Citation: Lan Yang, Yu Li, Mou Jiang, Rui Zhou, Hengjiang Cong, Minghui Yang, Lei Zhang, Shenhui Li, Yunhuang Yang, Maili Liu, Xin Zhou, Zhong-Xing Jiang, Shizhen Chen. Fluorinated [2]rotaxanes as sensitive ¹⁹F MRI agents: Threading for higher sensitivity[J]. Chinese Chemical Letters, ;2024, 35(10): 109512. doi: 10.1016/j.cclet.2024.109512 shu

Fluorinated [2]rotaxanes as sensitive ¹⁹F MRI agents: Threading for higher sensitivity

Lan Yang ^{a, c, 1} ,
Yu Li ^{a, 1} ,
Mou Jiang ^{a, b, 1} ,
Rui Zhou ^{a, b} ,
Hengjiang Cong ^c ,
Minghui Yang ^{a, b} ,
Lei Zhang ^{a, b} ,
Shenhui Li ^{a, b} ,
Yunhuang Yang ^{a, b} ,
Maili Liu ^{a, b} ,
Xin Zhou ^{a, b, d} ,
Zhong-Xing Jiang ^{a, b, *,} ,
Shizhen Chen ^{a, b, d, *,}

a.
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences-Wuhan National Laboratory for Optoelectronics, Wuhan 430071, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
School of Pharmaceutical Sciences & College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430071, China
d.
Optics Valley Laboratory, Wuhan 430074, China

zxjiang@apm.ac.cn

chenshizhen@apm.ac.cn

Received Date: 23 September 2023
Revised Date: 22 December 2023
Accepted Date: 8 January 2024
Available Online: 13 January 2024

Figures(3)

As a promising imaging technology, the low sensitivity of fluorine-19 magnetic resonance imaging (¹⁹F MRI) severely hinders its biomedical applications. Herein, we have developed an unprecedented rotaxane-based strategy to improve the sensitivity of ¹⁹F MRI agents. By threading the fluorinated macrocycle into 2-blade pinwheel [2]rotaxanes, the ¹⁹F longitudinal relaxation rate R₁ was dramatically increased, resulting in a significant ¹⁹F MRI signal intensity enhancement of up to 79%. Through comparative molecular dynamics studies using a series of solution and solid-state ¹H/¹⁹F nuclear magnetic resonance (¹H/¹⁹F NMR) and molecular dynamics simulations, it was found that the formation of mechanical bonds dramatically restricts the motion of the wheel fluorines and thus increasing the R₁ for higher ¹⁹F MRI sensitivity. Besides a novel strategy for improving ¹⁹F MRI sensitivity, this study has established ¹⁹F NMR/MRI as a valuable technology for monitoring the molecular dynamics of rotaxanes, which may shed new light on high-performance ¹⁹F MRI agents and molecular devices.
- Rotaxane,
- ¹⁹F MRI,
- Imaging agent,
- Mechanical bond,
- Relaxation rate
1. [1]
  M. Higuchi, N. Iwata, Y. Matsuba, et al., Nat. Neurosci. 8 (2005) 527–533. doi: 10.1038/nn1422
2. [2]
  M.J. Couch, I.K. Ball, T. Li, et al., Magn. Reson. Imaging 49 (2019) 343–354. doi: 10.1002/jmri.26292
3. [3]
  P. Bouvain, S. Temme, U. Flögel, WIREs Nanomed. Nanobiotechnol. 12 (2020) e1639. doi: 10.1002/wnan.1639
4. [4]
  H. Lin, X. Tang, A. Li, J. Gao, Adv. Mater. 33 (2021) 2005657. doi: 10.1002/adma.202005657
5. [5]
  S. Kunjachan, J. Ehling, G. Storm, F. Kiessling, T. Lammers, Chem. Rev. 115 (2015) 10907–10937. doi: 10.1021/cr500314d
6. [6]
  I. Tirotta, V. Dichiarante, C. Pigliacelli, et al., Chem. Rev. 115 (2015) 1106–1129. doi: 10.1021/cr500286d
7. [7]
  J. Ruiz-Cabello, B.P. Barnett, P.A. Bottomley, J.W.M. Bulte, NMR Biomed. 24 (2011) 114–129. doi: 10.1002/nbm.1570
8. [8]
  T. Wu, A. Li, K. Chen, et al., Chem. Commun. 57 (2021) 7743–7757. doi: 10.1039/D1CC02133H
9. [9]
  L. Mignion, J. Magat, O. Schakman, et al., Magn. Reson. Med. 69 (2013) 248–254. doi: 10.1002/mrm.24245
10. [10]
  E.T. Ahrens, R. Flores, H. Xu, P.A. Morel, Nat. Biotechnol. 23 (2005) 983–987. doi: 10.1038/nbt1121
11. [11]
  D. Xie, M. Yu, R.T. Kadakia, E.L. Que, Acc. Chem. Res. 53 (2020) 2–10. doi: 10.1021/acs.accounts.9b00352
12. [12]
  K.H. Chalmers, E. DeLuca, N.H.M. Hogg, et al., Chem. Eur. J. 16 (2010) 134–148. doi: 10.1002/chem.200902300
13. [13]
  L. Zhu, Y. Li, M. Jiang, et al., ACS Appl. Mater. Interfaces 15 (2023) 2665–2678. doi: 10.1021/acsami.2c19161
14. [14]
  A.T. Preslar, F. Tantakitti, K. Park, et al., ACS Nano 10 (2016) 7376–7384. doi: 10.1021/acsnano.6b00267
15. [15]
  Y. Takaoka, T. Sakamoto, S. Tsukiji, et al., Nat. Chem. 1 (2009) 557–561. doi: 10.1038/nchem.365
16. [16]
  P.L. Anelli, P.R. Ashton, R. Ballardini, et al., J. Am. Chem. Soc. 114 (1992) 193–218. doi: 10.1021/ja00027a027
17. [17]
  C.A. Schalley, K. Beizai, F. Vögtle, Acc. Chem. Res. 34 (2001) 465–476. doi: 10.1021/ar000179i
18. [18]
  B. Zheng, M. Zhang, S. Dong, X. Yan, M. Xue, Org. Lett. 15 (2013) 3538–3541. doi: 10.1021/ol401241w
19. [19]
  B.L. Feringa, Angew. Chem. Int. Ed. 56 (2017) 11060–11078. doi: 10.1002/anie.201702979
20. [20]
  R.E. Fadler, A.H. Flood, Front. Chem. 10 (2022) 856173. doi: 10.3389/fchem.2022.856173
21. [21]
  G. Gholami, K. Zhu, G. Baggi, et al., Chem. Sci. 8 (2017) 7718–7723. doi: 10.1039/C7SC03736H
22. [22]
  K. Yamauchi, A. Miyawaki, Y. Takashima, H. Yamaguchi, A. Harada, J. Org. Chem. 75 (2010) 1040–1046. doi: 10.1021/jo902393n
23. [23]
  Y.F. Yin, M.Y. Yun, L. Wu, et al., Angew. Chem. Int. Ed. 58 (2019) 12705–12710. doi: 10.1002/anie.201906761
24. [24]
  A. Garci, Y. Beldjoudi, M.S. Kodaimati, et al., J. Am. Chem. Soc. 142 (2020) 7956–7967. doi: 10.1021/jacs.0c02128
25. [25]
  P. Rajamalli, F. Rizzi, W. Li, et al., Angew. Chem. Int. Ed. 60 (2021) 12066–12073. doi: 10.1002/anie.202101870
26. [26]
  V. Blanco, A. Carlone, K.D. Hänni, D.A. Leigh, B. Lewandowski, Angew. Chem. Int. Ed. 51 (2012) 5166–5169. doi: 10.1002/anie.201201364
27. [27]
  X. Lu, C. Huang, M. Li, et al., J. Phys. Chem. B 124 (2020) 5271–5283.
28. [28]
  Y. Mo, C. Huang, C. Liu, et al., Macromol. Rapid Commun. 44 (2023) 2200744. doi: 10.1002/marc.202200744
29. [29]
  S.E. Kirberger, S.D. Maltseva, J.C. Manulik, et al., Angew. Chem. Int. Ed. 56 (2017) 6440–6444. doi: 10.1002/anie.201700426
30. [30]
  H. Shi, B. Lai, S. Chen, et al., Chin. J. Chem. 35 (2017) 1693–1700. doi: 10.1002/cjoc.201700240
1. [1]
  Ying Li , Yanjun Xu , Xingqi Han , Di Han , Xuesong Wu , Xinlong Wang , Zhongmin Su . A new metal–organic rotaxane framework for enhanced ion conductivity of solid-state electrolyte in lithium-metal batteries. Chinese Chemical Letters, 2024, 35(9): 109189-. doi: 10.1016/j.cclet.2023.109189
2. [2]
  Bingbing Shi , Yuchun Wang , Yi Zhou , Xing-Xing Zhao , Yizhou Li , Nuoqian Yan , Wen-Juan Qu , Qi Lin , Tai-Bao Wei . A supramolecular oligo[2]rotaxane constructed by orthogonal platinum(Ⅱ) metallacycle and pillar[5]arene-based host–guest interactions. Chinese Chemical Letters, 2024, 35(10): 109540-. doi: 10.1016/j.cclet.2024.109540
3. [3]
  Tao LIU , Yuting TIAN , Ke GAO , Xuwei HAN , Ru'nan MIN , Wenjing ZHAO , Xueyi SUN , Caixia YIN . A photothermal agent with high photothermal conversion efficiency and high stability for tumor therapy. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1622-1632. doi: 10.11862/CJIC.20240107
4. [4]
  Pei Cao , Yilan Wang , Lejian Yu , Miao Wang , Liming Zhao , Xu Hou . Dynamic asymmetric mechanical responsive carbon nanotube fiber for ionic logic gate. Chinese Chemical Letters, 2024, 35(6): 109421-. doi: 10.1016/j.cclet.2023.109421
5. [5]
  Hongdao LI , Shengjian ZHANG , Hongmei DONG . Magnetic relaxation and luminescent behavior in nitronyl nitroxide-based annuluses of rare-earth ions. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 972-978. doi: 10.11862/CJIC.20230411
6. [6]
  Yang Qin , Jiangtian Li , Xuehao Zhang , Kaixuan Wan , Heao Zhang , Feiyang Huang , Limei Wang , Hongxun Wang , Longjie Li , Xianjin Xiao . Toeless and reversible DNA strand displacement based on Hoogsteen-bond triplex. Chinese Chemical Letters, 2024, 35(5): 108826-. doi: 10.1016/j.cclet.2023.108826
7. [7]
  Zhigang Zeng , Changzhou Liao , Lei Yu . Molecules for COVID-19 treatment. Chinese Chemical Letters, 2024, 35(7): 109349-. doi: 10.1016/j.cclet.2023.109349
8. [8]
  Fangzhou Wang , Wentong Gao , Chenghui Li . A weak but inert hindered urethane bond for high-performance dynamic polyurethane polymers. Chinese Chemical Letters, 2024, 35(5): 109305-. doi: 10.1016/j.cclet.2023.109305
9. [9]
  Long Li , Kang Yang , Chenpeng Xi , Mengchao Li , Borong Li , Gui Xu , Yuanbin Xiao , Xiancai Cui , Zhiliang Liu , Lingyun Li , Yan Yu , Chengkai Yang . Highly-chlorinated inert and robust interphase without mineralization of oxide enhancing high-rate Li metal batteries. Chinese Chemical Letters, 2024, 35(6): 108814-. doi: 10.1016/j.cclet.2023.108814
10. [10]
  Xinpin Pan , Yongjian Cui , Zhe Wang , Bowen Li , Hailong Wang , Jian Hao , Feng Li , Jing Li . Robust chemo-mechanical stability of additives-free SiO₂ anode realized by honeycomb nanolattice for high performance Li-ion batteries. Chinese Chemical Letters, 2024, 35(10): 109567-. doi: 10.1016/j.cclet.2024.109567
11. [11]
  Qiongqiong Wan , Yanan Xiao , Guifang Feng , Xin Dong , Wenjing Nie , Ming Gao , Qingtao Meng , Suming Chen . Visible-light-activated aziridination reaction enables simultaneous resolving of C=C bond location and the sn-position isomers in lipids. Chinese Chemical Letters, 2024, 35(4): 108775-. doi: 10.1016/j.cclet.2023.108775
12. [12]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
13. [13]
  Jing-Jing Zhang , Lujun Lou , Rui Lv , Jiahui Chen , Yinlong Li , Guangwei Wu , Lingchao Cai , Steven H. Liang , Zhen Chen . Recent advances in photochemistry for positron emission tomography imaging. Chinese Chemical Letters, 2024, 35(8): 109342-. doi: 10.1016/j.cclet.2023.109342
14. [14]
  Shihong Wu , Ronghui Zhou , Hang Zhao , Peng Wu . Sonoafterglow luminescence for in vivo deep-tissue imaging. Chinese Chemical Letters, 2024, 35(10): 110026-. doi: 10.1016/j.cclet.2024.110026
15. [15]
  Benjian Xin , Rui Wang , Lili Liu , Zhiqiang Niu . Metal-organic framework derived MnO@C/CNTs composite for high-rate lithium-based semi-solid flow batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100116-100116. doi: 10.1016/j.cjsc.2023.100116
16. [16]
  Guangchang Yang , Shenglong Yang , Jinlian Yu , Yishun Xie , Chunlei Tan , Feiyan Lai , Qianqian Jin , Hongqiang Wang , Xiaohui Zhang . Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg²⁺/B³⁺ substitution achieves durable and high-rate cathode. Chinese Chemical Letters, 2024, 35(9): 109722-. doi: 10.1016/j.cclet.2024.109722
17. [17]
  Xiaohong Wen , Mei Yang , Lie Li , Mingmin Huang , Wei Cui , Suping Li , Haiyan Chen , Chen Li , Qiuping Guo . Enzymatically controlled DNA tetrahedron nanoprobes for specific imaging of ATP in tumor. Chinese Chemical Letters, 2024, 35(8): 109291-. doi: 10.1016/j.cclet.2023.109291
18. [18]
  Gongcheng Ma , Qihang Ding , Yuding Zhang , Yue Wang , Jingjing Xiang , Mingle Li , Qi Zhao , Saipeng Huang , Ping Gong , Jong Seung Kim . Palladium-free chemoselective probe for in vivo fluorescence imaging of carbon monoxide. Chinese Chemical Letters, 2024, 35(9): 109293-. doi: 10.1016/j.cclet.2023.109293
19. [19]
  Yaping Wang , Pengcheng Yuan , Zeyuan Xu , Xiong-Xiong Liu , Shengfa Feng , Mufan Cao , Chen Cao , Xiaoqiang Wang , Long Pan , Zheng-Ming Sun . Ti₃C₂T_x MXene in-situ transformed Li₂TiO₃ interface layer enabling 4.5 V-LiCoO₂/sulfide all-solid-state lithium batteries with superior rate capability and cyclability. Chinese Chemical Letters, 2024, 35(6): 108776-. doi: 10.1016/j.cclet.2023.108776
20. [20]
  Tao Long , Peng Chen , Bin Feng , Caili Yang , Kairong Wang , Yulei Wang , Can Chen , Yaping Wang , Ruotong Li , Meng Wu , Minhuan Lan , Wei Kong Pang , Jian-Fang Wu , Yuan-Li Ding . Reinforced concrete-like Na_3.5V_1.5Mn_0.5(PO₄)₃@graphene hybrids with hierarchical porosity as durable and high-rate sodium-ion battery cathode. Chinese Chemical Letters, 2024, 35(4): 109267-. doi: 10.1016/j.cclet.2023.109267

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(128)
HTML views(9)

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

Fluorinated [2]rotaxanes as sensitive 19F MRI agents: Threading for higher sensitivity

Metrics

通讯作者: 陈斌, bchen63@163.com

Fluorinated [2]rotaxanes as sensitive ¹⁹F MRI agents: Threading for higher sensitivity