been noted, many of which have been studied extensively and exploited for analytical applications. This perspective presents the development of mass spectrometry-based instrumentation for the study of the gas-phase ion/ion chemistry in which at least one of the reactants is multiply charged. The instrument evolution is presented within the context of three essential elements required for any ion/ion reaction study: the ionization source(s), the reaction vessel or environment, and the mass analyzer. Ionization source arrangements have included source combinations that allow for reactions between multiply charged ions of one polarity and singly charged ions of opposite polarity, arrangements that enable the study of reactions of multiply charged ions of opposite polarity and, most recently, arrangements that allow for ion formation from more than two ion sources. Gas-phase ion/ion reaction studies have been performed at near atmospheric pressure in flow reactor designs and within electrodynamic ion traps operated in the mTorr range. With ion trap as a reaction vessel, ionization and reaction processes can be independently optimized and ion/ion reactions can be implemented within the context of MSn experiments. Spatial separation of the reaction vessel from the mass analyzer allows for the use of any form of mass analysis in conjunction with ion/ion reactions. Time-of-flight mass analysis, for example, has provided significant improvements in mass analysis figures of merit relative to mass filters and ion traps.     

Ion detection limitations to mass resolution in matrix-assisted laser desorption time-of-flight mass spectrometry.

The ion detection process in a discrete-dynode electron multiplier can result in significant mass resolution losses in time-of-flight mass spectrometry (TOF-MS) for higher mass-to-charge (m/z) ion species. This resolution loss is attributed to propagation time delays and signal broadening in the ion detector. This is presumed to be due to the generation of a distribution of secondary ion species produced initially upon impact of a primary ion with the first dynode surface of the ion detector. Comparisons are made between the signals produced by a standard discrete dynode ion detector (which amplifies the negatively charged species produced by impact of a primary ion) and a detector modified to respond to only the positively charged secondary ion species produced by a primary ion impact. Ion signals for higher m/z ions with the standard detector geometry are seen to be due to a narrow signal component, most likely due to the generation of secondary electrons and/or very low mass secondary ions (H-), and a broad signal component, apparently due to secondary ions which take significant amounts of time to traverse the low potential fields between the first and second detector dynode. This results in ion signal tailing for higher m/z ion species. Numerical subtraction of the ion signal obtained with the standard and modified detector geometries (singly protonated molecular ion species of equine myoglobin) results in an improvement in mass resolution, such that a new adduct ion species (from trifluoroacetic acid) can be resolved.     

Product ion scanning using a Q-q-Q linear ion trap (Q TRAP) mass spectrometer

The use of a Q-q-Q(linear ion trap) instrument to obtain product ion spectra is described. The instrument is based on the ion path of a triple quadrupole mass spectrometer with Q3 operable as either a conventional RF/DC quadrupole mass filter or a linear ion trap mass spectrometer with axial ion ejection. This unique ion optical arrangement allows de-coupling of precursor ion isolation and fragmentation from the ion trap itself. The result is a high sensitivity tandem mass spectrometer with triple quadrupole fragmentation patterns and no inherent low mass cut-off. The use of the entrance RF-only section of the instrument as accumulation ion trap while the linear ion trap mass spectrometer is scanning enhances duty cycles and results in increased sensitivities by as much as a factor of 20. The instrument is also capable of all of the triple quadrupole scans including multiple-reaction monitoring (MRM) as well as precursor and constant neutral loss scanning. The high product ion scanning sensitivity allows the recording of useful product ion spectra near the MRM limit of quantitation.     

Ion/Neutral,Ion/Electron,Ion/Photon,and Ion/Ion Interactions in Tandem Mass Spectrometry: Do We Need Them All? Are They Enough?

A range of strategies and tools have been developed to facilitate the determination of primary structures of analyte molecules of interest via tandem mass spectrometry (MS/MS). The two main factors that determine the primary structural information present in an MS/MS spectrum are the type of ion generated from the analyte molecule and the dissociation method. The ion type subjected to dissociation is determined by the ionization method/conditions and ion transformation processes that might take place after initial gas-phase ion formation. Furthermore, the range of analyte-related ion types can be expanded via derivatization reactions prior to mass spectrometry. Dissociation methods include those that simply alter the population of internal states of the mass-selected ion (i.e., activation methods like collision-induced dissociation) as well as processes that rely on the transformation of the ion type prior to dissociation (e.g., electron capture dissociation). A variety of ion interactions have been studied for the purpose of ion dissociation and ion transformation, including ion/neutral, ion/photon, ion/electron, and ion/ion interactions. A wide range of phenomena have been observed, many of which have been explored/developed as means for structural analysis. The techniques arising from these phenomena are discussed within the context of the elements of structural determination in tandem mass spectrometry: ion-type definition and dissociation. Unique aspects of the various ion interactions are emphasized along with any barriers to widespread implementation.     

Key fragments for identification of positional isomer pair in glucuronides from the hydroxylated metabolites of RT-3003 (Vintoperol) by liquid chromatography/electrospray ionization mass spectrometry.

The mass spectral properties of glucuronides of the 9- and 10-hydroxylated metabolites of RT-3003 (Vintoperol; (-)-1beta-ethyl-1alpha-hydroxymethyl-1,2,3,4,6,7, 12balpha-octahydroindolo[2,3-a]quinolizine), which were fractionated by high-performance liquid chromatography with fluorescence detection, were investigated using the positive ion electrospray ionization mode. These glucuronides showed predominantly the protonated molecular ion ([M + H](+) ion), and the [M + H](+) ion provided a characteristic product ion spectrum in which abundant ions were obtained at m/z 301, 160 and 142. The first ion, corresponding to the [aglycone + H](+) ion, was produced by neutral loss of the glucuronic acid moiety from the [M + H](+) ion. The product ion spectrum of the [M + H](+) ion of hydroxy-RT-3003 revealed a number of ions common to the glucuronide spectra, suggesting that other two ions observed most likely represent fragmentation of hydroxy-RT-3003. In turn, these glucuronides were positional isomers with respect to the binding site of glucuronic acid. The structures of the isomer pairs were discriminated by the presence of the ion of m/z 318 or 336 in the product ion spectrum. These ions were produced by fission of the C-ring, the same as for the formation of the ions of m/z 160 and 142, as were observed in the product ion spectrum from the [M + H](+) ion of hydroxy-RT-3003. For the formation of these ions, an unusual fragmentation process was proposed, and these ion structures were supported by evidence from the accurate mass measurement data. Additionally, in the sulfates of hydroxylated metabolites, a similar product ion corresponding to the ion of m/z 336 found in the phenolic glucuronides was observed, and was applied for identification of the sulfate metabolites.     

离子色谱法分析金属离子的研究进展

综述了离子色谱法(IC)分析金属离子的研究进展,对目前应用于分析金属离子的阳离子交换IC、阴离子交换IC和螯合离子色谱进行了评述。阳离子交换IC是IC分析金属离子的主要形式,固定相为强酸(磺酸)型阳离子交换剂和弱酸(羧酸)型阳离子交换剂,结合适当的检测方法,阳离子交换IC可以测定碱金属、碱土金属、过渡金属、稀土离子、铵离子及低相对分子质量的有机胺类分子等。阴离子交换IC可以分析碱土金属、过渡金属、稀土离子等,对金属离子的分析具有更好的选择性,并可以实现金属离子和无机阴离子的同时测定。螯合离子色谱可以对复杂基体中的痕量金属离子进行测定。引用文献125篇。     

Current efficiency and titration efficiency in coulometric titrations with electrogenerated ceric ion determination of iodide

The current efficiency for the electrogeneration of cerie ion at a platinum anode falls considerably below 100% at both very small and at large current densities in both sulfuric and perchloric acid media. The maximal current efficiency is about 99.8%.Iodide ion can be titrated to iodine with an error of only about +0.3%, even under conditions where the cerie ion generation efficiency is only 98%. High titration efficiency, in spite of poor efficiency for ceric ion generation, is obtained because iodine is oxidized to iodate ion at a potential slightly in advance of the potential at which cerous ion is oxidized. Since the electrogenerated iodate ion oxidizes iodide ion only a minor fraction of the total quantity of electricity results from ceric ion generation, so the effect of its inefficient generation is greatly minimized. Satisfactory titrations of iodide ion to iodine can be performed without any cerous salt present, provided the generating current density is smaller than the limiting current density for oxidation of iodine to iodate ion.     

有机磷化合物的快原子轰击质谱研究 Ⅶ.N-对甲苯磺酰基-N''''-异丙基-N-取代-S-丙基磷酰二胺酯

本文讨论一类新合成的磷酰二胺酯的质谱特征。其电子轰击质谱(EIMS)分子离子峰很弱(<1%),我们采用快原子轰击质谱(FABMS),讨论其PFABMS与NFABMS的区别、取代基的影响,PFABMS与NFABMS的主要离子产生机理。     

Spatially resolved measurements of ion density behind the skimmer of an inductively coupled plasma mass spectrometer

Ions are extracted from the inductively coupled plasma through a conventional sampler and skimmer and then deposited on an array of graphite targets at the exit of a set of electrostatic ion lenses. The Sc⁺ signal is enhanced by choosing appropriate potentials on the ion lenses. The Sc⁺ signal is suppressed by the presence of concomitant Cs ions at high concentrations. Comparisons of grounded ion lenses and two different ion lens potential settings are made. The signal is enhanced more extensively by the ion lenses when there are no concentrated concomitant ions. This study indicates that matrix effects in inductively coupled plasma mass spectrometry could possibly be alleviated by choosing ion lens potentials such that the ions enter the ion optics with a relatively broad beam cross section, the beam then being focused to a smaller size. A photon stop inside the ion lens stack reduces ion transmission and changes the shape of the beam profile from conical to bimodal.     

Reduction of Iron(III) Ion by Activated Carbon Fiber

The mechanisms of adsorption of iron(II) ion, iron(III) ion, and reduced iron(III) ion onto an activated carbon fiber and the ability of carbon fibers to reduce iron(III) ion were investigated on the basis of the amounts of iron ion adsorbed. The amount of iron(II) ion adsorbed onto the activated carbon fiber increased with increasing adsorption temperature. Iron(II) ion was more easily removed by the activated carbon fiber than iron(III) ion. Iron(III) ion was adsorbed onto the activated carbon fiber after being reduced to iron(II) ion. The reduction ability of A-20 was stronger than that of A-10 because the hydrophilic groups of A-20 were larger than those of A-10. It is concluded that the activated carbon fiber has a reduction effect on iron(III) ion and that the reduction effect of the activated carbon fiber depended on the number of hydrophilic groups on the activated carbon fiber. Copyright 2000 Academic Press.     

Ion mobility spectrometric analysis of vaporous chemical warfare agents by the instrument with corona discharge ionization ammonia dopant ambient temperature operation

The ion mobility behavior of nineteen chemical warfare agents (7 nerve gases, 5 blister agents, 2 lachrymators, 2 blood agents, 3 choking agents) and related compounds including simulants (8 agents) and organic solvents (39) was comparably investigated by the ion mobility spectrometry instrument utilizing weak electric field linear drift tube with corona discharge ionization, ammonia doping, purified inner air drift flow circulation operated at ambient temperature and pressure. Three alkyl methylphosphonofluoridates, tabun, and four organophosphorus simulants gave the intense characteristic positive monomer-derived ion peaks and small dimer-derived ion peaks, and the later ion peaks were increased with the vapor concentrations. VX, RVX and tabun gave both characteristic positive monomer-derived ions and degradation product ions. Nitrogen mustards gave the intense characteristic positive ion peaks, and in addition distinctive negative ion peak appeared from HN3. Mustard gas, lewisite 1, o-chlorobenzylidenemalononitrile and 2-mercaptoethanol gave the characteristic negative ion peaks. Methylphosphonyl difluoride, 2-chloroacetophenone and 1,4-thioxane gave the characteristic ion peaks both in the positive and negative ion mode. 2-Chloroethylethylsulfide and allylisothiocyanate gave weak ion peaks. The marker ion peaks derived from two blood agents and three choking agents were very close to the reactant ion peak in negative ion mode and the respective reduced ion mobility was fluctuated. The reduced ion mobility of the CWA monomer-derived peaks were positively correlated with molecular masses among structurally similar agents such as G-type nerve gases and organophosphorus simulants; V-type nerve gases and nitrogen mustards. The slope values of the calibration plots of the peak heights of the characteristic marker ions versus the vapor concentrations are related to the detection sensitivity, and within chemical warfare agents examined the slope values for sarin, soman, tabun and nitrogen mustards were higher. Some CWA simulants and organic solvents gave the ion peaks eluting at the similar positions of the CWAs, resulting in false positive alarms.     

Transmission mode ion/ion reactions in the radiofrequency‐only ion guide of hybrid tandem mass spectrometers

Transmission mode ion/ion reactions have been performed within the first quadrupole, the Q0 radiofrequency (RF)‐only quadrupole, of two types of hybrid tandem mass spectrometers (viz., triple quadrupole/linear ion trap and QqTOF instruments). These transmission mode reactions involved the storage of either the reagent species and the transmission of the analyte species through the Q0 quadrupole for charge inversion reactions or the storage of the analyte ions and transmission of the reagent ions as in charge reduction experiments. A key advantage to the use of transmission mode ion/ion reactions is that they do not require any instrument hardware modifications to provide interactions of oppositely charged ions and can be implemented in any instrument that contains a quadrupole or linear ion trap. The focus of this work was to investigate the potential of using the RF‐only quadrupole ion guide positioned prior to the first mass‐resolving element in a tandem mass spectrometer for ion/ion reactions. Two types of exemplary experiments have been demonstrated. One involved a charge inversion reaction and the other involved a charge reduction reaction in conjunction with ion parking. Ion/ion reactions proved to be readily implemented in Q0 thereby adding significantly greater experimental flexibility in the use of ion/ion reaction experiments with hybrid tandem mass spectrometers. Copyright © 2009 John Wiley & Sons, Ltd.