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Published on: March 3, 2010
Ratiometric Sensing of Hydrogen Peroxide Utilizing Conformational Change in Fluorescent Boronic Acid Polymers
Kan Takeshima1, Kanako Mizuno1, Hitoshi Nakahashi1
1Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507, Japan.
Abstract:
We demonstrate that the copolymers containing boronic acid and pyrene units can be utilized for the fluorometric sensing of hydrogen peroxide (H2O2) in aqueous solutions. The copolymer exists in a relatively extended conformation in the absence of H2O2, whereas the polymer chain is contracted by the reaction of boronic acid moieties with H2O2 to form phenol groups. This conformational change induces aggregation of the originally isolated pyrene groups. As a result, relative intensity of excimer emission with respect to monomer emission increases with H2O2 concentration. Accordingly, the present methodology enables us to measure H2O2 by means of ratiometric fluorescence change in the range of 0-30 μM.
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Hydroboration-Oxidation of Alkenes
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.

