Facilitated proton ionization

Yeast pyrophosphatase uses a water molecule bound between two Mg2+ ions as the nucleophile to attack bound Mg-pyrophosphate. Aspll7 acts as a general base to deprotonate this bound water, whose pK is 5.85.42 It was suggested on the basis of X-ray structures and the similar pICs that the hydrogen bond between Aspll7 and the nucleophilic water was a low-barrier one.43 Coordination to both Mg2+ ions as well as formation of a low-barrier hydrogen bond should certainly be sufficient to lower the pX of the bound water to the observed value. 

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The FAB matrix is essentially a nonvolatile liquid material, such as those illustrated in Scheme 1, that serves to constantly replenish the surface with new sample as the incident ion beam bombards the surface. The matrix also serves to minimize sample damage from the high-energy particle beam by absorbing most of the incident energy and is believed to facilitate the ionization process. The spectrum produced often includes matrix peaks along with some fragments and a peak for the protonated or cationized (i.e., M + Na+) molecular ion. 

The presence of an ionized aspartic acid next to histidine raises its basicity and facilitates proton transfer from Ser-195 in the direction of His-57. If the proton resides on histidine, this side chain is positively charged. The charge is stabilized by the neighboring Asp-102, which may also stabilize the conformation of His-57. In some earlier proposals for SP mechanisms, it was assumed that a "double PT" or "charge relay" system is operating between the catalytic triad residues, and two PTs, the second being from His to Asp, take place. 

Owing to their relatively low ionization energies (IE) of ca 8.0-8.5 eV, phenols are also good electron donor solutes. Recent experimental studies of phenols in non-protic solvents showed that ionized solvent molecules react with phenol to yield not only phenol radical cations by electron transfer, but also phenoxy radicals by hydrogen transfer. An obvious question is whether, under these conditions, the latter radicals were formed from ionized phenols rather than by direct hydrogen abstraction, because proton transfer reactions could be facilitated upon ionization. This also raises a question about the influence of solvent properties, both by specific and non-specific interactions, on the mechanism and kinetics of deprotonation processes ... 

MALDI-TOF-MS facilitates the analysis of carotenoids and other natural products with detection limits that are lower than most other techniques. For example, subpicomole quantities can be detected (Wingerath et al., 1999). The enhanced sensitivity is the result of the efficiency of the pulsed ionization and detection system in which a complete mass spectrum is recorded with each laser flash. Like FAB and LSIMS, molecular ions are the most abundant sample ions, although some protonated molecules and [M-H]+ ions may be formed as well. Abundant molecular ions of carotenoid esters have been observed using MALDI-TOF-MS (Kaufmann et al., 1996 Wingerath et al., 1996),... 

The APCI interface uses a heated nebulizer to form a fine spray of the HPLC eluate, which is much finer than the particle beam system but similar to that formed during thermospray. A cross-flow of heated nitrogen gas is used to facilitate the evaporation of solvent from the droplets. The resulting gas-phase sample molecules are ionized by collisions with solvent ions, which are formed by a corona discharge in the atmospheric pressure chamber. Molecular ions, M+ or M , and/or protonated or de-protonated molecules can be formed. The relative abundance of each type of ion depends upon the sample itself, the HPLC solvent, and the ion source parameters. Next, ions are drawn into the mass spectrometer analyzer for measurement through a narrow opening or skimmer, which helps the vacuum pumps to maintain very low pressure inside the analyzer while the APCI source remains at atmospheric pressure. 

The number of solvents that have been used in SrnI reactions is somewhat limited in scope, but this causes no practical difficulties. Characteristics that are required of a solvent for use in SrnI reactions are that it should dissolve both the organic substrate and the ionic alkali metal salt (M+Nu ), not have hydrogen atoms that can be readily abstracted by aryl radicals (c/. equation 13), not have protons which can be ionized by the bases (e.g. Nth- or Bu O" ions), or the basic nucleophiles (Nu ) and radical ions (RX -or RNu- ) involved in the reaction, and not undergo electron transfer reactions with the various intermediates in the reaction. In addition to these characteristics, the solvent should not absorb significantly in the wavelength range normally used in photostimulated processes (300-400 nm), should not react with solvated electrons and/or alkali metals in reactions stimulated by these species, and should not undergo reduction at the potentials employed in electrochemically promoted reactions, but should be sufficiently polar to facilitate electron transfer processes. 

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