Structure&Properties Modulation Of Phenylboronic Acid-Based Polymers And Their Applications In Chemosensoring

Phenylboronic acid polymers have excellent chemical properties,such as forming reversible borates with diol molecules,the Lewis acid due to the lack of electrons of boron,coordinating with metal ions,stimulus responsiveness,etc.It is widely used as sugar detection,insulin release,chemical or physical sensor,etc.Among them,Phenylboronic acid polymers have wide applications in sugar-specific detection,insulin release,drug delivery and biomacromolecule separation due to their ability to form reversible boronic esters with diols.Borinic acid polymers have high stability,catalytic Lewis acidity,and excellent molecular binding properties,and can be used as multi-responsive polymers in the fields of thermoresponsive materials,supramolecular materials,and enzymatic biofuel cells.NBN-doped compounds from the combination of boronic acid groups and diamines,have excellent optoelectronic properties due to the existence of BN bonds,and can be applied in pharmacology,electronic materials and nanoscience.The starting point of this work is the structure and properties modulation of phenylboronic acid-based polymers and their applications in chemosensoring.Based on phenylboronic acid,4-Vinylphenylboronic acid polymer nanomaterials were constructed.The phenylboronic acid structure can form reversible dynamic chemical bonds with 1,2diol molecules to achieve specific and high-sensitivity detection of fructose.Utilizing the electron-deficient nature and Lewis acidity of borinic acid structure to achieve multi-ion responsiveness with tunable temperature responsiveness.NBN-doped compounds show excellent photophysical properties from the aromaticity of the NBN structure,and it can also be used as a fluorescence sensor to detect fluoride ions and metal ions.The main contents are as follow:1.Poly(4-vinylphenylboronic acid)-b-polystyrene(PVPBA-b-PS)nanomaterials were prepared by polymerization-induced self-assembly(PISA)of styrene(St)and poly(4vinylbenzeneboronic acid)(PVPBA)in a mixed solvent of methanol and water.The optimal reaction conditions were obtained by adjusting the water content and St/PVPBA in the system.The uniformly dispersed nanomaterials were prepared,and their structure and morphology were characterized.Through the fluorescence detection effect of 8hydroxyquinoline(HQ),the detection sensitivity of polymer chains and nanomaterials was compared.Fluorescent sensor for sugar detection were built via Nanomaterials combined with Alizarin Red S(ARS)and Quercetin(QC).The results show that the PVPBA-b-PS nanomaterials prepared by the optimal experimental conditions of PISA were core-shell nanospheres with two diameters of 135 nm and 527 nm,and the distribution was uniform.Compared with PVPBA chains,nanomaterials had higher detection sensitivity for 8hydroxyquinoline(HQ).The fluorescence sensor achieved specific and high-sensitivity detection of fructose,and its detection limit can be as low as 1.83 nM.2.Two borinic acid polymer monomers and polymer structural units with substituted ethyl and fluorine group were prepared by a simplified one-pot reaction of trimethoxyborane and Grignard reagent.The corresponding polymers were prepared by reversible addition-fragmentation chain transfer(RAFT)polymerization.The photophysical properties of polymer structural units and polymers were compared.At the same time,the fluorescence intensities of three ethyl-substituted borinic acid polymers with different molecular weight were compared,and their energy level orbitals and electron clouds were theoretically calculated.The detection properties of the above two types of polymers for fluoride ion,diol molecule ARS and electron-rich HQ were studied,and the temperature-sensitive properties in the mixed solvent of DMSO and water were also studied.The results show that the polymer solution in tetrahydrofuran exhibits blue fluorescence compared to the structural monomer.monohydroxy phenylboronic acid polymers can be used as quenching fluorescent probes for fluoride ions.At the same time,the diol molecule ARS and electron-rich HQ were detected by fluorescence color change.In addition,the borinic acid polymers had temperature-sensitive properties in a wide range of 34℃～90℃.3.NBN-doped molecules were prepared by catalyst-free intermolecular dehydration reaction using boronic acid molecules and diamine compounds,and NBN-doped polymers were prepared by RAFT method.The photophysical properties of NBN molecules were studied,and the theoretical calculation of aromaticity was carried out.The stability and fluorescence characteristics of this molecule at high and low concentrations were studied,the mechanism was explored by nuclear magnetic resonance and single crystal diffractometer,and the detection effect of fluoride ions was explored.The photophysical properties of NBN polymers and corresponding monomers were compared,and the energy level orbitals and electron cloud distributions of the polymers were theoretically calculated.NBN polymer was applied in metal ion detection to explore its detection performance as a fluorescence sensor.The research results show that NBN molecule is anti-aromaticity,no fluorescence phenomenon appears in its solid and liquid state,and it can be used as a lightemitting fluorescent probe for fluoride ions.Compared with the monomer,NBN polymer had stronger luminescence and solvatochromism.It can detect Fe3+ and Cr3+with high selectivity and high sensitivity,with the lowest detection limits of 7.30 nM and 14.69 nM,respectively,and a short response time is less than 1 min.In this paper,a series of novel polymers with different chemical structures were developed based on phenylboronic acid polymers,and their physicochemical properties and applications were explored.This work provides a reference for expanding the structural library of boron-containing compounds and developing new boron-containing materials and new light-emitting materials.