Field induced direct ionization

In-vivo and real-time monitoring of secondary metabolites, released from living animals and plants, using field-induced direct ionization MS, was also presented (Figure 13.8) [83]. Although real-time monitoring of metabolite profiles was not clearly demonstrated, one may suspect that the method could potentially be adopted for this purpose. However, considering that animals are positioned in front of the mass spectrometer (in the presence of an electric field and hot gas), one can only speculate on the practicality of this analytical approach. 

Figure 13.8 Real-time monitoring of animal metabolites by mass spectrometry, (a) Photograph of in-vivo analysis of a living scorpion by field-induced direct ionization mass spectrometry. (b) Mass spectrum obtained by field-induced direct ionization mass spectrometry analysis of the secretion released from a living scorpion upon stimulation [83], Reprinted by permission from Macmillan Publishers Ltd Scientific Reports [Hu, B., Wang, L, Ye, W.-C., Yao, Z.-P. (2013) In Vivo and Real-time Monitoring of Secondary Metabolites of Living Organisms by Mass Spectrometry. Sci. Rep. 3 2104]. Copyright (2013). See colour plate section for colour figure...

For most of the molecules, the electron flow is from D to A, which is supported by the anti-Aviram-Ratner mechanism of Fig. 11a. However, there may be yet another possibility, shown in Fig. 21 implicit in the analyses of Figs. 9-11 has been the Aviram and Ratner assumption [79] that auto-ionization is a less efficient competing process. If the electric field induces intramolecular ionization first by sufficiently altering the orbital energies, then the direction of electron flow may occur in the anti-AR direction (Fig. 21) ... 

Ambient MS is another advance in the field. It allows the analysis of samples with little or no sample preparation. Following the introduction of desorption electrospray ionization (DESI) [108,109], direct analysis in real time (DART) [110], and desorption atmospheric pressure chemical ionization (DAPCI) [111, 112], a number of ambient ionization methods have been introduced. They include electrospray-assisted laser desorption/ionization (ELDI) [113], matrix-assisted laser desorption electrospray ionization (MALDESI) [114], atmospheric solids analysis probe (ASAP) [115], jet desorption ionization (JeDI) [116], desorption sonic spray ionization (DeSSI) [117], field-induced droplet ionization (FIDI) [118], desorption atmospheric pressure photoionization (DAPPI) [119], plasma-assisted desorption ionization (PADI) [120], dielectric barrier discharge ionization (DBDI) [121], and the liquid microjunction surface sampling probe method (LMJ-SSP) [122], etc. All these techniques have shown that ambient MS can be used as a rapid tool to provide efficient desorption and ionization and hence to allow mass spectrometric characterization of target compounds. 

Electrodialysis. Electro dialysis processes transfer ions of dissolved salts across membranes, leaving purified water behind. Ion movement is induced by direct current electrical fields. A negative electrode (cathode) attracts cations, and a positive electrode (anode) attracts anions. Systems are compartmentalized in stacks by alternating cation and anion transfer membranes. Alternating compartments carry concentrated brine and purified permeate. Typically, 40—60% of dissolved ions are removed or rejected. Further improvement in water quaUty is obtained by staging (operation of stacks in series). ED processes do not remove particulate contaminants or weakly ionized contaminants, such as siUca. 

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... 

V (y) is the reverse bias applied in the perpendicular direction to the field-effect induced p-n junction created by the n-type surface inversion layer and the p-type substrate. The charge 2b (y) created by the immobile ionized atoms of the dopant forms the space charge region. The depletion approximation assumes that there are no mobile charges at all in the space charge regions. Under that assumption, (C.24) applies. 

Ionization Methods/Processes. The recent development of several new ionization methods in mass spectrometry has significantly improved the capability for the analysis of nonvolatile and thermally labile molecules [18-23]. Several of these methods (e.g., field desorption (FD), Californiun-252 plasma desorption (PD), fast heavy ion induced desorption (FHIID), laser-desorption (LD), SIMS, and fast atom bombardment (FAB) or liquid SIMS) desorb and ionize molecules directly from the solid state, thereby reducing the chance of thermal degradation. Although these methods employ fundamentally different excitation sources, similarities in their mass spectra, such as, the appearance of protonated, deprotonated, and/or cationized molecular ions, suggest a related ionization process. 

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