Abstract
Cysteine-linked cyclophane dimer having two rhodamine moieties (2) was synthesized as a reduction-responsive host. Owing to self-quenching property of the two rhodamine moieties, cyclophane dimer 2 showed weak fluorescence intensity relative to that of the rhodamine B moiety itself. The cleavage of disulfide bond of 2 was performed by a treatment with reducing agents such as dithiothreitol, to give the corresponding monomeric cyclophanes having a rhodamine moiety. Such reductive degradation of 2 was detected by the increase on fluorescence intensity. As a host, cyclophane dimer 2 was found to show a stronger guest-binding affinity than the monomeric cyclophanes due to concentration effects of the macrocycles. In addition, reduction-responsive release of entrapped guest molecules by 2 was also monitored by fluorescence spectroscopy.
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Notes
6: MALDI-TOF MS (positive mode); m/z 1374 [M–Cl]+, where M shows C79H97ClN12O8S as a triamine derivative of cyclophane (free amine).
It was reported as difference fluorescence intensity between the presence and absence of the guests, because of emission originating from rhodamine-hosts with the excitation wavelength at 326 nm (TNS) and 318 nm (2,6-ANS).
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The present work is supported in part by MEXT (No. 16K05761-0001), Japan.
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Hayashida, O., Nishino, K. & Kusano, S. Synthesis of a cysteine-linked cyclophane dimer having two rhodamine moieties and its reduction-responsive degradation as studied by fluorescence spectroscopy. J Incl Phenom Macrocycl Chem 87, 267–274 (2017). https://doi.org/10.1007/s10847-017-0696-6
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DOI: https://doi.org/10.1007/s10847-017-0696-6