Kotsuchibashi Yohei, Ebara Mitsuhiro, Sato Takeshi, Wang Yinan, Rajender Rajender, Hall Dennis G, Narain Ravin, Aoyagi Takao
International Center for Young Scientists (ICYS) and International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS) , 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
J Phys Chem B. 2015 Feb 12;119(6):2323-9. doi: 10.1021/jp506478p. Epub 2014 Sep 29.
We demonstrate here a local- and remote-control of gel disintegration by using photoinduced proton transfer chemistry of photoacid generator (PAG). The gels were prepared by simply mixing two polymers, poly(N-isopropylacrylamide-co-5-methacrylamido-1,2-benzoxaborole) (P(NIPAAm-co-MAAmBO)) and poly(3-gluconamidopropyl methacrylamide) (PGAPMA) via the synergistic interaction of benzoxaborole and diol groups. The o-nitrobenzaldehyde (o-NBA) was then loaded into the gel as a PAG. The benzoxaborole-diol interaction was successfully disintegrated upon UV irradiation due to the local pH decrease inside the gel. When the gel was irradiated to a specific gel region, the synergistic interactions were disintegrated only at the exposed region. Of special interest is that the whole material eventually transitioned from gel to sol state, as the generated protons diffused gradually toward the nonilluminated region. The ability of the proposed gel-sol transition system via photoinduced proton diffusion may be beneficial for not only prompt pH changes within the gel but also the design of predictive and programmable devices for drug delivery.
我们在此展示了通过使用光酸发生器(PAG)的光诱导质子转移化学来实现凝胶崩解的局部和远程控制。这些凝胶是通过将两种聚合物,即聚(N-异丙基丙烯酰胺-co-5-甲基丙烯酰胺基-1,2-苯并硼氧六环)(P(NIPAAm-co-MAAmBO))和聚(3-葡糖酰胺基丙基甲基丙烯酰胺)(PGAPMA),经由苯并硼氧六环和二醇基团的协同相互作用简单混合而制备的。然后将邻硝基苯甲醛(o-NBA)作为PAG载入凝胶中。由于凝胶内部局部pH值降低,苯并硼氧六环-二醇相互作用在紫外线照射下成功瓦解。当凝胶的特定区域受到照射时,协同相互作用仅在暴露区域瓦解。特别值得注意的是,随着产生的质子逐渐扩散到未照射区域,整个材料最终从凝胶态转变为溶胶态。所提出的通过光诱导质子扩散实现凝胶-溶胶转变系统的能力不仅可能有利于凝胶内pH值的快速变化,而且有利于设计用于药物递送的预测性和可编程装置。