Biology and Mechanics of Blood Flows : Biology by Marc Thiriet

By Marc Thiriet

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High salt concentrations, nonvolatile salts, surface-active components, for example, phospholipids in blood-related samples, and proteins are known for their matrix effects in small-molecule quantitative bioanalysis. Nonvolatile compounds, be it sample constituents or solvent additives, may result in ionization suppression, in reducing response or S/N by extensive formation of background ions at every m/z, formation of alkali metal ion adducts or H+ /Na+ -exchange products, and/or ion source contamination.

Theoretical prediction of the collision cross section, for example, for peptides, is also possible, generally showing good correlation to experimental values [116, 117]. The on-line combination of IMS with MS results in a very attractive tool to combine analysis of conformation and shape, as performed in IMS, with the analysis of m/z and structural features, as performed in MS. IMS–MS has been pioneered by the groups of Bowers [118] and Clemmer [119, 120], developing IMS interfaced to quadrupole or TOF instruments.

In this context, the nitrogen rule is important, which states that a molecule, a M+• , or any other OE+• with an odd mass or m/z should contain an odd number of N atoms, whereas a (single-charge) EE+ with an odd m/z contains an even number of N atoms. For a known elemental composition, the nitrogen rule allows discriminating between OE+• and EE+ ions. Another useful tool is the double-bond equivalent (DBE), “degree of unsaturation,” or “ring double bond” (RDB) parameter. The DBE can be calculated from the elemental composition of the molecule of ion, using the equation: 1 1 DBE = 1 + C– (H + F + Cl + Br + I) + (N + P) 2 2 The DBE is a measure of the number of unsaturations in the molecule, that is, the number of rings and/or double bonds.

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