Effects of cyclodextrins and saccharides on dual fluorescence of N,N-dimethyl-4-aminophenylboronic acid in water

Ozawa, Rimiko; Hayashita, Takashi; Matsui, Teruo; Nakayama, Chiaki; Yamauchi, Akiyo; Suzuki, I.

doi:10.1007/s10847-007-9373-5

Cited by 18 publications

(16 citation statements)

References 29 publications

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“…PBA reacts with cis-diol functional groups of sugars to form a five-or six-membered ring via ester bonds. As a result, PBA derivatives have been widely investigated as sugar-recognition motifs in chemical probes for sugar analysis [27][28][29][30][31][32] and sugar-sensitive Ins release systems [33][34][35]. We recently synthesized PBA-modified CyDs (PBA-CyDs) and found that they form supramolecular structures [36].…”

Section: Introductionmentioning

confidence: 99%

Sugar-responsive pseudopolyrotaxanes and their application in sugar-induced release of PEGylated insulin

Seki

Abe

Nakamura

et al. 2015

J Incl Phenom Macrocycl Chem

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We have designed a pseudopolyrotaxane (PPRX), known as a molecular necklace, consisting of phenylboronic acid-modified γ-cyclodextrin (PBA-γ-CyD) and naphthalene-modified polyethylene glycol (Naph-PEG) for developing sugar-responsive insulin delivery systems. Interestingly, structural analyses show that the Naph-PEG/PBA-γ-CyD PPRX obtained by our method was single stranded, whereas ordinary PPRXs using parent γ-CyD were double stranded. The Naph-PEG/PBA-γ-CyD PPRX was poorly water soluble at pH 7.4; however, sugar addition induced disintegration of the PPRX, and the components were dissolved, suggesting that the PBA moiety acts as a sugar sensor. We also have developed a PPRX consisting of Naph-PEG-appended insulin (Naph-PEG-Ins) and PBA-γ-CyD and have confirmed that the release rate of Naph-PEG-Ins was accelerated following sugar addition.

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Section: Introductionmentioning

confidence: 99%

Sugar-responsive pseudopolyrotaxanes and their application in sugar-induced release of PEGylated insulin

Seki

Abe

Nakamura

et al. 2015

J Incl Phenom Macrocycl Chem

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“…It is reasonable that the pKa of boronic acid exhibited a slight increase in the narrowest CD cavity because of the hydrophobic effect. 20 The conditional binding constant of the C1-APB/NH2-β-CD complex is comparable to that of the C1-APB/β-CD complex, although the fluorescence intensity is lower than that of the C1-APB/β-CD complex. Since the amino group on the β-CD rim is protonated under acidic and neutral conditions, 21 the electrostatic interaction stabilizing the anionic boronate ester should be taken into consideration.…”

Section: Ph Dependence Of the Fluorescence Spectramentioning

confidence: 87%

Effect of Cyclodextrins on Saccharide Sensing Function of a Fluorescent Phenylboronic Acid in Water

et al. 2008

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Sugars are essential biological molecules that play fundamental roles in metabolism and the maintenance of cell structure. They are also related to cell differentiation and immunity.1 Because of their important properties, researchers need simple methods that can quickly recognize sugars in aqueous solution. Enzymebased sensors are highly selective, but of limited use for continuous monitoring and in vivo analysis because of their poor stability and because they consume their substrate in the recognition process. Although chemosensors based on boronic acid are not as selective, they have attracted much attention because of their greater stability. 2,3 Phenylboronic acid can readily form stable cyclic esters with the diol moiety of sugars in water, 4 and various types of the boronic acid chemosensors with response mechanism based on internal charge transfer (ICT), 5-8 photoinduced electron transfer (PET), 9-11 and fluorescent resonance energy transfer (FRET) 12 have been developed. The versatile designs of chemosensors based on supramolecular chemistry are another approach to construct novel sugar sensors. [13][14][15] We reported that the complex consisting of the boronic acid fluorophore (C4-CPB) and β-cyclodextrin (β-CD) acts as a supramolecular saccharide sensor (Fig. 1). 16 The β-CD solubilizes the water-insoluble C4-CPB by forming an inclusion complex. The fluorescence response of this complex is based on the PET mechanism. The inherent fluorescence of C4-CPB is quenched by the internal PET from pyrene to the trigonal form of phenylboronic acid, but saccharide binding converts the boronic acid to the tetrahedral boronate, thereby inhibiting PET quenching and increasing the fluorescence intensity. In a previous study, the spacer effect of the boronic acid probe was examined in detail by using the fluorophores C1-CPB, C4-CPB, and C1-APB (Fig. 1). We found that the C1-APB/β-CD complex was a desirable fluorescent chemosensor for saccharide recognition because of its high affinity to saccharides as well as its relatively high fluorescence recovery upon saccharide binding. Since C1-APB is more soluble than C1-CPB and C4-CPB, because of possessing an amide group, it can be dissolved in water without adding β-CD at the level for the fluorescent measurement. This makes a precise comparison of the CD effect feasible. In the present work, therefore, we focused on C1-APB/CD complexes, and investigated how the sensing function of C1-APB for saccharide recognition in water was affected by differences in An inclusion complex consisting of a fluorescent phenylboronic acid (C1-APB) and β-cyclodextrin (β-CD) acts as a supramolecular saccharide sensor whose response mechanism is based on photoinduced electron transfer (PET). This study evaluated four kinds of cyclodextrins (α-CD, β-CD, γ-CD, and NH2-β-CD) by comparing their pH profiles, and confirmed that β-CD was the best host for C1-APB because the C1-APB/β-CD complex exhibited high affinity for saccharides as well as high fluorescent recovery upon saccharide binding. An ...

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“…In contrast, CyDs are composed of glucopyranose units; thus, the steric arrangement of their hydroxyl groups is unsuitable for the formation of cyclic esters with PBA. Some reports have shown that CyDs act as host molecules for PBA to form inclusion complexes rather than as sugars to form cyclic esters with PBA [27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Polyol-responsive pseudopolyrotaxanes based on phenylboronic acid-modified polyethylene glycol and cyclodextrins

Kojima

Okano

Seki

et al. 2017

J Incl Phenom Macrocycl Chem

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Phenylboronic acid (PBA), which reacts with polyols to form cyclic esters, was attached to the amino terminal of polyethylene glycol (PEG) via amide bonds. PBA-PEG was used to prepare pseudopolyrotaxanes (pPRXs) by combining it with cyclodextrins (CyDs). In the case of α-CyD, a single stranded pPRX formed that disintegrated in the presence of catechol (CA), D-fructose (Fru), and D-glucose (Glc). The order of response was CA > Fru > Glc, which corresponds with the affinities between the PBA moiety and the polyols. In contrast, a pPRX using γ-CyD, which has a double-stranded structure, showed sugar-induced disintegration but did not show a response to CA.We explained these apparently curious responses of the pPRXs using a mechanism based on the penetrability of the polyol-bound PBA toward the cavities of the CyDs. The pPRXs, which are a class of molecular machine, show two selectivities; one is derived from polyol selectivity, and the other is based on the penetrability for CyDs.

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Effects of cyclodextrins and saccharides on dual fluorescence of N,N-dimethyl-4-aminophenylboronic acid in water

Cited by 18 publications

References 29 publications

Sugar-responsive pseudopolyrotaxanes and their application in sugar-induced release of PEGylated insulin

Sugar-responsive pseudopolyrotaxanes and their application in sugar-induced release of PEGylated insulin

Effect of Cyclodextrins on Saccharide Sensing Function of a Fluorescent Phenylboronic Acid in Water

Polyol-responsive pseudopolyrotaxanes based on phenylboronic acid-modified polyethylene glycol and cyclodextrins

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