Synthesis, Characterization Of Phenylboronic Acid Derivatives And Its Recognition

The organic compounds with boronic acid group as the recognition group have been widely used in chemical and biosensor fields.Because of their hydrogen bonding or covalent interaction, they are widely used in the identification and detection of hydroxyl-containing compounds, which has been heatedly discussed in recent studies.In this paper, various borate-functional derivatives were synthesizedand used to detect different small biomolecule such as monosaccharide, inorganic ions and amino acid.Through experiments, we designed and synthesized 18 phenylboronic acid functionalized derivatives, and used them to prepare some phenylboronic acid derivatives/HTCs composites.In addition, we also characterized the structures of phenylboronic acid functionalized derivatives and discussed their spectral properties and recognition action.In this paper, two types of phenylboronic acid derivatives were synthesized.The first type includes 14 kinds of phenylboronic acid derivatives containing di-hydroxyl (1-8,13-18).They were synthesized with 2-formyl phenylboronic acid, para-position substituted aniline and its derivatives, fatty amine and diethyl phosphite by one-pot reaction.The other type compounds 4 kinds of phenylboronicacid derivatives (9-12) containing mono-hydroxywith B-N bond.They were synthesized by one-pot reaction with 2-methyl phenylboronic acid and a primary amine in the presence of diethyl phosphite.In these 18 phenylboronic acid derivatives,15 kinds of phenylboronic acid derivatives are not encompassed in SciFinder.There are 7 kinds of compounds obtained the crystal structures, six crystal structures have not reported in literatures.The structures of those compounds (1-18) were characterized by melting point measurement and characterized by IR and 1H NMR.Some of them were characterized by scanning electron microscopy (SEM), mass spectra, elemental analysis and thermogravimetric (TG).In this paper, two types of phenylboronic acid/HTCs composites were prepared.One is phenylboronic acid/HTCs composites (13'-18',19) solutions, obtained by non-covalent of phenylboronic acid functionalized derivatives (1, 13 to 18) and HTCs.The other is functionalized hydrothermal carbon spheres (20), obtained by condensation reaction of 3-aminobenzeneboronic acid and HTCs.The solutions of all phenylboronic acid derivatives showed excellent fluorescence luminous except for 5,13 to 18.The solid-state compounds 1-12 appeared excellent fluorescence as well. Although neither solid-statenor aqueous solution of compounds 13 to 18 showed the fluorescence properties, but it could enhance the fluorescence of alizarin red fluorescence (ARS). It is found that the compounds 1-4 showed excellent selectivity and sensitivity for efficient determination of D-fructose. A linear response in the Stern-Volmer plot within a total concentration range of 0.5000 mmol/L to 5.000 mmol/L was observed with an extremely low detection limit of 10 ppm.The novel synthesized fluorescent phenylboronic acid derivatives (9-12) showed little selectivity and sensitivity for efficient determination of monosaccharide molecular.But through studying on the interaction between compounds 9-12 and twelve inorganic anions, the compounds could selectively detect iodide ion and obtained a detection limit of 1 ppm.Theoretical calculations based on DFT illustrated that iodine ion may have interacted with boron atoms in the compounds.The solutions of phenylboronic acid (13-18)/HTCs composites (13'-18') showed better fluorescence luminous.The synthesized fluorescent phenylboronic acid/HTCs composites could selectively detect dopamine and obtained a detection limit of 0.1 ppm.The compound (1)/HTCs composite (19) also showed fine fluorescence and could selectively detect D-frutose and obtained a detection limit four orders of magnitude below compound (1).In addition, it also could be used to identify dopamine.The modification HTCs spheres (3-APBA-HTCs) showed excellent selectivity and sensitivity for efficient determination of L-tryptophan (L-Trp).The fluorescence sensors could selectivelyidentify for L-Trp at an extremely low detection limit of 10 ppm.In order to test the effect of those compounds in real and complex situation, acacia honey and linden honey were selected and tested on their D-fructose content, using compounds 1-4.The result was mostly consistent with the traditional method of HPLC.Furthermore,3-APBA-HTCs showed great potential to be a useful fluorescent probe.Moreover, we tried to label the liver tumor cells using 3-APBA-HTCs compound.The result showed that it is possible to directly label tumor cells with high tryptophan content without using a cell staining agent.This may contribute a new possible method to analyzing and testing similar samples in the medical field.