Abstract We report on preparation of block copolymer micelles with cores exhibiting upper critical solution temperature (UCST) behavior in the range of 40–45 °C at pH 7.5 and incorporation of such micelles into layer-by-layer (LbL) films to obtain UCST-type multilayer films. Pyridine units of poly(2-vinylpyridine- b -ethylene oxide) (P2VP- b -PEO) were partially quaternized and its self-assembly into micellar aggregates was achieved in the presence of potassium hexacyanoferrate (K 3 Fe(CN) 6 ) at pH 7.5 at either 25 °C or 37.5 °C. The cores of the resulting (QP2VP + [Fe(CN) 6 ] 3− )- b -PEO micelles exhibited UCST-type behavior at pH 7.5 and the critical temperature varied in the range of 40–45 °C depending on the micellization temperature and amount of K 3 Fe(CN) 6 . Our results showed that micellization temperature and K 3 Fe(CN) 6 concentration were highly critical on the UCST of the micellar cores. In case of (QP2VP + [Fe(CN) 6 ] 3− )- b -PEO micelles prepared at 25 °C, increasing K 3 Fe(CN) 6 concentration during micellization suppressed UCST behavior within a temperature range of 25-50 °C. In contrast, increasing K 3 Fe(CN) 6 concentration induced only small shifts in UCST when (QP2VP + [Fe(CN) 6 ] 3− )- b -PEO micelles were produced at 37.5 °C. Moreover, we showed that (QP2VP + [Fe(CN) 6 ] 3− )- b -PEO micelles could be incorporated into LbL films using Tannic Acid (TA) at pH 7.5. Multilayers which partially disintegrate near above 40 °C could be assembled by controlling micellization temperature and film deposition temperature. This study contributes to fundamental understanding of salt-induced micellization and structure–property relationship in hydrogen-bonded LbL films.

中文翻译：

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具有上临界溶解温度行为的芯的嵌段共聚物胶束的逐层薄膜

摘要 我们报道了在 pH 7.5 下具有 40–45 °C 范围内表现出上限临界溶解温度 (UCST) 行为的核心嵌段共聚物胶束的制备，并将此类胶束掺入逐层 (LbL) 膜中以获得 UCST型多层薄膜。聚（2-乙烯基吡啶-b-环氧乙烷）（P2VP-b-PEO）的吡啶单元被部分季铵化，并在六氰基高铁酸钾（K 3 Fe（CN） 6 ）存在下实现其自组装成胶束聚集体pH 7.5 在 25 °C 或 37.5 °C。所得 (QP2VP + [Fe(CN) 6 ] 3− )- b -PEO 胶束的核在 pH 7.5 下表现出 UCST 型行为，临界温度在 40–45 °C 范围内变化，具体取决于胶束化温度和K 3 Fe(CN) 6 的量。我们的结果表明，胶束化温度和 K 3 Fe(CN) 6 浓度对胶束核的 UCST 非常关键。在 (QP2VP + [Fe(CN) 6 ] 3− )- b -PEO 胶束在 25 °C 的情况下，在胶束化过程中增加 K 3 Fe(CN) 6 浓度会抑制 UCST 在 25-50 ° 温度范围内的行为C。相比之下，当 (QP2VP + [Fe(CN) 6 ] 3− )- b -PEO 胶束在 37.5 °C 下产生时，增加 K 3 Fe(CN) 6 浓度只会引起 UCST 的微小变化。此外，我们表明 (QP2VP + [Fe(CN) 6 ] 3- )- b -PEO 胶束可以在 pH 7.5 下使用单宁酸 (TA) 结合到 LbL 薄膜中。通过控制胶束温度和薄膜沉积温度，可以组装在接近 40°C 附近部分崩解的多层膜。