Abstract
High cholesterol grades are a significant threat factor for coronary heart disease, which leads to heart attacks. General practices focus on lowering cholesterol and saturated fatty acids in the diet to decrease the incidence of cardiovascular diseases. Milk is a primary food with high nutritional value and high consumption. Molecularly imprinted cryogels are an excellent alternative according to non-selective methods such as liquid–liquid and/or solid-phase extraction to elute cholesterol selectively from milk. Because the cryogels are low cost, they can be synthesized easily, and the sample can be applied directly to the cryogel without needing any pre-treatment. In this study, we synthesized cholesterol-imprinted (Chl-MIP) cryogel membranes employing aminoacid-based hydrophobic functional comonomer N-methacryloyl-L-phenylalanine to be used as a selective adsorbent to remove cholesterol from milk samples. Chl-MIP cryogel exhibited a maximum Chl adsorption capacity of 12.01 mg/g at 25 °C with an interaction time of 60 min. The selectivity of the cryogel was 2.89 times greater for estradiol molecules and 4.99 times greater for progesterone molecules. Chl-MIP cryogel provides a rapid mass transfer by a short diffusion path without any diffusion restrictions. This process is simple to implement, efficient, affordable, and feasible for use on modern manufacturing lines.
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References
Al Othman ZA, Badjah AY, Ali I (2019) Facile synthesis and characterization of multi walled carbon nanotubes for fast and effective removal of 4-tert-octylphenol endocrine disruptor in water. J Mol Liq 275:41–48. https://doi.org/10.1016/j.molliq.2018.11.049
Ali I, Singh P, Aboul-Enein HY, Sharma B (2009) Chiral analysis of ibuprofen residues in water and sediment. Anal Lett 42:1747–1760. https://doi.org/10.1080/00032710903060768
Ali I, Burakov AE, Melezhik AV, Babkin AV, Burakova IV, Neskoromnaya EA, Galunin EV, Tkachev AG, Kuznetsov DV (2019a) Removal of copper (II) and zinc (II) ions in water on a newly synthesized polyhydroquinone/graphene nanocomposite material: kinetics. Thermodyn Mech Chem Select 4:12708–12718. https://doi.org/10.1002/slct.201902657
Ali I, Basheer AA, Kucherova A, Memetov N, Pasko T, Ovchinnikov K, Pershin V, Kuznetsov D, Galunin E, Grachev V et al (2019b) Advances in carbon nanomaterials as lubricants modifiers. J Mol Liq 279:251–266. https://doi.org/10.1016/j.molliq.2019.01.113
Ali I, Afshinb S, Poureshgh Y, Azari A, Rashtbari Y, Feizizadeh A, Hamzezadeh A, Fazlzadeh M (2020) Green preparation of activated carbon from pomegranate peel coated with zero-valent iron nanoparticles (NZVI) and isotherm and kinetic studies of amoxicillin removal in water. Environ Sci Pollut Res 27:36732–36743. https://doi.org/10.1007/s11356-020-09310-1
Bakhshpour M, Göktürk I, Bereli N, Denizli A (2020) Molecularly imprinted cryogel cartridges for the selective recognition of tyrosine. Biotechnol Progress. https://doi.org/10.1002/btpr.3006
Basheer AA (2018a) New generation nano-adsorbents for the removal of emerging contaminants in water. J Mol Liq 261:583–593
Basheer AA (2018b) Chemical chiral pollution: impact on the society and science and need of the regulations in the 21st century. Chirality 30:402–406. https://doi.org/10.1002/chir.22808
Basheer AA (2020) Advances in the smart materials applications in the aerospace industries. Aircr Eng Aerosp Technol 92:1027–1035. https://doi.org/10.1108/AEAT-02-2020-0040
Basheer AA, Ali I (2018) Stereoselective uptake and degradation of (±)-o, p-DDD pesticide stereomers in water-sediment system. Chirality 30:1088–1095. https://doi.org/10.1002/chir.22989
Bereli N, Akgönüllü S, Asliyüce S, Çimen D, Göktürk İ, Türkmen D, Yavuz H, Denizli A (2020) Molecular ımprinting technology for biomimetic assemblies. Hacettepe J Biol Chem 48(5):575–601. https://doi.org/10.15671/hjbc.801427
Çaktü K, Baydemir G, Ergün B, Yavuz H (2014) Cholesterol removal from various samples by cholesterol-imprinted monosize microsphere-embedded cryogels. Artif Cells Nanomed Biotechnol 42:365–375. https://doi.org/10.3109/21691401.2013.832684
Chen L, Wang X, Lu W, Wu X, Li J (2016) Molecular imprinting: perspectives and applications. Chem Soc Rev 45:2137–2211. https://doi.org/10.1039/c6cs00061d
Clausen DN, Visentainer JV, Tarley CRT (2014) Development of molecularly imprinted poly(methacrylic acid)/silica for clean-up and selective extraction of cholesterol in milk prior to analysis by HPLC-UV. Analyst 139:5021–5027. https://doi.org/10.1039/c4an00517a
Dias HMAM, Berbicz F, Pedrochi F, Baesso ML, Matioli G (2010) Butter cholesterol removal using different complexation methods with beta-cyclodextrin, and the contribution of photoacoustic spectroscopy to the evaluation of the complex. Food Res Int 43:1104–1110
Effting L, Prete MC, Urbano A, Effting LM, González MEC, Bail A, Tarley CRT (2022) Preparation of magnetic nanoparticle-cholesterol imprinted polymer using semi-covalent imprinting approach for ultra-effective and highly selective cholesterol adsorption. React Funct Polym 172:105178
Fletouris DJ, Botsoglou NA, Psomas IE, Mantis AI (1998) Rapid determination of cholesterol in milk and milk products by direct saponification and capillary gas chromatography. J Dairy Sci 81:2833–2840
Göktürk I, Derazshamshir A, Yılmaz F, Denizli A (2016) Poly(vinyl alcohol)/polyethyleneimine (PVA/PEI) blended monolithic cryogel columns for the depletion of haemoglobin from human blood. Sep Sci Technol 51:1787–1797. https://doi.org/10.1080/01496395.2016.1183677
Grigaliūnaitė I, Ruiz-Méndez MV (2023) Cleaner lipid processing: Supercritical carbon dioxide (Sc-CO2) and short path distillation. Adv Food Nutr Res 105:255–300. https://doi.org/10.1016/bs.afnr.2022.12.001
Han EM, Kim SH, Ahn J, Kwak HS (2008) Comparison of cholesterol-reduced cream cheese manufactured using crosslinked β-cyclodextrin to regular cream cheese. Asian Australas J Anim Sci 21:131–137. https://doi.org/10.5713/ajas.2008.70189
Inanan T, Tüzmen N, Akgöl S, Denizli A (2016) Selective cholesterol adsorption by molecular imprinted polymeric nanospheres and application to GIMS. Int J Biol Macromol 92:451–460
Kartal F, Denizli A (2020) Molecularly imprinted cryogel beads for cholesterol removal from milk samples. Colloids Surfaces b: Biointerfaces 190:110860. https://doi.org/10.1016/j.colsurfb.2020.110860
Kryscio DR, Peppas NA (2012) Critical review and perspective of macromolecularly imprinted polymers. Acta Biomater 8:461–473
Lee Y-K, Ganesan P, Kwak H-S (2012) Optimisation of cross-linking β-cyclodextrin and its recycling efficiency for cholesterol removal in milk and cream. Int J Food Sci Technol 47:933–939. https://doi.org/10.1111/j.1365-2621.2011.02924.x
Li X, Tong Y, Jia L, Guan H (2015) Fabrication of molecularly cholesterol-imprinted polymer particles based on chitin and their adsorption ability. Monatshefte Für Chemie Chem Monthly 146:423–430. https://doi.org/10.1007/s00706-014-1369-4
Lozinsky VI (2018) Cryostructuring of polymeric systems. 50. Cryogels and cryotropic gel-formation: terms and definitions. Gels 4(3):77
Matos Cordeiro Borges M, de Leijito Oliveira H, Bastos Borges K (2017) Molecularly imprinted solid-phase extraction coupled with LC–APCI–MS–MS for the selective determination of serum cholesterol. Electrophoresis 38(17):2150–2159. https://doi.org/10.1002/elps.201600489
Nezhadali A, Es’Haghi Z, Khatibi A-D (2017) Selective extraction of cholesterol from dairy samples using a polypyrrole molecularly ımprinted polymer and determination by gas chromatography. Food Anal Methods 10:1397–1407. https://doi.org/10.1007/s12161-016-0686-0
Noseda DG, Gentili HG, Nani ML, Nusblat A, Tiedtke A, Florin-Christensen J, Nudel CB (2007) A bioreactor model system specifically designed for Tetrahymena growth and cholesterol removal from milk. Appl Microbiol Biotechnol 75:515–520. https://doi.org/10.1007/s00253-007-0843-x
Odabaşı M, Uzun L, Baydemir G, Aksoy NH, Acet Ö, Erdönmez D (2018) Cholesterol imprinted composite membranes for selective cholesterol recognition from intestinal mimicking solution. Colloids Surf B 163:266–274
Oliveira GR, Santos AV, Lima AS, Soares CMF, Leite MS (2015) Neural modelling in adsorption column of cholesterol-removal efficiency from milk. LWT Food Sci Technol 64(2):632–638. https://doi.org/10.1016/j.lwt.2015.05.051
Pollegioni L, Piubelli L, Molla G (2009) Cholesterol oxidase: biotechnological applications. FEBS J 276:6857–6870. https://doi.org/10.1111/j.1742-4658.2009.07379.x
Polyakova I, Borovikova L, Osipenko A, Vlasova E, Volchek B, Pisarev O (2016) Surface molecularly imprinted organic-inorganic polymers having affinity sites for cholesterol. React Funct Polym 109:88–98
Puoci F, Curcio M, Cirillo G, Iemma F, Spizzirri UG, Picci N (2008) Molecularly imprinted solid-phase extraction for cholesterol determination in cheese products. Food Chem 106:836–842
Rojas EEG, dos Reis Coimbra JS, Minim LA, Freitas JF (2007) Cholesterol removal in liquid egg yolk using high methoxyl pectins. Carbohyd Polym 69:72–78
Sahoo H, Dhillon P, Anand E, Srivastava A, Usman M, Agrawal PK, Johnston R, Unisa S (2023) Status and correlates of non-communicable diseases among children and adolescents in slum and non-slum areas of India’s four metropolitan cities. J Biosoc Sci 55(6):1064–1085. https://doi.org/10.1017/s0021932022000530
Saylan Y, Denizli A (2019) Supermacroporous composite cryogels in biomedical applications. Gels 5:20. https://doi.org/10.3390/gels5020020
Saylan Y, Göktürk I, Pospiskova K, Safarik I, Denizli A (2020) Magnetic bacterial cellulose nanofibers for nucleoside recognition. Cellulose 27:9479–9492. https://doi.org/10.1007/s10570-020-03425-x
Uzunoğlu G, Çimen D, Bereli N, Çetin K, Denizli A (2019) Cholesterol removal from human plasma with biologically modified cryogels. J Biomater Sci Polym Ed 30:1276–1290. https://doi.org/10.1080/09205063.2019.1627652
Wendeu-Foyet G, Bellicha A, Chajès V, Huybrechts I, Bard J-M, Debras C, Srour B, Sellem L, Fezeu LK, Julia C, Kesse-Guyot E, Agaësse C, Druesne-Pecollo N, Galan P, Hercberg S, Deschasaux-Tanguy M, Touvier M (2023) Different types of industry-produced and ruminant trans fatty acid intake and risk of type 2 diabetes: findings from the nutrinet-santé prospective cohort. Diabetes Care 46:321–330. https://doi.org/10.2337/dc22-0900
Zengin A, Yildirim E, Tamer U, Caykara T (2013) Molecularly imprinted superparamagnetic iron oxide nanoparticles for rapid enrichment and separation of cholesterol. Analyst 138:7238. https://doi.org/10.1039/c3an01458d
Zhang L, Wang X (2015) Mechanisms of graphyne-enabled cholesterol extraction from protein clusters. RSC Adv 5:11776–11785. https://doi.org/10.1039/c4ra16944a
Zhou B, Perel P, Mensah GA, Ezzati M (2021) Global epidemiology, health burden and effective interventions for elevated blood pressure and hypertension. Nat Rev Cardiol 18:785–802. https://doi.org/10.1038/s41569-021-00559-8
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This study is supported by Hacettepe University, Scientific Research Projects Coordination Unit (FHD-2018-15985).
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IG was involved in conceptualization, methodology, software, data curation, and writing—original draft. YS took part in conceptualization, methodology, software, and data curation. FY participated in visualization, ınvestigation, and writing—review and editing. FK contributed to visualization and ınvestigation. AD was responsible for supervision and writing—review and editing.
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Göktürk, I., Saylan, Y., Yılmaz, F. et al. Phenylalanine functionalized cryogels for selective cholesterol removal from milk. Chem. Pap. (2024). https://doi.org/10.1007/s11696-024-03392-8
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DOI: https://doi.org/10.1007/s11696-024-03392-8