三木 康嗣11Koji MIKI清水 章弘12Akihiro SHIMIZUカーボンナノチューブ超分子複合体を基盤とする抗がん剤の創出（2019採択）Development of Anticancer Agents Consisting of Supramolecularly-Functionalized Carbon Nanotubes(Project 2019)有機電解酸化反応を用いる新規π電子系双性イオンの迅速合成と機能開拓（2019採択）Rapid Synthesis of Novel π-Electronic Zwitterions Using Electroorganic Reactions and Their Application as Functional Materials(Project 2019)27がんの早期発見，早期治療につながるパイ共役分子およびそれを複合化した材料の開発は，重要な課題である．特に，低侵襲な光照射を活用する撮像法，治療法に利用される造影剤，抗がん剤の開発は，患者への負担軽減に役立つことから特に注目されている．本研究では，光照射下，細胞殺傷能を示す活性酸素種を効率よく発することが知られるカーボンナノチューブを腫瘍近傍に効率よく運搬させることを視野に，カーボンナノチューブと複合体を形成する水溶性官能基を含むナフタロシアニンを合成した．水溶性ナフタロシアニンがプロテアーゼに応答して光音響信号強度を増大させるアクティベータブル型造影剤として機能することを明らかにした．Tumor imaging and therapy utilizing photoirradiation have been intensively investigated due to their low in-vasiveness. π-Conjugated materials generating photoluminescence, photoacoustic signal, and cytotoxic spe-cies, such as reactive oxygen species, under photoirradiation are attractive compounds as contrast agents and therapeutic agents. In this study, we synthesized water-soluble substituent-grafted naphthalocyanines for dec-orating carbon nanotubes, which are well-known as an effective reactive oxygen generator. In the course of our study, we found that water-soluble naphthalocyanines efficiently generated an enhanced photoacoustic wave under the treatment of proteinase. Furthermore, water-soluble naphthalocyanines could act as a protein-ase-responsive photoacoustic contrast agent for tumor.最高占有分子軌道(HOMO)と非占有分子軌道(LUMO)のエネルギー差(ΔEH‒L)の小さな分子は，両性の酸化還元特性や低エネルギーの光吸収などの電気的・光学的特性や，機能性色素および情報貯蔵材料としての応用の観点から広く研究されている．本研究では，電子供与性のアニオンと電子受容性のカチオンから構成されるπ共役双性イオンに注目し，ドナーのHOMOおよびアクセプターのLUMOのエネルギー差(ΔED‒A)を小さくし，それらの間の相互作用(EInt)を小さくすることにより，ΔEH‒L が小さく，両性の酸化還元特性と近赤外吸収を示す，比較的小さなπ共役双性イオンを創出した．Molecules with a small energy difference (ΔEH-L) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) have been widely studied in terms of their electronic and optical properties, such as amphoteric redox properties and low-energy light absorption, as well as their applications as functional dyes and information storage materials. In this study, we focused on π-conjugated zwitterions, which consist of electron-donating anions and electron-accepting cations. We have successfully developed relatively small π-conjugated zwitterions with smallΔEH-L, amphoteric redox properties, and near-infrared absorption by reducing the energy difference between the HOMO of the donor and the LUMO of the acceptor (ΔED-A) and the interaction between them (EInt).
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