Synthese and characterization of boronic acid functionalized macroporous uniform poly(4-chloromethylstyrene-co-divinylbenzene) particles and its use in the isolation of antioxidant compounds from plant extracts

• Published in: Journal of chromatography. B, Analytical technologies in the biomedical and life sciences Vol. 909; pp. 51 - 60
• Main Authors: Çetinkaya, Onur, Duru, Mehmet Emin, Çiçek, Hüseyin
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 15.11.2012
• Subjects: Activated swelling method; Adsorption; Adsorption–desorption; Antioxidant activity; Antioxidants - analysis; Antioxidants - chemistry; Antioxidants - isolation & purification; Antioxidants - metabolism; apigenin; Biphenyl Compounds - metabolism; Boronic Acids - chemistry; chlorine; Chromatographic packing material; chromatography; Chromatography, High Pressure Liquid - instrumentation; Chromatography, High Pressure Liquid - methods; Chromatography, Reverse-Phase - instrumentation; Chromatography, Reverse-Phase - methods; desorption; dibutyl phthalate; ethanol; ethyl acetate; Flavonoids - analysis; Flavonoids - chemistry; Flavonoids - isolation & purification; Flavonoids - metabolism; free radical scavengers; Hypericum - chemistry; Hypericum perforatum; Microspheres; Particle Size; Picrates - metabolism; plant extracts; Plant Extracts - chemistry; Plant Stems - chemistry; polystyrenes; Polystyrenes - chemistry; Polyvinyls - chemistry; Porosity; quercetin; rutin; toluene; Uniform latex particles; Hypericum perforatum; Chromatographic packing material; Activated swelling method; Uniform latex particles; Adsorption–desorption; Antioxidant activity
• ISSN: 1570-0232; 1873-376X
• DOI: 10.1016/j.jchromb.2012.09.039

► Aminophenyl boronic acid functionalized macroporous particles was synthesized. ► Selectivity of particles to cis-diol-containing flavonoids was presented. ► The adsorption behavior of particles was tested with Hypericum perforatum extracts. ► Increment of antioxidant activity in desorption solution was observed. ► The highest radical scavenging capacity was obtained with post-adsorption solution. Aminophenyl boronic acid (APBA) carrying uniform-macroporous poly(chloromethylstyrene-co-divinylbenzene), poly(CMS-co-DVB) particles were synthesized for selective separation of cis-diol-containing flavonoids from plant extracts. For this purpose, 2.5μm polystyrene seed particles were first swelled by a mixture of dibutyl phthalate (DBP), toluene and dodecanol, then by a monomer mixture including CMS and DVB. The repolymerization of the monomer phase in the swollen seed particles provided macroporous and uniform particles, approximately 7μm in size. Chlorine atoms on the surface of these particles were derivatized with APBA to gain affinity properties for flavonoids containing vicinal hydroxyl groups. Model adsorption studies showed that these particles selectively adsorbed quercetin and rutin containing cis-diol groups, but did not adsorb apigenin similar to quercetin and not carrying cis-diol groups. These particles were also tested in adsorption/desorption studies for ethanol and ethyl acetate extracts of the Hypericum perforatum (HP) stems to obtain high antioxidant mixtures. With ethanol extract, the antioxidant activity of the desorption solution was a bit higher than that of the post-adsorption solutions. However, the DPPH radical scavenging activity of the desorption solution decreased with respect to the original extract and post-adsorption solutions. A similar result was obtained for the antioxidant activity of the desorption solution using ethyl acetate extract. An interesting result was obtained that DPPH radical scavenging activity of the post-adsorption solution was higher than that of the original ethyl acetate extract and desorption solutions. These results were attributed to selective adsorption of antioxidant characterized cis-diol-containing apolar molecules much more rather than that radical scavenger characterized polar molecules.