The preparation of flavin‐containing, water‐soluble terpolymers with varying contents of quaternary ammonium and neutral monomer units is described. The composition of the polymer, that is, the polarity of the polymer chain, affects the UV/VIS absorbance spectrum of the bound flavin moiety by influencing the flavin‐solvent interaction. Aerobic oxidation of 1‐benzyl‐1,4‐dihydronicotinamide (BNAH) is accelerated as much as 17‐fold by polymer‐bound flavins, compared with free flavin. Depending on the ratio of polar/nonpolar groups in the flavin polymer and the 2‐propanol content of the aqueous reaction medium (pseudo) first‐order or Michaelis‐Menten type kinetics were observed as a function of substrate concentration. The influence of the polymer composition on flavin/BNAH complex formation (Km−1) and rate‐limiting hydride transfer step (k2) is discussed. Accumulation of the substrate in the polymer domain due to apolar interactions is one of the major factors that determine the observed rate enhancements.
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