Phenylboronic Acid and Amino Bifunctional Modified Adsorbent for Quickly Separating Phenolic Acids from Crude Extract of Clerodendranthus spicatus and Evaluation of Their Antioxidant and Hypoglycemic Activities.

A novel phenylboronic acid and amino bifunctional modified silica gel (SiO2-NH2-FPBA) was prepared, which was 30-80 µm, had a pore size of 8.69 nm, a specific surface area of 206.89 m2/g, was stable at low temperature, and contained 0.4793 mmol/g of the phenylboronic acid group and 1.6377 mmol/g of the amino group. It was used to develop a rapid separation method for phenolic acids. The results showed that it could adsorb 93.64 mg/g caffeic acid, 89.35 mg/g protocatechuic acid and 79.66 mg/g gallic acid. The adsorption process was consistent with the pseudo-second-order model (R2 > 0.99), and fitted the Langmuir isotherm model well (R2 > 0.99). CH3COOH could effectively desorb phenolic acids (>90%) and did not destroy their structures. When SiO2-NH2-FPBA was added to crude extract of Clerodendranthus spicatus, 93.24% of the phenolic acids could be captured, and twenty-two kinds of phenolic acids were identified by Q Exactive HF LC-MS. Furthermore, the isolated phenolic acids from Clerodendranthus spicatus possessed great DPPH, ABTS, and hydroxyl radicals scavenging activities and ferric reducing power. They also demonstrated effective inhibition of α-amylase and α-glucosidase activities (IC50 = 110.63 ± 3.67 µg/mL and 64.76 ± 0.30 µg/mL, respectively). The findings indicate that SiO2-NH2-FPBA has significant potential in practical applications of separating active constituents from natural resources.

Preparation of a phenylboronic acid and aldehyde bi-functional group modified silica absorbent and applications in removing Cr(vi) and reducing to Cr(iii).

Cr(vi) is a great threat to the ecological environment and human health, so it is urgent to remove Cr(vi) from the environment. In this study, a novel silica gel adsorbent SiO2-CHO-APBA containing phenylboronic acids and aldehyde groups was prepared, evaluated and applied for removing Cr(vi) from water and soil samples. The adsorption conditions including pH, adsorbent dosage, initial concentration of Cr(vi), temperature and time were optimized. Its ability in removing Cr(vi) was investigated and compared with three other common adsorbents, SiO2-NH2, SiO2-SH and SiO2-EDTA. Data showed SiO2-CHO-APBA had the highest adsorption capacity of 58.14 mg g-1 at pH 2 and could reach adsorption equilibrium in about 3 h. When 50 mg SiO2-CHO-APBA was added in 20 mL of 50 mg L-1 Cr(vi) solution, more than 97% of Cr(vi) was removed. A mechanism study revealed that a cooperative interaction of both the aldehyde and boronic acid groups is attributed to Cr(vi) removal. The reducing function was gradually weakened with the consumption of the aldehyde group, which was oxidized to a carboxyl group by Cr(vi). This SiO2-CHO-APBA adsorbent was successfully used for the removal of Cr(vi) from soil samples with satisfactory results which indicates a good potential in agriculture and other fields.

Preparation of boronic acid and carboxyl-modified molecularly imprinted polymer and application in a novel chromatography mediated hollow fiber membrane to selectively extract glucose from cellulose hydrolysis.

A novel boronic acid and carboxyl-modified glucose molecularly imprinted polymer were prepared through suspension polymerization, which is based on 1.0 mmol glucose as a template, 1.2 mmol methacrylamidophenylboronic acid, and 6.8 mmol methacrylic acids as monomers, 19 mmol ethyleneglycol dimethacrylate, and 1 mmol methylene-bis-acrylamide as crosslinkers. The prepared glucose-molecularly imprinted polymer had a particle size of 25-70 µm, and was thermally stable below 215°C, with a specific surface area of 174.82 m2/ g and average pore size of 9.48 nm. The best selectivity between glucose and fructose was 2.71 and the maximum adsorption capacity of glucose- molecularly imprinted polymer was up to 236.32 mg/ g which was consistent with the Langmuir adsorption model. The similar adsorption abilities in six successive runs and the good desorption rate (99.4%) verified glucose-molecularly imprinted polymer could be reused. It was successfully used for extracting glucose from cellulose hydrolysis. The adsorption amount of glucose was 2.61 mg/mL and selectivity between glucose and xylose reached 4.12. A newly established chromatography (glucose-molecularly imprinted polymer) mediated hollow fiber membrane method in time separated pure glucose from cellulose hydrolysates on a large scale, and purified glucose solution with a concentration of 3.84 mg/mL was obtained, which offered a feasible way for the industrial production of glucose from cellulose hydrolysates.

Preparation of a magnetic and recyclable superparamagnetic silica support with a boronic acid group for immobilizing Pd catalysts and its applications in Suzuki reactions.

Palladium is one of the best metal catalysts for Suzuki cross-coupling reaction to synthesize unsymmetrical biaryl compounds. However, homogeneous palladium (Pd) is limited in an industrial scale due to the high cost, separation, removal, and recovery issues. In this paper, a novel, high activity magnetic nanoparticles (Fe3O4@SiO2-APBA-Pd) catalyst was prepared by a simple, cost-effective procedure. The as-prepared functional nanoparticles (Fe3O4@SiO2-APBA) with boric acid group immobilized Pd through adding Pd(OAc)2 to Fe3O4@SiO2-APBA in absolute ethanol and maintaining for a certain time under a nitrogen atmosphere. The as-prepared catalyst was characterized by FT-IR, SEM, EDX, TEM, ICP-MS, XPS, and XRD. The results showed that the Pd (0.2-0.6 nm) was successfully anchored on the magnetic silica material with boric acid group. The amount of Pd was 0.800 mmol g-1. This magnetic nanostructure (8-15 nm) is especially beneficial as a nanocatalyst because each nanoparticle can catalyze a reaction in a certain time without steric restriction, which could effectively improve the reaction efficiency. The current nanoparticles with the Pd catalyst could be used as a novel, green, and efficient heterogeneous catalyst for Suzuki reactions. This catalyst showed promising catalytic activity and excellent yields toward 14 kinds of Suzuki coupling reactions under mild reaction conditions, which was similar to homogeneous Pd and many reported heterogeneous Pd catalysts. In addition, the turnover number (TON) and turnover frequency (TOF) for the Suzuki reaction were high. TOF and TON were 9048 h-1 and 20 250 for the Suzuki reaction of bromobenzene and phenylboronic acid. Furthermore, the nanoparticles could be easily separated by a magnet, and could be used repeatedly seven times without any significant loss in activity.