Search PubMed⌕ Search

SEARCH · Search PubMed

Results for “IONS”

Search indexed PubMed citations on genomics, clinical trials, systematic reviews and public health. Explore titles, authors and supplied subject terms, then open the PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6Linked to original sources
PubMed2002

Ion parking during ion/ion reactions in electrodynamic ion traps.

Under appropriate ion density conditions, it is possible to selectively inhibit rates of ion/ion reactions in a quadrupole ion trap via the application of oscillatory voltages to one or more electrodes of the ion trap. The phenomenon is demonstrated using dipolar resonance excitation applied to the end-cap electrodes of a three-dimensional quadrupole ion trap. The application of a resonance excitation voltage tuned to inhibit the ion/ion reaction rate of a specific range of ion mass-to-charge ratios is referred to as "ion parking". The bases for rate inhibition are (i) an increase in the relative velocity of the ion/ion reaction pair, which reduces the cross section for ion/ion capture and, at least in some cases, (ii) reduction in the time of physical overlap of positively charged and negatively charged ion clouds. The efficiency and specificity of the ion parking experiment is highly dependent upon ion densities, trapping conditions, ion charge states, and resonance excitation conditions. The ion parking experiment is illustrated herein along with applications to the concentration of ions originally present over a range of charge states into a selected charge state and in the selection of a particular ion from a set of ions derived from a simple protein mixture.

Animals↗
PubMed1959

Parameters of gaseous ion effects on the mammalian trachea. A. Duration of effects. B. Minimal effective ion densities.

A. Duration of Effects Groups of mice exposed to high densities of unipolar light air ions for 72 hours exhibited persistent alterations in the functional efficiency of their tracheas. These effects lasted at least 4 weeks, and in the case of animals treated with (+) ions included diminished ciliary activity, pale and contracted tracheal mucosa, and enhanced vulnerability to trauma. Following treatment with (-) ions, animals displayed increased ciliary activity with no other detectable changes. It required at least 60 minutes of exposure to ions to induce such "permanent" functional changes. B. Minimal Effective Ion Densities The minimal ion densities producing changes in ciliary activity within an arbitrary period of 30 minutes were determined with extirpated tracheal strips from rabbits and guinea pigs. The threshold value for (-) ions was approximately 2.5 x 10(3) ions/cm.(2)/sec. and that for (+) ions was in the range between 1 x 10(4) and 2.5 x 10(5) ions/cm.(2)/sec.The minimal ion densities producing changes in ciliary activity within an arbitrary period of 30 minutes were determined with extirpated tracheal strips from rabbits and guinea pigs. The threshold value for (-) ions was approximately 2.5 x 10(3) ions/cm.(2)/sec. and that for (+) ions was in the range between 1 x 10(4) and 2.5 x 10(5) ions/cm.(2)/sec. The evidence indicates that ion-induced functional changes in the ciliated epithelium of the pulmonary tree are the results of direct contact of ions with surface cells and do not involve participation of the central nervous system or circulation. So far as ciliary activity is concerned, the number of ions required to produce a change in rate is very small.

Animals↗
PubMed1994

The responses to choline ions induced by transition metal ions in single water fibers of the frog glossopharyngeal nerve.

In single water-sensitive fibers (water fibers) of the frog glossopharyngeal nerve, application of a solution of 500 mM choline C1 to the tongue elicited responses of varying magnitude. Some water fibers (plain choline-insensitive water fibers) barely responded to the solution, while some water fibers (plain choline-sensitive water fibers) exhibited a considerable response to this solution. NiCl2, which is barely effective in producing neural response at concentrations below 5 mM, induced the response of plain choline-insensitive water fibers to choline+ ions. It was confirmed, in a collision test, that the Ni(2+)-induced responses to choline+ ions were derived from water fibers. However, NiCl2 did not affect the magnitude of the response generated by choline+ ions in plain choline-sensitive water fibers. The concentration-response curve for choline C1 in the presence of 1 mM NiCl2 for plain choline-insensitive water fibers was similar to the curves obtained in the absence of NiCl2 for plain choline-sensitive water fibers. Other organic salts, such as tris(hydroxymethyl)aminomethane-HCl, triethanolamine-HCl and tetraethylammonium C1, elicited no response or only a very small response from water fibers, and NiCl2 did not affect these responses. It is suggested that there exists a choline receptor for the response to choline+ ions in the apical membrane of frog taste cells and that Ni2+ ions expose the sites of such choline receptors, which are deeply embedded in the receptor membrane, to the outside medium. The effect of Ni2+ ions results in an increase in the number of the choline receptor sites available for binding of choline+ ions. The rank order of effectiveness of transition metal ions in eliciting the appearance or enhancement of the response to choline C1 was Ni2+ > Co2+ > Mn2+. Mg2+ ions had no effect on the response to choline+ ions. A similar rank order was previously obtained in enhancement of the responses to Ca2+, Mg2+ and Na+ ions (Kitada, 1994a). It seems likely that the mechanism for enhancement or elicitation of the response to choline+ ions by the transition metal ions has features in common with that for enhancement of the responses to Ca2+, Mg2+ and Na+ ions.

Animals↗
PubMed1992

Secondary-ion and electron production from surfaces bombarded by large polyatomic ions.

Heavy molecular ions with energies in the range 10-20 keV and masses from 276 u to 132,000 u, produced by matrix-assisted laser desorption, were used as primary projectiles to produce secondary-ion spectra from a variety of surfaces in a tandem time-of-flight mass spectrometer. In the negative mode the ratio of electron emission to secondary-ion emission was found to decrease rapidly with increasing projectile mass. Ion emission was found to dominate for primary ions larger than approximately 10,000 u. Positive or negative molecular ions and cations were observed from several organic targets of masses up to 1140 u (gramicidin S) for incident projectiles up to mass 132,000 u, i.e., for projectile speeds down to approximately 7000 m/s. Other ions characteristic of the target were also observed for these projectiles. Thus, large polyatomic ions can cause secondary-ion desorption even at very low velocity. The background ions of both polarities are similar to those found in keV particle bombardment by monatomic projectiles. The same ions are observed for all the projectiles; most can be identified with hydrocarbon background. The relative intensities of the background positive ions are largely independent of projectile, and for both polarities the ratio of the ions characterizing the target to those forming the background is approximately constant for all the projectiles. These results strongly suggest that the background ions come from the usual layer of organic impurities attached to the target surface. No direct evidence for surface-induced dissociation was observed in this mass and energy range.

Mass Spectrometry↗
PubMed2000

An interface with a linear quadrupole ion guide for an electrospray-ion trap mass spectrometer system.

A new ion sampling interface for an electrospray ionization 3D ion trap mass spectrometer system is described. The interface uses linear rf quadrupoles as ion guides and ion traps to enhance the performance of the 3D trap. Trapping ions in the linear quadrupoles is demonstrated to improve the duty cycle of the system. Dipolar excitation of ions trapped in a linear quadrupole is used to eject unwanted ions. A resolution of ejection of up to 254 is demonstrated for protonated reserpine ions (m/z 609.3). A composite waveform with a notch in frequency space is used to eject a wide range of matrix ions and to isolate trace analyte ions in a linear quadrupole before ions are injected into the 3D trap. This is useful to overcome space charge problems in the 3D trap caused by excess matrix ions. For trace reserpine in a 500-fold molar excess of poly(propylene glycol) (PPG), it is demonstrated that the resolution and sensitivity of the 3D trap can be increased dramatically with ejection of the excess PPG matrix ions. In comparison to ejection of matrix ions in the 3D trap with a similar broad-band waveform, a 5-fold increase in sensitivity with a 7 times shorter acquisition time was achieved.

Journal Article↗
PubMed2002

An absorption-based surface plasmon resonance sensor applied to sodium ion sensing based on an ion-selective optode membrane.

A surface plasmon resonance (SPR) sodium ion sensor using an ion optode membrane film was experimentally and theoretically described based on an absorption-based SPR principle proposed in our previous article (Kurihara, K; Suzuki, K. AnaL Chem. 2002, 74, 696-701). The sodium ion concentrations from 10(-6) to 10(-1) have been successfully determined not only by the resonance angle diagnosis of the SPR curve but also by the minimum reflectance one. The ion optode film was plasticized poly(vinyl chloride) including a neutral sodium ionophore, a pH-sensitive cationic dye, and an anionic additive. Its optical absorption intensity changed with the sodium ion concentrations. The SPR ion sensor physically measured the complex refractive index caused by the absorption in the ion optode film. We have exhaustively investigated the experimental response behavior of the SPR curve relative to the sodium ion concentrations by comparison with numerically simulated SPR curves using a three-layer Fresnel equation including experimental values for the sodium ion optode membrane film. As predicted by the absorption-based SPR principle, the SPR curve behavior of the SPR ion sensors depended on two factors: one was the relation between the excitation frequency of the light source and the absorption maximum frequency in the ion optode film while the other was the gold metallic thickness in the Kretchmann configuration. The concept and practical theory of an absorption-based SPR sensor not only have been proved by the experimental results of the SPR sodium ion sensor but also have successfully allowed flexible ion sensing in an SPR sensor, which would be very difficult without the absorption mechanism in the ion optode film.

Journal Article↗
PubMed1999

Analysis of VX on soil particles using ion trap secondary ion mass spectrometry.

The direct detection of the nerve agent VX (methylphosphonothioic acid, S-[2-[bis(1-methylethyl)amino]ethyl] O-ethyl ester) on milligram quantities of soil particles has been achieved using ion trap secondary ion mass spectrometry (IT-SIMS). VX is highly adsorptive toward a wide variety of surfaces; this attribute makes detection using gas-phase approaches difficult but renders the compound very amenable to surface detection. An ion trap mass spectrometer, modified to perform SIMS, was employed in the present study. A primary ion beam (ReO4-) was fired on axis through the ion trap, where it impacted the soil particle samples. [VX + H]+, [VX + H]+ fragment ions, and ions from the chemical background were sputtered into the gas-phase environment of the ion trap, where they were either scanned out or isolated and fragmented (MS2). At a surface concentration of 0.4 monolayer, intact [VX + H]+, and its fragment ions, were readily observable above background. However, at lower concentrations, the secondary ion signal from VX became obscured by ions derived from the chemical background on the surface of the soil particles. MS2 analysis using the ion trap was employed to improve detection of lower concentrations of VX: detection of the 34S isotopic ion of [VX + H]+, present at a surface concentration of approximately 0.002 monolayer, was accomplished. The study afforded the opportunity to investigate the fragmentation chemistry of VX. Semiempirical calculations suggest strongly that the molecule is protonated at the N atom. Deuterium labeling showed that formation of the base peak ion (C2H4)N(i-C3H7)2+ involves transfer of the amino proton to the phosphonothioate moiety prior to, or concurrent with, C-S bond cleavage. To manage the risk associated with working with the compound, the vacuum unit of the IT-SIMS was located in a hood, connected by cables to the externally located electronics and computer.

Chemical Warfare Agents↗
PubMed1981

Metal ion substitution at the catalytic site of horse-liver alcohol dehydrogenase: results from solvent magnetic relaxation studies. 2. Binding of manganese(II) and competition with zinc(II) and cadmium(II) ions.

The interaction of Mn2+ aquo ions with native horse-liver alcohol dehydrogenase demetalized specifically at the catalytic sites has been investigated by studying the magnetic field dependence and time dependence of the magnetic spin-lattice relaxation rate of solvent water protons. We find no detectable binding of Mn2+ ions to the catalytic sites in times on the order of hours; however, we do find that these ions bind to the enzyme at two previously unreported types of sites: one, characterized by a low dissociation constant (0.01 mM at pH 7.7, 5 degrees C), low relaxivity, and a stoichiometry of one per two catalytic sites, and a second, with a high dissociation constant (1.5 mM at pH 7.7, 5 degrees C) and high relaxivity. The stoichiometry of the second type of site could not be determined because of the relatively weak bindng of Mn2+ ions to these sites. Both Zn2+ and Cd2+ ions bind to the newly found tight-binding sites, displacing Mn2+ ions and thereby altering the relaxation rates of solvent protons. By monitoring the return to equilibrium of these altered rates, we find that Zn2+ ions enter the catalytic sites from the new tight-binding sites with an on-rate of approximately 0.1 M-1 s-1. It is not clear whether binding to these new sites is an obligatory intermediate for reintroduction of Zn2+ ions into the catalytic sites, but a small excess of Zn2+ ions beyond one per monomer causes the protein to precipitate. Cd2+ ions, by contrast, enter the catalytic sites at least 1 order of magnitude more rapidly than do Zn2+ ions, a rate too rapid to observe by our techniques. However, once the catalytic sites are filled, Cd2+ ions displace Mn2+ ions at the new sites as do Zn2+ ions.

Alcohol Dehydrogenase↗
PubMed2006

Simulations of ion trapping in a micrometer-sized cylindrical ion trap.

We have performed detailed SIMION simulations of ion behavior in micrometer-sized cylindrical ion traps (r0 = 1 microm). Simulations examined the effects of ion and neutral temperature, the pressure and nature of cooling gas, ion mass, trap voltage and frequency, space-charge, fabrication defects, and other parameters on the ability of micrometer-sized traps to store ions. At this size scale voltage and power limitations constrain trap operation to frequencies about 1 GHz and rf amplitudes of tens of volts. Correspondingly, the pseudopotential well depth of traps is shallow, and thermal energies contribute significantly to ion losses. Trapping efficiency falls off gradually as qz approaches 0.908, possibly complicating mass-selective trapping, ejection, or quantitation. Coulombic repulsion caused by multiple ions in a small-volume results in a trapping limit of a single ion per trap. If multiple ions are produced in a trap, all but one ion are ejected within a few microseconds. The remaining ion tends to have favorable trapping parameters and a lifetime about hundreds of microseconds; however, this lifetime is significantly shorter than it would have been in the absence of space-charge. Typical microfabrication defects affect ion trapping only minimally. We recently reported (IJMS 2004, 236, 91-104) on the construction of a massively parallel array of ion traps with dimensions of r0 = 1 microm. The relationship of the simulations to the expected performance of the microfabricated array is discussed.

Computer-Aided Design↗
PubMed2001

Effect of lipophilic ion-exchanger leaching on the detection limit of carrier-based ion-selective electrodes.

The equilibrium partitioning of lipophilic ion-exchanger salts from ion-selective polymeric membrane electrodes (ISEs) and its possible effect on the lower detection limit of these sensors is described. Predictions are made on the basis of various parameters, including the knowledge of tetraphenylborate potassium salt partitioning constants, the selectivity of ionophore-free ion-exchanger membranes, and ionophore stability constants in the membrane. Ion-exchanger lipophilicities are significantly increased if the membrane contains an ionophore that strongly binds the primary ion. Predicted detection limits are on the order of 10(-5)-10(-8) M for ionophore-free membranes, and may reach levels as low as 10(-18) M with adequate ionophores in the membrane. Experiments are performed for well-described lead-selective membranes containing different tetraphenylborate derivatives, and detection limits appear to be independent of the ion-exchanger used. However, they are much higher if a more hydrophilic carborane cation-exchanger is incorporated in the membrane. The first finding confirms recent theory, which states that transmembrane ion fluxes, given by a small level of ion-exchange at the sample side by interfering ions, normally dictate the detection limit of these sensing systems. Predicted detection limits on the basis of ion-exchanger leaching alone are here listed for a number of analytically relevant cases. For potassium-selective electrodes containing BME-44 and tetraphenylborate as ion-exchanger, the experimental detection limits are in agreement with predicted values. These results suggest that the detection limit of many current ISEs for ultratrace level analysis are, in optimal cases, dictated by transmembrane ion fluxes; however, because improved chemical solutions are being developed to reduce such effects, simple ion-exchanger partitioning may indeed become an important mechanism that can give higher detection limits than practically desired, and should not be ruled out.

Biosensing Techniques↗
PubMed2001

Electrospray ionization tandem mass spectrometric study of salt cluster ions. Part 1--investigations of alkali metal chloride and sodium salt cluster ions.

Salt cluster ions of alkali metal chlorides ACl (A = Li(+), Na(+), K(+), Rb(+) and Cs(+)) and sodium salts NaB (B = I(-), HCOO(-), CH(3)COO(-), NO(2)(-), and NO(3)(-)), formed by electrospray ionization, were studied systematically by mass spectrometry. The influences on the total positive ion and negative ion currents of variation of solvent, solution concentration, desolvation temperature, solution flow-rate, capillary voltage and cone voltage were investigated. Only cone voltage was found to influence dramatically the distribution of salt cluster ions in the mass spectra observed. Under conditions of normal cone voltage of approximately 70 V, cluster ions having magic numbers of molecules are detected with high relative signal intensity. Under conditions of low cone voltage of approximately 10 V, the distribution of cluster ions detected is characterized by a relatively low average mass/charge ratio due to the presence of multiply charged cluster ions; in addition, there is a marked reduction in cluster ions having a magic number of molecules. Product ion mass spectra obtained by tandem mass spectrometry of cluster ions are characterized by a base peak having a magic number of molecules that is less than and closest to the number of molecules in the precursor ion. Structures have been proposed for some dications and some quadruply charged ions. At pH 3 and 11, the mass spectra of NaCl clusters show the presence of mixed clusters of NaCl with HCl and NaOH, respectively. The effects of ionic radius on 20 distributions of cluster ions for 10 salts were investigated; however, the fine structure of these effects is not readily discerned.

Journal Article↗
PubMed2005

Comparison of the effects of ionization mechanism, analyte concentration, and ion "cool-times" on the internal energies of peptide ions produced by electrospray and atmospheric pressure matrix-assisted laser desorption ionization.

The propensities of a series of peptide ions produced by both electrospray and atmospheric pressure matrix assisted laser desorption ionization (AP-MALDI) to fragment in an ion trap mass spectrometer under various conditions were studied in detail by measuring the extent of fragmentation of precursor ions by collision induced dissociation (CID) as a function of applied resonance excitation RF voltage. For the most basic peptides, the energy required to fragment MH+ ions generated by electrospray exceeded that required to fragment equivalent AP-MALDI ions under identical instrumental conditions; the reverse was observed for a peptide incorporating no basic residues, while peptides of intermediate basicity showed little difference between the ionization methods. This correlation between peptide basicity and the difference in the energy required to induce fragmentation of MH+ ions generated by AP-MALDI and electrospray is attributed primarily to a trend in the internal energies of the ions generated by AP-MALDI (the greater the difference in gas-phase basicities between the matrix and the analyte the greater the internal energy of the analyte ions produced). Furthermore the internal energies of ions produced by AP-MALDI, but not the equivalent ions formed by electrospray, were observed to decrease with decreasing analyte concentration. We attribute this finding to the cooling effect of endothermic dissociation of analyte ion/matrix molecule clusters following the matrix assisted laser desorption step. Time-resolved analyses (measurement of extent of fragmentation of precursor ions by CID as a function of pre-CID "cool times") revealed that cooling periods in excess of 250 ms were required to achieve internal energy equilibrium through cooling collisions with the helium buffer gas. Furthermore, these analyses demonstrated that, even after these extended cooling times, equivalent ions formed by the two ionization techniques showed different propensities to fragment. We conclude that the two different ionization techniques produce ion populations that may differ in their three-dimensional structure.

Atmospheric Pressure↗
PubMed2000

Measurement of collision-induced dissociation rates for tantalum oxide ions in a quadrupole ion trap.

A study of factors influencing the collision-induced dissociation (CID) rate of strongly bound diatomic ions effected via resonance excitation in a quadrupole ion trap is presented. From these studies, an approach to measuring the CID rates is described wherein product ion recovery is optimized and the effect of competitive processes (e.g., parent ion ejection and product ion reactions) on rate measurements are prevented from influencing rate measurements. Tantalum oxide ions (dissociation energy = 8.2 eV), used as a model system, were formed via reactions of glow discharge generated Ta+ ions with residual gases in the ion trap. Neon (0.5 mtorr) was found to be a more favorable target gas for the dissociation of TaO+ than He and Ar, but collisional activation of TaO+ ions in neon during ion isolation by mass selective instability necessitated ion cooling prior to dissociation. A 25 ms delay time at qz = 0.2 allowed for kinetic cooling of stored TaO+ ions and enabled precise dissociation rate measurements to be made. CID of TaO+ was determined to be most efficient at qz = 0.67 (226 kHz for m/z 197). Suitable resonance excitation voltages and times ranged from 0.56 to 1.2 V(p-p) and 1 to 68 ms, respectively. Under these conditions, measurement of rates approaching 80 s(-1) for the dissociation of TaO+ could be made without significant complications associated with competing processes, such as ion ejection.

Journal Article↗
PubMed2002

Reactivity and selectivity of the N-acetyl-Glu-P-1, N-acetyl-Glu-P-2, N-acetyl-MeIQx, and N-acetyl-IQx nitrenium ions: comparison to carbocyclic N-arylnitrenium ions.

The model ultimate carcinogens 1a-d, related to the metabolites of the food-derived carcinogenic heterocyclic amines Glu-P-1, Glu-P-2, MeIQx, and IQx, spontaneously decompose in neutral aqueous solution to generate the heterocyclic nitrenium ions, 2a-d. The less reactive esters 1a and 1b also undergo acid-catalyzed ester hydrolysis to generate the corresponding hydroxamic acids at pH <2, while the more reactive 2c and 2d are prone to rearrangement in nonaqueous solvents. The reactions of the nitrenium ions with AcO(-), HPO(4)(2-), N(3)(-), and 2'-deoxyguanosine (d-G) were characterized in aqueous solution by using a combination of competitive trapping methods and product isolation and identification. The reactions with N(3)(-) and d-G generally follow patterns previously established for carbocyclic nitrenium ions, but the reactions with AcO(-) and HPO(4)(2-) are unusual. Similar reactions have previously only been reported for heterocyclic 1-alkyl-2-imidazolium ions. The N(3)(-)/solvent selectivities of these ions (5.1 x 10(6) M(-1) for 2a, 2.3 x 10(6) M(-1) for 2b, 1.2 x 10(5) M(-1) for 2c, and 5.2 x 10(4) M(-1) for 2d) are comparable to those of highly selective carbocyclic nitrenium ions. If k(az) for these ions is diffusion limited at ca. 5 x 10(9) M(-1) s(-1) the aqueous solution lifetimes of these ions range from 10 micros (2d) to 1 ms (2a). These ions are also highly selective for trapping by d-G, but comparisons to other nitrenium ions show that they are 10- to 50-fold less selective for trapping by d-G than they would be if both the N(3)(-) and d-G reactions were diffusion limited. This is not a consequence of their heterocyclic structures. Several carbocyclic ions show similar behavior. The relatively inefficient trapping of 2c and 2d by d-G may account for the observation of the unusual minor N-2 d-G adduct that is isolated for both of these nitrenium ions, but has not previously been observed for the reactions of other nitrenium ions with monomeric d-G.

Acetylation↗
PubMed1997

Injection of externally generated ions into an increasing trapping field of a quadrupole ion trap mass spectrometer.

Trapping ions injected into a quadrupole ion trap (QIT) by increasing the trapping r.f. voltage on a ring electrode is an effective and widely recognized method of interfacing an ion trap with pulsed ion sources such as matrix-assisted laser desorption/ionization (MALDI). In this paper, the problem of mass discrimination during the injection and trapping of ions by the increasing r.f. field was studied both experimentally and by numerical simulation using SIMION software. For a MALDI/QIT interface design with a remote external ion source described here, experiments with polyethylene glycol (PEG 1000 and PEG 1500) showed little mass discrimination for trapping ions in a wide mass range (500-2000 Dn) for a broad range of experimental conditions, which include kinetic energies of 5-40 eV for the injected ions and an r.f. voltage of 400-4000 Vo-p amplitude ramped at a rate of 30-140 Vo-p mus-1. In the numerical simulation, complex and sharp dependences of the trapping efficiency on the phase of the r.f. voltage and initial kinetic energy of ions were observed. However, after averaging over the r.f. phase and over a reasonable range of kinetic energy, the simulation resulted in relatively constant and high values for the trapping efficiency (normally 0.2-0.3) for any mass and kinetic energy considered, which are consistent with the weak sensitivity to injection parameters observed in the experiment. A simple model for the qualitative description of ion injection and trapping is suggested that relies on phase interaction of injected ions with the r.f. field rather than on collisions with the buffer gas molecules to decrease the ion kinetic energy.

Computer Simulation↗