Atmospheric photoionization

A 30-lb field-portable quadrupole ion trap TOF (QitTof) mass spectrometer with an atmospheric photoionization source was constructed [17]. The photoionization source has the ability to choose a narrow-band ionization energy that is sufficiently high to ionize and detect most compounds of interest but low enough to avoid ionization of most common air constituents, such as N2, 02, H20, C02, CO, Ar, etc. Fragmentation is minimal because ionization occurs just above the ionization thresholds, with very little excess energy. The ion trap stores ions from a continuous ionization source followed by pulsed extraction into the TOF mass analyzer. 

Detailed structural calculations have been carried out for this system. This is because the neutral isomer, C2HsO, which is implicated in the thermochemistry of ethanol, is of interest in pollution control, atmospheric chemistry, and combustion. Also, there is new information available from photoionization experiments with which to compare theoretical calculations. For details of these comparisons, see Curtiss et al.73 In the earlier theoretical studies of Nobes et al.,74 calculations were performed at the MP2 and MP3 levels with basis sets of double plus polarization (6-13G ) with electron correlation. These studies revealed four stable minima for the system protonated acetaldehyde, CHj-C H-OH <-> CH3-CH=0+H the methoxymethyl cation, CH3OCH2 protonated oxirane, (CH2)2OH+ and vinylox-... 

LC-MS-MS was also the method of choice for the analysis of UV filters in solid matrices. Both LC and UPLC have been applied in three out of the four methods available for the determination of UV filters in sludge. Separation was performed on C8 and C18 LC-chromatographic columns (Zorbax, Eclipse, Vydac, and Purosphere) using binary gradient elution of mobile phases consisting of water/ methanol or water/acetonitrile. MS-MS detection was performed in SRM with ESI and atmospheric pressure photoionization (APPI) in both positive and negative modes. For each compound, two characteristics transitions were monitored. In addition to MS and MS-MS, diode array detection (DAD) was occasionally applied to the determination of OT. Spectra were recorded between 240 and 360 nm and discrete channels at 310 nm. 

The most important techniques belonging to this class are electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and, more recently, atmospheric pressure photoionization (APPI). At present the latter does not have applications in cultural heritage, so it will be not described here. 

Rauha JP, Vuorela H and Kostiainen R. 2001. Effect of eluent on the ionization efficiency of flavonoids by ion spray, atmospheric pressure photoionization mass spectrometry. J Mass Spectrom 36 1269-1280. 

DGE a AC AMS APCI API AP-MALDI APPI ASAP BIRD c CAD CE CF CF-FAB Cl CID cw CZE Da DAPCI DART DC DE DESI DIOS DTIMS EC ECD El ELDI EM ESI ETD eV f FAB FAIMS FD FI FT FTICR two-dimensional gel electrophoresis atto, 10 18 alternating current accelerator mass spectrometry atmospheric pressure chemical ionization atmospheric pressure ionization atmospheric pressure matrix-assisted laser desorption/ionization atmospheric pressure photoionization atmospheric-pressure solids analysis probe blackbody infrared radiative dissociation centi, 10-2 collision-activated dissociation capillary electrophoresis continuous flow continuous flow fast atom bombardment chemical ionization collision-induced dissociation continuous wave capillary zone electrophoresis dalton desorption atmospheric pressure chemical ionization direct analysis in real time direct current delayed extraction desorption electrospray ionization desorption/ionization on silicon drift tube ion mobility spectrometry electrochromatography electron capture dissociation electron ionization electrospray-assisted laser desorption/ionization electron multiplier electrospray ionization electron transfer dissociation electron volt femto, 1CT15 fast atom bombardment field asymmetric waveform ion mobility spectrometry field desorption field ionization Fourier transform Fourier transform ion cyclotron resonance... 

Atmospheric pressure photoionization APPI Photoionization Nonvolatile molecular ions LC-MS Nonpolar compounds... 

I. A. Revel skii, Y. S. Yashin, V. N. Voznesenskii, V. K. Kurochkin, and R. G. Kostyanovskii. Mass Spectrometry with Photoionization of n-Alkanes, Alcohols, Ketones, Esters, and Amines at Atmospheric Pressure. Izv. AkadNauk SSSR Ser. Khim., 9(1986) 1987-1992. 

D. R. Robb, T. R. Covey, and A. P. Bruins. Atmospheric Pressure Photoionization An Ionization Method for Liquid Chromatography-Mass Spectrometry. Anal. Chem., 72(2000) 3653-3659. 

T. J. Kauppila, T. Kuuranne, E. C. Meurer, M. N. Eberlin, T. Kotiaho, and R. Kostiainen. Atmospheric Pressure Photoionization Mass Spectrometry Ionization Mechanism and the Effect of Solvent on the Ionization of Naphthalenes. Anal. Chem., 74(2002) 5470-5479. 

A. Raffaelli and A. Saba. Atmospheric Pressure Photoionization Mass Spectrometry. Mass Spectrom. Rev., 22(2003) 318-331. 

Recently, atmospheric pressure photoionization (APPl) has been introduced. [144] APPl can serve as a complement or alternative to APCl. [142,145] In APPl, a UV light source replaces the corona discharge-powered plasma, while the pneumatic heated sprayer remains almost unaffected (Pig. 11.28). [146-148]... 

Yang, C. Henion, J.D. Atmospheric Pressure Photoionization Liquid Chromatographic-Mass Spectrometric Determination of Idoxifene and Its Metabolites in Human Plasma. J. Chromatogr. A 2002, 970,155-165. 

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