Skip to main page content
Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Nov 27;7:806.
doi: 10.3389/fchem.2019.00806. eCollection 2019.

Selective Sugar Recognition by Anthracene-Type Boronic Acid Fluorophore/Cyclodextrin Supramolecular Complex Under Physiological pH Condition

Affiliations
Free PMC article

Selective Sugar Recognition by Anthracene-Type Boronic Acid Fluorophore/Cyclodextrin Supramolecular Complex Under Physiological pH Condition

Ko Sugita et al. Front Chem. .
Free PMC article

Abstract

We synthesized novel PET (photoinduced electron transfer)-type fluorescence glucose probe 1 [(4-(anthracen-2-yl-carbamoyl)-3-fluorophenyl)boronic acid], which has a phenylboronic acid (PBA) moiety as the recognition site and anthracene as the fluorescent part. Although the PBA derivatives dissociate and bind with sugar in the basic condition, our new fluorescent probe can recognize sugars in the physiological pH by introducing an electron-withdrawing fluorine group into the PBA moiety. As a result, the pK a value of this fluorescent probe was lowered and the probe was able to recognize sugars at the physiological pH of 7.4. The sensor was found to produce two types of fluorescent signals, monomer fluorescence and dimer fluorescence, by forming a supramolecular 2:1 complex of 1 with glucose inside a γ-cyclodextrin (γ-CyD) cavity. Selective ratiometric sensing of glucose by the 1/γ-CyD complex was achieved in water at physiological pH.

Keywords: boronic acid; cyclodextrin; fluorescence; sugar recognition; supramolecular chemistry.

Figures

Figure 1
Figure 1
Chemical structure of anthracene boronic acid probes.
Figure 2
Figure 2
Fluorescence spectral changes of (A) 1/β-CyD complex with glucose and (B) 1/γ-CyD complex with glucose in 2% DMSO−98% water (v/v) with various pH. [1] = 10 μM, [CyD] = 5 mM, [glucose] = 30 mM, [NaCl] = 100 mM, [phosphate buffer] = 10 mM, λex = 323 nm.
Figure 3
Figure 3
Estimated structure of 1/γ-CyD complex.
Figure 4
Figure 4
(A) Fluorescence spectra of 1/γ-CyD complex with various sugars (none: black; green: fructose; blue: glucose; red: galactose) in 2% DMSO−98% water (v/v) at basic condition around pH 10. [1] = 10 μM, [γ-CyD] = 5 mM, [sugar] = 0 or 30 mM, [phosphate buffer] = 10 mM, [NaCl] = 100 mM, λex = 323 nm. (B) Fluorescence image of 1/γ-CyD complex solution without and with 30 mM of various sugars at pH 7.4 under UV irradiation.
Figure 5
Figure 5
pH profiles of probe [(A) 1, (B) 2]/γ-CyD complexes in 2% DMSO−98% water (v/v). [probe] = 10 μM, [γ-CyD] = 5 mM, [sugar] = 0 or 30 mM, [phosphate buffer] = 10 mM, [NaCl] = 100 mM, λex = 323 nm.
Figure 6
Figure 6
(A) Fluorescence spectral changes of 1/γ-CyD complex in 2% DMSO−98% water (v/v) at pH 7.4 with the addition of glucose. (B) Ratiometric plots of 1/γ-CyD complex in 2% DMSO−98% water (v/v) at pH 7.4 with the addition of various concentrations of sugars. [1] = 10 μM, [γ-CyD] = 5 mM, [sugar] = 0–30 mM, [phosphate buffer] = 10 mM, [NaCl] = 100 mM, λex = 323 nm.
Figure 7
Figure 7
ICD spectral changes of 1/γ-CyD complex in 2% DMSO−98% water (v/v) with the addition of various concentrations of sugars [(A) glucose, (B) galactose, (C) fructose] at pH 7.4. [1] = 10 μM, [γ-CyD] = 5 mM, [sugar] = 0–30 mM, [phosphate buffer] = 10 mM, [NaCl] = 100 mM.

Similar articles

See all similar articles

References

    1. Anslyn E. V. (2007). Supramolecular analytical chemistry. J. Org. Chem. 72, 687–699. 10.1021/jo0617971 - DOI - PubMed
    1. Brewer C. F., Miceli M. C., Baum L. G. (2002). Clusters, bundles, arrays and lattices: novel mechanisms for lectin–saccharide-mediated cellular interactions. Curr. Opin. Struct. Biol. 12, 616–623. 10.1016/S0959-440X(02)00364-0 - DOI - PubMed
    1. Brodesser S., Sawatzki P., Kolter T. (2003). Bioorganic chemistry of ceramide. Eur. J. Org. Chem. 2003, 2021–2034. 10.1002/ejoc.200200518 - DOI
    1. Davis B. G. (2002). Synthesis of glycoproteins. Chem. Rev. 102, 579–601. 10.1021/cr0004310 - DOI - PubMed
    1. Deorea B., Freund M. S. (2003). Saccharide imprinting of poly(aniline boronic acid) in the presence of fluoride. Analyst 128, 803–806. 10.1039/b300629h - DOI - PubMed

LinkOut - more resources

Feedback