Adsorption capacity of phenolics compounds by polyaniline materials in model solution

María Navarro, JOHN AMALRAJ, V. FELIPE LAURIE
Talca University

Email contact: mnavarrof[@[utalca.cl

AIM: The aim of this work was to study the trapping capacity of four polyaniline polymers towards phenolic compounds in wine-like model solutions.
METHODS: The model wine solution was composed of 12% (v/v) and 4 g/L of tartaric acid adjusted to pH = 3.6. A series of centrifuge tubes (15 mL) were filled with 10 mL of model solution enriched with 50 mg/L of five phenolic compounds (i.e., Gallic acid, caffeic acid, (+)-catechin, (-)-epicatechin, and rutin), and treated with different doses of PANI polymer (i.e., 0, 2, 4 and 8 g/L). After the addition of the polymer, the samples were stirred using a platform shaker at room temperature (20 ºC) for 2, 8, 16 and 24 h. All treatments included three replications.
The synthesis and characterization of polyaniline emeraldine base (PANI-EB) and different PANI 50, 100, 150 (polyaniline-PVPP composites where 50, 100, 150 are amount of PVPP) was prepared according to what was reported by Marican et al. (2014)1
Once the selected contact times were over, the samples were filtered and were by HPLC-DAD, following the methodology described by Gómez-Alonso et al. (2007)2. In brief, the separation was performed using a reverse-phased LiChrosorb® RP-18 (5 μm) column (250 mm × 4 mm ID) operating at 20 ºC. The injection volume was 25 μL, and for detection and quantification of compounds, the chromatograms were recorded at 280, 320 and 360 nm.
RESULTS: Regardless of the polymer used, the compounds having more affinity for PANI were gallic and caffeic acid, whereas rutin and (+)-catechin were the least removed. For instance, the adsorption percentage of gallic and caffeic acid, with a 4 g/L PANI concentration and 8 h of contact time, reached more than 90% whereas the removal of rutin was lower than 40%. Instead, the phenolic concertation of the samples where no polymer was added (0 g/L of PANI) remain stable over time, very close to 50 mg /L for each of the phenols evaluated.
As expected, the concentration of the five phenols decreased as the contact time increased. As an example, a 2 g/L addition of PANI 50 produced a reduction of (-)-epicatechin concentration of 17 mg/L after 8 h of contact time and 25 mg/L after 24 h. Like so, the decrease in the concentration of all phenols was greater when more polymer was added.  
CONCLUSIONS: The results obtained suggest that PANI Polymers could be an interesting alternative for analytical or experimental applications
in which polyphenolcs need to be removed.

References:

1. A. Marican, V. Carrasco-Sánchez, A. John, V.F. Laurie, L.S. Santos. The binding of 4-ethylguaiacol with polyaniline-based materials in wines. Food Chemistry, 159 (2014), pp. 486-492
2. S. Gómez-Alonso, E. García-Romero, I. Hermosín-Gutiérrez. HPLC analysis of diverse grape and wine phenolics using direct injection and multidetection by DAD and fluorescence. Journal of Food Composition and Analysis 20 (2007) 618–626