The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids.

ortho-Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the o-aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debate. Further, the aminomethyl group is believed to be involved in the turn-on of the emission properties of appended fluorophores upon diol binding.

On the Rate of Boronate Ester Formation in ortho-Aminomethyl Functionalized Phenyl Boronic Acids.

The role of the ortho-aminomethyl functional group in phenyl boronic acids for sugar complexation is a topic of debate. To decipher its effect on the kinetics of boronate ester formation, we first performed pseudo-first order kinetics analyses at five pH values up to 4 mM in fructose, revealing a first-order kinetic dependence upon fructose. Under these conditions, the reaction is in equilibrium and does not reach completion, but at 50 mM fructose saturation is achieved revealing zero-order dependence upon fructose.

Probing intramolecular B-N interactions in ortho-aminomethyl arylboronic acids.

This work investigates the interplay between the intramolecular B-N dative bonding and solvent insertion in various ortho-methylamino arylboronic acids in protic media. (11)B NMR experiments were conducted to study the effect that the degree of substitution of the amine group has on B-N bonding versus solvent insertion. It was found that there is a slight increase in the amount of B-N dative bonding on going from a tertiary to a secondary to a primary amine group, but that solvent insertion dominates in all cases of the boronate esters.

Pattern-based peptide recognition.

Nature's use of sensor arrays in the mammalian olfactory and gustatory systems has encouraged supramolecular chemists to take a new approach to molecular recognition. Pattern-based recognition involves the use of sensor arrays to create fingerprints for analytes. The use of sensing arrays has paved the way for systems capable of identifying biological analytes that would have been difficult targets using the traditional "lock-and-key" approach to sensor design.