What Ion Is Generated When Ionizing Acetonitrile?

Petris, Giulia de; Fornarini, Simonetta; Crestoni, Maria Elisa; Troiani, Anna; Mayer, Paul M.

doi:10.1021/jp051484u

Cited by 14 publications

(23 citation statements)

References 15 publications

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“…Several calculations concerning isomerization and dissociation of molecular cations similar to acrylonitrile have been carried out in the past few years [27][28][29] using aspects of the transition state theory. However, to our knowledge no such theoretical study has been published for molecular dications of simple nitrile molecules.…”

Section: Dissociation and Isomerizationmentioning

confidence: 99%

Fragmentation patterns of doubly charged acrylonitrile molecule following carbon core ionization

Itälä

Kukk

et al. 2009

The Journal of Chemical Physics

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Dissociation of acrylonitrile into pairs of cations and neutral fragments following molecular core ionization was investigated using the photoelectron-photoion-photoion coincidence (PEPIPICO) technique. The fragment ion mass spectra were recorded in coincidence with the carbon 1s photoelectrons. Deuterated and (13)C-substituted samples were used for resolving fragment mass ambiguities. Slope analysis of the PEPIPICO patterns was used in determining the fragment separation sequences in case of multiparticle processes. The results show that there are several fragmentation channels producing a wide range of charged coincident fragments. The dynamics of the dominant fragmentation processes is investigated in detail.

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Section: Dissociation and Isomerizationmentioning

confidence: 99%

Fragmentation patterns of doubly charged acrylonitrile molecule following carbon core ionization

Itälä

Kukk

et al. 2009

The Journal of Chemical Physics

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“…We also pinpoint the effects due to solvation by separate simulations. The molecule has been suggested to exist in H 3 C-CRN and H 2 CQCQNH isomers, 20,21 which we study separately. We present an experiment performed at several incident energies and find basic agreement with a previous experiment performed at 400.45 eV.…”

mentioning

confidence: 99%

Density functional simulation of resonant inelastic X-ray scattering experiments in liquids: acetonitrile

Niskanen

Kooser

Koskelo

et al. 2016

Phys. Chem. Chem. Phys.

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In this paper we report an experimental and computational study of liquid acetonitrile (HC-C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the HC-C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.

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“…The MS spectrum showed that the product NQ2b was formed though it was observed that ACN (solvent used to dissolve the crystal) reacted with the product to give the structure identified in the mass spectrum for NQ2b in the Supplementary Information. It has been reported that ACN (CH 3 CN) can ionise in a mass spectrometer possibly as CH 3 CN + , CH 2 CN + , CHCN + , CCN + , CN + , CH 3 + , C + and H + [41–44] . The characterisation results of NQ2a, NQ2b and NQ2c showed that they are all the same compound and NQ2b is a crystalline form of the product.…”

Section: Resultsmentioning

confidence: 99%

“…It has been reported that ACN (CH 3 CN) can ionise in a mass spectrometer possibly as CH 3 CN + , CH 2 CN + , CHCN + , CCN + , CN + , CH 3 + , C + and H + . [41][42][43][44] The characterisation results of NQ2a, NQ2b and NQ2c showed that they are all the same compound and NQ2b is a crystalline form of the product. The characterisation results for products NQ2b, NQ2c, NQ1, AQP and PQP are provided in Supplementary Information.…”

Section: Product Analysismentioning

confidence: 99%

Understanding the Role of pH in Protein‐Haptenation Reaction: Kinetics and Mechanisms of the Protein‐Haptenation Reactions of Selected Quinones Present in the Environment

Olusegun

Martincigh

2020

ChemistrySelect

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There are several xenobiotics (allergens) in the environment which may induce allergic contact dermatitis (ACD), an occupational and environmental health disease. This health disease is of global concern because it has no cure and can only be managed in affected individuals by preventing them from further exposure to these allergens. The following quinones (Q) are known to be air pollutants: 1,2‐naphthoquinone (1,2‐NQ), 1,4‐naphthoquinone (1,4‐NQ), 9,10‐phenanthraquinone (PQ), and 9,10‐anthraquinone (AQ). There have been studies on the cytotoxicity of these air pollutants, but no kinetic studies have been carried out on them to determine their chemical reactivity and, more especially, their interaction with model proteins so as to ascertain if they can react with skin proteins thereby causing allergic reactions. This article provides details on the kinetics studies carried out on the protein‐haptenation reactions of these quinones with 4‐nitrobenzenethiol (NBT), a model nucleophile, as well as the mechanisms of their reactions. The NBT−Q reactions were investigated under pseudo‐first‐order conditions at various concentration ratios at a temperature of 25 °C at three different pH values by either ultraviolet‐visible (UV‐Vis) or stopped‐flow spectrophotometry, as appropriate. The reaction rate constants obtained for the NBT−Q reactions were in the following order: at pH 7.42: 1,2‐NQ>1,4‐NQ>PQ>AQ while at pH 5.65, the order was observed to be 1,2‐NQ>1,4‐NQ>PQ>AQ and at pH 8.41, it was 1,4‐NQ>PQ>AQ>1,2‐NQ. These trends for the reaction rate constants of the Q at the three pH values can be attributed to inductive effects and the position of oxo‐groups on the phenyl rings. The NBT−Q reactions were further investigated by determining the effect of ionic strength on the reaction rate constants with potassium sulphate as the background electrolyte. Our findings showed that there are no charged species at the transition state of the NBT−Q reactions. The products of the NBT−Q reactions were isolated and characterized by means of UV‐Vis and FTIR spectrophotometry and NMR and TOF‐MS spectrometry. The deduced mechanisms for the NBT−Q reactions were validated by computer simulation with “Simkine3” software.

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What Ion Is Generated When Ionizing Acetonitrile?

Cited by 14 publications

References 15 publications

Fragmentation patterns of doubly charged acrylonitrile molecule following carbon core ionization

Fragmentation patterns of doubly charged acrylonitrile molecule following carbon core ionization

Density functional simulation of resonant inelastic X-ray scattering experiments in liquids: acetonitrile

Understanding the Role of pH in Protein‐Haptenation Reaction: Kinetics and Mechanisms of the Protein‐Haptenation Reactions of Selected Quinones Present in the Environment

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