Formation and fragmentation of doubly and triply charged ions in the negative ion spectra of neutral N-glycans from viral and other glycoproteins

Structural determination of N-glycans by mass spectrometry is ideally performed by negative ion collision-induced dissociation because the spectra are dominated by cross-ring fragments leading to ions that reveal structural details not available by many other methods. Most glycans form [M – H]- or [M + adduct]- ions but larger ones (above approx. m/z 2000) typically form doubly charged ions. Differences have been reported between the fragmentation of singly and doubly charged ions but a detailed comparison does not appear to have been reported. In addition to [M + adduct]- ions (this paper uses phosphate as the adduct) other doubly, triply, and quadruply charged ions of composition [Mn + (H2PO4)n]n- have been observed in mixtures of N-glycans released from viral and other glycoproteins. This paper explores the formation and fragmentation of these different types of multiply charged ions with particular reference to the presence of diagnostic fragments in the CID spectra and comments on how these ions can be used to characterize these glycans. Graphical abstract

Identification and Study of Biomarkers from Novichok-Inhibited Butyrylcholinesterase in Human Plasma

To identify biomarkers of ethyl (1-(diethylamino)ethylidene)phosphoramidofluoridate (A234)- or methyl (1-(diethylamino)ethylidene)phosphoramidofluoridate (A232)-inhibited butyrylcholinesterase (BChE), we investigated nonapeptide adducts containing the active site serine, which plays a key role in enzyme activity, using LC-MS/HRMS. Biomarkers were acquired as expected, and they exhibited a significant amount of fragment ions from the inhibiting agent itself, in contrast to the MS2 spectra of conventional nerve agents. These biomarkers had a higher abundance of [M+2H]2+ ions than [M+H]+ ions, making doubly charged ions more suitable for trace analysis.

The influence of photo-induced processes and charge transfer on carbon and oxygen in the lower solar atmosphere

To predict line emission in the solar atmosphere requires models which are fundamentally different depending on whether the emission is from the chromosphere or the corona. At some point between the two regions, there must be a change between the two modelling regimes. Recent extensions to the coronal modelling for carbon and oxygen lines in the solar transition region have shown improvements in the emission of singly- and doubly-charged ions, along with Li-like ions. However, discrepancies still remain, particularly for singly-charged ions and intercombination lines. The aim of this work is to explore additional atomic processes that could further alter the charge state distribution and the level populations within ions, in order to resolve some of the discrepancies. To this end, excitation and ionisation caused by both the radiation field and by atom-ion collisions have been included, along with recombination through charge transfer. The modelling is carried out using conditions which would be present in the quiet Sun, which allows an assessment of the part atomic processes play in changing coronal modelling, separately from dynamic and transient events taking place in the plasma. The effect the processes have on the fractional ion populations are presented, as well as the change in level populations brought about by the new excitation mechanisms. Contribution functions of selected lines from low charge states are also shown, to demonstrate the extent to which line emission in the lower atmosphere could be affected by the new modelling.

Inelastic Processes of Electron Interaction with Chalcogens in the Gaseous Phase (a Review)

Complex research of elementary pair collision processes occurring when low-energy (0–70 eV) electrons pass through chalcogen (S, Se, Te) vapor has been carried out in the evaporation temperature intervals of those elements (T = 320÷700 K for sulfur, 420÷490 K for selenium, and 400÷600 K for tellurium). The vapor compositions of indicated elements are studied using the mass spectroscopy method. The radiation spectra are analyzed in the wavelength interval from 200 to 600 nm with the help of optical spectroscopy. Using highly monoenergetic electron beams, the total (integral) formation cross-sections for positive and negative S, Se, and Te ions are measured. It is found that, under the experimental conditions, the main components of chalcogen vapor are molecules containing 2 to 8 atoms. At the energies of bombarding electrons below 10 eV, the emission spectra mainly consist of bands of diatomic molecules, and, at higher energies (E > 15 eV), there appear separate atomic and ionic lines. At E = 50 eV, the lines of singly charged ions are the most intense ones. It is shown that the most effective reaction channel is the interaction of electrons with diatomic molecules of indicated elements, whereas other processes are mainly associated with the decay of polyatomic molecules. The excitation and ionization thresholds for interaction products are found by analyzing the energy dependences of process characteristics. Specific features are also observed in the energy dependences of the excitation and ionization functions. Doubly charged ions of diatomic sulfur molecules, as well as selenium and tellurium atoms, are revealed for the first time. The appearance of triply charged ions of diatomic sulfur molecules is also detected. The main contribution to the total (integral) effective ionization cross-section of both positive and negative ions is proved to be made by the interaction processes of electrons with diatomic molecules S2, Se2, and Te2. Besides the experimental research, a detailed theoretical study is carried out. Calculations with a theoretical analysis of their results are performed for the structural characteristics of homoatomic sulfur, Sn, selenium, Sen, and tellurium, Ten, molecules with n = 2÷8; namely, interatomic distances, ionization potentials, electron affinity energies, and dissociation energies. The energy characteristics are applied to calculate the appearance energies for singly and doubly charged ionic fragments of those molecules at the dissociative ionization. The obtained results are carefully compared with the available experimental and theoretical data.

IONOMETRIC DETERMINATION OF ZINC IN MILK

The possibility of ionometric determination of zinc in the rhodanide complex form in milk is represented. The indicator electrode was ion-selective electrode (ISE) with solution of tetradecylammonium bromide in nitrobenzene as a membrane. As a complexing agent the potassium thiocyanate with 1.0 mol/l optimal concentration in investigated solutions was selected. The calibration dependence E = f(pCZn(II)) were typical anionic functions. The steepness of the electrode function (29±2 mV/pC), close to the theoretical value for the doubly−charged ions, suggests that the electrochemically active anions are [Zn(NCS)4]2-. The interval of linearity of calibration curves is 1.0 to 5.7 pC, the detection limit is equal to 1∙10-6 mol/l. The selectivity of determination of zinc in the rhodanide complex form was investigated with “The mixed solutions” method in the presence of potassium, calcium, aluminum, iron (III), manganese (II), copper (II) chlorides potassium iodide and nitric acid solutions. The background concentration of extraneous (j) substances in investigated solutions was calculated with usage of published data and corresponds to their maximum content in milk. It was founded that the ionometric determination of zinc is possible in range from 1.0 to 5.0 pC for all investigated j-ions. The technique for different types of milk was developed including preliminary sample preparation, used in special certified laboratories and based on dry mineralization of sample and dissolving in nitric acid solution. The concentrations of zinc-ions in analyzed samples were determined with “limiting solutions” method. The correctness of obtained data was confirmed with “entered-found” scheme. The relative standard deviation was not higher then 0.08.

Triatomic molecules

Double ionisation of the triatomic molecules presented in this chapter shows an added degree of complexity. Besides potentially having many more electrons, they have three vibrational degrees of freedom (three normal modes) instead of the single one in a diatomic molecule. For asymmetric and bent triatomic molecules multiple modes can be excited, so the spectral bands may be congested in all forms of electronic spectra, including double ionisation. Double photoionisation spectra of H2O, H2S, HCN, CO2, N2O, OCS, CS2, BrCN, ICN, HgCl2, NO2, and SO2 are presented with analysis to identify the electronic states of the doubly charged ions. The order of the molecules in this chapter is set first by the number of valence electrons, then by the molecular weight.

Molecules with four, five or seven atoms

Double photoionisation spectra of NH3, C2H2, HCHO, C2N2, PCl3, CH4, the methyl halides CH3F, CH3Cl, CH3I, the methylene halides CH2Cl2, CH2Br2, CH2I2, the carbon tetrahalides CF4, CCl4, CBr4, germanium tetrahalides GeCl4, GeBr4, and SF6 are presented with analysis to identify the electronic states of the doubly charged ions. The effects of indirect double ionisation pathways are discussed. There are relatively few important molecules with just four atoms, but most of the ones included here are present and sometimes abundant in planetary and astrophysical environments. The range of five-atom molecules includes methane and all its simple derivatives. Where possible closely related molecules are grouped together in this chapter, as much of the discussion of their electronic structure is the same for all members of a group. This chapter also includes SF6 as a closely related molecule, even though its atom count goes beyond those of some molecules in later chapters.