Surface ionization of terpene hydrocarbons

By means of a surface ionization indicator for traces of materials in the atmosphere it has been established that many natural materials containing terpenes and their derivatives are ionized on the surface of heated molybdenum oxide at atmospheric air pressure. A mass-spectrometer method has been used to explain the mechanism of ionization of individual terpene hydrocarbons and to establish its principles. The ionization of -pinene, alloocimene, camphene, and also adamantane on oxidized tungsten under vacuum conditions has been investigated. The -pinene and alloocimene are ionized by surface ionization but camphene and adamantane are not ionized under vacuum conditions. The surface ionization mass spectra of -pinene and alloocimene are of low line brightness in comparison with electron ionization mass spectra and differ between themselves. The temperature relations for currents of the same compositions of ions during ionization of a-pinene and alloocimene are also different, which leads to the possibility of surface ionization analysis of mixtures of terpenes being ionized. The ionization coefficients of alloocimene and -pinene on oxidized tungsten under temperatures optimum for ionization and the ionization potentials of alloocimene molecules and of radicals (M-H) of both compounds have been evaluated. The routes of monomolecular decompositions of metastable vibrationally excited ions have been followed. An explanation has been given for the difference in ionization capacities of different terpenes and the possibility of surface ionization of many hydrocarbons of a certain structure has been considered.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 2, pp. 180–188, March–April, 1986.     

Orbital electronegativity and electron affinity of rare earth atoms using Xα-theory

Slater's transition state concept and the relativistic numerical Hartree-Fock-Slater theory has been used to calculate the electronegativity and first ionization potential for the rare earth atoms. Based on these results the electron affinity has also been estimated. The theory predicts almost constant values of the electronegativity as 2 eV, first ionization potential as 8 eV and the electron affinity of -(4–5) eV respectively.This work is dedicated to the memory of Prof. J. C. Slater.Alexander von Humboldt fellow, on leave from school of chemistry, University of Hyderabad, India.     

Spectral change in X-ray absorption near edge structure of DNA thin films irradiated with monochromatic soft X-rays

To reveal the chemical changes induced in DNA by irradiation with ionizing radiation, we have investigated the spectral change in the X-ray absorption near edge structure (XANES) of DNA resulting from exposure to monochromatic soft X-rays. We used a thin film of calf thymus DNA as a sample and observed nitrogen K-shell and oxygen K-shell XANES spectra. The typical monochromatic soft X-ray energies used for the irradiation (395, 408, 528, and 538 eV) were obtained from a soft X-ray beamline (BL23SU, SPring-8). These energies correspond to those just below or just above the nitrogen and oxygen K-shell ionization energy, respectively. The obtained XANES spectra show significant changes by irradiation. Particularly a new π* resonance peak in oxygen XANES spectra evidently appeared by the irradiation above oxygen K-shell ionization potential. These results suggest that carbonyl groups, presumably a propenal group (OC–CC), may be produced in the sample by oxygen ionization. Thus characteristic damage induced by induction in the DNA molecule would be predicted following exposure to monochromatized synchrotron soft X-rays.     

Effect of solvation on the ionization of guanine nucleotide: A hybrid QM/EFP study

Ionization of nucleobases is affected by their biological environment, which includes both the effect of adjacent nucleotides as well as the presence of water around it. Guanine and its nucleotide have the lowest ionization potentials among the various DNA bases. Therefore, the threshold of ionization is dependent on that of guanine and its characterization is crucial to the prediction of interaction of light with DNA. We investigate the effect of solvation on the vertical ionization energies (VIEs) of guanine and its nucleotide. In this work, we have used hybrid quantum mechanics/molecular mechanics (QM/MM) approach with effective fragment potential as the MM method of choice and equation‐of‐motion coupled‐cluster for ionization potential with singles and doubles (EOM‐IP‐CCSD) as the QM method. The performance of the hybrid scheme with respect to the full QM method shows an accuracy of 0.02–0.04 eV. The lowest few ionizations of the nucleotide are found to be from different parts of the moiety, that is, the nucleic acid base, phosphate, or sugar, and these ionization energies are very closely spaced giving rise to a very complicated spectrum. Furthermore, microsolvation has large effects on these ionizations and can lead to red or blue shift depending on the position of the water molecule. Even a single water molecule can change the order of ionized states in the nucleotide. The VIEs of the bulk solvated chromophores are predicted and compared to existing experimental spectra. The predominant role of polarization in the solvatochromic shift is noticed. © 2017 Wiley Periodicals, Inc.     

Thermodynamics of lonization of aqueous lodic acid,an “almost-strong” electrolyte

We have made calorimetric measurements of enthalpies of dilution of aqueous iodic acid and have used these results for evaluation of the standard enthalpy of ionization of HIO₃(aq.). We have also made calorimetric measurements of enthalpies of addition of perchloric acid solution to aqueous solutions of KIO₃, KNO₃, NaIO₃, and NaNO₃ and have used these results to obtain further values for the standard enthalpy of ionization of HIO₃(aq.). On the basis of all these results, we have selected H^o=–660±125 cal-mole^–1 as the best available standard enthalpy of ionization of HIO₃(aq.) at 298.15°K, compared to the previously accepted –2400 cal-mole^–1. Using the best available K=0.157 for ionization, we also obtain G^o=1097 cal-mole^–1 and S^o=–5.9 cal-^oK^–1-mole^–1 for ionization of HIO₃(aq) at 298.15°K.On study leave from Department of Inorganic and Analytical Chemistry, LaTrobe University, Bundoora, Victoria, 3083, Australia, to University of Lethbridge.On study leave from Department of Chemistry, University of Wollongong, Wollongong, N.S.W. 2500, Australia, to University of Lethbridge.     

A Radical-Mediated Pathway for the Formation of [M + H]<Superscript>+</Superscript> in Dielectric Barrier Discharge Ionization

Active capillary plasma ionization is a highly efficient ambient ionization method. Its general principle of ion formation is closely related to atmospheric pressure chemical ionization (APCI). The method is based on dielectric barrier discharge ionization (DBDI), and can be constructed in the form of a direct flow-through interface to a mass spectrometer. Protonated species ([M + H]⁺) are predominantly formed, although in some cases radical cations are also observed. We investigated the underlying ionization mechanisms and reaction pathways for the formation of protonated analyte ([M + H]⁺). We found that ionization occurs in the presence and in the absence of water vapor. Therefore, the mechanism cannot exclusively rely on hydronium clusters, as generally accepted for APCI. Based on isotope labeling experiments, protons were shown to originate from various solvents (other than water) and, to a minor extent, from gaseous impurities and/or self-protonation. By using CO₂ instead of air or N₂ as plasma gas, additional species like [M + OH]⁺ and [M ? H]⁺ were observed. These gas-phase reaction products of CO₂ with the analyte (tertiary amines) indicate the presence of a radical-mediated ionization pathway, which proceeds by direct reaction of the ionized plasma gas with the analyte. The proposed reaction pathway is supported with density functional theory (DFT) calculations. These findings add a new ionization pathway leading to the protonated species to those currently known for APCI.

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Transferring Ions from Solution to the Gas Phase: The Two Basic Principles

The efficient formation of gaseous ions is the crucial step in all successful mass spectrometric experiments. The invention of electrospray ionization (ESI) has strongly facilitated this step by transferring preformed ions directly from solution to the gas phase – thereby circumventing the need to first convert analytes to the gas phase and then ionize them – and therefore ESI has become an extremely useful and widely applied MS technique. The invention of sonic spray ionization (SSI) has also allowed for the transfer of ions from solution into the gas phase, but without the assistance of a voltage or heating. Numerous ionization techniques, using similar principles to those applied in either ESI or SSI, have subsequently been developed. Although experimental conditions used in such techniques vary markedly, herein we argue that they are all based on either one of two basic principles by which ions can be transferred from solution to the gas phase, that is: via (1) neutralizing the counter ion, or (2) separating the ions. We have selected 35 such techniques and categorized them accordingly. This article thereby aims to establish the basic principles by which gaseous ions can be obtained from solvated ions. We further propose that any new ionization technique used to transfer solvated ions to the gas phase will similarly fall into one of these two mechanistic categories.

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Approximate Calculations of Ionization Potential in Electronic Cluster Models

A simple formulation of generalized Koopmans' theorem is suggested for multiconfigurational wave functions. In a coupled cluster approximation (CCD variant), -electron estimates have been obtained for the first ionization potential in a series of linear polyenes and polyacenes. The calculated data satisfactorily reproduce the electron correlation effects characteristic of the ionized states of molecules.     

Structural and electronic study of neutral,positive, and negative small rhodium clusters [Rhn,Rh, and Rh]

We have carried out a systematic study for the determination of the structure and the fundamental state of neutral and ionic small rhodium clusters [Rh_n, Rh, Rh (n = 5–10)] using ab initio Hartree‐Fock methods with a LANL2DZ basis set. A range of spin multiplicities is studied for each cluster. We present the bond lengths and angles and geometric configuration adopted for the clusters in its minimum energy conformation showing the differences when the clusters have different number of unpaired electrons. In addition, we report the vertical ionization potential and the adiabatic potential calculated by the Koopman's theorem. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2541–2547, 2010     

Carbon Nanotube Fiber Ionization Mass Spectrometry: A Fundamental Study of a Multi-Walled Carbon Nanotube Functionalized Corona Discharge Pin for Polycyclic Aromatic Hydrocarbons Analysis

Mass spectrometry continues to tackle many complicated tasks, and ongoing research seeks to simplify its instrumentation as well as sampling. The desorption electrospray ionization (DESI) source was the first ambient ionization source to function without extensive gas requirements and chromatography. Electrospray techniques generally have low efficiency for ionization of nonpolar analytes and some researchers have resorted to methods such as direct analysis in real time (DART) or desorption atmospheric pressure chemical ionization (DAPCI) for their analysis. In this work, a carbon nanotube fiber ionization (nanoCFI) source was developed and was found to be capable of solid phase microextraction (SPME) of nonpolar analytes as well as ionization and sampling similar to that of direct probe atmospheric pressure chemical ionization (DP-APCI). Conductivity and adsorption were maintained by utilizing a corona pin functionalized with a multi-walled carbon nanotube (MWCNT) thread. Quantitative work with the nanoCFI source with a designed corona discharge pin insert demonstrated linearity up to 0.97 (R²) of three target PAHs with phenanthrene internal standard.

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Target Plate Material Influence on Fullerene-C<Subscript>60</Subscript> Laser Desorption/Ionization Efficiency

Systematic laser desorption/ionization (LDI) experiments of fullerene-C₆₀ on a wide range of target plate materials were conducted to gain insight into the initial ion formation in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The positive and negative ion signal intensities of precursor, fragment, and cluster ions were monitored, varying both the laser fluence (0–3.53 Jcm^?2) and the ion extraction delay time (0–950 ns). The resulting species-specific ion signal intensities are an indication for the ionization mechanisms that contribute to LDI and the time frames in which they operate, providing insight in the (MA)LDI primary ionization. An increasing electrical resistivity of the target plate material increases the fullerene-C₆₀ precursor and fragment anion signal intensity. Inconel 625 and Ti90/Al6/V4, both highly electrically resistive, provide the highest anion signal intensities, exceeding the cation signal intensity by a factor ~1.4 for the latter. We present a mechanism based on transient electrical field strength reduction to explain this trend. Fullerene-C₆₀ cluster anion formation is negligible, which could be due to the high extraction potential. Cluster cations, however, are readily formed, although for high laser fluences, the preferred channel is formation of precursor and fragment cations. Ion signal intensity depends greatly on the choice of substrate material, and careful substrate selection could, therefore, allow for more sensitive (MA)LDI measurements.

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Study of Electron Ionization and Fragmentation of Non-hydrated and Hydrated Tetrahydrofuran Clusters

Mass spectroscopic investigations on tetrahydrofuran (THF, C₄H₈O), a common model molecule of the DNA-backbone, have been carried out. We irradiated isolated THF and (hydrated) THF clusters with low energy electrons (electron energy ~70 eV) in order to study electron ionization and ionic fragmentation. For elucidation of fragmentation pathways, deuterated TDF (C₄D₈O) was investigated as well. One major observation is that the cluster environment shows overall a protective behavior on THF. However, also new fragmentation channels open in the cluster. In this context, we were able to solve a discrepancy in the literature about the fragment ion peak at mass 55 u in the electron ionization mass spectrum of THF. We ascribe this ion yield to the fragmentation of ionized THF clusters.

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Comparison of various hyphenated chromatography — Mass spectrometry methods for the analysis of β-agonists

Summary Different chromatography — mass spectrometry techniques for the analysis of -agonists have been compared.Gas chromatography — mass spectrometry (electron impact) has been used, as also has liquid chromatography coupled to the mass spectrometer by either thermospray or electrospray interfaces. The results obtained by the three method were compared in terms of sensitivity, selectivity, and richness of information provided by the analysis. It was found that using electrospray ionization, very powerful analysis could be achieved with high sensitivity, thus providing significant potential for the analysis of -agonists.     

Thermodynamics properties of pyridoxal 5 phosphate

The ionization constants and heats of ionization of pyridoxal 5 phosphate groups in the pH range 2–10 have been determined by potentiometric and calorimetric techniques at 20, 25, 30, and 37°C in 0.1M KCl.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Electrospray ionization mass spectrometry of cyclodextrin complexes of amino acids and peptides

Appropriate complex-forming side-chains of peptides and proteins can bind cyclodextrins. We have characterized interactions of amino acids with cyclodextrins by electrospray ionization mass spectrometry. The stoichiometry of various -cyclodextrin/protonated tryptophan complexes sampled from solution to the gas phase by ESI was revealed by taking advantage of the extended mass range and high mass resolution of a Fourier-transform ion cyclotron resonance instrument. Binding of -cyclodextrin to recombinant human insulin has been demonstrated.     

Thermophoretic force on a metallic or nonmetallic particle immersed into a rarefied Plasma

Analytical results of the thermophoretic force on a metallic or nonmetallic spherical particle immersed into a rarefied plasma with a heat flux within the plasma are presented for the extreme case of free-molecule regime and thin plasma sheath. It has been shown that the thermophoresis is predominantly caused by atoms at low plasma temperatures with negligible gas ionization, while it is mainly due to ions and electrons at high plasma temperatures with great degree of ionization. The ion flux incident to a particle is constant on the whole sphere surface, while the electron flux to the metallic sphere is dependent on the -position with slightly greater value at the fore stagnation point. Consequently, there is a small difference between the metallic and nonmetallic spheres in their -distributions of the floating potential on the surface, which causes the thermophoretic force on a nonmetallic sphere to be appreciably greater than that on a metallic sphere at high plasma temperatures. Expressions for the total thermophoretic force on a metallic sphere and its components due to, respectively, atoms, ions, and electrons have been given in a closed form. Calculated results are also presented on the effects of pressure and of electron/heavy-particle temperature ratio. These results can be understood based on the variation of atom, ion, and electron thermal conductivities with the gas pressure, the temperature, and the temperature ratio.     

Ultraviolet absorption of flavonoids VIII. Ionization constants of kaempferol and quercetin

Summary The ionization constants of the 4- and 7-OH groups in quercetin and of the 3-, 4-, 5-, and 7-OH groups in kaempferol have been determined by the spectrophotometric method. The sequence of their ionization has been established.Irkutsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 708–711, November–December, 1975.     

A Versatile Integrated Ambient Ionization Source Platform

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples.

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A novel laser desorption/ionization method using through hole porous alumina membranes

Rationale

A novel matrix‐free laser desorption/ionization method based on porous alumina membranes was developed. The porous alumina membranes have a two‐dimensional (2D) ordered structure consisting of closely aligned straight through holes of sub‐micron in diameter that are amenable to mass production by industrial fabrication processes.

Methods

Considering a balance between the ion generating efficiency and the mechanical strength of the membranes, the typical values for the hole diameter, open aperture ratio and membrane thickness were set to 200 nm, 50% and 5 μm, respectively. The membranes were coated with platinum on a single side that was exposed to the laser. Evaluation experiments were conducted on the feasibility of this membrane structure for an ionization method using a single peptide and mixed peptides and polyethylene glycol samples and a commercial matrix‐assisted laser desorption/ionization (MALDI) time‐of‐flight mass spectrometer in the positive ion mode.

Results

Results showed a softness of ionization and no sweet spot nature. The capillary action of the through holes with very high aspect ratio enables several loading protocols including sample impregnation from the surface opposite to the laser exposure side.

Conclusions

The feasibility study indicates that the through hole porous alumina membranes have several advantages in terms of usefulness over the conventional surface‐assisted laser desorption ionization (SALDI) methods. The proposed novel ionization method is termed Desorption Ionization Using Through Hole Alumina Membrane (DIUTHAME).