Abstract: A method is provided for calibrating mass-to-charge ratio measurements obtained from a time-of-flight mass spectrometer used as a detector for a chromatographic system. The method can include introducing a calibrant material into the time-of-flight mass spectrometer after a sample is introduced to the chromatographic system, but before the analysis of the sample is complete, such that calibrant material and sample material are not present at the ion source of the mass spectrometer, contemporaneously. The method can include acquiring a multiplicity of mass spectra of the calibrant material during an analytical run, and in some embodiments, calculating a multiplicity of mass calibrations on the basis of mass spectra obtained from the calibrant material introduced during the analytical run.

Abstract: A method is provided for calibrating mass-to-charge ratio measurements obtained from a time-of-flight mass spectrometer used as a detector for a chromatographic system. The method can include introducing a calibrant material into the time-of-flight mass spectrometer after a sample is introduced to the chromatographic system, but before the analysis of the sample is complete, such that calibrant material and sample material are not present at the ion source of the mass spectrometer, contemporaneously. The method can include acquiring a multiplicity of mass spectra of the calibrant material during an analytical run, and in some embodiments, calculating a multiplicity of mass calibrations on the basis of mass spectra obtained from the calibrant material introduced during the analytical run.

Abstract: A method of thermally modulating a tubular member carrying a sample substance therethrough is provided. The method includes the steps of (a) directing at least one gas stream toward a tubular member in a direction substantially transverse to the tubular member, wherein the temperature of the gas stream differs from the temperature of the tubular member; and (b) varying the gas flow rate of the at least one gas stream as a function of time to thermally modulate the tubular member. An apparatus is also provided for thermal modulation and includes: a tubular member for carrying a sample substance therethrough in a fluid medium; a gas stream source for directing a gas stream toward the tubular member in a direction substantially transverse to the tubular member; a gas stream supplied from the source with a temperature that differs from the temperature of the tubular member; and a gas stream of varying gas flow rate supplied from the gas stream source as a function of time to thermally modulate the tubular member.