Effect of Macrocycles on the Temperature-Responsiveness of Poly[(methoxy diethylene glycol methacrylate)-graft-PEG]†
Effect of Macrocycles on the Temperature-Responsiveness of Poly[(methoxy diethylene glycol methacrylate)-graft-PEG]†
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DOI：
10.1002/macp.200400135
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发表时间：
2004-08
影响因子：
2.5
通讯作者：
H. Kitano;T. Hirabayashi;Makoto Gemmei-Ide;Mayumi Kyogoku
中科院分区：
文献类型：
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作者：
H. Kitano;T. Hirabayashi;Makoto Gemmei-Ide;Mayumi Kyogoku
溶解在纯水中的2-（2 '-甲氧乙氧基）甲基丙烯酸乙酯（DM）均聚物在临界温度（LCST）下显示其浊度突然增加。同时，DM与ω-甲氧基（低聚乙烯氧基（甲基丙烯酸乙酯）（PaM）的共聚物（PmaM）的LCST随PmaM残基含量的增加而显著增加。此外，大环化合物如六亚甲基杯[6]六磺酸（SCX 6）、（DM-β-CD）的加入改变了LCST，SCX 6使LCST显著升高，DM-β-CD使LCST略有升高，α-CD使LCST略有降低，这可能是由于在共聚物的接枝PEG链上形成了包合物（聚六亚甲基多轮烷）。ROESY，荧光测量和粘度行为的SCX 6 -PEG二甲醚（PEG-DME）的混合物支持的理论，SCX 6与PEG链的络合。用荧光光谱法和紫外-可见吸收光谱法分别测定了PEG-DME和接枝PEG与SCX 6和α-CD的表观缔合常数（Kapp）。SCX 6-聚合物缀合物与PDMPaM的络合也通过浊度的时间演化测量来检查。详细讨论了主客体分子结构对共聚物LCST的影响。
A homopolymer of 2-(2'-methoxyethoxy(ethyl methacrylate (DM) dissolved inpure water demonstrated an abrupt increase in its turbidity at a critical temperature (LCST). Meanwhile, the LCST for a copolymer of DM and ω-methoxy(oligoethyleneoxy(ethyl methacrylate (PaM) (PDMP a M) significantly increased with increasing content of P a M residue. Furthermore, the addition of macrocycles such as hexasodium calix[6]arehexasulfonic acid (SCX 6 ), (DM-β-CD) changed the LCST, SCX6 raised the LCST significantly, DM-β-CD slightly raised the LCST and α-CD slightly lowered it. These phenomena could be attributed to the formation of an inclusion complex (polypseudorotaxane) at the grafted PEG chain of the copolymer. ROESY, fluorescence measurements and the visvosity behavior of the SCX 6 -PEG dimethylether (PEG-DME) mixture supported the theory of the complexation of SCX 6 with the PEG chain. The apparent association constants (K app ) of PEG-DME or grafted PEG with SCX 6 and α-CD were determined using fluorescence and UV-vis absorption measurements, respectively. The complexation of the SCX6-polymer conjugate with PDMPaM was also examined by time-evolution measurements of the turbidity. The effect of the structure of the guest and host molecules on the LCST for the copolymer was discussed in detail.