Poisoning with saturated ethanol (or rectified spirit) solution of Mercuric Chloride (HgCl2) is best done before pressing the collected specimens to avoid microbial infections and insect infestation besides help prevent formation of abscission layer in angiosperms. During drying process some specimens may also need additional dose of poisoning if found with fungal or bacterial infections. For more details, Ref: Jain, S.K. and Rao, R.R. (1976) A Hand Book of Field and Herbarium Methods. Today and Tomorrow's Printers and Publishers, New Delhi.
After drying, either before or after pressing. Generally after pressing, however, if the material is prone to contamination during pressing then the material could also be poisoned before as well as after pressing.