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Supramolecular Phosphatases Formed by the Self‐Assembly of the Bis(Zn2+–Cyclen) Complex,Copper(II), and Barbital Derivatives in Water
Authors:Dr. Mohd Zulkefeli  Dr. Yosuke Hisamatsu  Asami Suzuki  Yuya Miyazawa  Dr. Motoo Shiro  Prof. Dr. Shin Aoki
Affiliation:1. Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278‐8510 (Japan), Fax: (+81)?4‐7121‐3670;2. Faculty of Pharmacy, Universiti Teknologi MARA, Puncak Alam, Selangor 42300 (Malaysia);3. Center for Technologies against Cancer, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278‐8510 (Japan);4. Rigaku Corporation X‐ray Research Laboratory, 3‐9‐12 Matsubaracho, Akishima, Tokyo 196‐8666 (Japan)
Abstract:In our previous paper, we reported that a dimeric Zn2+ complex with a 2,2′‐bipyridyl linker (Zn2L1), cyanuric acid (CA), and a Cu2+ ion automatically assemble in aqueous solution to form 4:4:4 complex 3 , which selectively catalyzes the hydrolysis of mono(4‐nitrophenyl)phosphate (MNP) at neutral pH. Herein, we report that the use of barbital (Bar) instead of CA for the self‐assembly with Zn2L1 and Cu2+ induces 2:2:2 complexation of these components, and not the 4:4:4 complex, to form supramolecular complex 6 a , the structure and equilibrium characteristics of which were studied by analytical and physical measurements. The finding show that 6 a also accelerates the hydrolysis of MNP, similarly to 3 . Moreover, inspired by the crystal structure of 6 a , we prepared barbital units that contain functional groups on their side chains in an attempt to produce supramolecular phosphatases that possess functional groups near the Cu2(μ‐OH)2 catalytic core so as to mimic the catalytic center of alkaline phosphatase (AP).
Keywords:copper  hydrolysis  self‐assembly  supramolecular chemistry  zinc
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