Enhanced silver cationization of polycyclic aromatic hydrocarbons containing bay regions in molecular secondary ion mass spectrometry

Abstract

The relative abundances of silver cationized molecules [Ag + m+ relative to molecular ions (M") in the secondary ion mass spectra of polycyclic aromatic hydrocarbons (PAHs) are directly related to the structures of the PAHs. Compounds containing a 'bay region', a concave area at the periphery of the molecule, give [Ag + MI+ : M+' abundance ratios which exceed 0.62, whereas this ratio is less than 0.18 for the molecules that lack this structural feature. This allows the recognition of PAHs containing bay regions and the distinction of certain isomeric PAHs, such as phenanthrene and anthracene. Other metals, including copper and nickel, show similar behavior.

Rapid In Vivo Fingerprinting of Nonvolatile Compounds in Breath by Extractive Electrospray Ionization Quadrupole Time‐of‐Flight Mass Spectrometry

“…However, the spectrum showed no signals corresponding to nonpolar sulfur-containing compounds. To address this problem, a highly sulfurselective in situ silver cationization method, [35][36][37][38][39] in which an AgNO 3 /water solution was used to generate the electrospray, was implemented in the EESI. In the positive ESI mode, this method generates silver cations, followed by selective ion/ molecule (Ag + /M) reactions occurring in the EESI source (see Figure 1) to facilitate detection of sulfur-containing molecules.…”

Detection and Monitoring of PAH and Oxy-PAHs by High Resolution Mass Spectrometry: Comparison of ESI, APCI and APPI Source Detection

“…Yet, ESI can also be used for the detection of nonpolar compounds when ionization is favored using additives like silver [6] or tropylium [7,8]. The original work using silver cationization was performed by Hand et al [6] in solid phase using secondary ion mass spectrometry (SIMS).…”

“…Yet, ESI can also be used for the detection of nonpolar compounds when ionization is favored using additives like silver [6] or tropylium [7,8]. The original work using silver cationization was performed by Hand et al [6] in solid phase using secondary ion mass spectrometry (SIMS). Then, electron transfer reactions using an oxidant in liquid phase (methylene chloride with trifluoroacetic acid for instance) extended the application field of the ES ionization by allowing the detection of non polar compounds such as PAHs [9,10].…”

Mass spectrometry imaging under ambient conditions

“…(Girod, et al, 2010) Similarly, it is possible to improve the sensitivity of detecting trace biologically important molecules, such as olefins by silver cationization during DESI (Jackson et al, 2010) as was done earlier in SIMS. (Hand et al, 1989; Nicola et al, 1996) The success of these derivatization experiments on the millisecond time scale used for examination of individual pixels in DESI imaging is a consequence of the rate acceleration of chemical reaction in the micro droplets (Girod, 2010). This accelerated droplet chemistry is an intrinsically interesting aspect of DESI.…”