Modification of a Thin Gold Film with Boronic Acid Membrane and Its Application to a Saccharide Sensor Based on Surface Plasmon Resonance

Abstract

A study of the response behavior of saccharides to surface plasmon resonance (SPR) based sensor, in which a boronic acid membrane-modified thin gold film was used as a sensor chip is described. The following three procedures were used in the modification of the sensor chip: first, 3-aminophenylboronic acid (3-APB) was coupled with 11-mercaptoundecanoic acid to form a self-assembled monolayer (SAM) on the gold film of the sensor chip, second, 3-APB was immobilized on the sensor chip by electrochemical polymerization, and third, the sensor chip was coated with a vinyl polymer by the radical polymerization of vinylphenylboronic acid. SPR responses were measured in a flow system, where the above three types of sensor chip were assembled in the flow cell of the SPR sensor. The SPR responses caused by the interaction between the boronic acid membrane modified on the sensor chip and saccharides were evaluated by measurement of an angle shift of the SPR sensor. A weak response was observed for the SPR sensor using the sensor chip modified with SAM and the electropolymerized membrane, while the sensor chip modified with the vinylboronic acid polymer membrane showed a selective and enhanced response to saccharides. From the SPR response for the latter sensor, the findings indicate that the interaction between the boronic acid membrane on the sensor chip and the saccharides was in the order glucose < mannose < galactose < fructose. Namely, the interaction between the boronic acid and cis-diol moiety in the saccharides appears to be stronger in the order 2,3-cis-diol < 3,4-cis-diol < 1,2-cis-diol. The adsorption behavior of sorbose to the sensor chip modified with the boronic acid polymer membrane followed the Freundlich-type adsorption isotherm. The electrochemical polymerization of 3-APB on the gold film of the SPR sensor chip was monitored in situ by combining an SPR system with an electrochemical analyzer system.

Thermodynamic analysis of the interaction between 3-aminophenylboronic acid and monosaccharides for development of biosensor

“…This situation could be explained by the low surface coverage of 3-APB during monolayer formation, similar results were reported in Ref. [37].…”

“…The boronic acids, which recognize cis-diol configuration in saccharides and form reversible covalent complexes in aqueous media, represent an ideal synthetic molecular receptor having the ability to selectively recognize saccharides [14][15][16]. Phenylboronic acid derivatives have been developed for saccharide sensing in various methods based on piezoresistive microcantilevers [17], UV-vis absorption [18][19][20][21][22][23][24], fluorescence [22,[25][26][27][28][29][30], electrochemistry [31][32][33][34], plasmonics [35][36][37], holography [38][39][40]. Consequently, boronic acids can be used as the recognition moiety for detecting saccharides in solution.…”

Boronic acid-modified thin film interface for specific binding of glycated hemoglobin (HbA1c) and electrochemical biosensing

“…There has been great interest in immobilizing boronic acids on a solid electrode surface and in investigating their affinity interaction with low-molecular-weight sugars and glycoproteins [22]. These properties of boronic acid have been applied to boronate affinity chromatography [23], construction of biosensors for saccharide with piezoelectrics [24], surface plasmon resonance transducers [25], and fluorescence [26,27] and electrochemical detection [28,29].…”

Electrochemical Characterization of In Situ Functionalized Gold Cysteamine Self‐Assembled Monolayer with 4‐Formylphenylboronic Acid for Detection of Dopamine

“…This interaction has been used; for sugar determination on the SAM modified electrode functionalized by BA via ex situ [52 -54] or in situ method [55,56]; for dopamine (DA) determination by florescence spectroscopy [58,59], conductimetry [60], and electrochemistry [61 -63]; or for selective dopamine transportation from organic to aqueous solutions [64]. The interaction between BA and DA is interesting in viewpoint of sensor fabrication.…”