Apinya Obma ^a, Rawiwan Bumrungpuech ^a, Pattamaporn Hemwech ^a, Sasinun Detsangiamsak ^a, Supa Wirasate ^b, Peter C. Hauser ^c, and Rattikan Chantiwas ^a,*

^a Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Rama VI Rd., Bangkok 10400, Thailand
^b Rubber Technology Research Centre 999 Science Building 3, Phuttamonthon 4 Road, Salaya, Nakhon Pathom 73170, Thailand
^c The University of Basel, Department of Chemistry, Klingelbergstrasse 80, CH-4056 Basel, Switzerland
* Corresponding author. Tel.: +66 2 201 5199; Fax: +66 2 354 7151 E-mail: rattikan.cha@mahidol.ac.th, rattikan.cha@mahidol.edu

Abstract:

Background: Capillary electrophoresis (CE) has the advantage of rapid anion analysis, when employing a reverse electroosmotic flow (EOF). The conventional CE method utilizes dynamic coatings with surfactants like cetyltrimethylammonium bromide (CTAB) in the run buffer to reverse the EOF. However, this method suffers from very slow equilibration leading to drifting effective migration times of the analyte anions, which adversely affects the identification and quantification of peaks. Permanent coating of the capillary surface may obviate this problem but has been relatively little explored. Thus, permanent capillary surface modification by the covalent binding of 3-aminopropyltriethoxysilane (APTES) was studied as an alternative.

Results: This study investigates the effect of APTES concentration for surface functionalization on EOF mobility, separation efficiency, and reproducibility of anion separation. The performance data was complemented by X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The XPS measurements showed that the coverage with APTES was dependent on its concentration in the coating solution. The XPS measurements correlated well with the EOF values determined for the capillaries tested. A standard mixture of 21 anions could be baseline separated within 10 minutes in the capillaries with lower EOF, but not in the capillary with the highest EOF as the residence time of the analytes was too short in this case. Compared to conventional dynamic coating with CTAB, APTES-functionalized capillaries provide faster equilibration and long-term EOF stability. The application of APTES-functionalized capillaries in analyzing different beverages demonstrates the precision, reliability, and specificity in determining organic anions, providing valuable insights of their compositions.

Significance: APTES coating on capillaries provides a facile approach to achieve a permanent reversal of the stable EOF to determine anions. The control of the coverage via the concentration of the reagent solution allows the tailoring of the EOF to different needs, a faster EOF for less complex samples where resolution is not challenging, while a lower EOF for higher complex samples where the focus is on separation efficiency. This enhancement in efficiency and sensitivity has been applied to analyzing organic acids in several beverages.

KEYWORDS

APTES-functionalized capillary; Reversed EOF; Anion separation; Surface Modification; Beverages; CE-C⁴D

Reference:

Obma, A.; Bumrungpuech, R.; Hemwech, P.; Detsangiamsak, S.; Wirasate, S.; Hauser, P. C.; Chantiwas, R. Efficient Separation of Organic Anions in Beverages using Aminosilane-Functionalized Capillary Electrophoresis with Contactless Conductivity Detection. Analytica Chimica Acta 2024, 342815.
doi: /10.1016/j.aca.2024.342815