Positive Molecular Ions Research Articles

Atmospheric pressure field desorption-trapped ion mobility-mass spectrometry coupling

While field ionization (FI) and field desorption (FD) are established soft vacuum ionization methods in mass spectrometry (MS), the technique of atmospheric pressure field desorption (APFD) has only recently been added to the repertoire. Similar to FI and FD, APFD can yield both positive even-electron ions of highly polar or ionic compounds and positive molecular ions, M+•, e.g., of polycyclic aromatic compounds. Thus, a dedicated APFD source assembly has been constructed and demonstrated to allow for robust APFD operation. This device also enabled observation of the emitter during operation and allowed for resistive emitter heating, thereby speeding up the desorption of the analytes and expanding the range of analytes accessible to APFD. While initial work was done using a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer, the new APFD source offered the flexibility to also be used on a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument, and thus, it would be possible to be mounted to any Bruker mass spectrometer featuring an atmospheric pressure (AP) interface. Operating an APFD source at a TIMS-Q-TOF instrument called for the exploration of the combined use of APFD and TIMS. Here, operation, basic properties, and capabilities of this new atmospheric pressure field desorption-trapped ion mobility-mass spectrometry (APFD-TIMS-MS) coupling are described. APFD-TIMS-MS is employed for the separation of individual components of oligomers and for the accurate determination of their collision cross section (CCS). This work describes the application of APFD-TIMS-MS on poly(ethylene glycol) forming [M + Na]+ ions by cationization and on an amine-terminated poly(propylene glycol) yielding [M + H]+ ions. Some compounds forming molecular ions, M+•, by field ionization such as [60]fullerene and a mixture of four polycyclic aromatic hydrocarbons (PAHs) are examined. In APFD-TIMS-MS, the limits of detection (LODs) of fluoranthene and benzo[a]pyrene M+• ions are determined as ≈100 pg and <1 pg, respectively. Finally, [60]fullerene is analyzed by negative-ion APFD-TIMS-MS where it yields a molecular anion, M−•.Graphical abstract

Robust and versatile assembly for emitter positioning, observation, and heating in atmospheric pressure field desorption mass spectrometry.

Atmospheric pressure field desorption (APFD) mass spectrometry (MS) has recently been introduced as a new variant of field desorption (FD) mass spectrometry. The development aimed at providing the basic characteristics of FD-MS in combination with instruments equipped with an atmospheric pressure (AP) interface. Hitherto, APFD has been demonstrated to yield both positive and negative even electron ions of highly polar or ionic compounds as well as to enable the generation of positive molecular ions, M+•, of polycyclic aromatic compounds. The prototype setup for APFD was based on a nano-electrospray ionization (nanoESI) source slightly modified to allow for emitter positioning in front of the AP interface of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. The entrance electrode of the interface was set to negative or positive high voltage with respect to the emitter at ground potential, thereby permitting the formation of positive or negative ions, respectively. This work describes a custom-built device for quicker and more reproducible sample loading on and positioning of field emitters at the entrance electrode of the atmospheric pressure interface of a mass spectrometer. In addition, the device provides means for observation of the emitter during operation and for resistive emitter heating as employed in traditional FD-MS. Emitter heating both speeds up the desorption of the analytes and allows for the desorption/ionization of analytes of higher molecular weight than without emitter heating. In some cases, the signal-to-noise ratio of APFD mass spectra is improved due to higher ion currents effected by compressing the entire process into shorter periods of spectral acquisition. The new setup enables robust and reliable operation in APFD-MS. Moreover, it has been designed as to allow for use on a range of instruments as it can either be used on an FT-ICR mass spectrometer or in combination with a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument.

Monoisotopic targets production from atomic and molecular positive ion implantation in a tandem accelerator at low energies

We produced monoisotopic targets of 13C and 28,29Si with 1015−16 atoms/cm2 areal density by ion implantation in different matrices at the Accelerator Mass Spectrometry (AMS) facility in Mexico. The tandem accelerator terminal voltage was set at the lowest achievable value (200 kV) that yield beams with energy of 435 keV. It is possible to do ion implantation at lower energies in our facility through the use of molecular beams, so in this work we looked for, and successfully found, bound positively charged molecular beams, although with very low intensity. We inject 235 keV molecules into the charge of exchange canal (argon) of our tandem accelerator and detected the survival fraction of C2,3,4 molecules in 1+ and 2+ charge states or above. Our results showed that some molecules remain bound, with one or more electrons missing, after being forced through a low density gas stripper at relatively high energy. In the production process of negative molecular fluxes in the Source of Negative Ions by Cesium Sputtering (SNICS) we found an odd-even effect in their intensity that we understand as the coupling between the fragment size distribution of a dynamic fragmentation of graphite by cesium impact and the electron affinity of the molecules with n-carbon atoms. The availability of these kind of high energy molecular beams opens the door for discovery both in the study of the physics of negative and positive molecular ions.

Application of atmospheric pressure field desorption for the analysis of anionic surfactants in commercial detergents

Recent work has shown that field desorption (FD) and field ionization (FI) using activated field emitters may be performed at atmospheric pressure, too. While some limitations apply to atmospheric pressure field desorption (APFD) mass spectrometry (MS), the method can deliver both positive and negative even electron ions of highly polar or ionic compounds. Furthermore, APFD even permits the generation of positive molecular ions of polycyclic aromatic compounds. Here, an application of negative-ion APFD for the analysis of anionic surfactants contained in commercial detergent products for body care, household, and technical uses is presented. The samples include liquid soaps and shower gels, dishwashing liquids, and cooling lubricants. Surfactant solutions in methanol/water or pure methanol at 2–10 µl ml−1 were deposited on commercial 13-µm activated tungsten emitters. The emitters were positioned in front of the atmospheric pressure interface of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer by means of a slightly modified nano-electrospray ionization (nanoESI) source. The entrance electrode of the interface was set to positive high voltage with respect to the emitter at ground potential. Under these conditions, negative-ion desorption was achieved. The surfactant anions, organic sulfates and organic sulfonates, were characterized by accurate mass-based formula assignments, and in part, by tandem mass spectrometry. The negative-ion APFD spectra were compared to results by negative-ion electrospray ionization (ESI) either obtained using the FT-ICR mass spectrometer or by using a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument when product ions of low m/z needed to be detected in tandem MS.Graphical

Molecular ion formation on activated field emitters in atmospheric pressure field desorption mass spectrometry

Atmospheric pressure field desorption (APFD) mass spectrometry (MS) has recently been explored as a new contribution to the field of ambient desorption/ionization (ADI). Depending on the selected polarity applied to the field emitter, ionic and polar analytes were demonstrated to deliver positive as well as negative ions. Whereas this recent study solely reported on the formation of even-electron ions of either polarity, the present work on APFD-MS demonstrates the abundant formation of positive molecular ions, M+•, from polycyclic aromatic compounds. Molecular ions were formed on and desorbed from standard 13-µm activated tungsten wire emitters at atmospheric pressure. The commercial field emitters were positioned at about 2 mm distance in front of the atmospheric pressure interface of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer and the entrance electrode of the interface was set to –4.5 to –5.5 kV with respect to the emitter. Emitter-disrupting electric discharges did normally not occur under these conditions. The electric field strengths achieved at the dendritic microneedles were sufficient to allow for the abundant formation of M+• ions of various polycyclic aromatic compounds such as benzo[a]pyrene, anthracene, fluoranthene, 1,1,4,4-tetraphenyl-butadiene, and 1-aza-[6]helicene. In case of the extremely basic 1-aza-[6]helicene protonation strongly competed with molecular ion formation and tended to suppress the field ionization process. All molecular ion compositions were assured by accurate mass-based formula assignments.Graphical

Determination of the Characteristics of the Molecular Structure of Trialkyl Phosphates by the Joint Application of Electronic Ionization Mass Spectra with Registration of Positive Ions and Negative Ions of Resonance Coupling

Trialkylphosphates are of considerable interest from the military-chemical point of view as precursors of highly toxic organophosphorus toxicants, possible products of their decontamination, complexing agents in processes of reprocessing of used nuclear fuel, etc. Meanwhile, the development of ways to identify these substances is still in its infancy. In addition, trialkylphosphates are an interesting subject for the search of a solution to the analytical problem of establishing the structure of O-alkyl fragments in molecules of M(O) (OR) n esters of multibasic acids, where M is the central atom (central core), n is the basicity of the acid, R are alkyl radicals with an unknown and in general case different number of carbon atoms in each of them. No general solution to this problem could be found in the book sources. The aim of this work is to develop an algorithm for in-depth identification of trialkyl phosphates, which includes establishing the belonging of the investigated substance to this class, as well as a general and reliable method for determining the number of carbon atoms in each of the O-alkyl radicals of the investigated substances. On the basis of the revealed regularities of the decay of positive molecular ions of trialkyl phosphates, as well as negative ions of resonant capture of electrons of the same compound obtained under conditions of electron ionization, an algorithm for in-depth identification of trialkyl phosphates is proposed, which includes establishing the belonging of the investigated substance to this class, as well as a general and reliable method determining the number of carbon atoms in each of the O-alkyl radicals of the substance molecule

Investigation of the process of reactive ion-beam sputtering of gallium arsenide using optical emission spectroscopy

The aim of this work was to study the process of reactive ion-beam sputtering of gallium arsenide using optical emission analysis of plasma in the target region to determine the optimal conditions for the formation of intrinsic GaAs oxides. The ion source was a plasmatron based on an anode layer accelerator (UAS), which generated a stream of accelerated argon and oxygen ions with an energy of 400–1200 eV. The target was made from tellurium doped gallium arsenide. Intense GaI lines (2874.2 Å, 2943.6 Å, 4033.0 Å and 4172.1 Å), atomic argon ArI, argon ions, and also FeI lines were detected in the spectrum upon sputtering of GaAs by Ar+ ions. The appearance of iron lines can be explained by the sputtering of the pole tips of the magnetic system of the ion source. An increase in the accelerating voltage from 1 to 3 kV leads to an increase in the intensity of the peaks of atomic gallium GaI (4172.1 Å) by 2.38 times, the GaI line (4033.0 Å) by 3.25 times, the GaI line (2943.6 Å) 3.4 times, GaI lines (2874.2 Å) 5 times. It was found that an increase in the partial pressure of oxygen leads to a sharp decrease in the peaks of GaI (4033.0 Å) and GaI (4172.1 Å) due to the chemical interaction of gallium and oxygen. Sputtering in pure oxygen reduces the intensity of these peaks by 8 and 5 times, respectively. The intensities of the peaks of atomic gallium GaI (2874.2 Å) and GaI (2943.6 Å) decreased in 2 and 1.78 times, respectively. In the presence of a positive potential on the target, the intensity of all lines of atomic gallium monotonically decreases with increasing potential. In the emission spectrum, lines of atomic oxygen OI (7774.2 Å) and molecular positive ions O+2 (6418.7 Å, 6026.4 Å, 5631.9 Å and 5295.7 Å) were detected. In the presence of a positive potential on the target, a monotonic decrease in the intensity of the above oxygen lines was observed. This indicates an intensification of chemical interaction of oxygen with target elements and, accordingly, a decrease in the free active oxygen particles.

A novel rocket-borne ion mass spectrometer with large mass range: instrument description and first-flight results

Abstract. We present a novel rocket-borne ion mass spectrometer named ROMARA (ROcket-borne MAss spectrometer for Research in the Atmosphere) for measuring atmospheric positive and negative ions (atomic, molecular and cluster ions) and positively and negatively charged meteor smoke particles. Our ROMARA instrument has, compared to previous rocket-borne ion mass spectrometers, a markedly larger mass range of up to m/z 2000 and a larger sensitivity, particularly for meteor smoke particle detection. The major objectives of this first ROMARA flight included the following: a functional test of the ROMARA instrument, measurements between 55 and 121 km in the mass range of atmospheric positive and negative ions, a first attempt to conduct mass spectrometric measurements in the mass range of meteor smoke particles with mass-to-charge ratios up to m/z 2000, and measurements inside a polar mesospheric winter echo layer as detected by ground-based radar. Our ROMARA measurements took place on the Arctic island of Andøya, Norway, at around noon in April 2018 and represented an integral part of the polar mesospheric winter radar echo (PMWE) rocket campaign. During the rocket flight, ROMARA was operated in a measurement mode, offering maximum sensitivity and the ability to qualitatively detect total ion signatures even beyond its mass-resolving mass range. On this first ROMARA flight we were able to meet all of our objectives. We detected atmospheric species including positive atomic, molecular and cluster ions along with negative molecular ions up to about m/z 100. Above m/z 2000, ROMARA measured strong negative-ion signatures, which are likely due to negatively charged meteor smoke particles.

IDENTIFIKASI FITOSTEROL MELALUI KROMATOGRAFI GAS – SPEKTROFOTOMETER MASSA PADA EKSTRAK KLOROFORM BIJI BUAH ATUNG (Parinarium glaberimum Hassk) ASAL KABUPATEN SBB, MALUKU

Five main compounds have been identified in the chloroform extract of Atung fruit seeds (Parinarium glaberimum Hassk) which are linoleic acid (8.88%); stearic acid (8.23%); stigmasta-5,22-dien-3-ol,(3β,22E) or stigmasterol (10.37%); stigmast-5-en-3-ol,(3β) or β-sitosterol (19.59%); and stigmast-5-en-3-ol, (3β, 24S) or γ-sitosterol ( 33.74%) through gas chromatography-mass spectroscopy by analyzing the similarity of molecular weight and positive ion mass/charge fragments and based on the comparison of the GC-MS retention time of phytosterols. This study is the first to report the presence of stigmasterol, β-sitosterol and γ-sitosterol in the chloroform extract of Atung fruit seeds (Parinarium glaberimum Hassk). γ -Sitosterol, the epimer of β-sitosterol, has the greatest abundance in the chloroform extract of Atung fruit seeds. Phytosterol compounds namely stigmasterol, β-sitosterol, and γ-sitosterol have been reported to have many benefits such as reducing blood cholesterol levels, antioxidants, anti-diabetic, anti-inflammatory, and anti-cancer.

Resonance States of Hadronic Three-Body Ions: Stabilization Method

Bound and resonance states of symmetric three-body exotic \(pXX\) negative atomic ions \((X=\mu^{-}, \pi^{-}, K^{-})\) as well as exotic \(ppX\) positive molecular ions for total angular momentum \(J=0\), are studied in details under the framework of Stabilization method. The resonance states under consideration lie below \(N=2\) ionization threshold of the corresponding \(pX\) atom. The wave-function is expanded in correlated multi-exponent Hylleraas type basis set for explicit incorporation of \(p\)-\(p\), \(\mu\)-\(\mu\), \(\pi\)-\(\pi\) or \(K\)-\(K\) correlations. The methodology has been tested by estimating the parameters of the resonance states of \((p\mu\mu)^{-}\), \((pp\mu)^{+}\), \((p\pi\pi)^{-}\) and \((pp\pi)^{+}\) and comparing with the results existing in the literature. The interparticle interactions for all the systems under consideration are purely Coulombic.

Non-Born–Oppenheimer study of the muonic molecule ion 4He μ+**Project supported by the National Natural Science Foundation of China (Grant No. 11704399), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB21030300), and the National Key Research and Development Program of China (Grant No. 2017YFA0304402).

Accurate non-Born–Oppenheimer variational calculations of all bound states of the positive muon molecular ion 4Heμ+ have been performed using explicitly correlated Gaussian functions in conjunction with the global vectors. All the energies obtained are accurate in the order of 10−6 Hartree (1 Hartree = 27.2114 eV). Compared with the binding energies obtained from calculations based on the Born–Oppenheimer potential with the mass-weighted adiabatic corrections (Chem. Phys. Lett. 110 487 (1984)), the largest relative deviation is up to 15%. By analyzing the average interparticle distances and possibility distributions of interparticle distances of this system, it is confirmed that the Born–Oppenheimer approximation is reasonable for this system and that 4He μ+ can be regarded as a system of positive muon bound to a slightly distorted helium atom.

Enhanced Ion Yields Using High Energy Water Cluster Beams for Secondary Ion Mass Spectrometry Analysis and Imaging.

Previous studies have shown that the use of a 20 keV water cluster beam as a primary beam for the analysis of organic and bio-organic systems resulted in a 10-100 times increase in positive molecular ion yield for a range of typical analytes compared to C60 and argon cluster beams. This resulted in increased sensitivity to important lipid molecules in the bioimaging of rat brain. Building on these studies, the present work compares 40 and 70 keV water cluster beams with cluster beams composed of pure argon, argon and 10%CO2, and pure CO2. First, as previously, we show that for E/nucleon about 0.3 eV/nucleon water and nonwater containing cluster beams generate very similar ion yields, but below this value, the water beams yields of BOTH negative and positive "molecular" ions increase, in many cases reaching a maximum in the <0.2 region, with yield increases of ∼10-100. Ion fragment yields in general decrease quite dramatically in this region. Second, for water cluster beams at a constant E/nucleon, "molecular" ion yield increases with beam energy and hence cluster size due to increased sputter yield (ionization probability is constant). Third, as a consequence of the increased ion yield and the improved focusability using high-energy cluster beams, imaging in the 1 μm spatial resolution region is demonstrated on HeLa cells and rat brain tissue, monitoring molecules that were previously difficult to detect with other primary beams. Finally, the suggestion that the secondary ion emission zone has quasi-aqueous character seems to be sustained.

Nanostructure of Gasification Charcoal (Biochar).

In this work, we investigate the molecular composition and nanostructure of gasification charcoal (biochar) by comparing it with heat-treated fullerene arc-soot. Using ultrahigh resolution Fourier transform ion-cyclotron resonance and laser desorption ionization time-of-flight mass spectrometry, Raman spectroscopy, and high resolution transmission electron microscopy we analyzed charcoal of low tar content obtained from gasification. Mass spectrometry revealed no magic number fullerenes such as C60 or C70 in the charcoal. The positive molecular ion m/ z 701, previously considered a graphitic part of the nanostructure, was found to be a breakdown product of pyrolysis and not part of the nanostructure. A higher mass distribution of ions similar to that found in thermally treated fullerene soot indicates that they share a nanostructure. Recent insights into the formation of all carbon fullerenes reveal that conditions in charcoal formation are not optimal for the formation of fullerenes, but instead, curved carbon structures coalesce into fulleroid-like structures. Microscopy and spectroscopy support such a stacked, fulleroid-like nanostructure, which was explored using reactive molecular dynamics simulations.

Sensitive and robust MALDI-TOF-MS glycomics analysis enabled by Girard's reagent T on-target derivatization (GTOD) of reducing glycans

Sensitive glycomics analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) is of great importance but significantly hampered by their low ionization efficiency and labile sialic acid moieties. Chemical derivatization offers a viable way to improve both the ionization efficiency and analytical sensitivity of the glycans in MS analysis by altering their hydrophobicity or charge property. Here we employed Girard's reagent T (GT) for on-target derivatization (GTOD) of reducing glycan under mild acid condition to form stable hydrazones at room temperature, allowing rapid and sensitive identification of neutral and sialylated glycans in positive-ion mode as only permanently positive charged molecular ions without multiple ion adducts by MALDI-TOF-MS. The MS signal intensities of lactose, sialylated N-glycans derived from bovine fetuin and neutral N-glycans derived from RNaseB and ovalbumin were boosted by 7.44, 9.13, 12.96 and 13.47 folds on average (n = 3), respectively. More importantly, after GTOD strategy, unwanted desialylation of sialylated glycans during MS was suppressed. The detection limit of the assay is desirable since the nanogram of N-glycans derived from 0.16 μg ovalbumin could be detected. The assay demonstrated good stability (RSD≤2.95%, within 10 days), reliable reproducibility (RSD = 2.96%, n = 7) and a desirable linear dynamic range from 78 nmol/mL to 10 μmol/mL. The strategy has been successfully applied to MS analysis of reducing glycans from human milks, neutral and sialylated O-, N-glycans from glycoproteins, and reducing glycans derived from glycosphingolipids, presenting neater [M]+ signals which allow detection of more low-abundance glycans and assignation of Neu5Ac vs. Neu5Gc or fucose vs. hexose in glycans due to the absence of the ambiguous interpretation from multiple peaks (ion adducts [M+Na]+ and [M+K]+). Moreover, the GTOD assay prevents desialylation during MALDI-TOF-MS profiling and enables distinct linkage-specific characterization of terminal sialic acids of N-glycans derived from human serum protein when combines with an esterification.

Fragmentation of Methanol Molecules after Core Excitation and Core Ionization Studied by Negative-Ion/Positive-Ion Coincidence Experiments.

We have studied the fragmentation of the methanol molecule after core excitation and core ionization by observing coincidences between negative and positive ions. Five different negative ions (H-, C-, CH-, O-, and OH-) were observed at both the C 1s and O 1s edges. As negative ion formation occurs after resonant and normal Auger decay of core-hole states, it is necessarily linked with the release of positively charged fragments. Our data show that such fragmentation can happen in many different ways: We found approximately 30 negative-ion/positive-ion/positive-ion coincidence (NIPIPICO) channels. All involve only singly charged positive ions. Fragmentation channels leading to atomic ions are the most probable, but positive molecular ions are also frequently found in the context of anion formation. Coincidence yields as a function of photon energy were determined for the most intense NIPIPICO channels. Adding together the data measured at different photon energies, we could also verify the occurrence of four-ion coincidences, which involved one negative ion (H- or O-) and three positive ions.

On the E-H transition in inductively coupled radio frequency oxygen plasmas: II. Electronegativity and the impact on particle kinetics

In this series of two papers we present results about the E-H transition of an inductively coupled oxygen discharge driven at radio frequency (13.56 MHz) for different total gas pressures. The mode transition from the low density E-mode to the high density H-mode is studied using comprehensive plasma diagnostics. The measured electron density can be used to distinguish between the different operation modes. This paper focuses on the determination of the negative atomic ion density and the electronegativity by two experimental methods and global rate equation calculation. As a result, the electronegativity significantly decreases over two orders of magnitude from about 25 in the E-mode to about 0.1 in the H-mode. The temporal behavior of the electronegativity in pulsed ICP shows that the negative atomic ion density reaches a steady state after 10 ms. Negative atomic ions are mainly produced by the dissociative attachment with the molecular ground state. The ion–ion recombination with the positive molecular ions and the collisional detachment with the singlet molecular metastables contribute significantly to the loss of the negative atomic ions.

Tandem mass spectrometry of novel ether-linked phospholipid analogs of anionic pulmonary surfactant phospholipids.

Structural analogs of the bioactive lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol were synthesized with a xylitol polar head group and both diacyl and diether radyl groups. Mass spectral characterization of xylitol phospholipids (PX) was carried out using collisional activation and high-resolution mass measurements of positive molecular ion species and compared with the phosphatidylglycerol (PG) analogs. PX were synthesized using a transphosphatidylation reaction catalyzed by phospholipase D and purified by high-performance liquid chromatography (HPLC). Compounds were subjected to electrospray ionization and collision-induced dissociation (CID) was performed using a tandem quadrupole mass spectrometer to generate positive and negative molecular ions. Diether phospholipids were additionally analyzed by high-resolution mass spectrometry as protonated and sodiated molecular species in positive ion mode. Ester-linked PX analogs behaved similarly to PG after collisional activation of [M-H]- . The product ions formed by CID of the diether PG and PX negative ions only revealed information about the head group with no information about the aliphatic chains. In contrast, CID of protonated and sodiated diether phospholipid positive ions revealed reactions corresponding to cleavage of the ether chain, likely occurring by charge-driven reaction mechanisms. Novel PX analogs with diacyl and diether radyl substituents of the glycerol backbone were characterized by tandem mass spectrometry. These unique diether phospholipid analogs enabled exploration of ether cleavage reactions of the positive molecular ion species resulting from collision-induced decomposition. Copyright © 2016 John Wiley & Sons, Ltd.

Temperature dependent Cs retention, distribution, and ion yield changes during Cs+ bombardment SIMS

Combining Cs+ bombardment with positive secondary molecular ion detection (MCs+) can extend the analysis capability of secondary ion mass spectrometry (SIMS) from the dilute limit (&amp;lt;1 at. %) to matrix elements. The MCs+ technique has had great success in quantifying the sample composition of III–V semiconductors. However, the MCs+ has been less effective at reducing the matrix effect for group IV materials, particularly Si-containing compounds. The lack of success in quantifying group IV materials is primarily attributable to the high Cs surface concentrations overloading the sample surface and lowering ion yields. The Cs overload issue is caused by the mobility and relocation of the implanted Cs to the surface during an analysis. Critical to understanding the material-dependent success of the MCs+ technique and elucidating the Cs mobility is understanding how Cs is incorporated and distributed into the sample and how the Cs surface concentration affects the ionization processes. The authors provide both new insight for improving the MCs+ technique by investigating the Cs retention, distribution, and ion yield differences between group III–V and IV materials and a greater understanding of the temperature-dependent mobility and relocation of the implanted Cs. There have been many studies on improving the MCs+ technique; however, our novel approach to use temperature as a means of controlling the Cs mobility has not been previously explored. Cesium build-up curves were acquired to assess the in situ Cs incorporation differences. By utilizing the newly developed variable temperature stage on our SIMS, cesium build-up curves were acquired over a wide range of temperatures (−150 to 300 °C) to show the temperature-dependent relocation of Cs and the effect it has on the ionization processes. Additionally, Cs ionization and neutralization were quantified as a function of Cs fluence and temperature. The Cs retention and distribution differences were determined ex situ by measuring the Cs concentration using heat-treatment x-ray photoelectron spectroscopy and heat-treatment medium energy ion scattering. These results allow for a more thorough understanding of the material-dependent success of the MCs+ technique, the Cs+-sample interaction, and the temperature component of the Cs mobility.

Solid-state polymerization of EDTA and ethylenediamine as one-step approach to monodisperse hyperbranched polyamides

Hyperbranched polyamides (HBPAs), a special class of polymers with extended use in colloidal systems, is synthesized by an innovative method taking advantage of the ordered aggregation of positive and negative molecular ions in solid-state.

Ion field-evaporation from ionic liquids infusing carbon xerogel microtips

Ionic liquid ion sources capable of producing positive and negative molecular ion beams from room-temperature molten salts have applications in diverse fields, from materials science to space propulsion. The electrostatic stressing of these ionic liquids places the liquid surfaces in a delicate balance that could yield unwanted droplet emission when not properly controlled. Micro-tip emitter configurations are required to guarantee that these sources will operate in a pure ionic regime with no additional droplets. Porous carbon based on resorcinol-formaldehyde xerogels is introduced as an emitter substrate. It is demonstrated that this material can be shaped to the required micron-sized geometry and has appropriate transport properties to favor pure ionic emission. Time-of-flight mass spectrometry is used to verify that charged particle beams contain solvated ions exclusively.