高分子合成新方法：聚合物的光合成：以可见光活化的光化学为例

1、课 程 内 容,基础科学与应用科学的再认识 化学的发展态势：回顾近20年诺贝尔化学奖 化学的研究前沿：定位、前沿、国家发展战略 聚合物的光合成：以可见光活化的光化学为例,向大自然学习,感知和模仿：生物大分子在不同尺度的精妙构建，感知与响应等众多生命功能,分子设计与材料构建：从分子水平师法自然,清洁活化源柔和的可见光 ,太阳光：自然光，连续发射光谱,UV light: less in the solar spectrum, potentially harmful, costly in generation and maintenance. visible light: abundant in s

2、olar light, safe, less costly, less damaging to chemicals, easy to use, more favored in synthetic applications,荧光蛋白,菌紫质,视紫质,光敏黄蛋白,羧肽酶Y,视黄质,植物光敏色素,类胡萝卜素,胆红素,叶绿素,维生素B12,生物界中的光化学 动物：视觉、保护色 植物：光合作用、光致变色、趋光性 微生物：趋光性、光合成、太阳能转换,动物的保护色：你能找到我吗,Biological activity,hn,植物光敏色素,控制开花 打破某些需光种子休眠 下胚轴弯钩的伸长 幼叶和子叶变绿及展开

3、 含羞草感震运动 抑制花色素苷的形成,光敏色素的生物功能,H. Ihee, S. Rajagopal, et al. PNAS 2005, 102, 7145,Photoactive Yellow Protein (PYP,Halorhodospira halophila water-soluble protein (125-amino-acid) Responsible for negative photo-taxis on exposure to blue light 4-hydroxycinnamic acid link to Cys69 via a thiol ester linkag

4、e,Isomerization N. Hampp, Chem. Rev. 2000, 100, 1755,太阳光照下的光循环过程,氢离子传递机理,GFP: Green Fluorescent Protein,Isomerization of GFP Chromophores,J. Dong, L. M. Tolbert, et al. J. Am. Chem. Soc. 2008, 130, 14096,Directly; b) addition/elimination; c) isomerization by tautomerization,视觉的形成：光致异构驱动,B. Bohran, M

5、. L. Souto, et al. Science 2000, 288, 2209,Summary: From Structural Transition to Biological Function,Reversible changes in a complex relationship between chromophore and the surrounding protein environment: formation and breaking of hydrogen bonds, stabilizing charge redistribution, manipulation of

6、 the potential energy surfaces,Smart Polymers: Respond to a stimulus or environment to produce a dynamic & reversible change in critical properties,Although most synthetic materials still lack switchability, new synthetic tools and enhanced fundamental understanding have brought such smart materials

7、 within reach of the materials research community. M. Yoshida, J. Lahann, ACS NANO 2008, 2, 1101,Synthesis of Block Copolymers by Combination of ATRP and Visible Light Radical Photopolymerization Methods,G. Acik, et al. Macromolecules 2010, 43, 9198,The preparation of block copolymers by combination

8、 of ATRP and visible light radical polymerization (VLRP,Free Radical Polymerization Initiated and Controlled by Visible Light Photocatalysis at Ambient Temperature,Ru(bpy)3Cl2,G. Zhang, Macromolecules 2011, 44, 7594,Iridium Photocatalysts in Free Radical Photo-Polymerization under Visible Lights,J.

9、Lalevee, et al. ACS Macro Lett., 2012, 1, 286,The key parameters that govern the polymerization rates are the reduction ability of the excited states (*Ir) as well as the excited state lifetimes,Photoredox catalysis approach,On the Use of Bis(cyclopentadienyl)titanium(IV) Dichloride in Visible-Light

10、-Induced Ring-Opening Photopolymerization,环戊二烯,It opens up a way to carry out cationic photo-polymerization under air and upon visible wavelengths,M.-A. Tehfe, et al. Macromolecules 2012, 45, 356,ThioxanthoneDiphenyl Anthracene: Visible Light Photo-initiator,噻吨酮：紫外光固化涂料用光引发剂,Photoinduced Radical Gen

11、eration Mechanism of TX-DPA Photoinitiator in the presence of Oxygen,Photoinduced radical generation mechanism of TX-DPA photoinitiator with N-methyldiethanolamine,D. K. Balta, et al., Macromolecules 2012, 45, 119,Publication online: March 29, 2012 DOI: 10.1021/ja300178r,Nature, 2011, 472, 334-338,n

12、anoporous thin films,S. Nojima, Y. Ohguma, K.-I. Kadena, T. Ishizone, Y. Iwasaki, K. Yamaguchi, Macromolecules 2010, 43, 3916 3923,DOI: 10.1021/ja211888a Publication online: March 5, 2012,PROMETHEUS CONQUERED THE FIRE, we can not give it back,Eve picking the Forbidden Fruit of the Tree of Knowledge

13、the Birth of Science,Our path leads us From the TREE OF KNOWLEDGE To the CONTROL OF OUR DESTINY,David HILBERT希尔伯特,1862-1943,WIR MSSEN WISSEN WIR WERDEN WISSEN,WE MUST KNOW WE WILL KNOW -David Hilbert,L dove natura finisce di produrre le sue spezie, quivi luomo comincia con le cose naturali, con lauditorio di essa natura, a creare infinite spezie. -Leonardo da Vinci (14