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Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis
Oleh:
Pluth, Michael D.
;
Bergman, Robert G.
;
Raymond, Kenneth N.
Jenis:
Article from Bulletin/Magazine
Dalam koleksi:
SCIENCE (keterangan: ada di Proquest) vol. 316 no. 5821 (Apr. 2007)
,
page 85.
Ketersediaan
Perpustakaan FK
Nomor Panggil:
S01.K.2007.04
Non-tandon:
1 (dapat dipinjam: 0)
Tandon:
tidak ada
Lihat Detail Induk
Isi artikel
Although many enzymes can promote chemical reactions by tuning substrate properties purely through the electrostatic environment of a docking cavity, this strategy has proven challenging to mimic in synthetic host-guest systems. Here, we report a highly charged, water-soluble, metal¬ligand assembly with a hydrophobic interior cavity that thermodynamically stabilizes protonated substrates and consequently catalyzes the normally acidic hydrolysis of orthoformates in basic solution, with rate accelerations of up to 890-fold. The catalysis reactiol] obeys Michaelis-Menten ~inetics and exhibits competitive inhibition, and the substrate scope displays size selectivity, consistent with the constrained binding environment of the molecular host.
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