Synthetic potential of molluscan sulfatases for the library synthesis of regioselectively O-sulfonated D-galacto-sugars.
The substrate specificities of three molluscan sulfatases (E.C. 3.1.6.1; snail, abalone, and limpet origins) were investigated with assorted p-nitrophenyl (pNP) di-O-sulfonated beta-D-galactopyranosides and beta-lactosides [3,6-SO(3) Gal (1), 3',6'-SO(3) Lac (2), 4, 6SO(3) Gal (3), 2,6-SO(3) Gal (4), 3,4-SO(3) Gal (5), and 3,6-SO(3) GalNAc (6); Ac, acetyl; Gal, galactose; Lac, lactose] together with mono-O-sulfonated beta-D-galactopyranoside [pNP 3SO(3)-Gal (7)] and tri-O-sulfonated alpha-D-galactopyranoside [2,3,6-SO(3)-alpha-Gal (11)]. Some notable differences between the substrate specificity of the three sulfatases were disclosed; snail sulfatase hydrolyzed the 3O- and 2O-sulfo groups of 1 and 4, respectively, to afford 6SO(3) Gal (9) in high yields, while the abalone enzyme did not act on 4. Only the limpet enzyme could cleave the 3O-sulfo groups of 7 to give pNP beta-galactoside. In contrast, every enzyme could utilize 11 as a good substrate to afford a mixture of 6SO(3)-alpha-Gal (13) and 2,6-SO(3) alpha-Gal (12). None of the enzymes could cleave the O-sulfo groups of 5 and 6, which indicates that a primary 6O-sulfo group tends to promote the enzymatic hydrolysis of O-sulfo groups at the secondary positions.
Uzawa
Hirotaka
H
Laboratory of Advanced Bioelectronics, National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 11-1 Higashi, Tsukuba 305-8565, Japan. h.uzawa@aist.go.jp
Nishida
Yoshihiro
Y
Sasaki
Kenji
K
Minoura
Norihiko
N
Kobayashi
Kazukiyo
K
D000818:Animals; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D020650:Combinatorial Chemistry Techniques / Q000379:methods; D005690:Galactose / Q000031:analogs & derivatives* / Q000096:biosynthesis / Q000138:chemical synthesis*; D007700:Kinetics; D008969:Molecular Sequence Data; D008974:Mollusca / Q000201:enzymology*; D013237:Stereoisomerism; D013379:Substrate Specificity; D013429:Sulfatases / Q000378:metabolism*; D013450:Sulfones / Q000737:chemistry*
D013450:Sulfones; D013429:Sulfatases; D005690:Galactose