L-Fenilalaninin Kiral Ayrımı için Moleküler Baskılanmış Mikropartikül Gömülü Kompozit Kriyojel Kolon

Year 2026, Volume: 21 Issue: 1 , 167 - 178 , 30.03.2026

Semra Akgönüllü

https://doi.org/10.55525/tjst.1760255

https://izlik.org/JA42CE32GD

Abstract

Moleküler baskılanmış polimerler (MIP’ler) enantiyomerik bileşiklerin kiral ayrımı için oldukça önemlidir. MIP temelli mikropartiküllerin kriyojellere dahil edilmesi, kompozitin yüzey alanını artırır ve daha fazla bağlanma noktası sağlayarak ve etkileşimleri kolaylaştırarak kütle transferini geliştirir. Bu çalışmada, L-fenilalanin (L-Phe)'nin seçici ayrımı için mikropartikül gömülü bir kompozit kriyojel kolon geliştirilmiştir. L-Phe baskılanmış mikropartiküllerin eş boyut, şekil ve yüzey morfolojisi taramalı elektron mikroskobu (SEM) kullanılarak karakterize edilmiştir. Ardından, adsorpsiyonu incelemek için L-Phe derişimi, sıcaklık, iyonik şiddet ve adsorpsiyon süresi incelenmiştir. Özellikle 25 °C'deki en yüksek adsorpsiyon 39.40 mg g-1 olarak bulunmuştur. L-Phe baskılanmış mikropartiküllerle gömülü kompozit kriyojel kolonun, L-Phe enantiyomerik ayrımında tekrar tekrar kullanıma uygun olduğu gösterilmiştir. Son olarak, adsorpsiyon mekanizması hem adsorpsiyon izotermleri hem de adsorpsiyon kinetiği için deneysel veriler teorik modellerle karşılaştırılarak araştırılmıştır.

Keywords

Enantiyoseçici adsorpsiyon , L-fenilalanin , kiral ayırma , moleküler baskılanmış polimer , mikropartiküller

Molecularly Imprinted Microparticles Embedded Composite Cryogel Column for Chiral Separation of L-Phenylalanine

https://izlik.org/JA42CE32GD

Abstract

Molecularly imprinted polymers (MIPs) play a key role in the chiral separation of enantiomers. Incorporating MIP-based microparticle structures into cryogels increases the composite's surface area and enhances mass transfer by offering more binding sites and facilitating interactions. Here, we developed a composite cryogel column embedded with MIP microparticles for the selective separation of L-phenylalanine (L-Phe). L-Phe-imprinted microparticles of uniform size, shape, and surface morphology were characterized using scanning electron microscopy (SEM). Then, the L-Phe concentration, temperature, ionic strength, and adsorption time were investigated to study the adsorption process. Notably, the highest adsorption at 25 °C was 39.40 mg g-1. The composite cryogel column embedded with L-Phe-imprinted microparticles was shown to be suitable for repeated use in L-Phe enantioseparation. Finally, the adsorption mechanism was studied by analyzing both adsorption isotherms and kinetics and comparing the results with established theoretical models.

Keywords

Enantioselective adsorption , chiral separation , cryogel , L-phenylalanine , molecularly imprinted polymer , microparticles

References

• Zhang Z, Zhang M, Liu Y, Yang X, Luo L, Yao S. Preparation of L-phenylalanine imprinted polymer based on monodisperse hybrid silica microsphere and its application on chiral separation of phenylalanine racemates as HPLC stationary phase. Sep Purif Technol 2012;87:142–8. https://doi.org/10.1016/j.seppur.2011.11.037.
• Daneshvar Tarigh G. Enantioseparation/Recognition based on nano techniques/materials. J Sep Sci 2023;46. https://doi.org/10.1002/jssc.202201065.
• Urbańska M. Optimization of Liquid Crystalline Mixtures Enantioseparation on Polysaccharide-Based Chiral Stationary Phases by Reversed-Phase Chiral Liquid Chromatography. Int J Mol Sci 2024;25. https://doi.org/10.3390/ijms25126477.
• Zhu Q, Xu X, Xu J, Ma X. Cyclodextrins-based deep eutectic supramolecules as chiral selectors for enhanced enantioseparation in capillary electrophoresis. J Chromatogr A 2025;1740. https://doi.org/10.1016/j.chroma.2024.465599.
• Miao P, Yan Y, Du S, Du Y. Capillary electrochromatography synergistic enantioseparation system for racemate malic acid based on a novel nanomaterial synthesized by chiral molecularly imprinted polymer and chiral metal-organic framework. Anal Chim Acta 2024;1330. https://doi.org/10.1016/j.aca.2024.343303.
• Qian X, Xia L, Ji B, Huang Y, Xia Z. Chiral Separation Enhancement in Capillary Electrophoresis by Electrophoretic Mobility Differences without Electroosmosis. Anal Chem 2025. https://doi.org/10.1021/acs.analchem.5c00553.
• Ma S, Li F, Tan Z. Enantioselective liquid-liquid extraction of tryptophan enantiomers by a recyclable aqueous biphasic system based on stimuli-responsive polymers. J Chromatogr A 2021;1656. https://doi.org/10.1016/j.chroma.2021.462532.
• Sallacan N, Zayats M, Bourenko T, Kharitonov AB, Willner I. Imprinting of nucleotide and monosaccharide recognition sites in acrylamidephenylboronic acid-acrylamide copolymer membranes associated with electronic transducers. Anal Chem 2002;74:702–12. https://doi.org/10.1021/ac0109873.
• Akgönüllü S, Denizli A. Molecular imprinting-based sensors: Lab-on-chip integration and biomedical applications. J Pharm Biomed Anal 2023;225:115213. https://doi.org/10.1016/j.jpba.2022.115213.
• Savina IN, English CJ, Whitby RLD, Zheng Y, Leistner A, Mikhalovsky S V., et al. High efficiency removal of dissolved As(III) using iron nanoparticle-embedded macroporous polymer composites. J Hazard Mater 2011;192:1002–8. https://doi.org/10.1016/j.jhazmat.2011.06.003.
• Le Noir M, Plieva F, Hey T, Guieysse B, Mattiasson B. Macroporous molecularly imprinted polymer/cryogel composite systems for the removal of endocrine disrupting trace contaminants. J Chromatogr A 2007;1154:158–64. https://doi.org/10.1016/j.chroma.2007.03.064.
• Osman B, Sagdilek E, Gümrükçü M, Göçenoğlu Sarıkaya A. Molecularly imprinted composite cryogel for extracorporeal removal of uric acid. Colloids Surf B Biointerfaces 2019;183. https://doi.org/10.1016/j.colsurfb.2019.110456.
• Kirsebom H, Topgaard D, Galaev IY, Mattiasson B. Modulating the porosity of cryogels by influencing the nonfrozen liquid phase through the addition of inert solutes. Langmuir 2010;26:16129–33. https://doi.org/10.1021/la102917c.
• Saylan, Denizli. Supermacroporous Composite Cryogels in Biomedical Applications. Gels 2019;5:20. https://doi.org/10.3390/gels5020020.
• Bakhshpour M, Göktürk I, Bereli N, Denizli A. Molecularly imprinted cryogel cartridges for the selective recognition of tyrosine. Biotechnol Prog 2020. https://doi.org/10.1002/btpr.3006.
• Hroboňová K, Lomenova A. Molecularly imprinted polymer as stationary phase for HPLC separation of phenylalanine enantiomers. Monatsh Chem 2018;149:939–46. https://doi.org/10.1007/s00706-018-2155-5.
• Akgönüllü S, Yavuz H, Denizli A. Preparation of imprinted cryogel cartridge for chiral separation of l-phenylalanine. Artif Cells Nanomed Biotechnol 2017;45:800–7. https://doi.org/10.1080/21691401.2016.1175445.
• Sümbelli Y, Keçili R, Hür D, Ersöz A, Say R. Molecularly imprinted polymer embedded-cryogels as selective genotoxic impurity scavengers. Sep Sci Technol 2021;56:3066–78. https://doi.org/10.1080/01496395.2020.1869259.
• Laishevkina S, Skurkis Y, Shevchenko N. Preparation and properties of cryogels based on poly(sulfopropyl methacrylate) or poly(sulfobetaine methacrylate) with controlled swelling. J Solgel Sci Technol 2022;102:343–56. https://doi.org/10.1007/s10971-022-05770-8.
• Shanthakumar P, Klepacka J, Bains A, Chawla P, Dhull SB, Najda A. The Current Situation of Pea Protein and Its Application in the Food Industry. Molecules 2022;27. https://doi.org/10.3390/molecules27165354.
• Kuila S, Dey S, Singh P, Shrivastava A, Nanda J. Phenylalanine-based fibrillar systems. Chemical Communications 2023;59:14509–23. https://doi.org/10.1039/d3cc04138g.
• Mól PCG, Veríssimo LAA, Minim LA, da Silva R. Adsorption and immobilization of β-glucosidase from Thermoascus aurantiacus on macroporous cryogel by hydrophobic interaction. Prep Biochem Biotechnol 2023;53:297–307. https://doi.org/10.1080/10826068.2022.2081860.
• Cristina Oliveira Neves I, Aparecida Rodrigues A, Teixeira Valentim T, Cristina Freitas de Oliveira Meira A, Henrique Silva S, Ayra Alcântara Veríssimo L, et al. Amino acid-based hydrophobic affinity cryogel for protein purification from ora-pro-nobis (Pereskia aculeata Miller) leaves. J Chromatogr B Analyt Technol Biomed Life Sci 2020;1161. https://doi.org/10.1016/j.jchromb.2020.122435.
• Mkrtchyan ES, Ananyeva OA, Burakova I V., Memetova AE, Burakov AE, Tkachev AG. Removal of Lead Ions from Aqueous Media by a Cryogel Based on Graphene Oxide Modified with Lignosulfonate: A Kinetic Study. Prot Met Phys Chem Surf 2023;59:123–8. https://doi.org/10.1134/S2070205123700168.
• Hu W, Zhang J. Adsorption of Cr(VI) and Methyl Orange on Polyethyleneimine Cryogels in Single and Binary Solutions Using Batch and Fixed-bed Systems. Water Air Soil Pollut 2025;236. https://doi.org/10.1007/s11270-025-08283-6.
• Reynaud F, Tsapis N, Deyme M, Vasconcelos TG, Gueutin C, Guterres SS, et al. Spray-dried chitosan-metal microparticles for ciprofloxacin adsorption: Kinetic and equilibrium studies. Soft Matter 2011;7:7304–12. https://doi.org/10.1039/c1sm05509g.
• Chen S, Huang X, Yao S, Huang W, Xin Y, Zhu M, et al. Highly selective recognition of L-phenylalanine with molecularly imprinted polymers based on imidazolyl amino acid chiral ionic liquid. Chirality 2019;31:824–34. https://doi.org/10.1002/chir.23110.
• Sajini T, Thomas R, Mathew B. Rational design and synthesis of photo-responsive molecularly imprinted polymers for the enantioselective intake and release of L-phenylalanine benzyl ester on multiwalled carbon nanotubes. Polymer 2019;173:127–40. https://doi.org/10.1016/j.polymer.2019.04.031.
• Zhang Z, Zhang M, Liu Y, Yang X, Luo L, Yao S. Preparation of L-phenylalanine imprinted polymer based on monodisperse hybrid silica microsphere and its application on chiral separation of phenylalanine racemates as HPLC stationary phase. Sep Purif Technol 2012;87:142–8. https://doi.org/10.1016/j.seppur.2011.11.037.
• Li Y, Xu G, Chen J, Yu T, Miao P, Du Y. One-step synthesis of chiral molecularly imprinted polymer TiO2 nanoparticles for enantioseparation of phenylalanine in coated capillary electrochromatography. Microchim Acta 2023;190. https://doi.org/10.1007/s00604-023-05854-4.