Structural effect of fluorophore on phenylboronic acid fluorophore/cyclodextrin complex for selective glucose recognition

doi:10.1007/s11705-019-1851-y

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (1) : 53-60 https://doi.org/10.1007/s11705-019-1851-y

RESEARCH ARTICLE

Structural effect of fluorophore on phenylboronic acid fluorophore/cyclodextrin complex for selective glucose recognition

Takeshi Hashimoto¹(

), Mio Kumai¹, Mariko Maeda¹, Koji Miyoshi¹, Yuji Tsuchido^1,², Shoji Fujiwara^1,³, Takashi Hayashita¹(

)

¹. Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, Tokyo, 102-8554, Japan
². Department of Life Science and Medical Bioscience, Graduate School of Advanced Science and Engineering, Waseda University (TWIns), Tokyo, 162-8480, Japan
³. Department of Current Legal Studies, Faculty of Law, Meiji Gakuin University, Kanagawa, 244-8539, Japan

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Abstract

Based on the design of the fluorescent site of a fluorescent probe, we have created a unique system that changes its twisting response to sugar. Two probes were synthesized, in which phenylboronic acid and two kinds of aromatic fluorescent site (pyrene or anthracene) were conjugated by an amide bond. In the fluorescence measurement of pyrene-type probe 1, dimer fluorescence was observed at high pH. In induced circular dichroism (ICD) experiments, a response was observed only in the presence of glucose and γ-cyclodextrin, and no response was seen with fructose. On the other hand, in the fluorescence measurement of anthracene-type probe 2, dimer fluorescence was observed in the presence of both glucose and galactose, and the fluorescence was different from the case of fructose. When the ICD spectra of these inclusion complexes were measured, an inversion of the Cotton effect, which indicates a change in the twisted structure, was observed in galactose and glucose. These differences in response to monosaccharides may originate in the interaction between the fluorescent site and the cyclodextrin cavity.

Keywords sugar recognition phenylboronic acid cyclodextrin fluorescence response induced circular dichroism

Corresponding Author(s): Takeshi Hashimoto,Takashi Hayashita

Just Accepted Date: 04 September 2019 Online First Date: 08 November 2019 Issue Date: 20 January 2020

Cite this article:

Takeshi Hashimoto,Mio Kumai,Mariko Maeda, et al. Structural effect of fluorophore on phenylboronic acid fluorophore/cyclodextrin complex for selective glucose recognition[J]. Front. Chem. Sci. Eng., 2020, 14(1): 53-60.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1851-y
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I1/53

Fig.1 Scheme 1 Synthesis of pyrene-type probe 1.

Fig.2 Scheme 2 Synthesis of anthracene-type probe 2.

Fig.3 pH dependence of fluorescence spectra for 1/γ-CyD in 2% DMSO–98% water (v/v), (a) without sugar, (b) in 30 mmol?L⁻¹ fructose, and (c) in 30 mmol?L⁻¹ glucose. [1] = 1.0 ×10⁻⁵ mol?L⁻¹ in 2% DMSO–98% water (v/v), [γ -CyD] = 5 mmol?L⁻¹, pH adjusted with 0.01 mol?L⁻¹ phosphate buffer, at 25°C, I (ionic strength) = 0.1 mol?L⁻¹ with NaCl, λ_ex= 328 nm.

Fig.4 Fluorescence intensity changes at 496 nm for 1/γ-CyD versus sugar concentration in 2% DMSO–98% water (v/v). [1] = 1.0 × 10^–⁵ mol?L⁻¹ in 2% DMSO–98% water (v/v), [γ-CyD] = 5 mmol?L⁻¹, pH adjusted to 11.3 with 0.01 mol?L⁻¹ Na₂CO₃ buffer, at 25 °C, I = 0.1 mol?L⁻¹ with NaCl, λ_ex= 328 nm.

Fig.5 (a) UV-Vis spectra without sugar or in 30 mmol?L⁻¹ monosaccharides and (b) UV-vis spectral change with addition of glucose (b) for 1/γ-CyD in 2% DMSO–98% water (v/v). [1] = 1.0×10⁻⁵ mol?L⁻¹, [γ-CyD] = 5 mmol?L⁻¹, pH adjusted to 11.3 with 0.01 mol?L⁻¹ Na₂CO₃ buffer, at 25°C, I = 0.1 mol?L⁻¹ with NaCl.

Fig.6 ICD spectra for 1/γ-CyD in 2% DMSO–98% water (v/v), (a) without sugar, (b) in 30 mmol?L⁻¹ fructose, and (c) in 30 mmol?L⁻¹ glucose. [1] = 1.0 × 10⁻⁵ mol?L⁻¹, [γ-CyD] = 5 mmol?L⁻¹, pH adjusted to 11.3 with 0.01 mol?L⁻¹ Na₂CO₃ buffer, at 25°C, I = 0.1 mol?L⁻¹ with NaCl.

Fig.7 Estimated structures of 1/γ-CyD inclusion complexes with (a) fructose and (b) glucose.

Fig.8 pH dependence of fluorescence spectra for 2/γ-CyD in 2% DMSO–98% water (v/v), in 30 mmol?L⁻¹ glucose. [2] = 5.0 × 10^–⁶ mol?L⁻¹, [γ-CyD] = 5 mmol?L⁻¹, pH adjusted with 0.01 mol?L⁻¹ phosphate buffer, at 25°C, I = 0.1 mol?L⁻¹ with NaCl, λ_ex= 325 nm.

Fig.9 Fluorescence intensity changes at 472 nm for 2/γ-CyD versus sugar concentration in 2% DMSO–98% water (v/v). [2] = 0.5 × 10^–⁵ mol?L⁻¹, [γ-CyD] = 5 mmol?L⁻¹, pH adjusted to 11.0 with 0.01 mol?L⁻¹ Na₂CO₃/NaHCO₃ buffer, at 25°C, I = 0.1 mol?L⁻¹ with NaCl, λ_ex= 325 nm.

Fig.10 ICD spectral changes of 2/γ-CyD in 4% DMSO–96% water (v/v) with (a) fructose, (b) glucose, or (c) galactose. [2] = 1.0 × 10^–⁵ mol?L⁻¹, [γ-CyD] = 5 mmol?L⁻¹, pH adjusted to 11.0 with 0.01 mol?L⁻¹ Na₂CO₃ buffer, at 25°C, I = 0.1 mol?L⁻¹ with NaCl. [Sugar] = 0?5.0 mmol?L⁻¹.

Fig.11 Estimated structures of 2/γ-CyD inclusion complex (a) with/without sugar, (b) with fructose/mannose, and (c) with glucose/galactose.

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