Citation: Jiao Yang, Zhang Xi. Supramolecular Free Radicals: Fabrication, Modulation and Functions[J]. Acta Chimica Sinica, ;2018, 76(9): 659-665. doi: 10.6023/A18070273 shu

Supramolecular Free Radicals: Fabrication, Modulation and Functions

Jiao Yang ,
Zhang Xi ^,

Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering, Tsinghua University, Bei-jing 100084

Corresponding author: Zhang Xi, xi@mail.tsinghua.edu.cn
Received Date: 16 July 2018
Available Online: 21 September 2018
Fund Project: the National Natural Science Foundation of China 21434004Project supported by the National Natural Science Foundation of China (Nos. 21434004, 91527000)the National Natural Science Foundation of China 91527000

Figures(8)

Modulating the activity of radicals is of great importance for the applications in radical-based materials and radical-mediated reactions. To this end, we have proposed a new concept of "supramolecular free radicals", which refers to the free radicals stabilized or activated through supramolecular approaches. Based on the host-guest chemistry of cucurbiturils (CB), we have fabricated three kinds of supramolecular free radicals to modulate the activity and realize diverse functions. Firstly, radical anions can be stabilized by the steric effect and electrostatic effect of CB. As a result, we have constructed a highly efficient near-infrared photothermal conversion system, which displays selective antibacterial performance. Secondly, owing to the electrostatic effect of CB, radical cations can be activated to induce a significant acceleration of Fenton oxidation reaction. Thirdly, by taking advantage of the dynamic nature of host-guest interactions, we can endow the reaction intermediate with adaptive reactivity, which greatly improves the catalytic efficiency of alcohol oxidation. It is highly anticipated that this series of research opens a new horizon in supramolecular materials and supramolecular catalysis.
- supramolecular free radicals,
- cucurbiturils,
- host-guest interactions,
- near-infrared photothermal conversion,
- supramolecular catalysis
1. [1]
  Janoschka, T.; Martin, N.; Martin, U.; Friebe, C.; Morgenstern, S.; Hiller, H.; Hager, M. D.; Schubert, U. S. Nature 2015, 527, 78. doi: 10.1038/nature15746
2. [2]
  Ortony, J. H.; Newcomb, C. J.; Matson, J. B.; Palmer, L. C.; Doan, P. E.; Hoffman, B. M.; Stupp, S. I. Nat. Mater. 2014, 13, 812. doi: 10.1038/nmat3979
3. [3]
  Peng, Q.; Obolda, A.; Zhang, M.; Li, F. Angew. Chem., Int. Ed. 2015, 54, 7091. doi: 10.1002/anie.201500242
4. [4]
  Rajca, A.; Wang, Y.; Boska, M.; Paletta, J. T.; Olankitwanit, A.; Swanson, M. A.; Mitchell, D. G.; Eaton, S. S.; Eaton, G. R.; Rajca, S. J. Am. Chem. Soc. 2012, 134, 15724. doi: 10.1021/ja3079829
5. [5]
  Studer, A.; Curran Dennis, P. Angew. Chem. Int. Ed. 2016, 55, 58. doi: 10.1002/anie.201505090
6. [6]
  Wang, D.; Zhang, L.; Luo, S. Acta Chim. Sinica 2017, 75, 22.
7. [7]
  Yan, M.; Lo, J. C.; Edwards, J. T.; Baran, P. S. J. Am. Chem. Soc. 2016, 138, 12692. doi: 10.1021/jacs.6b08856
8. [8]
  Zetterlund, P. B.; Thickett, S. C.; Perrier, S.; Bourgeat-Lami, E.; Lansalot, M. Chem. Rev. 2015, 115, 9745. doi: 10.1021/cr500625k
9. [9]
  Gomberg, M. J. Am. Chem. Soc. 1900, 22, 757. doi: 10.1021/ja02049a006
10. [10]
  Lebelev, O. L.; Kazarnovskii, S. N. Zhur. Obshch. Khim. 1960, 30, 1631.
11. [11]
  Segura José, L.; Martín, N. Angew. Chem., Int. Ed. 2001, 40, 1372.
12. [12]
  Hicks, R. G. Org. Biomol. Chem. 2007, 5, 1321. doi: 10.1039/b617142g
13. [13]
  Woodward, A. N.; Kolesar, J. M.; Hall, S. R.; Saleh, N. A.; Jones, D. S.; Walter, M. G. J. Am. Chem. Soc. 2017, 139, 8467. doi: 10.1021/jacs.7b01005
14. [14]
  Moulin, E.; Niess, F.; Maaloum, M.; Buhler, E.; Nyrkova, I.; Giuseppone, N. Angew. Chem., Int. Ed. 2010, 49, 6974. doi: 10.1002/anie.201001833
15. [15]
  Li, H.; Zhu, Z.; Fahrenbach, A. C.; Savoie, B. M.; Ke, C.; Barnes, J. C.; Lei, J.; Zhao, Y. L.; Lilley, L. M.; Marks, T. J.; Ratner, M. A.; Stoddart, J. F. J. Am. Chem. Soc. 2013, 135, 456. doi: 10.1021/ja310060n
16. [16]
  Benson, C. R.; Fatila, E. M.; Lee, S.; Marzo, M. G.; Pink, M.; Mills, M. B.; Preuss, K. E.; Flood, A. H. J. Am. Chem. Soc. 2016, 138, 15057. doi: 10.1021/jacs.6b09459
17. [17]
  Ulas, G.; Lemmin, T.; Wu, Y.; Gassner, G. T.; DeGrado, W. F. Nat. Chem. 2016, 8, 354. doi: 10.1038/nchem.2453
18. [18]
  Lee, J. W.; Samal, S.; Selvapalam, N.; Kim, H. J.; Kim, K. Acc. Chem. Res. 2003, 36, 621. doi: 10.1021/ar020254k
19. [19]
  Lagona, J.; Mukhopadhyay, P.; Chakrabarti, S.; Isaacs, L. Angew. Chem., Int. Ed. 2005, 44, 4844.
20. [20]
  Barrow, S. J.; Kasera, S.; Rowland, M. J.; del Barrio, J.; Scherman, O. A. Chem. Rev. 2015, 115, 12320. doi: 10.1021/acs.chemrev.5b00341
21. [21]
  Song, Q.; Li, F.; Wang, Z.; Zhang, X. Chem. Sci. 2015, 6, 3342. doi: 10.1039/C5SC00862J
22. [22]
  Tauber, M. J.; Kelley, R. F.; Giaimo, J. M.; Rybtchinski, B.; Wasielewski, M. R. J. Am. Chem. Soc. 2006, 128, 1782. doi: 10.1021/ja057031k
23. [23]
  Marcon, R. O.; Brochsztain, S. J. Phys. Chem. A 2009, 113, 1747. doi: 10.1021/jp808383e
24. [24]
  Jiao, Y.; Liu, K.; Wang, G.; Wang, Y.; Zhang, X. Chem. Sci. 2015, 6, 3975. doi: 10.1039/C5SC01167A
25. [25]
  Yang, Y.; He, P.; Wang, Y.; Bai, H.; Wang, S.; Xu, J.-F.; Zhang, X. Angew. Chem., Int. Ed. 2017, 56, 16239. doi: 10.1002/anie.v56.51
26. [26]
  Neyens, E.; Baeyens, J. J. Hazard. Mater. 2003, 98, 33. doi: 10.1016/S0304-3894(02)00282-0
27. [27]
  Pignatello, J. J.; Oliveros, E.; MacKay, A. Crit. Rev. Environ. Sci. Technol. 2006, 36, 1. doi: 10.1080/10643380500326564
28. [28]
  Jiao, Y.; Li, W.-L.; Xu, J.-F.; Wang, G.; Li, J.; Wang, Z.; Zhang, X. Angew. Chem., Int. Ed. 2016, 55, 8933. doi: 10.1002/anie.201603182
29. [29]
  Kim, K.; Selvapalam, N.; Ko, Y. H.; Park, K. M.; Kim, D.; Kim, J. Chem. Soc. Rev. 2007, 36, 267. doi: 10.1039/B603088M
30. [30]
  Ko, Y. H.; Kim, H.; Kim, Y.; Kim, K. Angew. Chem., Int. Ed. 2008, 47, 4106.
31. [31]
  Smith, L. C.; Leach, D. G.; Blaylock, B. E.; Ali, O. A.; Urbach, A. R. J. Am. Chem. Soc. 2015, 137, 3663. doi: 10.1021/jacs.5b00718
32. [32]
  Tang, B.; Li, W.-L.; Jiao, Y.; Lu, J.-B.; Xu, J.-F.; Wang, Z.; Li, J.; Zhang, X. Chem. Sci. 2018, 9, 5015. doi: 10.1039/C8SC01434E
33. [33]
  Lucio Anelli, P.; Biffi, C.; Montanari, F.; Quici, S. J. Org. Chem. 1987, 52, 2559. doi: 10.1021/jo00388a038
34. [34]
  Ding, B.; Ye, Y.; Yin, Q.; Cui, J.; Wang, K.; Luo, J.; Jiang, B. Acta Chim. Sinica 2009, 67, 1383. doi: 10.3321/j.issn:0567-7351.2009.12.017
35. [35]
  Endo, T.; Miyazawa, T.; Shiihashi, S.; Okawara, M. J. Am. Chem. Soc. 1984, 106, 3877. doi: 10.1021/ja00325a038
36. [36]
  Yang, C.; Fontaine, O.; Tarascon, J. M.; Grimaud, A. Angew. Chem., Int. Ed. 2017, 56, 8652. doi: 10.1002/anie.v56.30
37. [37]
  Jiao, Y.; Tang, B.; Zhang, Y.; Xu, J.-F.; Wang, Z.; Zhang, X. Angew. Chem., Int. Ed. 2018, 57, 6077. doi: 10.1002/anie.v57.21
1. [1]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
2. [2]
  Qi Wang , Yicong Gao , Feng Lu , Quli Fan . Preparation and Performance Characterization of the Second Near-Infrared Phototheranostic Probe: A New Design and Teaching Practice of Polymer Chemistry Comprehensive Experiment. University Chemistry, 2024, 39(11): 342-349. doi: 10.12461/PKU.DXHX202404141
3. [3]
  Jia Yao , Xiaogang Peng . Theory of Macroscopic Molecular Systems: Theoretical Framework of the Physical Chemistry Course in the Chemistry “101 Plan”. University Chemistry, 2024, 39(10): 27-37. doi: 10.12461/PKU.DXHX202408117
4. [4]
  Rui Li , Jiayu Zhang , Anyang Li . Two Levels of Understanding of Chemical Bonds: a Case of the Bonding Model of Hypervalent Molecules. University Chemistry, 2024, 39(2): 392-398. doi: 10.3866/PKU.DXHX202308051
5. [5]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
6. [6]
  Yang YANG , Pengcheng LI , Zhan SHU , Nengrong TU , Zonghua WANG . Plasmon-enhanced upconversion luminescence and application of molecular detection. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 877-884. doi: 10.11862/CJIC.20230440
7. [7]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
8. [8]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073
9. [9]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
10. [10]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
11. [11]
  Shuang Meng , Haixin Long , Zhou Zhou , Meizhu Rong . Inorganic Chemistry Curriculum Design and Implementation of Based on “Stepped-Task Driven + Multi-Dimensional Output” Model: A Case Study on Intermolecular Forces. University Chemistry, 2024, 39(3): 122-131. doi: 10.3866/PKU.DXHX202309008
12. [12]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
13. [13]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
14. [14]
  Xiyuan Su , Zhenlin Hu , Ye Fan , Xianyuan Liu , Xianyong Lu . Change as You Want: Multi-Responsive Superhydrophobic Intelligent Actuation Material. University Chemistry, 2024, 39(5): 228-237. doi: 10.3866/PKU.DXHX202311059
15. [15]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
16. [16]
  Cunming Yu , Dongliang Tian , Jing Chen , Qinglin Yang , Kesong Liu , Lei Jiang . Chemistry “101 Program” Synthetic Chemistry Experiment Course Construction: Synthesis and Properties of Bioinspired Superhydrophobic Functional Materials. University Chemistry, 2024, 39(10): 101-106. doi: 10.12461/PKU.DXHX202408008
17. [17]
  Yong Shu , Xing Chen , Sai Duan , Rongzhen Liao . How to Determine the Equilibrium Bond Distance of Homonuclear Diatomic Molecules: A Case Study of H₂. University Chemistry, 2024, 39(7): 386-393. doi: 10.3866/PKU.DXHX202310102
18. [18]
  Chunai Dai , Yongsheng Han , Luting Yan , Zhen Li , Yingze Cao . Preparation of Superhydrophobic Surfaces and Their Application in Oily Wastewater Treatment: Design of a Comprehensive Physical Chemistry Innovation Experiment. University Chemistry, 2024, 39(2): 34-40. doi: 10.3866/PKU.DXHX202307081
19. [19]
  Jiaxi Xu , Yuan Ma . Influence of Hyperconjugation on the Stability and Stable Conformation of Ethane, Hydrazine, and Hydrogen Peroxide. University Chemistry, 2024, 39(11): 374-377. doi: 10.3866/PKU.DXHX202402049
20. [20]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421

Get Citation

PDF

XML

Metrics

PDF Downloads(46)
Abstract views(1833)
HTML views(457)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142