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. 2021 Apr 28;22(9):4683.
doi: 10.3390/ijms22094683.

Supramolecular Zn(II)-Dipicolylamine-Azobenzene-Aminocyclodextrin-ATP Complex: Design and ATP Recognition in Water

Shohei Minagawa  1 , Shoji Fujiwara  1   2 , Takeshi Hashimoto  1 , Takashi Hayashita  1
Affiliations

Supramolecular Zn(II)-Dipicolylamine-Azobenzene-Aminocyclodextrin-ATP Complex: Design and ATP Recognition in Water

Shohei Minagawa et al. Int J Mol Sci. .

Abstract

Cyclodextrins (CyDs) are water-soluble host molecules possessing a nanosized hydrophobic cavity. In the realm of molecular recognition, this cavity is used not only as a recognition site but also as a reaction medium, where a hydrophobic sensor recognizes a guest molecule. Based on the latter concept, we have designed a novel supramolecular sensing system composed of Zn(II)-dipicolylamine metal complex-based azobenzene (1-Zn) and 3A-amino-3A-deoxy-(2AS,3AS)-γ-cyclodextrin (3-NH2-γ-CyD) for sensing adenosine-5'-triphosphate (ATP). 1-Zn showed redshifts in the UV-Vis spectra and induced circular dichroism (ICD) only when both ATP and 3-NH2-γ-CyD were present. Calculations of equilibrium constants indicated that the amino group of 3-NH2-γ-CyD was involved in the formation of supramolecular 1-Zn/3-NH2-γ-CyD/ATP. The Job plot of the ICD spectral response revealed that the stoichiometry of 1-Zn/3-NH2-γ-CyD/ATP was 2:1:1. The pH effect was examined and 1-Zn/3-NH2-γ-CyD/ATP was most stable in the neutral condition. The NOESY spectrum suggested the localization of 1-Zn in the 3-NH2-γ-CyD cavity. Based on the obtained results, the metal coordination interaction of 1-Zn and the electrostatic interaction of 3-NH2-γ-CyD were found to take place for ATP recognition. The "reaction medium approach" enabled us to develop a supramolecular sensing system that undergoes multi-point interactions in water. This study is the first step in the design of a selective sensing system based on a good understanding of supramolecular structures.

Keywords: ATP recognition; circular dichroism; cyclodextrin; dipicolylamine; supramolecular complex.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Chemical structures of (a) 1-Zn, (b) 3-NH2-γ-CyD, and (c) ATP.
Figure 2
Figure 2
Changes in UV-Vis spectra of 1-Zn in the (a) absence or (b) presence of 3-NH2-γ-CyD with increasing concentrations of ATP. [1-Zn] = 0.020 mM, [HEPES] = 5.0 mM; [3-NH2-γ-CyD] = 2.0 mM; [ATP] = 0, 0.020, 0.20, 0.40, 0.60, 0.80, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0 mM, in 1% DMSO aq. at pH 7.4.
Figure 3
Figure 3
Changes in UV-Vis spectra of 1-Zn in the (a) absence or (b) presence of ATP with increasing concentrations of 3-NH2-γ-CyD. [1-Zn] = 0.020 mM; [HEPES] = 5 mM; [ATP] = 2.0 mM; [3-NH2-γ-CyD] = 0, 0.020, 0.20, 0.40, 0.60, 0.80, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0 mM, in 1% DMSO aq. at pH 7.4.
Figure 4
Figure 4
(a) Changes in UV-Vis spectra of 1-Zn in the presence of ATP with increasing concentrations of γ-CyD. (b) Plot of the absorbance ratio (A474/A434) of 1-Zn versus concentrations of (●) 3-NH2-γ-CyD and (▲) γ-CyD in the presence of ATP. [1-Zn] = 0.02 mM; [HEPES] = 5 mM; [ATP] = 2 mM; [CyD] = 0, 0.020, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0 mM, in 1% DMSO aq. at pH 7.4.
Figure 5
Figure 5
ICD spectra of 1-Zn, 1-Zn/ATP, 1-Zn/3-NH2-γ-CyD, and 1-Zn/3-NH2-γ-CyD /ATP. [1-Zn] = 0.040 mM, [ATP] = 4.0 mM, [3-NH2-γ-CyD] = 4.0 mM, [HEPES] = 5.0 mM, in 2% DMSO aq. at pH 7.4.
Figure 6
Figure 6
(a) ICD spectra of 1-Zn/3-NH2-γ-CyD/ATP at different pH values. (b) Plot of θ490—of 1-Zn/3-NH2-γ-CyD /ATP versus pH. [1-Zn] = 0.040 mM, [ATP] = 4.0 mM, [3-NH2-γ-CyD] = 4.0 mM, in 2% DMSO aq.
Figure 7
Figure 7
NOESY spectrum of 1-Zn/3-NH2-γ-CyD/ATP (22 ℃, mixing time: 0.5 s, 160 scans).
Scheme 1
Scheme 1
Suggested conformation of 1-Zn and 3-NH2-γ-CyD in the presence of ATP.
Scheme 2
Scheme 2
Suggested supramolecular structure of 1-Zn/3-NH2-γ-CyD/ATP.
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