[eng] The protonation state of the pyridine and imine nitrogen atoms on the ''electron-sink" effect was studied by DFT(B3LYP/6-31+G*) calculations in the Schiff bases formed between 3-hydroxypyridine-4-aldehyde and alanine and their Ca-carbanionic counterparts. Results indicate that the protonation of pyridine nitrogen promotes the enolimine-ketoenamine tautomerism. The importance of pyridine nitrogen on the ''electron-sink" effect in the carbanionic molecules clearly depends on the protonation state of the imine nitrogen: in the enolimine tautomers, where the imine nitrogen is deprotonated, a 70% of the electron charge is delocalized on the pyridine ring, whereas in the ketoenamine type structures, where the imine nitrogen is fully protonated, just a 20% of this charge is delocalized in this molecular moiety. The results are discussed in relation to the chemistry of some PLPdependent enzymes and the structure of their active sites.