Ion Source Of Mass Spectrometer Research Articles

Onset of oxidative damage in α-crystallin by radical probe mass spectrometry

The early onset oxidative damage within segments of the protein α-crystallin is examined by radical probe mass spectrometry by its treatment with reactive oxygen species under low-, moderate-, and high-oxidizing conditions. Five regions comprising the first 11 residues of the N-termini of the A and B subunits (A/B:1–11), central domains from each subunit B:57–69 and A:104–112, and a C-terminal segment of the A subunit A:120–145 were found to be the initial sites of oxidation. The susceptibility of each segment to oxidation and oxidative damage is investigated by subjecting the intact protein to different oxidation conditions within the ion source of an electrospray ionization mass spectrometer. LC–MS of the oxidized protein digests enables the sites and levels of oxidation to be monitored. The onset of oxidative damage and the levels of oxidation observed before damage occurs differ across the protein surface. The regions comprising residues A/B:1–11 and A:104–112 are shown to be more susceptible to oxidative damage than those comprising residues B:57–69 and A:120–145. The results are discussed in the context of available experimental and homology-modeled theoretical structures for the subunits of α-crystallin.

Shotgun lipidomics of phosphoethanolamine-containing lipids in biological samples after one-step in situ derivatization

This article presents a novel methodology for the analysis of ethanolamine glycerophospholipid (PE) and lysoPE molecular species directly from lipid extracts of biological samples. Through brief treatment of lipid extracts with fluorenylmethoxylcarbonyl (Fmoc) chloride, PE and lysoPE species were selectively derivatized to their corresponding carbamates. The reaction solution was infused directly into the ion source of an electrospray ionization mass spectrometer after appropriate dilution. The facile loss of the Fmoc moiety dramatically enhanced the analytic sensitivity and allowed the identification and quantitation of low-abundance molecular species. A detection limitation of attomoles (amoles) per microliter for PE and lysoPE analysis was readily achieved using this technique (at least a 100-fold improvement from our previous method) with a >15,000-fold dynamic range. Through intrasource separation and multidimensional mass spectrometry array analysis of derivatized species, marked improvements in signal-to-noise ratio, molecular species identification, and quantitation can be realized. The procedure is both simple and effective and can be extended to analyze many other lipid classes or other cellular metabolites by adjustments in specific derivatization conditions. Thus, through judicious derivatization, a new dimension exploiting specific functional reactivities in each lipid class can be used in conjunction with shotgun lipidomics to penetrate farther into the low-abundance regime of cellular lipidomes.

Gas-Phase Halide Affinity of Aliphatic Alcohols Estimated by the Kinetic Method

The chloride affinity of ethanol was determined by the kinetic method by examining the dissociation of the [EtOH—Cl—HOR]− dimers (ROH=methanol, 1-propanol, 2-propanol and tert-butanol), generated in the ion source of a triple quadrupole mass spectrometer using chloroform as the chemical ionization reagent. Dimer mass selection and collision-induced dissociation using argon furnished, as products, the two individual alcohol–chloride anionic complexes, i.e. [EtOH+Cl]− and [ROH+Cl]−. The natural logarithm of the ratio of their abundances, i.e. ln ([ROH+Cl]–/[EtOH+Cl]−), correlated linearly with the experimental ROH chloride affinity. Using this linear relationship, the chloride affinity of ethanol is determined to be 43±3 kJ mol−1, which is consistent with the literature value of 43.5±8.4 kJ mol−1. From the slope of the kinetic method plot, an effective temperature of 643 ± 25 K was calculated, suggesting the weakly-bound nature of the cluster ions. The validity of the results was confirmed using the extended version of the kinetic method which showed that there is a negligible difference (–0.06 J mol K−1) in the entropy requirements of the two fragmentation channels. It is also demonstrated that this methodology can be applied to estimate the analogous bromide and fluoride affinities of aliphatic alcohols and to estimate halide affinities not previously known. Thus, these cases constitute additional examples of the advantageous application of the kinetic method in the determination of unknown thermochemical properties. Furthermore, in the dissociation of [EtOH—Cl—HO–CH2–CH2–Y]− cluster ions (Y=F, Cl, OMe and Me), a remarkable linear relationship was observed between the natural logarithm of abundance of product ratios, i.e. ln ([Y–CH2–CH2OH+Cl]−/[EtOH+Cl]−) and the electronegativity of the Y substituent. This is ascribed to the inductive effect in stabilizing the charge on chloride in the cluster ion.

Rearrangements of transient neutral molecules in the gas phase. Does the conversion of CCCHO to HCCCO involve oxygen or hydrogen migration?

Stable (CC13CHO)- may be formed in the chemical ionisation ion source of a VG ZAB 2HF mass spectrometer by the SN2(Si) reaction between Me3SiC[triple bond]C13CHO and F-. Vertical (Franck-Condon) one-electron oxidation of (CC13CHO)- in the first of the tandem collision cells of a VG ZAB 2HF mass spectrometer gives CC13CHO. Some of these neutrals have sufficient excess energy to effect rearrangement to HCC13CO, some of which are energised and to decompose to HCC. and 13CO. Thus the neutral rearrangement exclusively involves H migration: no products from O migration are detected. The corresponding two-electron oxidation of (CC13CHO)- gives mainly unrearranged (CC13CHO)+. A minority of these cations are energised and rearrange by H and O migration to yield (HCC13CHO)+ and (OCC13CHO)+ respectively. All experimental observations are backed up by molecular modelling at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory.

The effect of N2O on the isotopic composition of air‐CO2 samples

The ionisation efficiencies of N2O vs. CO2 as well as their ratios were measured in detail introducing clean N2O and CO2 into the electron impact ion source of an isotope ratio mass spectrometer. Changes in the ionisation efficiency ratio (IER) were found for different electron energy settings and compared with the ratios of literature ionisation cross-section values for pure N2O and CO2. To establish the influence of mixtures of N2O and CO2 in a mass spectrometer, artificial air mixtures were prepared by mixing different amounts of N2O and CO2 from well-calibrated spike cylinders with CO2-free air. The mixing ratios varied from 8-512 ppb for N2O and from 328-744 ppm for CO2. With these mixtures the effects of varying N2O concentrations on apparent CO2 isotope ratios in air samples were determined. After applying a mass balance correction the delta13C results were consistent within small error margins. The data seemed almost independent from a particular choice for the IER of N2O vs. CO2 in the correction algorithm. For delta18O a small effect of the ionisation efficiency ratio of N2O vs. CO2 was found. Several sets of calculations were made varying the IER between 0.88 and 0.62. The dependence of delta18O was the smallest with an adopted IER of 0.68-0.72 in the mass balance correction equation for isotopic analysis of CO2 in air. For high-precision measurements of the CO2 stable isotope ratios in air samples a careful assessment of the mass spectrometer performance is necessary. Different ion sources, even different ion source settings, alter the IER of N2O vs. CO2 which is used in the N2O correction algorithm. Preferably, the specific mass spectrometric behaviour should be established with clean N2O/CO2 mixtures or with air mixtures covering a larger range of N2O concentrations.

Effective elimination of isobaric ions interference and precise thermal ionization mass spectrometer analysis for boron isotope

An ionization depressor, 1% H 3PO 4 was used to eliminate the isobaric interference that has been of a great concern during the procedure of boron isotopic ratio analysis by thermal ionization mass spectrometer (TIMS). Our experiments have shown that it appears to be an effective method to completely restrain the formation of isobaric ions of CNO − and Cs 2CNO + in the ionization source of mass spectrometer. We have also discussed the optimum proportion of depressor to nitrite for precise analysis of boron isotopes in natural samples based on a conditional experiment. In this case, the pretreatment of boron extraction from natural samples is greatly simplified since it is not necessary to remove nitrite and organic matter completely. In virtue of the method, we determined boron isotope in different types of natural samples, and our results are consistent with previous reports.

The computer controlling of the time delay of the extraction of ions from the ion source of the TOF mass spectrometer

Computer control of time delay of the extraction of ions from the ion source of the TOF mass spectrometer is presented. Owing to the computer, the user has the full control of power parameters and ion current delay, which is about microseconds.

Direct quantitative analysis of organic compounds in the gas and particle phase using a modified atmospheric pressure chemical ionization source in combination with ion trap mass spectrometry.

A slightly modified atmospheric pressure chemical ionization source is employed for direct quantitative analysis of volatile or semivolatile organic compounds in air. The method described here is based on the direct introduction of an analyte in the gas or particle phase, or both, into the ion source of a commercial ion trap mass spectrometer. For quantitation, a standard solution is directly transferred into the vaporizer unit of the ion source via a deactivated fused-silica capillary by using the sheath liquid syringe pump, which is part of the mass spectrometer. The standard addition procedure is conducted by varying the pump rate of a diluted solution of the standard compound in methanol/water. A N2 sheath gas flow is applied for optimal vaporization and mixing with the analyte gas stream. By performing detailed reagent ion monitoring experiments, it is shown that the relative signal intensity of [M + H]+ ions is dependent on the relative humidity of the analyte gas stream as well as the composition and concentration of CI reagent ions. The method is validated by a comparison of the standard addition results with a calibration test gas of known concentration. To demonstrate the potential of atmospheric pressure chemical ionization mass spectrometry as a quantitative analytical technique for on-line investigations, a tropospherically relevant reaction is carried out in a 493-L reaction chamber at atmospheric pressure and 296 K in synthetic air at 50% relative humidity. Finally, the applicability of the technique to rapidly differentiate between analytes in the gas and particle phase is demonstrated.

Gas phase generation of the neutrals H2CCCCO, HCCCCDO and CCCHCHO from anionic precursors. Rearrangements of HCCCCDO and CCCHCHO. A joint experimental and theoretical study.

The reaction between O-. and MeO-CH2-C identical to C-CDO in the ion source of a VG ZAB 2HF mass spectrometer gives a number of product anions including [H2CCCCO]-. and [HCCCCDO]-. (in the ratio 1:5). Neutralisation-reionisation (NR+) of [H2CCCCO]-. results in the sequential two-electron vertical oxidation [H2CCCCO]-.-->H2CCCCO-->[H2CCCCO](+.). Singlet H2CCCCO lies 158 kJ mol-1 below the triplet [at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory]. The majority of neutrals H2CCCCO are stable for the microsecond duration of the NR experiment, but some are energized and decompose to give H2CCC and CO. A similar NR+ experiment with [HCCCCDO]-. yields neutrals HCCCCDO, some of which are excited and rearrange. Calculations show that it is the singlet form of HCCCCHO which rearranges (the singlet lies 36 kJ mol-1 above the ground state triplet): the rearrangement occurs by the sequential H transfer process, HCCCCHO-->HCC(CH)CO<--H2CCCCO. Neutral HCCCCHO needs an excess energy of only 43 kJ mol-1 to effect this reaction, which is exothermic by 230 kJ mol-1. Both HCC(CH)CO and H2CCCCO formed in this way should have sufficient excess energy to cause some loss of CO. The anions [CC(CH)CHO]-. and [CC(CD)CHO]-. are formed in the ion source of the mass spectrometer by the reactions of HO- with Me3SiC identical to C-CH = CHOMe and Me3SiC identical to C-CD = CHOMe respectively. NR+ of these anions indicate that energized forms of CC(CH)CHO and CC(CD)CHO may rearrange to isomer(s) which decompose by loss of CO. Singlet CC(CH)CHO rearranges to HCC(CH)CO and H2CCCCO, both of which are energized and fragment by loss of CO.

Effect of Bleeding Oxygen on Processes in the Ion Source of an EMAL-2 Mass Spectrometer in the Analysis of Oxygen-Containing Samples

When bleeding oxygen into the ion source of an EMAL-2 laser mass spectrometer, an oxygen monolayer was formed on atomically pure sample surfaces produced by laser scanning. It was found that the signal of this oxygen can be used for calculating sensitivity factors. Bleeding oxygen increased the yield of test sample matrix ions; for example, the yield of Fe+ ions was doubled. The qualitative analysis of a gas atmosphere introduced into the ion source of an EMAL-2 mass spectrometer can be performed. Chloroform, which was present in a prepared gas mixture, was identified by the lines of molecular ions. The intensity of its molecular lines in the mass spectrum in the case using carbon reagent ions was higher by an order of magnitude than that in the case using silicon.

Protein identification by peptide mass fingerprinting and peptide sequence tagging with alternating scans of nano-liquid chromatography/infrared multiphoton dissociation Fourier transform ion cyclotron resonance mass spectrometry.

We have developed a method for protein identification with peptide mass fingerprinting and sequence tagging using nano liquid chromatography (LC)/Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). To achieve greater sensitivity, a nanoelectrospray (nano-ES) needle packed with reversed-phase medium was used and connected to the nano-ES ion source of the FTICR mass spectrometer. To obtain peptide sequence tag information, infrared multiphoton dissociation (IRMPD) was carried out in nano-LC/FTICR-MS analysis. The analysis involves alternating nano-ES/FTICR-MS and nano-ES/IRMPD-FTICR-MS scans during a single LC run, which provides sets of parent and fragment ion masses of the proteolytic digest. The utility of this alternating-scan nano-LC/IRMPD-FTICR-MS approach was evaluated by using bovine serum albumin as a standard protein. We applied this approach to the protein identification of rat liver diacetyl-reducing enzyme. It was demonstrated that this enzyme was correctly identified as 3-alpha-hydroxysteroid dehydrogenase by the alternating-scan nano-LC/IRMPD-FTICR-MS approach with accurate peptide mass fingerprinting and peptide sequence tagging.

Formation of Cyanate (OCN) and Fulminate (ONC) Radicals from Anionic Precursors in the Gas Phase. A Joint Experimental and Theoretical Study

The cyanate anion (OCN)- may be formed in the ion source of a reverse sector VG ZAB 2HF mass spectrometer by dissociative electron capture of phenyl cyanate (PhOCN). The isomeric fulminate anion (ONC)- is formed by (i) deprotonation of nitromethane (with HO-) followed by elimination of H2O (-CH2NO2 → [(CHN(O)(OH)]- → (ONC)- + H2O) and (ii) the reaction between CH2NOCH3 and O•- [CH2NOCH3 + O•- → (ONC)- + H2O + CH3•]. Neutralization of the cyanate and fulminate anions by Franck−Condon vertical one-electron oxidation (in the first of two tandem collision cells of the mass spectrometer) yields the cyanate (OCN) and fulminate (ONC) radicals, both of which are stable for at least 1 μs. Ionization of these neutrals by one-electron oxidation in a second collision cell produces the cyanate and fulminate cations. A proportion of each of these cations undergoes isomerization. Theoretical and experimental studies show that (i) these rearrangements involve the less stable singlet forms of the cations, (ii) the cationi...

Comparison of isotope pairing and N2:Ar methods for measuring sediment denitrification—Assumption, modifications, and implications

Denitrification has been measured during the last few years using two different methods in particular: isotope pairing measured on a triple-collector isotopic ratio mass spectrometer and N2:Ar ratios measured on a membrane inlet mass spectrometer (MIMS). This study compares these two techniques in short-term batch experiments. Rates obtained using the original N2∶Ar method were up to 3 to 4 times higher than rates obtained using the isotope pairing technique due to O2 reacting with the N2 during MIMS analysis. Oxygen combines with N2 within the mass spectrometer ion source forming NO+ which reduces the N2 concentration. The decrease in N2 is least at lower O2 concentrations and since oxygen is typically consumed during incubations of sediment cores, the result is often a pseudo-increase in N2 concentration being interpreted as denitrification activity. The magnitude of this ocygen effect may be instrument specific. The reaction of O2 with N2 and the subsequent decrease in N2 was only partly correctly using an O2 correction curve for the relationship between N2 and O2 concentrations. The O2 corrected N2∶Ar denitrification rates were lower, but still did not match the isotope pairing rates and the variability between replicates was much higher. Using a copper reduction column heated to 600°C to remove all of the O2 from the sample before MIMS analysis resulted in comparable rates (slightly lower), and comparable variability between replicates, to the isotope pairing technique. The N2:Ar technique determines the net N2 production as the difference between N2 production by denitrification and N2 consumption by N-fixation, while N-fixation has little effect on the isotope pairing technique which determines a rate very close to the gross N2 production. When the two different techniques were applied on the same sediment, the small difference in rates obtained by the two methods seemed to reflect N-fixation as also supported from measurements of ethylene production in acetylene enriched sediment cores. The N2:Ar and isotope pairing techniques may be combined to provide simultaneous measurements of denitrification and N-fixation. Both techniques have several assumptions that must be met to achieve accurate rates; a number of tests are outlined that can be applied to demonstrate that these assumptions are being meet.

On-line characterization of gaseous and particulate organic analytes using atmospheric pressure chemical ionization mass spectrometry

A modified atmospheric pressure chemical ionization ion source is applied for direct analysis of volatile or low volatile organic compounds in air. The method is based on the direct introduction of the analytes in the gas phase and/or particle phase into the ion source of a commercial ion-trap mass spectrometer. Two methods are employed for the production of primary ions at atmospheric pressure, photoionization and corona discharge. It is shown that in the presence of a dopant, photoionization can be a highly efficient ionization method also for real-time analysis with detection limits for selected analytes in the lower ppt-range. Using corona discharge for the production of primary ions, which is instrumentally easier since no additional chemicals have to be added to the sample flow, we demonstrate the analytical potential of on-line atmospheric pressure chemical ionization mass spectrometry for reaction monitoring experiments. To do so, an atmospherically relevant gas phase reaction is carried out in a 500 l reaction chamber and gaseous and particulate compounds are monitored in the positive and negative ion mode of the mass spectrometer.

Isotopic Analogs as Internal Standards for Quantitative GC/MS Analysis—Molecular Abundance and Retention Time Difference as Interference Factors

The following analyte/isotope-labeled internal standard (IS) systems are adapted to further study the interference phenomenon previously reported from our laboratory--the intensity ratio of the ion-pair designated for a specific analyte/2H-analog system increases as the solvent used to reconstitute the extraction/derivatization residue is increased: (a) Three analyte/2H-analog pairs with 2H-atoms positioned at allylic sites (butalbital, secobarbital, methohexital); (b) Two analyte/2H-analog pairs without these structural features (pentobarbital, phenobarbital); and (c) Two analyte/13C-analog pairs (butalbital, secobarbital). Major experimental parameters adapted in this study include: (a) Varying reconstitution solvent volume while keeping a constant analyte/IS concentration ratio; (b) Varying analyte/IS concentration ratio; (c) Varying gas chromatograph (GC) injection port temperature; and (d) Varying GC column temperature programming conditions, rendering difference in the degree of overlap of the peaks derived from the analyte and the 2H-analog. This study results in the following observations: (a) Changes in the intensity ratio of the ion-pair designated for a specific analyte/2H-analog system depend on molecular abundance, regardless of whether the 2H-atoms are positioned at active allylic positions or not--thus, ruling out hydrogen/deuterium exchange as the cause of the observed interference phenomenon; (b) Variations in GC injection port temperature do not alter the observed interference phenomenon-thus, ruling out chemical reactions at the injection port as the underlying cause; (c) Variations in peak-overlapping between the analyte and the 2H-analog, facilitated by changing GC column programming conditions, alter the observed interference phenomenon. Abundance of the analyte and the 2H-analog and their overlapping characteristic in the mass spectrometer ion source are believed to be the underlying cause of the observed interference phenomenon. The interference phenomenon observed for a specific analyte/2H-analog system has significant consequences on the linearity of the thereby generated calibration curves. Nonlinear approaches can better describe the calibration data and are needed more in comparison to systems in which 13C-analogs are used as the ISs.

Hydrogen abstraction and decomposition of bromopicrin and other trihalogenated disinfection byproducts by GC/MS.

Tribromonitromethane (bromopicrin), dibromochloronitromethane, bromodichloronitromethane, and trichloronitromethane (chloropicrin) have been identified as drinking water disinfection byproducts (DBPs). They are thermally unstable and decompose under commonly used injection port temperatures (200-250 degrees C) during gas chromatography (GC) or GC/mass spectrometry (GC/MS) analysis. The major decomposition products are haloforms (such as bromoform), which result from the abstraction of a hydrogen atom from the solvent bythermally generated trihalomethyl radicals. A number of other products formed by radical reactions with the solvent and other radicals were also detected. The trihalonitromethanes also decompose in the hot GC/MS transfer line, and the mass spectra obtained are mixed spectra of the undecomposed parent compound and decomposition products. This can complicate the identification of these compounds by GC/MS. Trihalomethyl compounds that do not have a nitro group, such as tribromoacetonitrile, carbon tetrabromide, methyl tribromoacetate, and tribromoacetaldehyde, do not decompose or only slightly decompose in the GC injection port and GC/MS transfer line. The brominated trihalomethyl compounds studied also showed H/Br exchange by some of their fragment ions. This H/Br exchange also makes the identification of these compounds in drinking water more difficult. The extent of H/Br exchange was found to depend on the mass spectrometer ion source temperature, and it is proposed that the internal surface of the ion source is involved in this process.

Atom Scrambling of Linear C5 in the Gas Phase: a Joint Experimental and Theoretical Study

The radical anion [CC 1 3 CCC] - . , with known bond connectivity, has been synthesized in the ion source of a VG ZAB 2HF mass spectrometer by the reaction of (CH3) 3 Si-C≡C 1 3 C(=NNH-tosyl)-C≡C-Si(CH 3 ) 3 with HO - followedby F - (from SF 6 ). The collision-induced mass spectrum of [CC 1 3 CCC] - . shows only one fragmentation: exclusive loss of 1 2 C. Computational studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G-(d) level of theory indicate that this experimental observation means that [CC 1 3 CCC] - . does not rearrange under the conditions of collisional activation. The charge reversal [ - CR + , synchronous charge stripping of the radical anion (by a vertical Franck-Condon process) to the radical cation], and the neutralization/reionization [ - NR + , stepwise vertical oxidation of the radical anion to the neutral, then of the neutral to the radical cation] spectra of [CC 1 3 CCC] - . show partial and complete atom scrambling, respectively. Under the experimental conditions used, the neutral has a lifetime of 10 - 6 s before being converted to the corresponding radical cation. Computational studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory suggest that the major atom-scrambling pathway of the neutral involves cyclization of singlet CC 1 3 CCC to equilibrating and degenerate carbon-substituted rhombic structures that fragment to yield linear singlet 1 3 C 1 2 C 4 structures. Overall, the label is randomized. A similar mechanism is proposed to account for the partial atom scrambling of the radical cations formed in the - CR + experiment from [CC 1 3 CCC] - . .

Application of parallel liquid chromatography/mass spectrometry for high throughput microsomal stability screening of compound libraries

Solution-phase and solid-phase parallel synthesis and high throughput screening have enabled biologically active and selective compounds to be identified at an unprecedented rate. The challenge has been to convert these hits into viable development candidates. To accelerate the conversion of these hits into lead development candidates, early assessment of the physicochemical and pharmacological properties of these compounds is being made. In particular, in vitro absorption, distribution, metabolism, and elimination (ADME) assays are being conducted at earlier and earlier stages of discovery with the goal of reducing the attrition rate of these potential drug candidates as they progress through development. In this report, we present an eight-channel parallel liquid chromatography/mass spectrometry (LC/MS) system in combination with custom Visual Basic and Applescript automated data processing applications for high throughput early ADME. The parallel LC/MS system was configured with one set of gradient LC pumps and an eight-channel multiple probe autosampler. The flow was split equivalently into eight streams before the multiple probe autosampler and recombined after the eight columns and just prior to the mass spectrometer ion source. The system was tested for column-to-column variation and for reproducibility over a 17 h period (approximately 500 injections per column). The variations in retention time and peak area were determined to be less than 2 and 10%, respectively, in both tests. The parallel LC/MS system described permits time-course microsomal incubations (t o, t 5, t 15, t 30) to be measured in triplicate and enables estimations of t 1/2 microsomal stability. The parallel LC/MS system is capable of analyzing up to 240 samples per hour and permits the complete profiling up to two microtiter plates of compounds per day (i.e., 176 test substrate compounds + sixteen controls).

Influence of Gas Atmosphere in an Ion Source of a Laser Mass Spectrometer on the Results of Elemental Analysis

The effect of bleeding oxygen or a mixture of inert gases (Ne, Ar, and Xe) in the ion source of an EMAL-2 mass spectrometer on the results of elemental analysis (EI 696 steel, L 68 brass, and Br 663 bronze standard reference samples) was examined. Filling the ion source with gases to a pressure of 10–2 Pa increased the number of singly charged ions and decreased the number of multiply charged ions in a laser-induced plasma. This fact allowed us to enhance analytical signals by a factor of ∼1.5. The effect was most pronounced for ions of elements whose second ionization potentials lie in a range of 15–20 eV. The effects were almost identical for bleeding oxygen and inert gases.

Temperature controller for thermal ionization mass spectrometry.

We describe the use of a simple voltage stabilizer that controls the filament temperature (T(f)) in the ion source of a thermal ionization mass spectrometer. The filament voltage (V(f)) is measured by means of a separate pair of wires connected inside of the ion source in parallel to the wires supplying power. It has been demonstrated that V(f) is directly proportional to T(f) in a wide range of filament temperature. The T(f) value is solely controlled by the reference voltage (V(r)) that can be manually selected from a voltage divider or by means of a computer. Digital signals from the computer in the form of a series of pulses are transmitted opto-electronically and subsequently converted to analog signals. The temperature controller described here was successfully applied for analysis of potassium concentration by the isotope dilution method.