title: Production of polyselenodipenicillamines, unique selenium compounds.
abstract: Selenite (H(2)SeO(3)) reacts with thiol compounds (RSH) under acidic conditions to form selenotrisulfides (RSSeSR, i.e. monoselenodithiols). The stoichiometry of the reaction is proposed as 4RSH+H(2)SeO(3)-->RSSeSR+RSSR+3H(2)O. Surprisingly, we found novel polynuclear selenium-containing compounds, i.e. polyselenodipenicillamines (PenSSe(2-4)SPen), in the reaction of D-penicillamine (PenSH) with H(2)SeO(3). The selenium-centered features of PenSSe(2-4)SPen were determined by (1)H-NMR and LC-MS/MS analyses, showing that the selenium isotope abundance patterns of the compounds were in good agreement with the theoretically-calculated ones. In order to better understand the mechanisms for PenSSe(2-4)SPen production, various molar ratio of H(2)SeO(3) (1/8 to 4 times of PenSH) was reacted with PenSH, and the concentration of the products was calculated from integral values of dimethyl proton signals for PenSSe(1-2)SPen as compared with methyl proton signals for acetic acid (an internal standard). Total PenSSe(1-2)SPen concentration was increased with increasing of H(2)SeO(3), in which concomitant decrease of PenSSPen (disulfide form of PenSH) was observed. Based on these results, we proposed the PenSSe(2-4)SPen production mechanisms being involved in penicillamine selenopersulfides (PenSSe(1-2)H).
authors.affiliation: Faculty of Pharmacy, Meijo University, Nagoya 468-8503, Japan.
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Nishida
authors.forename: Motozumi
authors.initials: M
authors.lastname: Ando
authors.forename: Kazuo
authors.initials: K
authors.lastname: Itoh
authors.forename: Koji
authors.initials: K
authors.lastname: Ueda
authors.forename: Yujiro
authors.initials: Y
authors.lastname: Nishida
authors.forename: Yoshinori
authors.initials: Y
authors.lastname: Okamoto
authors.forename: Chitose
authors.initials: C
authors.lastname: Toda
authors.forename: Nakao
authors.initials: N
authors.lastname: Kojima
mesh_terms: D002851:Chromatography, High Pressure Liquid; D009682:Magnetic Resonance Spectroscopy; D016566:Organoselenium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010396:Penicillamine / Q000737:chemistry*; D018036:Selenium Compounds / Q000737:chemistry; D018038:Sodium Selenite / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry; D053719:Tandem Mass Spectrometry
chemical_list: D016566:Organoselenium Compounds; D018036:Selenium Compounds; D013440:Sulfides; C059755:selenotrisulfide; D010396:Penicillamine; D018038:Sodium Selenite