Adsorption of the low density lipoproteins on the micropatterned polymer brush: computer simulations

J. Ilnytskyi; D. Yaremchuk; O. Komarytsia

doi:10.5488/cmp.29.33801

Authors

J. Ilnytskyi Yukhnovskii Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine, 1 Svientsitskii Str., 79011 Lviv, Ukraine; Institute of Applied Mathematics and Fundamental Sciences, Lviv Polytechnic National University, 5 Mytropolyta Andreia Str., 79013 Lviv, Ukraine https://orcid.org/0000-0002-1868-5648
D. Yaremchuk Yukhnovskii Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine, 1 Svientsitskii Str., 79011 Lviv, Ukraine https://orcid.org/0000-0003-2888-5878
O. Komarytsia Department of Internal Medicine No. 2, Danylo Halytskyi Lviv Medical University, 69 Pekarska Str., 79010 Lviv, Ukraine https://orcid.org/0000-0002-5822-8281

DOI:

https://doi.org/10.5488/cmp.29.33801

Keywords:

lipoproteins, adsorption, azobenzene, molecular dynamics

Abstract

Photorenewable polymer adsorbents, aimed at reducing the low density lipoproteins (LDLs) level, are reported experimentally. Previously we developed a mesoscale model for this setup with uniformly grafted chains, and examined the role played by chains length and grafting density [Ilnytskyi, et al., Processes, 2023, 11, 2913]. The analysis is extended here to the cases of bunch-like and grid-like grafting micropatterns. The bunch-like arrangement is the most efficient one displaying low- and high-density peaks for adsorbing effectiveness. The former peak is twice higher compared with uniform grafting, as a consequence of a match between LDLs dimensions and the micropattern pitch. Adsorption isotherms are fitted well by either Langmuir or logistic growth forms, indicating a higher growth rate compared with uniform grafting. The high-density peak exists only for this micropattern and extends the applicability of an adsorbent. At the highest LDL concentration, adsorption is hampered by self-assembly of LDLs into a packed cubic phase.

References

Sacks F. M., Campos H., J. Clin. Endocrinol. Metab., 2003, 88, No. 10, 4525–4532. DOI: https://doi.org/10.1210/jc.2003-030636

Sikorski J., In: Comprehensive medicinal chemistry II, Elsevier, 2007, 459–494. DOI: https://doi.org/10.1016/B0-08-045044-X/00180-2

Mundi S., Massaro M., Scoditti E., Carluccio M. A., van Hinsbergh V. W. M., Iruela-Arispe M. L., Caterina R. D., Cardiovasc. Res., 2017, 114, No. 1, 35–52. DOI: https://doi.org/10.1093/cvr/cvx226

BasuRay S., Wang Y., Smagris E., Cohen J. C., Hobbs H. H., Proc. Natl. Acad. Sci. U.S.A., 2019, 116, No. 19, 9521–9526. DOI: https://doi.org/10.1073/pnas.1901974116

Thierer J. H., Ekker S. C., Farber S. A., Nat. Commun., 2019, 10, No. 1, 3426. DOI: https://doi.org/10.1038/s41467-019-11259-w

Ronco C., Bellomo R., Crit. Care, 2022, 26, No. 1, 135. DOI: https://doi.org/10.1186/s13054-022-04009-w

Zhao L., Sun D., Liu M., Carbohydr. Polym., 2009, 78, No. 4, 828–832. DOI: https://doi.org/10.1016/j.carbpol.2009.07.008

Gunkel G., Huck W. T. S., J. Am. Chem. Soc., 2013, 135, No. 18, 7047–7052. DOI: https://doi.org/10.1021/ja402126t

Yu Y., Dong J., Ma B., Jiang X., Guo C., Liu Z., Chai Y., Wang L., Sun L., Ou L., Li W., J. Mater. Chem. B, 2021, 9, No. 32, 6364–6376. DOI: https://doi.org/10.1039/D1TB01220G

Dehghan R., Barzin J., J. Membr. Sci., 2021, 620, 118878. DOI: https://doi.org/10.1016/j.memsci.2020.118878

Fang F., Zhao H., Wang R., Chen Q., Wang Q., Zhang Q., Materials, 2024, 17, No. 5, 988. DOI: https://doi.org/10.3390/ma17050988

Cheng Y., Wang S., Yu Y., Yuan Y., Biomaterials, 2003, 24, No. 13, 2189–2194. DOI: https://doi.org/10.1016/S0142-9612(03)00047-4

Yu Y., Ma B., Jiang X., Guo C., Liu Z., Li N., Chai Y., Wang L., Du Y., Wang B., Li W., Ou L., J. Mater. Chem. B, 2022, 10, No. 25, 4856–4866. DOI: https://doi.org/10.1039/D2TB00291D

Ergun C., Eskizengin H., J. Biomed. Mater. Res. A, 2025, 113, No. 3, e37883. DOI: https://doi.org/10.1002/jbm.a.37883

Lanzalaco S., Armelin E., Gels, 2017, 3, No. 4, 36. DOI: https://doi.org/10.3390/gels3040036

Sudre G., Siband E., Gallas B., Cousin F., Hourdet D., Tran Y., Polymers, 2020, 12, No. 1, 153. DOI: https://doi.org/10.3390/polym12010153

Yaremchuk D., Kalyuzhnyi O., Ilnytskyi J., Condens. Matter Phys., 2023, 26, No. 3, 33302. DOI: https://doi.org/10.5488/CMP.26.33302

Tian L., Dou H., Shao Y., Yi Y., Fu X., Zhao J., Fan Y., Ming W., Ren L., Chem. Eng. J., 2023, 456, 141093. DOI: https://doi.org/10.1016/j.cej.2022.141093

Malm J., Sahramo E., Karppinen M., Ras R. H. A., Chem. Mater., 2010, 22, No. 11, 3349–3352. DOI: https://doi.org/10.1021/cm903831c

Bahl S., Nagar H., Singh I., Sehgal S., Mater. Today Proc., 2020, 28, 1302–1306. DOI: https://doi.org/10.1016/j.matpr.2020.04.505

Guo C., Yu Y., Jiang X., Ma B., Liu Z., Chai Y., Wang L., Wang B., Du Y., Li N., Fan H., Ou L., ACS Appl. Mater. Interfaces, 2022, 14, No. 30, 34388–34399. DOI: https://doi.org/10.1021/acsami.2c07193

Guo C., Jiang X., Guo X., Liu Z., Wang B., Du Y., Tian Z., Wang Z., Ou L., Regen. Biomater., 2024, 860, r253–262.

Wei Y.-b., Tang Q., Gong C.-b., Lam M. H.-W., Anal. Chim. Acta, 2015, 900, 10–20. DOI: https://doi.org/10.1016/j.aca.2015.10.022

De Martino S., Mauro F., Netti P. A., Riv. Nuovo Cimento, 2020, 43, No. 12, 599–629. DOI: https://doi.org/10.1007/s40766-021-00014-x

Merritt I. C. D., Jacquemin D., Vacher M., Phys. Chem. Chem. Phys., 2021, 23, No. 35, 19155–19165. DOI: https://doi.org/10.1039/D1CP01873F

Sandhu S., Yianni Y., Morgan C., Taylor D., Zaba B., Biochim. Biophys. Acta, Biomembr., 1986, 860, No. 2, 253–262. DOI: https://doi.org/10.1016/0005-2736(86)90521-3

Song X., Geiger C., Vaday S., Perlstein J., Whitten D. G., J. Photochem. Photobiol. Chem., 1996, 102, No. 1, 39–45. DOI: https://doi.org/10.1016/S1010-6030(96)04362-6

Delova A., Makhloutah A., Bernhard Y., Pasc A., Monari A., Chem. Eur. J., 2025, 31, No. 69, e01824. DOI: https://doi.org/10.1002/chem.202501824

Pritzl S. D., Morstein J., Pritzl N. A., Lipfert J., Lohmüller T., Trauner D. H., Commun. Mater., 2025, 6, No. 1, 59. DOI: https://doi.org/10.1038/s43246-025-00773-8

Tomoshige S., Kawasaki Y., Morimoto J., Sato N., Hashimoto Y., Ishikawa M., Chem. Pharm. Bull., 2025, 73, No. 6, 568–573. DOI: https://doi.org/10.1248/cpb.c25-00252

Guinart A., Qutbuddin Y., Schwille P., Feringa B. L., Nat. Rev. Chem., 2025, 10, No. 1, 12–30. DOI: https://doi.org/10.1038/s41570-025-00783-7

Ilnytskyi J., Yaremchuk D., Komarytsia O., Processes, 2023, 11, No. 10, 2913. DOI: https://doi.org/10.3390/pr11102913

Ilnytskyi J., Saphiannikova M., Neher D., Condens. Matter Phys., 2006, 9, No. 1, 87. DOI: https://doi.org/10.5488/CMP.9.1.87

Ilnytskyi J. M., Neher D., Saphiannikova M., J. Chem. Phys., 2011, 135, No. 4, 044901. DOI: https://doi.org/10.1063/1.3614499

Ilnytskyi J. M., Saphiannikova M., ChemPhysChem, 2015, 16, No. 15, 3180–3189. DOI: https://doi.org/10.1002/cphc.201500500

Ilnytskyi J., Slyusarchuk A., Saphiannikova M., Math. Model. Comput., 2016, 3, No. 1, 33–42. DOI: https://doi.org/10.23939/mmc2016.01.033

Ilnytskyi J. M., Slyusarchuk A., Saphiannikova M., Macromolecules, 2016, 49, No. 23, 9272–9282. DOI: https://doi.org/10.1021/acs.macromol.6b01871

Ilnytskyi J. M., Slyusarchuk A., Sokołowski S., Soft Matter, 2018, 14, No. 19, 3799–3810. DOI: https://doi.org/10.1039/C8SM00356D

Ilnytskyi J. M., Toshchevikov V., Saphiannikova M., Soft Matter, 2019, 15, No. 48, 9894–9908. DOI: https://doi.org/10.1039/C9SM01853K

Slyusarchuk A. Y., Yaremchuk D. L., Ilnytskyi J. M., Math. Model. Comput., 2020, 7, No. 2, 207–218. DOI: https://doi.org/10.23939/mmc2020.02.207

Yaremchuk D., Patsahan T., Ilnytskyi J., Condens. Matter Phys., 2022, 25, No. 3, 33601. DOI: https://doi.org/10.5488/CMP.25.33601

Xue C., Yonet-Tanyeri N., Brouette N., Sferrazza M., Braun P. V., Leckband D. E., Langmuir, 2011, 27, No. 14, 8810–8818. DOI: https://doi.org/10.1021/la2001909

Dehghan R., Barzin J., Sep. Purif. Technol., 2021, 278, 119512. DOI: https://doi.org/10.1016/j.seppur.2021.119512

Steinbach A., Paust T., Pluntke M., Marti O., Volkmer D., ChemPhysChem, 2013, 14, No. 15, 3523–3531. DOI: https://doi.org/10.1002/cphc.201300516

Zhou Z., Yu P., Geller H. M., Ober C. K., Biomacromolecules, 2013, 14, No. 2, 529–537. DOI: https://doi.org/10.1021/bm301785b

Wang X., Berger R., Ramos J. I., Wang T., Koynov K., Liu G., Butt H.-J., Wu S., RSC Adv., 2014, 4, No. 85, 45059–45064. DOI: https://doi.org/10.1039/C4RA07623K

Kim Y., Laradji A. M., Sharma S., Zhang W., Yadavalli N. S., Xie J., Popik V., Minko S., Angew. Chem., 2021, 134, No. 7, e202110990. DOI: https://doi.org/10.1002/ange.202110990

Açari I. K., Sel E., Özcan I., Ateş B., Köytepe S., Thakur V. K., Adv. Colloid Interface Sci., 2022, 305, 102694. DOI: https://doi.org/10.1016/j.cis.2022.102694

Badenhorst R., Makaev S., Yaremchuk D., Sajjan Y., Sulimov A., Reukov V. V., Lavrik N. V., Ilnytskyi J., Minko S., Langmuir, 2024, 40, No. 13, 7008–7020. DOI: https://doi.org/10.1021/acs.langmuir.4c00062

Badenhorst R., Makaev S. V., Parker M., Marunych R., Reukov V., Bdzińska A., Korchynskyi O., Kalyuzhnyi O., Yaremchuk D., Ilnytskyi J., Patsahan T., Minko S., ACS Appl. Mater. Interfaces, 2025, 17, No. 35, 49193–49209. DOI: https://doi.org/10.1021/acsami.5c08747

Mir M., Wilson L. D., Surf. Interfaces, 2025, 73, 107545. DOI: https://doi.org/10.1016/j.surfin.2025.107545

Adroher-Benítez I., Morozova T. I., Catalini G., García N. A., Barrat J.-L., Luengo G. S., Léonforte F., Macromolecules, 2023, 56, No. 24, 10285–10295. DOI: https://doi.org/10.1021/acs.macromol.3c01503

Ilnytskyi J., Yaremchuk D., Minko S., Langmuir, 2025, 41, No. 20, 12731–12744. DOI: https://doi.org/10.1021/acs.langmuir.5c00929

Ma S., Zhang X., Yu B., Zhou F., NPG Asia Mater., 2019, 11, No. 1, 24. DOI: https://doi.org/10.1038/s41427-019-0121-2

Pyun J., Kowalewski T., Matyjaszewski K., Macromol. Rapid Commun., 2003, 24, No. 18, 1043–1059. DOI: https://doi.org/10.1002/marc.200300078

Edmondson S., Osborne V. L., Huck W. T. S., Chem. Soc. Rev., 2004, 33, No. 1, 14. DOI: https://doi.org/10.1039/b210143m

Ouchi M., Terashima T., Sawamoto M., Chem. Rev., 2009, 109, No. 11, 4963–5050. DOI: https://doi.org/10.1021/cr900234b

Ahmad S. A., Leggett G. J., Hucknall A., Chilkoti A., Biointerphases, 2011, 6, No. 1, 8–15. DOI: https://doi.org/10.1116/1.3553579

Johnson J. A., Lu Y. Y., Burts A. O., Xia Y., Durrell A. C., Tirrell D. A., Grubbs R. H., Macromolecules, 2010, 43, No. 24, 10326–10335. DOI: https://doi.org/10.1021/ma1021506

Olivier A., Meyer F., Raquez J.-M., Dubois P., e-Polymers, 2013, 13, No. 1, 009. DOI: https://doi.org/10.1515/epoly-2013-0109

Zhao H., Gao H., Chen T., Xie L., Ma Y., Sha J., Eur. Polym. J., 2022, 179, 111469. DOI: https://doi.org/10.1016/j.eurpolymj.2022.111469

Welch M. E., Xu Y., Chen H., Smith N., Tague M. E., Abruna H. D., Baird B., Ober C. K., J. Photopolym. Sci. Technol., 2012, 25, No. 1, 53–56. DOI: https://doi.org/10.2494/photopolymer.25.53

Yu B., Chang B., Loo W., Dhuey S., O’Reilly P., Ashby P., Connolly M., Tikhomirov G., Zuckermann R., Ruiz R., ACS Nano, 2024, 18, 7411–423. DOI: https://doi.org/10.1021/acsnano.3c10204

Jeon N. L., Choi I. S., Whitesides G. M., Kim N. Y., Laibinis P. E., Harada Y., Finnie K. R., Girolami G. S., Nuzzo R. G., Appl. Phys. Lett., 1999, 75, No. 26, 4201–4203. DOI: https://doi.org/10.1063/1.125582

Austin M., Krauss R., Lancet, 1986, 328, No. 8507, 592–595. DOI: https://doi.org/10.1016/S0140-6736(86)92425-6

Campos H., Genest J. J., Blĳlevens E., McNamara J. R., Jenner J. L., Ordovas J. M., Wilson P. W., Schaefer E. J., Arterioscler. Thromb. J. Vasc. Biol., 1992, 12, No. 2, 187–195. DOI: https://doi.org/10.1161/01.ATV.12.2.187

Austin M. A., JAMA J. Am. Med. Assoc., 1988, 260, No. 13, 1917. DOI: https://doi.org/10.1001/jama.1988.03410130125037

Stampfer M. J., JAMA J. Am. Med. Assoc., 1996, 276, No. 11, 882. DOI: https://doi.org/10.1001/jama.1996.03540110036029

Lamarche B., Tchernof A., Moorjani S., Cantin B., Dagenais G. R., Lupien P. J., Després J.-P., Circulation, 1997, 95, No. 1, 69–75. DOI: https://doi.org/10.1161/01.CIR.95.1.69

Scheffer P. G., Bakker S. J. L., Heine R. J., Teerlink T., Clin. Chem., 1997, 43, No. 10, 1904–1912. DOI: https://doi.org/10.1093/clinchem/43.10.1904

Segrest J. P., Jones M. K., Loof H. D., Dashti N., J. Lipid Res., 2001, 42, No. 9, 1346–1367. DOI: https://doi.org/10.1016/S0022-2275(20)30267-4

Antwerpen R. V., Gilkey J. C., J. Lipid Res., 1994, 35, No. 12, 2223–2231. DOI: https://doi.org/10.1016/S0022-2275(20)39928-4

Teerlink T., Scheffer P. G., Bakker S. J., Heine R. J., J. Lipid Res., 2004, 45, No. 5, 954–966. DOI: https://doi.org/10.1194/jlr.M300521-JLR200

Ren G., Rudenko G., Ludtke S. J., Deisenhofer J., Chiu W., Pownall H. J., Proc. Natl. Acad. Sci. U.S.A., 2009, 107, No. 3, 1059–1064. DOI: https://doi.org/10.1073/pnas.0908004107

Kumar V., Butcher S. J., Öörni K., Engelhardt P., Heikkonen J., Kaski K., Ala-Korpela M., Kovanen P. T., PLoS ONE, 2011, 6, No. 5, e18841. DOI: https://doi.org/10.1371/journal.pone.0018841

Laguerre M., Lecomte J., Villeneuve P., Prog. Lipid Res., 2007, 46, No. 5, 244–282. DOI: https://doi.org/10.1016/j.plipres.2007.05.002

Hevonoja T., Pentikäinen M. O., Hyvönen M. T., Kovanen P. T., Ala-Korpela M., Biochim. Biophys. Acta, Mol. Cell. Biol. Lipids, 2000, , No. 3, 189–210. DOI: https://doi.org/10.1016/S1388-1981(00)00123-2

Prassl R., Laggner P., Eur. Biophys. J., 2008, 38, No. 2, 145–158. DOI: https://doi.org/10.1007/s00249-008-0368-y

Dai L., Li S., Hao Q., Zhou R., Zhou H., Lei W., Kang H., Wu H., Li Y., Ma X., Nanoscale Adv., 2023, 5, No. 4, 1011–1022. DOI: https://doi.org/10.1039/D2NA00883A

Murtola T., Vuorela T. A., Hyvönen M. T., Marrink S.-J., Karttunen M., Vattulainen I., Soft Matter, 2011, 7, No. 18, 8135. DOI: https://doi.org/10.1039/c1sm05367a

Pan Y., Tang X., Eur. Polym. J., 2008, 44, No. 2, 408–414. DOI: https://doi.org/10.1016/j.eurpolymj.2007.11.004

Han G., Zhang H., Chen J., Sun Q., Zhang Y., Zhang H., New J. Chem., 2015, 39, No. 2, 1410–1420. DOI: https://doi.org/10.1039/C4NJ01658K

Liu D., Zhao J., Ma Y., Zhao X., Shi S., Li S., Song Q., Cheng X., Zhang W., Polym. Chem., 2024, 15, No. 15, 1469–1474. DOI: https://doi.org/10.1039/D4PY00099D

Kong Q., Zhang J., Zhang K., Wang S., He M., Guo Y., Gu J., Angew. Chem. Int. Ed., 2025, 64, No. 37, e202512721. DOI: https://doi.org/10.1002/anie.202512721

Hughes Z. E., Wilson M. R., Stimson L. M., Soft Matter, 2005, 1, No. 6, 436. DOI: https://doi.org/10.1039/b511082c

Gil Herrero C., Duve T., Thallmair S., J. Chem. Theory Comput., 2025, 22, No. 1, 708–22. DOI: https://doi.org/10.1021/acs.jctc.5c01654

Kihara T., J. Phys. Soc. Jpn., 1951, 6, No. 5, 289–296. DOI: https://doi.org/10.1143/JPSJ.6.289

Kihara T., In: Advances in Chemical Physics, Vol. 5, Prigogine I. (Ed.), Wiley, 1963, 147–188. DOI: https://doi.org/10.1002/9780470143513.ch3

Lintuvuori J. S., Wilson M. R., J Chem Phys, 2008, 128, No. 4, J. Chem. Phys., 044906.

Groot R. D., Warren P. B., J. Chem. Phys., 1997, 107, No. 11, 4423–4435. DOI: https://doi.org/10.1063/1.474784

Wilson M. R., J. Chem. Phys., 1997, 107, No. 20, 8654–8663. DOI: https://doi.org/10.1063/1.475017

Frauenthal J. C., Introduction to Population Modeling, Birkhäuser, Boston, MA, 1979. DOI: https://doi.org/10.1007/978-1-4684-7322-3

Price T., In: Ecology of a changed world, chap. 2, Oxford University Press, New York, 2023, 9–20. DOI: https://doi.org/10.1093/oso/9780197564172.003.0002