Boronate Affinity Fluorescent Nanoparticles for Förster Resonance Energy Transfer Inhibition Assay of cis-Diol Biomolecules

Abstract

Förster resonance energy transfer (FRET) has been essential for many applications, in which an appropriate donor-acceptor pair is the key. Traditional dye-to-dye combinations remain the working horses but are rather nonspecifically susceptive to environmental factors (such as ionic strength, pH, oxygen, etc.). Besides, to obtain desired selectivity, functionalization of the donor or acceptor is essential but usually tedious. Herein, we present fluorescent poly(m-aminophenylboronic acid) nanoparticles (poly(mAPBA) NPs) synthesized via a simple procedure and demonstrate a FRET scheme with suppressed environmental effects for the selective sensing of cis-diol biomolecules. The NPs exhibited stable fluorescence properties, resistance to environmental factors, and a Förster distance comparable size, making them ideal donor for FRET applications. By using poly(mAPBA) NPs and adenosine 5'-monophosphate modified graphene oxide (AMP-GO) as a donor and an acceptor, respectively, an environmental effects-suppressed boronate affinity-mediated FRET system was established. The fluorescence of poly(mAPBA) NPs was quenched by AMP-GO while it was restored when a competing cis-diol compounds was present. The FRET system exhibited excellent selectivity and improved sensitivity toward cis-diol compounds. Quantitative inhibition assay of glucose in human serum was demonstrated. As many cis-diol compounds such as sugars and glycoproteins are biologically and clinically significant, the FRET scheme presented herein could find more promising applications.

Structure-Based Design and Synthesis of a New Phenylboronic-Modified Affinity Medium for Metalloprotease Purification

“…Boronate affinity materials have gained increasing attention in recent years [ 31 , 32 , 33 ]. The mechanism involved is similar to other conventional boronate affinity chromatography.…”

“…Our preliminary virtual screening and experimental verification indicated that boronic acid derivatives (BADs) could reversibly inhibit the activity of MP [ 30 ]. Phenylboronate group, which can form a temporary covalent bond with any molecule that contains a 1,2- cis -diol group, is widely used in the affinity purification of 1,2- cis -diol-containing biomolecules such as glycoproteins, glycopeptides, nucleosides, and nucleic acids [ 31 , 32 , 33 , 34 , 35 ]. However, application of the resins modified by phenylboronate in the purification of metalloproteases has never been reported.…”

Quantitative SERS Detection of Dopamine in Cerebrospinal Fluid by Dual-Recognition-Induced Hot Spot Generation

“…To solve this problem, we report here the use of a dual-molecular recognition strategy in which the target molecule is consecutively recognized by two molecules at different sites . The combination of such a detection scheme with SERS has been exploited for sensing of various analytes from glucose to glycoprotein in a sandwich assay format. − However, to date, no studies have reported the use of dual recognition-based SERS for DA detection in biofluids. In this work, we demonstrate the first design and fabrication of a dual-recognition-based sensing platform capable of sensitively detecting DA in human CSF samples.…”

Two Are Better than One: Halloysite Nanotubes-Supported Surface Imprinted Nanoparticles Using Synergy of Metal Chelating and Low pKa Boronic Acid Monomers for Highly Specific Luteolin Binding under Neutral Condition

“…14−17 The excellent affinity of boronic acid toward cis-diol moieties arises from forming stable cyclic esters by special reversible covalent interaction in mild basic condition, while the cyclic esters dissociate in the presence of acidic pH medium. 18,19 Surprisingly, LTL molecules possess the cis-diol-containg structure served as the binding sites that can form the covalent interaction with boronic acid. 20 In our laboratory, several porous adsorbents based on boronate affinity for recognition and separation of LTL have been reported, and the as-prepared adsorbents could capture LTL from general compounds (non-cis-diol-containing compounds).…”

“…Inspired from this important work, our group fabricated magnetic microspheres composed of Fe 3 O 4 core and Zn 2+ -immobilized poly­(vinyl imidazole) (PVLD) shell by the means of reflux-precipitation polymerization and subsequent coordination process, and the as-prepared high magnetic-response microspheres can make LTL purified from 85% to 94.26% approximately . Boronic acid-based affinity chromatography is a novel strategy for recognition and separation of cis -diol containing compounds (for example, saccharides, glycoproteins, catechols, and nucleosides). − The excellent affinity of boronic acid toward cis -diol moieties arises from forming stable cyclic esters by special reversible covalent interaction in mild basic condition, while the cyclic esters dissociate in the presence of acidic pH medium. , Surprisingly, LTL molecules possess the cis -diol-containg structure served as the binding sites that can form the covalent interaction with boronic acid . In our laboratory, several porous adsorbents based on boronate affinity for recognition and separation of LTL have been reported, and the as-prepared adsorbents could capture LTL from general compounds (non- cis -diol-containing compounds). , Nevertheless, the excellent boronate affinity ability has to be performed in alkaline media (usually pH above 8.5), which is easy to oxidize the cis -diols of LTL under this pH condition .…”