Comparison of the stable products formed by fast atom bombardment and γ‐irradiation of glycerol

Keough, T.; Ezra, F. S.; Russell, Anne F.; Pryne, J. D.

doi:10.1002/oms.1210220503

Cited by 33 publications

(11 citation statements)

References 21 publications

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“…The proposed bubble model does not contradict notions concerning accumulation in the liquid of beam‐induced reaction products32,78,91–93 originating from the zone immediately adjacent to the bombarding particle track. On short experiment timescales, the stabilizing role of the liquid matrix and the surface ‘self‐cleaning’ process90,94,95 provide clean spectra regardless of the sputtering mechanism.…”

Section: Resultsmentioning

confidence: 74%

‘Bubble chamber model’ of fast atom bombardment induced processes

Kosevich

Shelkovsky

Boryak

et al. 2003

Rapid Comm Mass Spectrometry

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A hypothesis concerning FAB mechanisms, referred to as a 'bubble chamber FAB model', is proposed. This model can provide an answer to the long-standing question as to how fragile biomolecules and weakly bound clusters can survive under high-energy particle impact on liquids. The basis of this model is a simple estimation of saturated vapour pressure over the surface of liquids, which shows that all liquids ever tested by fast atom bombardment (FAB) and liquid secondary ion mass spectrometry (SIMS) were in the superheated state under the experimental conditions applied. The result of the interaction of the energetic particles with superheated liquids is known to be qualitatively different from that with equilibrium liquids. It consists of initiation of local boiling, i.e., in formation of vapour bubbles along the track of the energetic particle. This phenomenon has been extensively studied in the framework of nuclear physics and provides the basis for construction of the well-known bubble chamber detectors. The possibility of occurrence of similar processes under FAB of superheated liquids substantiates a conceptual model of emission of secondary ions suggested by Vestal in 1983, which assumes formation of bubbles beneath the liquid surface, followed by their bursting accompanied by release of microdroplets and clusters as a necessary intermediate step for the creation of molecular ions. The main distinctive feature of the bubble chamber FAB model, proposed here, is that the bubbles are formed not in the space and time-restricted impact-excited zone, but in the nearby liquid as a 'normal' boiling event, which implies that the temperature both within the bubble and in the droplets emerging on its burst is practically the same as that of the bulk liquid sample. This concept can resolve the paradox of survival of intact biomolecules under FAB, since the part of the sample participating in the liquid-gas transition via the bubble mechanism has an ambient temperature which is not destructive for biomolecules. Another important feature of the model is that the timescale of bubble growth is no longer limited by the relaxation time of the excited zone ( approximately 10(-12) s), but rather resembles the timescale characteristic of common boiling, sufficient for multiple interactions of gas molecules and formation of clusters. Further, when the bubbles burst, microdroplets are released, which implies that FAB processes are similar to those in spraying techniques. Thus, two processes contribute to the ion production, namely, release of volatile solvent clusters from bubbles and of non-volatile solute from sputtered droplets. This view reconciles contradictory views on the dominance of either gas-phase or liquid-phase effects in FAB. Some other effects, such as suppression of all other ions by surface-active compounds, are consistent with the suggested model.

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Section: Resultsmentioning

confidence: 74%

‘Bubble chamber model’ of fast atom bombardment induced processes

Kosevich

Shelkovsky

Boryak

et al. 2003

Rapid Comm Mass Spectrometry

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“…The samples of ethylene glycol and glycerol were crimpsealed within 20 ml round-bottomed GC-MS (Gas Chromatography-Mass Spectrometry) headspace vials with a mostly inert nitrogen atmosphere. In existing radiolysis literature, [8][9][10] organic volatile losses were problematic when preparing samples for analysis.…”

Section: A Irradiation Methodsmentioning

confidence: 99%

“…Radiation research has been limited to explore the effects of gamma and ion beams. [8][9][10] There has been no available literature for the interactions of neutrons on glycerol or many other organic compounds, therefore the use of neutron or 'pile' irradiation has potentially been overlooked as a source of intense energy to catalyse reactions.…”

Section: Introductionmentioning

confidence: 99%

Producing Useful Chemicals Using a Nuclear Reactor

et al. 2020

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In this paper, the irradiation of glycerol and ethylene glycol by either mixed (neutron-γ) or γ-only (γ) fields at the TRIGA reactor of the Jožef Stefan Institute is described. This is highly relevant to future applications of fission reactor systems to produce useful feedstock derivatives from organic waste, beyond the production of heat and power. Samples of glycerol and ethyl glycol have been exposed to neutron-gamma radiation with fast neutron fluxes ranging from 7.7×1010 to 3×1012 cm−2s−1 and gamma-only irradiation at maximum dose-rates of 492 and 10 kGy hr−1, respectively. A study of the dependence of product yield versus absorbed dose has been conducted, for total dose ranges of 1 to 100 kGy. The products of these exposures have been identified through Gas Chromatography – Mass Spectrometry (GC-MS) techniques. Analysis comparing neutron-gamma irradiated samples of ethylene glycol and glycerol with gamma-irradiated samples shows no detectable qualitative difference between either irradiation type. Although, additional radiolysis products were detected when compared with available literature; ethyl acetate from ethylene glycol and solketal from glycerol. Quantitatively, neutron-gamma irradiation seems to be less effective at producing acetaldehyde from ethylene glycol, compared with gamma-only which can be explained through neutron moderation and consequent heating effects due to the borosilicate vials.

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“…Equations [2], [5], and [6], with application of the steady- [l], [3], [4], and [7], also leads to a predicted independence of C+ concentration. In the particular case where the rate of protonation of C' (eq.…”

Section: Dependence On Cation Concentrationmentioning

confidence: 99%

“…Adduct ion formation and dehalogenation reactions may result from reaction of the "analyte" with atomic or free radical species generated from the matrix by particle bombardment (1)(2)(3). Reduction reactions have been reported for organic and inorganic salts (4, 5), organometallics (6), nucleosides (7), and organic dyestuffs (5,8).…”

Section: Introductionmentioning

confidence: 99%

Reduction processes in the fast atom bombardment mass spectra of pyridinium salts. The effect of reduction potential and concentration

Kazakoff¹,

Rye²,

Tee³

1989

Can. J. Chem.

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The enhancement of the (C + 1)/C ratio in the fast atom bombardment mass spectra of seven pyridinium cations has been measured. No dependence of the enhancement on the cation reduction potential could be identified. The N-methyl pyridinium cation, which showed no enchancement under matrix-free conditions, exhibited an increase in the (C + l)/Cratio with decreasing concentration. This concentration dependence was eliminated when the bombardment energy was reduced from 9 to 5 keV. Possible mechanisms for the concentration dependence and the variation with bombardment energy are proposed.

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Comparison of the stable products formed by fast atom bombardment and γ‐irradiation of glycerol

Cited by 33 publications

References 21 publications

‘Bubble chamber model’ of fast atom bombardment induced processes

‘Bubble chamber model’ of fast atom bombardment induced processes

Producing Useful Chemicals Using a Nuclear Reactor

Reduction processes in the fast atom bombardment mass spectra of pyridinium salts. The effect of reduction potential and concentration

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