Adsorption of CO on a Pt electrode in acidic solution: Ir-acttve and -inactive CO'S adsorbed in the double-layer region

Carbon monoxide adsorbed on a smooth platinum electrode in the double-layer region was investigated in 1 M HClO₄ solution by using in situ polarization modulation IR reflection spectroscopy and an electrochemical oxidation. From the electrochemical oxidation, the adsorbed CO could be distinguished to be comprised of stable and unstable adsorbed CO's. The unstable adsorbed CO constituted about of the adsorbed CO, and corresponded to linearly adsorbed CO, but the band intensity of the linearly adsorbed CO was not proportional to the amount of unstable adsorbed CO. The stable adsorbed CO constituted about ; it was one-site adsorbed, and was an IR-inactive species. It is presumed that the IR-inactive species is adsorbed on two Pt atoms with the C-O axis parallel to the electrode surface and one of the Pt atoms bound to two CO molecules.     

Design and synthesis of carboxylate inhibitors for matrix metalloproteinases

A series of carboxylate compounds were prepared from N(alpha)-substituted 2,3-diaminopropionic acid and were tested for efficacy as matrix metalloproteinase (MMP) inhibitors. During modeling of the initial compound 10a, we utilized three-dimensional structure modeling software (InsightII/Discover Ver. 2.98). Some of the prepared carboxylate derivatives, such as carbamate compounds (12c,d, 22) and sulfonamide compounds (14b,c), proved to be effective MMP-1 inhibitors (with IC50 values of a 10(-6) M order), depending on the substituent at the N(alpha)-position of 2,3-diaminopropionic acid. Some of them were also evaluated for inhibition of stromelysin-1 (MMP-3), and the sulfonamide compound 14c exceeded the lead compound 5b in its MMP-3 inhibitory potency. For the carbamate compounds, we investigated the minimum molecular size at which the MMP-1 inhibitory potency was maintained, and found that this was P3-P1' compound 10b.     

A symmetric oxyselenenylation of simple olefins using optically active selenobinaphthyls

Asymmetric trans-addition reactions of simple olefins have been performed by using optically active 2-selenobinaphthyls 1 , 2a–g. Introduction of an amide group at the 2′-position in the binaphthyl skeleton enhances considerably the diastereomeric excess (de) of the asymmetric methoxyselenenylation. In the case of trans-olefins, introduction of another chiral center in the amide group further enhances the de due to double stereodifferentiation between the (R)-binaphthyl skeleton and the chiral amide group introduced at the 2′-position in the binaphthyl skeleton. The use of chiral nucleophiles is also effective to enhance the de for symmetrical cis-olefins.     

New crystalline polymers: poly(2,5‐dialkyl‐1,4‐phenylene oxide)s

New heat‐reversibly crystalline poly‐(alkylated phenylene oxide)s are described. the oxidative polymerization of 2,5‐dimethylphenol catalyzed by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane) copper dichloride produced poly(2,5‐dimethyl‐1,4‐phenylene oxide), which showed heat‐reversible crystallinity with a high melting point at ca. 300°C, although the isomeric polymer, poly(2,6‐dimethyl‐1,4‐phenylene oxide), never recrystallizes once melted. The polymerization of 2,5‐diethylphenol and 2,5‐dipropylphenol gave the polymers consisting of 1,4‐phenylene oxide units; the latter polymer possessed heat‐reversible crystallinity, however, the former one did not.