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

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.

Graphical abstract

Keywords

sugar recognition / phenylboronic acid / cyclodextrin / fluorescence response / induced circular dichroism

References

[1] Stick R V, Williams S. Carbohydrates: The Essential Molecules of Life. 2nd ed. New York: Elsevier, 2009, 225–251

[2] Geddes C D, Lakowicz J R. Glucose Sensing: Topics in Fluorescence Spectroscopy. New York: Springer, 2006, 237–258

[3] Zhang X T, Liu G J, Ning Z W, Xing G W. Boronic acid-based chemical sensors for saccharides. Carbohydrate Research, 2017, 452(27): 129–148

[4] Updike S J, Hicks G P. The enzyme electrode. Nature, 1967, 214: 986–988

[5] Clark L C Jr, Lyons C. Electrode systems for continuous monitoring in cardiovascular surgery. Annals of the New York Academy of Sciences, 1962, 102: 29–45

[6] Kin J, Campbell A S, Wang J. Wearable non-invasive epidermal glucose sensors: A review. Talanta, 2018, 177: 163–170

[7] Sun X, James T D. Glucose sensing in supramolecular chemistry. Chemical Reviews, 2015, 115: 8001–8037

[8] Tong A J, Yamauchi A, Hayashita T, Zhang Z Y, Smith B D, Teramae N. Boronic acid fluorophore/β-cyclodextrin complex sensors for selective sugar recognition in water. Analytical Chemistry, 2001, 73: 1530–1536

[9] Tsuchido Y, Fujiwara S, Hashimoto T, Hayashita T. Development of supramolecular saccharide sensors based on cyclodextrin complexes and self-assembling systems. Chemical & Pharmaceutical Bulletin, 2017, 65(4): 318–325

[10] James T D, Sandanarake K R A S, Shinkai S. Saccharide sensing with molecular receptors based on boronic acid. Angewante Chemie International Edition in English, 1996, 35: 1910–1922

[11] Hashimoto T, Yamazaki M, Ishii H, Yamada T, Hayashita T. Design and evaluation of selective recognition on supramolecular gel using soft molecular template effect. Chemistry Letters, 2014, 43(2): 228–230

[12] Minamiki T, Sasaki Y, Su S, Minami T. Development of polymer field-effect transistor-based immunoassays. Polymer Journal, 2019, 51: 1–9

[13] Minamiki T, Minami T, Sasaki Y, Wakida S, Kurita R, Niwa O, Tokito S. Label-free detection of human glycoprotein (CgA) using an extended-gated organic transistor-based immunosensor. Sensors (Basel), 2016, 16(12): 2033

[14] Tsai C H, Tang Y H, Chen H T, Yao Y W, Chien T C, Kao C L. A selective glucose sensor: the cooperative effect of monoboronic acid-modified poly(amidoamine) dendrimers. Chemical Communications, 2018, 54(36): 4577–4580

[15] Endo A, Minesaka H, Hashimoto T, Hayashita T. Electrochemical sugar recognition using a ruthenium complex with boronic acid assembled on polyamidoamine (PAMAM) dendrimer. Analytical Methods, 2012, 4(9): 2657–2660

[16] Tsuchido Y, Sakai Y, Aimu K, Hashimoto T, Akiyoshi K, Hayashita T. Design of phenylboronic acid azoprobe/polyamidoamine dendrimer complexes as a supramolecular sensor for saccharide recognition in water. New Journal of Chemistry, 2015, 39: 2620–2626

[17] Endo A, Kimura M, Hashimoto T, Hayashita T. Novel electrochemical sugar recognition system using ruthenium complex and phenylboronic acid assembled on gold nanoparticles. Analytical Methods, 2014, 6(22): 8874–8877

[18] Chen W H, Luo G F, Vazquez-Gonzalez M, Cazelles R, Sohn Y S, Nechushtai R, Mandel Y, Willner I. Glucose-responsive metal-organic-framework nanoparticles act as “smart” sense-and-treat carriers. ACS Nano, 2018, 12(8): 7538–7545

[19] Tang J, Ma D, Pecic S, Huang C, Zheng J, Li J, Yang R. Noninvasive and highly selective monitoring of intracellular glucose via a two-step recognition-based nanokit. Analytical Chemistry, 2017, 89(16): 8319–8327

[20] Fujiwara S, Nonaka K, Yamaguchi M, Hashimoto T, Hayashita T. Structural effect of ditopic azoprobe-cyclodextrin complexes on the selectivity of guest-induced supramolecular chirality. Chemical Communications, 2018, 54(90): 12690–12693

[21] Fujita K, Fujiwara S, Yamada T, Tsuchido Y, Hashimoto T, Hayashita T. Design and function of supramolecular recognition systems based on guest-targeting probe-modified cyclodextrin receptors for ATP. Journal of Organic Chemistry, 2017, 82(2): 976–981

[22] Shimpuku C, Ozawa R, Sasaki A, Sato F, Hashimoto T, Yamauchi A, Suzuki I, Hayashita T. Selective glucose recognition by boronic acid azoprobe/g-cyclodextrin complexes in water. Chemical Communications, 2009, (13): 1709–1711

[23] Kano H, Tanoue D, Shimaoka H, Katano K, Hashimoto T, Kunugita H, Nanbu S, Hayashita T, Ema K. Effects of cyclodextrins on intramolecular photoinduced electron transfer in a boronic acid fluorophore. Analytical Sciences, 2014, 30(6): 643–648

[24] Kumai M, Kozuka S, Samizo M, Hashimoto T, Suzuki I, Hayashita T. Glucose recognition by a supramolecular complex of boronic acid fluorophore with boronic acid-modified cyclodextrin in water. Analytical Sciences, 2012, 28(2): 121–126

[25] Kumai M, Kozuka S, Hashimoto T, Hayashita T. Design of boronic acid fluorophore/aminated cyclodextrin complexes for sugar sensing in water. Journal of Ion Exchange, 2010, 21(3): 249–254

[26] Chakraborti H, Bramhaiah K, John N S, Kalyan P S. Excited state electron transfer from aminopyrene to graphene: A combined experimental and theoretical study. Physical Chemistry Chemical Physics, 2013, 15: 19932–19938

[27] Davydov A S. Theory of Molecular Excitons. New York: Springer US, 1971, 23–111

[28] Tinoco I Jr. Theoretical aspects of optical activity. Part two: Polymers. Advances in Chemical Physics, 1962, 4: 113–160

[29] Kodaka M, Furuya T. Induced circular dichroism spectrum of a α-cyclodextrin complex with heptylviologen. Bulletin of the Chemical Society of Japan, 1989, 62(4): 1154–1157

[30] Kodaka M. A general rule for circular dichroism induced by a chiral macrocycle. Journal of the American Chemical Society, 1993, 115(9): 3702–3705

[31] Kodaka M. Sign of circular dichroism induced by β-cyclodextrin. Journal of Physical Chemistry, 1991, 95(6): 2110–2112

[32] Harata K, Uedaira H. The circular dichroism spectra of the β-cyclodextrin complex with naphthalene derivatives. Bulletin of the Chemical Society of Japan, 1975, 48(2): 375–378

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