Ionization Scenarios Research Articles

Monitoring organic reactions with on‐line atmospheric pressure ionization mass spectrometry: the hydrolysis of isatin

Time-resolved electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for interrogating solution-phase reaction systems. Both mechanistic and kinetic information can be obtained using this technique. The title reaction offers the opportunity to examine the effects of different ionization scenarios with regard to monitoring reactant consumption and product formation. The hydrolysis of isatin was monitored in real time using a variety of ESI schemes: positive ion ([M + H]+, [M + Li]+, [M + Na]+) and negative ion [M − H]−. The utility of each ionization approach, with respect to the spectral features afforded for reaction tracking was examined. A comparison of first-order hydrolysis kinetics data obtained using negative ion mass spectrometry is made with data acquired via an optical technique. Copyright © 2001 John Wiley & Sons, Ltd.

Monitoring organic reactions with on‐line atmospheric pressure ionization mass spectrometry: the hydrolysis of isatin

AbstractTime‐resolved electrospray ionization mass spectrometry (ESI‐MS) is a powerful tool for interrogating solution‐phase reaction systems. Both mechanistic and kinetic information can be obtained using this technique. The title reaction offers the opportunity to examine the effects of different ionization scenarios with regard to monitoring reactant consumption and product formation. The hydrolysis of isatin was monitored in real time using a variety of ESI schemes: positive ion ([M + H]+, [M + Li]+, [M + Na]+) and negative ion [M − H]−. The utility of each ionization approach, with respect to the spectral features afforded for reaction tracking was examined. A comparison of first‐order hydrolysis kinetics data obtained using negative ion mass spectrometry is made with data acquired via an optical technique. Copyright © 2001 John Wiley & Sons, Ltd.

Is There a Detectable Vishniac Effect?

The dominant linear contribution to cosmic microwave background (CMB) fluctuations at small angular scales (≲1') is a second-order contribution known as the Vishniac or Ostriker-Vishniac effect. This effect is caused by the scattering of CMB photons off free electrons after the universe has been reionized, and is dominated by linear perturbations near the RV = 2 Mpc/(hΓ/0.2) scale in the cold dark matter cosmogony. As the reionization of the universe requires that nonlinear objects exist on some scale, however, one can compare the scale responsible for reionization to RV and ask whether a linear treatment is even feasible in different scenarios of reionization. For an Ω0 = 1 cosmology normalized to cluster abundances, only ~65% of the linear integral is valid if reionization is due to quasars in halos of mass ~109 M☉, while ~75% of the integral is valid if reionization was caused by stars in halos of ~106 M☉. In Λ or open cosmologies, both the redshift of reionization and zV are pushed farther back, but still only ~75% to ~85% of the linear integral is valid, independent of the ionization scenario. We point out that all odd higher order moments from Vishniac fluctuations are zero, while even moments are nonzero, regardless of the Gaussianity of the density perturbations. This provides a defining characteristic of the Vishniac effect that differentiates it from other secondary perturbations and may be helpful in separating them.