Boronic Acid Interactions Research Articles

Double Photocrosslinked Responsive Hydrogels Based on Hydroxypropyl Guar.

Double crosslinked hydrogels based on a biodegradable polymer were prepared by photocopolymerization of methacrylated hydroxypropyl guar (HPG-MA) and 3-acrylamidophenylboronic acid. Along with irreversible strong covalent crosslinks by methacrylic groups, these hydrogels contained labile boronate crosslinks formed as a result of the interaction of boronic acid with cis-diol moieties of HPG. These hydrogels demonstrated higher elasticity than HPG-MA hydrogels with only irreversible covalent crosslinks. Labile boronate crosslinks not only strengthened the hydrogels but also imparted to them pronounced responsive properties. It was demonstrated that the mechanical properties, the swelling behavior, as well as the uptake and release of some substances from the double crosslinked hydrogel were pH controlled. For instance, the hydrogels could release cationic disinfectant at a rate regulated by pH. Such photocrosslinkable in situ forming hydrogels are very promising for the production of smart coatings that release targeted substances at the desired rate.

Adsorption of DNA Oligonucleotides by Boronic Acid-Functionalized Hydrogel Nanoparticles.

Boronic acid-functionalized hydrogels were commonly used for covalent binding of cis-diol-contained molecules such as glucose, but noncovalent adsorption by boronic acids was less studied. DNA as an important polymer has been used to enhance the function of hydrogels including boronic acid-containing gels. In this work, noncovalent interactions between DNA oligonucleotides and boronic acid-containing hydrogel nanoparticles were studied in detail. The gels were composed of either poly(N-isopropylacrylamide) or with additional 5.6 mol % of 3-acrylamidophenylboronic acid (AAPBA). DNA adsorption on the AAPBA-containing gels was achieved with a high salt concentration, which can be explained by electrostatic repulsion between DNA and boronic acid. The critical role of boronic acid was confirmed by adding competing cis-diol-containing molecules such as glucose, fructose, and cytidine. Hydrogen bonding and hydrophobic interactions are important for DNA adsorption based on inhibited adsorption by urea and dimethyl sulfoxide. Polycytosine DNA showed a higher adsorption capacity compared to the other three types of DNA homopolymers. When T15 and T14-rU were compared, no covalent binding was detected for T14-rU, suggesting that a single terminal diol was insufficient to support covalent binding at the low concentration of DNA used. Finally, the boronic acid-containing gels were able to adsorb an aptamer and inhibit its binding function. Binding was rescued by adding glucose to block the boronic acids. This study demonstrates noncovalent boronic acid interactions with DNA, and this information could be useful for designing and optimization of related biosensors and materials.

ChemInform Abstract: Reversible Click Reactions with Boronic Acids to Build Supramolecular Architectures in Water

AbstractReview: 65 refs.

A carbon nanofiber-based label free immunosensor for high sensitive detection of recombinant bovine somatotropin.

A carbon nanofiber-based label free electrochemical immunosensor for sensitive detection of recombinant bovine somatotropin (rbST) was developed. In this immunosensor design, a mild site-directed antibody immobilization via interaction of boronic acid and oligosaccharide moiety found on Fc region of an antibody was performed to preserve the biological activity of antibody and improve the sensor's sensitivity. Electrochemical characterization of the immunosensor fabrication was carried out by differential pulse voltammetry (DPV) in Fe(CN)6(3-)/Fe(CN)6(4-) probe. A comparison study between different transducer platforms showed carbon nanofiber gave higher current signal response than single-walled carbon nanotube. In this work, calibration curve was obtained from the decrease of DPV peak current of Fe(CN)6(3-)/Fe(CN)6(4-) after immunocomplexed was formed. A linear relationship between DPV current change signal response and rbST concentrations from 1 pg/mL to 10 ng/mL (correlation coefficient of 0.9721) was achieved with detection limit of 1 pg/mL. Our developed immunosensor demonstrated high selectivity in cross-reactivity studies and a good percentage recovery in spiked bovine serum sample.

Boronic acids for sensing and other applications - a mini-review of papers published in 2013.

Boronic acids are increasingly utilised in diverse areas of research. Including the interactions of boronic acids with diols and strong Lewis bases as fluoride or cyanide anions, which leads to their utility in various sensing applications. The sensing applications can be homogeneous assays or heterogeneous detection. Detection can be at the interface of the sensing material or within the bulk sample. Furthermore, the key interaction of boronic acids with diols allows utilisation in various areas ranging from biological labelling, protein manipulation and modification, separation and the development of therapeutics. All the above uses and applications are covered by this mini-review of papers published during 2013.

Reversible click reactions with boronic acids to build supramolecular architectures in water.

The interaction of boronic acids with various bifunctional reagents offers great potential for the preparation of responsive supramolecular architectures. Boronic acids react with 1,2-diols yielding cyclic boronate esters that are stable at pH>7.4 but can be hydrolyzed at pH<5.0. The phenylboronic acid (PBA)-salicylhydroxamic acid (SHA) system offers ultra-fast reaction kinetics and high binding affinities. This Focus Review summarizes the current advances in exploiting the bioorthogonal interaction of boronic acids to build pH-responsive supramolecular architectures in water.

A simple chip free‐flow electrophoresis for monosaccharide sensing via supermolecule interaction of boronic acid functionalized quencher and fluorescent dye

Here, a simple micro free-flow electrophoresis (μFFE) was developed for fluorescence sensing of monosaccharide via supermolecule interaction of synthesized boronic acid functionalized benzyl viologen (ο-BBV) and fluorescent dye. The μFFE contained two open electrode cavities and an ion-exchange membrane was sandwiched between two polymethylmethacrylate plates. The experiments demonstrated the following merits of developed μFFE: (i) up to 90.5% of voltage efficiency due to high conductivity of ion-exchange membrane; (ii) a strong ability against influence of bubble produced in two electrodes due to open design of electrode cavities; and (iii) reusable and washable separation chamber (45 mm × 17 mm × 100 μm, 77 μL) avoiding the discard of μFFE due to blockage of solute precipitation in chamber. Remarkably, the μFFE was first designed for the sensing of monosaccharide via the supermolecule interaction of synthesized ο-BBV, fluorescent dye, and monosaccharide. Under the optimized conditions, the minimum concentration of monosaccharide that could be detected was 1 × 10(-11) M. Finally, the developed device was used for the detection of 0.3 mM glucose spiked in human urine. All of the results demonstrated the feasibility of monosaccharide detection via the μFFE.

Label-free and sensitive strategy for microRNAs detection based on the formation of boronate ester bonds and the dual-amplification of gold nanoparticles

MicroRNAs (miRNAs), regulating gene expression by translational repression or degradation of messenger RNAs, are believed to be important for cancer diagnosis and prognosis serving as reliable molecular biomarkers. Simple, sensitive, and cost-effective assays for miRNAs are therefore in urgent demand. The main difference in the structure of RNA versus DNA is the presence of a hydroxyl group at the 2′ position of the ribose sugar in RNA, which makes the RNA molecule contain cis-diol at the end of the chain. Hydrophilic boronic acids are well known to form covalent bonds with cis-diols. In this work, we reported a label-free and sensitive method for the detection of miRNAs based on the formation of boronate ester covalent bonds and the dual-amplification of gold nanoparticles (AuNPs). Specifically, miRNAs were captured by the pre-immobilized DNA probes at the gold electrode, and derivatized with 4-mercaptophenylboronic acid (MBA)-capped AuNPs (MBA-AuNPs) through the formation of tight covalent bonds between the boronic acids of MBA-AuNPs and diols of miRNAs. Electrochemically active dopamine (DA)-capped AuNPs (DA-AuNPs) were then attached by the anchored MBA-AuNPs via the interaction of boronic acids and DA tags, which facilities the amplified voltammetric detection of miRNAs. Analytical merits (e.g., sensitivity, reproducibility, storage stability, dynamic range, and selectivity) were addressed. We believe that the results will be valuable for the development of biosensor for the detection of miRNAs in a biological matrix.

Sandwich-type electrochemical biosensor for glycoproteins detection based on dual-amplification of boronic acid-gold nanoparticles and dopamine-gold nanoparticles

Glycoproteins play important roles in a wide variety of biological processes. The change in the concentration levels has been associated with many cancers, as well as other diseases. Thus, rapid, sensitive and selective determination of glycoproteins is much preferred. In this work, we reported a sandwich-type electrochemical biosensor based on dual-amplification of 4-mercaptophenylboronic acid (MBA)-capped gold nanoparticles (MBA-AuNPs) and dopamine (DA)-capped AuNPs (DA-AuNPs). Biological recognition elements such as synthetic receptor and aptamer immobilized onto gold electrodes were used to capture glycoproteins. The captured glycoproteins were then derivatized with MBA-AuNPs through the formation of tight covalent bonds between the boronic acids of MBA-AuNPs and diols of glycoproteins. Electroactive DA-AuNPs were attached by the anchored MBA-AuNPs via the interaction of boronic acids with DA tags, which facilities the amplified voltammetric detection of glycoproteins. With avidin and prostate specific antigen (PSA) as model analytes, we demonstrated the feasibility and sensitivity of the proposed method. The results indicated that sub-picomolar avidin/PSA can be readily measured. We believe that this strategy will be valuable for the electrochemical detection of other glycoproteins.

A Selective Spectrofluorometric Determination of Micromolar Level of Cyanide in Water Using Naphthoquinone Imidazole Boronic-Based Sensors and a Surfactant Cationic CTAB Micellar System

We developed a new spectrofluorometric method for qualitative and quantitative determination of cyanide in water using the incorporation of naphthoquinone imidazole boronic-based sensors (m-NQB and p-NQB) and a cationic surfactant, certyltrimethyl ammonium bromide (CTAB). This micellar system exhibited great selectivity for cyanide detection with an assistance of the cationic surface of micelle. The interaction of boronic acid of the sensor toward cyanide in CTAB micellar media gave a quantitative measure of cyanide concentration in the micromolar level. Under the optimal condition, fluorescence intensity at 460 nm of m-NQB and p-NQB provided two sets of linear ranges, 0.5-15 μM and 20-40 μM and the limit of cyanide detection of 1.4 μM. Hence, both sensors in CTAB aqueous micellar system offered a considerably promising cyanide detection with 1000-fold enhancement of the detection limit compared to those studied in DMSO: H(2)O. The proposed sensors could also be used to determine cyanide in water with good analytical characteristics.

Hierarchical carbon nanotube assemblies created by sugar–boric or boronic acid interactions

We previously found that polysaccharide "schizophyllan (SPG)" can entrap as-grown and cut single-walled carbon nanotubes (as-SWNTs and c-SWNTs, respectively): we here reported that the c-SWNT-s-SPG (single stranded SPG) composites thus obtained can be aligned regularly using the covalent bond formation between boric acid or boronic acid derivatives and the 4,6-dihydroxyl group of the glucose side-chain unit.

Syntheses of boronic-acid-appended metalloporphyrins as potential colorimetric sensors for sugars and carbohydrates

Boronic-acid-based dyes have been widely studied in the past decade as potential sensors for sugars and carbohydrates, owing to the strong interaction of boronic acid and diols. In this work, two boronic-acid-appended metalloporphyrins were synthesized by new routes and tested as potential sugar and carbohydrate sensors. Boronic acid substituents were attached either to a β-pyrrolic position ((2-dihydroxylboryl-5,10,15,20-tetraphenylporphyrinato)zinc(II), 1) or to the meso-position ((10-dihydroxylboryl-5,15-diphenylporphyrinato)zinc(II), 2) of the porphyrin core. These complexes were tested as potential carbohydrate sensors; unfortunately, no UV-vis or fluorescence spectra changes were observed with the addition of glucose or fructose. Molecular orbital calculations confirm little electronic conjugation between the porphyrin π-system and the boronic acid substituents in either pyrrolic or meso-positions.

Immobilization of Glycosylated Enzymes on Carbon Electrodes, and its Application in Biosensors

A novel approach was used to immobilize glycosylated enzymes on a glassy carbon electrode (GCE) based on the interaction of boronic acid and carbohydrate moiety within the glycoproteins. 4-Aminomethylphenylboronic acid (4-AMBA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. The boronic acid group immobilized in this way could recognize glycoproteins such as glucose oxidase, horseradish peroxidase, dehydrogenase and others. X-ray photoelectron spectroscopy measurement proved the presence of a 4-AMBA monolayer on the GCE. The adsorptions of three kinds of enzymes were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The activity of the immobilized horseradish peroxidase was also studied.

Quartz crystal biosensor for detection of sugars and glycated hemoglobin

3-Aminophenylboronic acid (APBA) was used for construction of affinity mass sensors for determination of saccharides and glycated hemoglobin using complexation reaction with diol groups. Two approaches were tested for the bioligand layer fabrication—incorporation of APBA inside a thicker matrix and immobilization as a self-assembled monolayer, respectively. The direct affinity sensor with APBA embeded in the structure of glutaraldehyde-crosslinked bovine serum albumine provided linear response to mono- and dissacharides in the range from 0.1 to 15.0 mg/ml. This biosensor was also used for kinetic analysis of the interaction of boronic acid with diols; the values of association and dissociation constants were determined. The sensors with a monolayer of boronic groups were better suited for binding of glycated hemoglobin, probably due to improved steric access to the ligand.

Thermodynamic analysis of receptors based on guanidinium/boronic acid groups for the complexation of carboxylates, alpha-hydroxycarboxylates, and diols: driving force for binding and cooperativity.

The thermodynamics of guanidinium and boronic acid interactions with carboxylates, alpha-hydroxycarboxylates, and diols were studied by determination of the binding constants of a variety of different guests to four different hosts (7-10). Each host contains a different combination of guanidinium groups and boronic acids. The guests included molecules with carboxylate and/or diol moieties, such as citrate, tartrate, and fructose, among others. The Gibbs free energies of binding were determined by UV/Vis absorption spectroscopy, by use of indicator displacement assays. The receptor based on three guanidinium groups (7) was selective for the tricarboxylate guest. The receptors that incorporated boronic acids (8-10) had higher affinities for guests that included alpha-hydroxycarboxylate and catechol moieties over guests containing only carboxylates or alkanediols. Isothermal titration calorimetry revealed the enthalpic and entropic contributions to the Gibbs free energies of binding. The binding of citrate and tartrate was investigated with hosts 7-10, for which all the binding events were exothermic, with positive entropy. Because of the selectivity of hosts 8-10, a simple boronic acid (14) was also investigated and determined to be selective for alpha-hydroxycarboxylates and catechols over amino acids and alkanediols. Further, the cooperativity of 8 and 9 in binding tartrate was also investigated, revealing little or no cooperativity with 8, but negative cooperativity with 9. A linear entropy/enthalpy compensation relationship for all the hosts 7-10, 14, and the carboxylate-/diol-containing guests was also obtained. This relationship indicates that increasing enthalpy of binding is offset by similar losses in entropy for molecular recognition involving guanidinium and boronic acid groups.

Structures of carbohydrate-boronic acid complexes determined by NMR and molecular modelling in aqueous alkaline media.

The structures of thermodynamically stable aromatic boronic acid : cyclic carbohydrate chelates in aqueous alkaline media have been studied using 1H NMR spectroscopy and molecular modelling. It is found that interacting saccharides must necessarily possess a synperiplanar diol functionality for complexation to occur. While this is possible for furanose structures which tend to have a puckered planar geometry, for pyranose forms it is postulated that bis-complexation occurs with twist conformers of the pyranose ring, providing the ring has the requisite 1,2 : 3,4 polyol stereochemistry; specifically axial,equatorial : equatorial,axial or equatorial,axial : axial,equatorial orientations. In this respect it is possible to be predictive with regard to individual carbohydrate boronic acid interactions and to give reasonably comprehensive structural assignments to complexed components. In this paper twenty four polyhydroxy compounds have been screened using 1H NMR to monitor complexation along with computational techniques on a model system to substantiate proposed structures. It has been found that all of these materials interact with aromatic mono boronic acids as expected and structures for the resulting chelates are proposed.

Supramolecular macrocycles self-assembled by phenanthroline–Cu(I) and sugar–boronic acid interactions

Two kinds of ligand which have two phenanthroline groups linked by a C 2-symmetrical chiral tetrol were synthesized by a boronic acid–diol interaction. It was shown that these ligands form unique dinuclear chiral macrocycles by a Cu(I)–phenanthroline interaction. The results indicate that a novel supramolecular system can be exploited by combination of the Cu(I)–phenanthroline interaction with the boronic acid–diol interaction.

Sugar–boronic acid interactions in the formation of novel chiral porphyrin dimers with various porphyrin–porphyrin angles

Monoboronic acid-appended porphyrin 1 forms sugar–1 complexes (1:2) which have various porphyrin–porphyrin angles, depending on the sugar absolute configuration; the system is very useful in the study of the photochemical properties of dimeric porphyrins and the role of a so-called ‘essential pair’.

Novel Saccharide-Photoinduced Electron Transfer Sensors Based on the Interaction of Boronic Acid and Amine

Two boronic acid systems, monoboronic acid 3 and diboronic acid 8, were synthesized. When saccharides form cyclic boronate esters with these boronic acids, the Lewis acid-base interaction between the boronic acid moiety and tertiary amine is strengthened; when saccharides form cyclic boronate esters with boronic acids the acidity of the boronic acid is enhanced. The strength of this acid-base interaction modulates the photoinduced electron transfer (PET) from the amine to anthracene. Both of these compounds show increased fluoresecence at pH 7.77 through supression of the photoinduced electron transfer from nitrogen to anthracene on saccharide binding, a direct result of the stronger boron-nitrogen bond. Compound 3 shows the typical selectivity of monoboronic acids towards saccharides. Compound 8 which has a cleftlike structure is particularly selective and sensitive for, glucose due to the formation of an intramolecular 1:1 complex between the two boronic acids and the 1,2- and 4,6-hydroxyls of glucose. This is the first example in which ditopic recognition of monosaccharides is achieved in a PET sensor system.

Novel photoinduced electron-transfer sensor for saccharides based on the interaction of boronic acid and amine

Download options Please wait... Article information DOI https://doi.org/10.1039/C39940000477 Article type Paper Download Citation J. Chem. Soc., Chem. Commun., 1994, 477-478 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Novel photoinduced electron-transfer sensor for saccharides based on the interaction of boronic acid and amine T. D. James, K. R. A. S. Sandanayake and S. Shinkai, J. Chem. Soc., Chem. Commun., 1994, 477 DOI: 10.1039/C39940000477 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Tony D. James K. R. A. Samankumara Sandanayake Seiji Shinkai