Summary: The copolymer of N‐isopropylacrylamide and 3‐(acrylamido)phenylboronic acid (82:18, $\overline M _{\rm n}$ = 47 000 g · mol−1) was prepared by free radical polymerization. The copolymer showed typical thermal precipitation behavior in aqueous solutions, its precipitation temperature (TP) being increased from 23 to 32 °C by increasing the pH from 6.5 to 9.7, because of ionization of the phenylboronate units. The pKa was evaluated as 8.9 ± 0.1 from the effect of pH on TP. At pH > 9, i.e., in the anionic form of the copolymer, TP was affected by a very low concentration of glucose (5.6 μM, ΔTP = 1–1.5 °C), because of complex formation with a high binding constant. At a higher concentration of polyols (560 μM, pH > 8) the increase of TP was maximal for the copolymer complexes with fructose (7–10 °C) and decreased in the order: fructose > glucose ≈ mannitol > pentaerythritol > galactose > Tris >glycerol. Di‐ and oligosaccharides (lactose, sucrose, and dextran) caused a slight increase of TP at pH 7.5–8.7 while no effect was observed at pH > 9. Isothermal dissolution of the copolymer suspension in water (27 °C, pH 8.5) was possible in the presence of fructose or mannitol but required higher concentrations (1.4–3.6 × 103 μM) as compared to those which enabled the shift of TP in the soluble copolymer. The dissolution rate increased with fructose concentrations.

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The copolymer of 3-(acrylamido)phenylboronic acid and N-isopropylacrylamide (82:18, Mn = 47000 g/mol) was prepared by free radical polymerization. The copolymer showed typical thermoprecipitation behavior in aqueous solutions; its phase transition temperature (TP) was 26.5 +/- 0.2 degrees C in 0.1 M glycine-NaOH buffer containing 0.1 M NaCl, pH 9.2. Due to specific complex formation of the pendant boronates with sugars, TP was strongly affected by the type of sugar and its concentration at pH 9.2. Fructose, lactulose, and glucose caused the largest increase in TP (up to 4 degrees C) at 0.56 mM concentration, attributed to the high binding affinity of the sugars to borate and phenylboronate. Among the sugars typical of nonreducing ends of oligosaccharides, N-acetylneuraminic acid had the strongest effect on TP (ca. 2 degrees C at 0.56 mM concentration and pH 9.2), while the effects of other sugars are well expressed at the higher concentrations (16 and 80 mM) and decreased in the order xylose approximately galactose >or= N-acetyllactosamine >or= mannose approximately fucose >> N-acetylglucosamine. The effect exerted on the phase transition by glycoproteins was the strongest with mucin from porcine stomach and decreased in the series mucin > horseradish peroxidase > human gamma-globulin at pH 9.2. As a first approximation, the weight percentage and/or the number of oligosaccharides in glycoproteins determined the character of their interaction with the pendant phenylboronates and, therefore, the effect on the copolymer phase transition.

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