偶氮吡啶衍生物的合成、光物理和光異構化性質研究

Synthesis, photophysical and photochemical isomerization properties of azopyridine derivatives

黃宜青(Yi-Ching Huang)

指導教授 ： 葉美鈺

中原大學/理學院/化學系/碩士(2022年)

https://doi.org/10.6840/cycu202201418

摘要

光控開關(photoswitch)是一種分子可以在光的照射下改變其結構幾何形狀和化學性質，被廣泛的應用在化學、生物學和材料科學。本篇論文是合成具有不同化學位向的偶氮吡啶(AP)衍生物，即meta-, para-，探討meta-AP及para-AP在不同酸鹼值下經紫外光照射後的E/Z光致異構化以及可見光照射後回復到E構型的效率，實驗發現meta-AP在酸性、中性及鹼性都會有良好的光切換性質；而para-AP則是只有在鹼性才有光切換的性質，從實驗結果發現偶氮吡啶(AP)衍生物同時具有pH值響應的特性。實驗結果說明我們成功藉由AP的位向來調控材料的光物理和光異構化的性質，其中以meta-AP具有優異的光異構化能力，因此未來可將meta-AP運用在光儲存、光藥理學、組織工程等應用。
水凝膠，為現在科學以及醫學上常常使用的聚合物，而我們將meta-AP及para-AP分子應用在水凝膠上面，使其具有光響應的特質，也因為其對pH值具有響應特應的特性，所以在不同的pH值下或者是照光之後，都會有不同的機械性質產生，也因為這些特性，可以使我們的水凝膠在未來的醫學應用上面，有很大的發展潛力。

關鍵字

偶氮?啶

並列摘要

A photoswitch is a molecule that can change its structural geometry and chemical properties under the irradiation of light, and is widely used in chemistry, biology and materials science. This paper is to synthesize azopyridine (AP) derivatives with different chemical orientations, namely meta- and para-, and to investigate the E/Z of meta-AP and para-AP under UV light irradiation at different pH values. Photoisomerization and the efficiency of returning to the E configuration after visible light irradiation. It was found that meta-AP has good photoswitching properties in acid, neutral and basic conditions, while para-AP is only available in basic conditions. The properties of photoswitching, it was found from the experimental results that the azopyridine (AP) derivatives also have pH-responsive properties. The experimental results show that we have successfully controlled the photophysical and photoisomerization properties of the material by the orientation of AP. Among them, meta-AP has excellent photoisomerization ability, so meta-AP can be used in light storage, light Pharmacology, tissue engineering and other applications.
Hydrogels are polymers that are often used in science and medicine, and we apply meta-AP and para-AP molecules to hydrogels to make them light-responsive and pH-responsive Atopic properties, so under different pH values or after illumination, there will be different mechanical properties, and because of these properties, our hydrogels have great potential for future medical applications.

並列關鍵字

azopyridine

參考文獻

1. Shin, S.-H.; Lee, W.; Kim, S.-M.; Lee, M.; Koo, J. M.; Hwang, S. Y.; Oh, D. X.; Park, J. Ion-conductive self-healing hydrogels based on an interpenetrating polymer network for a multimodal sensor. Chem. Eng. J.2019, 371, 452-460.

2. Zhou, W.; Qiao, Z.; Nazarzadeh Zare, E.; Huang, J.; Zheng, X.; Sun, X.; Shao, M.; Wang, H.; Wang, X.; Chen, D.; et al. 4D-Printed Dynamic Materials in Biomedical Applications: Chemistry, Challenges, and Their Future Perspectives in the Clinical Sector. J. Med. Chem.2020, 63 (15), 8003-8024.

3. McCracken, J. M.; Rauzan, B. M.; Kjellman, J. C. E.; Kandel, M. E.; Liu, Y. H.; Badea, A.; Miller, L. A.; Rogers, S. A.; Popescu, G.; Nuzzo, R. G. 3D-Printed Hydrogel Composites for Predictive Temporal (4D) Cellular Organizations and Patterned Biogenic Mineralization. Adv. Healthc. Mater. 2019, 8 (1), 1800788,

4. Lanzalaco, S.; Turon, P.; Weis, C.; Mata, C.; Planas, E.; Alemán, C.; Armelin, E. Toward the New Generation of Surgical Meshes with 4D Response: Soft, Dynamic, and Adaptable. Adv. Funct. Mater. 2020, 30 (36), 2004145,

5. El-Husseiny, H. M.; Mady, E. A.; Hamabe, L.; Abugomaa, A.; Shimada, K.; Yoshida, T.; Tanaka, T.; Yokoi, A.; Elbadawy, M.; Tanaka, R. Smart/stimuli-responsive hydrogels: Cutting-edge platforms for tissue engineering and other biomedical applications. Mater. Today. Bio 2022, 13, 100186.