Unveiling the Hidden Movements in the Shuttling of Rotaxanes

doi:10.1007/s40242-020-0092-4

高等学校化学研究 ›› 2020, Vol. 36 ›› Issue (5): 748-754.doi: 10.1007/s40242-020-0092-4

Unveiling the Hidden Movements in the Shuttling of Rotaxanes

GUO Yichang¹, FU Haohao¹, SHAO Xueguang^1,2, CAI Wensheng¹

1. Research Center for Analytical Sciences, College of Chemistry, Tianjin Key Laboratory of Biosensing and Molecular Recognition, Nankai University, Tianjin 300071, P. R. China;
2. State Key Laboratory of Medicinal Chemical Biology, Tianjin 300071, P. R. China

收稿日期:2020-04-06 修回日期:2020-05-22 出版日期:2020-10-01 发布日期:2020-10-01
通讯作者: CAI Wensheng, SHAO Xueguang E-mail:wscai@nankai.edu.cn;xshao@nankai.edu.cn
基金资助:
Supported by the National Natural Science Foundation of China(No.21773125), the Fundamental Research Funds for the Central Universities, China(No.63191743), the Natural Science Foundation of Tianjin, China(No.18JCYBJC20500) and the China Postdoctoral Science Foundation(No.bs6619012).

Unveiling the Hidden Movements in the Shuttling of Rotaxanes

GUO Yichang¹, FU Haohao¹, SHAO Xueguang^1,2, CAI Wensheng¹

1. Research Center for Analytical Sciences, College of Chemistry, Tianjin Key Laboratory of Biosensing and Molecular Recognition, Nankai University, Tianjin 300071, P. R. China;
2. State Key Laboratory of Medicinal Chemical Biology, Tianjin 300071, P. R. China

Received:2020-04-06 Revised:2020-05-22 Online:2020-10-01 Published:2020-10-01
Contact: CAI Wensheng, SHAO Xueguang E-mail:wscai@nankai.edu.cn;xshao@nankai.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(No.21773125), the Fundamental Research Funds for the Central Universities, China(No.63191743), the Natural Science Foundation of Tianjin, China(No.18JCYBJC20500) and the China Postdoctoral Science Foundation(No.bs6619012).

摘要/Abstract

摘要： Movements in molecular machines are usually diverse and coupled, but some of them are often implicit and hard to be observed in experiments. In the present work, the two-or three-dimensional free-energy landscapes characterizing the coupled shuttling and other movements of a series of pH-triggered rotaxanes composed of a crown ether and an H-shaped axle with distinct number of phenyl rings(n=1-3) have been explored. The results show that although the calculated free-energy barriers against shuttling in the rotaxanes(n=2 and 3) change slightly, the movements coupled with the shuttling vary significantly with the axle length. At high pH, the shuttling in the rotaxane of n=2 is coupled with the isomerization of the wheel, while the shuttling in the one of n=3 is accompanied by both the isomerization and the rotation of the macrocycle. In addition, the crown ether underwent greater conformational change during shuttling at low pH compared to that at high pH. These results indicate that disentangling the coupled movements is important to reveal the underlying molecular mechanism of the shuttling.

关键词: Rotaxane, Molecular machine, Molecular movement, Free-energy landscape

Abstract: Movements in molecular machines are usually diverse and coupled, but some of them are often implicit and hard to be observed in experiments. In the present work, the two-or three-dimensional free-energy landscapes characterizing the coupled shuttling and other movements of a series of pH-triggered rotaxanes composed of a crown ether and an H-shaped axle with distinct number of phenyl rings(n=1-3) have been explored. The results show that although the calculated free-energy barriers against shuttling in the rotaxanes(n=2 and 3) change slightly, the movements coupled with the shuttling vary significantly with the axle length. At high pH, the shuttling in the rotaxane of n=2 is coupled with the isomerization of the wheel, while the shuttling in the one of n=3 is accompanied by both the isomerization and the rotation of the macrocycle. In addition, the crown ether underwent greater conformational change during shuttling at low pH compared to that at high pH. These results indicate that disentangling the coupled movements is important to reveal the underlying molecular mechanism of the shuttling.

Key words: Rotaxane, Molecular machine, Molecular movement, Free-energy landscape

GUO Yichang, FU Haohao, SHAO Xueguang, CAI Wensheng. Unveiling the Hidden Movements in the Shuttling of Rotaxanes[J]. 高等学校化学研究, 2020, 36(5): 748-754.

GUO Yichang, FU Haohao, SHAO Xueguang, CAI Wensheng. Unveiling the Hidden Movements in the Shuttling of Rotaxanes[J]. Chemical Research in Chinese Universities, 2020, 36(5): 748-754.

参考文献 19

[1]	Zhang H., Shao X. G., Chipot C., Cai W. S., J. Phys. Chem. C, 2019, 123, 11304
[2]	Yu G. C., Yung B. C., Zhou Z. J., Mao Z. W., Chen X. Y., ACS Nano., 2018, 12, 7
[3]	Cheng S. C., Chen K. J., Suzaki Y., Tsuchido Y., Kuo T. S., Osakada K., Horie M., J. Am. Chem. Soc., 2018, 140, 90
[4]	Wang X. Q., Wang W., Li W. J., Chen L. J., Yao R., Yin G. Q., Wang Y. X., Zhang Y., Huang J. L., Tan H. W., Yu Y. H., Li X. P., Xu L., Yang B., Nat. Commun., 2018, 9, 1
[5]	Garaudée S., Silvi S., Venturi M., Credi A., Flood A. H., Stoddart J. F., ChemPhysChem, 2005, 6, 2145
[6]	Du S. L., Fu H. H., Shao X. G., Chipot C., Cai W. S., J. Phys. Chem. C., 2018, 122, 9229
[7]	Bissell R. A., Córdova E., Kaifer A. E., Stoddart J. F., Nature, 1994, 369, 133
[8]	Wolf M., Ogawa A., Bechtold M., Vonesch M., Wytko J. A., Oohora K., Campidelli S., Hayashi T., Guldi D. M., Weiss J., Chem. Sci., 2019, 10, 3846
[9]	Deutman A. B. C., Cantekin S., Elemans J. A. A. W., Rowan A. E., Nolte R. J. M., J. Am. Chem. Soc., 2014, 136, 9165
[10]	Gunbas D. D., Brouwer A. M., J. Org. Chem., 2012, 77, 5724
[11]	Yu C. Y., Ma L. S., He J. J., Xiang J. F., Deng X. B., Wang Y., Chen X. B., Jiang H., J. Am. Chem. Soc., 2016, 138, 15849
[12]	Wang S. S., Shao X. G., Cai W. S., J. Phys. Chem. C, 2017, 121, 25547
[13]	Gholami G., Zhu K. L., Baggi G., Schott E., Zarate X., Loeb S. J., Chem. Sci., 2017, 8, 7718
[14]	Fu H. H., Shao X. G., Chipot C., Cai W. S., J. Chem. Theory. Comput., 2016, 12, 3506
[15]	Fu H. H., Shao X. G., Chipot C., Cai W. S., Acc. Chem. Res., 2019, 52, 3254
[16]	Fu H. H., Zhang H., Chen H. C., Shao X. G., Chipot C., Cai W. S., J. Phys. Chem. Lett., 2018, 9, 4738
[17]	Fiorin G., Klein M. L., Hénin J., Mol. Phys., 2013, 111, 3345
[18]	Ensing B., Laio A., Parrinello M., Klein M. L., J. Phys. Chem. B, 2005, 109, 6676
[19]	Phillips J. C., Braun R., Wang W., Gumbart J., Tajkhorshid E., Villa E., Chipot C., Skeel R. D., Kale L., Schulten K., J. Comput. Chem., 2005, 26, 1781

Unveiling the Hidden Movements in the Shuttling of Rotaxanes

Unveiling the Hidden Movements in the Shuttling of Rotaxanes

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