Belma ZENGİN KURT, Aydan DAĞ, Pınar Sinem OMURTAG ÖZGEN, Zehra DURMUŞ

Increasing the biocompatibility of graphene-based hybrid nanostructures with glycopolymer

Hybrid nanostructures decorated with glycopolymers are appropriate for biomedical applications. In this paper, the results are obtained from nanographene (NG) decorated with glycoblock copolymer to increase their potential in use in therapies and in examining lectin interactions. A pyren-1-ylmethyl 4-cyano-4-((phenylcarbonothioyl)thio)pentanoate (CPADB-py) chain transfer agent was used in the synthesis of methyl methacrylate glycoblock copolymers (P2 and P3) by reversible addition-fragmentation chain transfer (RAFT) polymerization to adhere the polymer to the nanographene surface. Hybrid nanographenes (NG-1 and NG-2) were obtained by the non-covalent interaction of deprotected P2 and P3 with different fructopyranose groups (3-O-methacryloyl-1,2:4,5- di-O-isopropylidene-β-D-fructopyranose and 1-O-methacryloyl-2,3:4,5-di-O-isopropylidene-β-D-fructopyranose) in their backbones. Images obtained from transmission electron microscopy (TEM) of NG-1 and NG-2 show that glycoblock copolymer coating was performed homogeneously. Moreover, thermal gravimetric analysis (TGA) also confirmed a glycoblock copolymer coating of NG-1 and NG-2 by weight loss of 41% and 31%, respectively. In the last step of the study, the binding ability of glycoblock copolymers (P2-hyd and P3-hyd) with concanavalin A (ConA) lectin was investigated by a turbidimetric assay. Promising results were obtained from P3-hyd for the ConA interactions. Hence, this study may open a new avenue in the design of new multifunctional glyconanomaterials that show favorable binding properties with lectins.

PDF

___

1. Losada-Garcia N, Rodriguez-Oliva I, Simovic M, Bezbradica DI, Palomo JM. New advances in fabrication of graphene glyconanomaterials for application in therapy and diagnosis. ACS Omega. 2020; 5 (9): 4362-9. doi: 10.1021/acsomega.9b04332
2. Nemati F, Pebdeni AB, Hosseini M. Chapter 13 - Graphene-based devices for cancer diagnosis. In: Khan R, Parihar A, Sanghi SK, editors. Biosensor Based Advanced Cancer Diagnostics: Academic Press; 2022. p. 225-43.
3. Barani M, Mukhtar M, Rahdar A, Sargazi G, Thysiadou A et al. Progress in the Application of Nanoparticles and Graphene as Drug Carriers and on the Diagnosis of Brain Infections. Molecules 2021; 26 (1): 186. doi: 10.3390/molecules26010186
4. Cao Y, Dong H, Yang Z, Zhong X, Chen Y et al. Aptamer-conjugated graphene quantum dots/porphyrin derivative theranostic agent for intracellular cancer-related MicroRNA detection and fluorescence-guided photothermal/photodynamic synergetic therapy. ACS Applied Materials & Interfaces 2017; 9 (1): 159-66. doi: 10.1021/acsami.6b13150
5. Birlik Demirel G, Aygul E, Dag A, Atasoy S, Cimen Z et al. Folic Acid-Conjugated pH and Redox-Sensitive Ellipsoidal Hybrid Magnetic Nanoparticles for Dual-Triggered Drug Release. ACS Applied Bio Materials 2020; 3 (8): 4949-61. doi: 10.1021/acsabm.0c00488
6. Tu Z, Qiao H, Yan Y, Guday G, Chen W et al. Directed graphene-based nanoplatforms for hyperthermia: overcoming multiple drug resistance. Angewandte Chemie 2018; 57 (35): 11198-11202. doi: 10.1002/anie.201804291
7. Geim AK, Novoselov KS. The rise of graphene. Nature Materials 2007; 6: 183. doi: 10.1038/nmat1849
8. Bahadır EB, Sezgintürk MK. Applications of graphene in electrochemical sensing and biosensing. TrAC Trends in Analytical Chemistry 2016; 76: 1-14. doi: 10.1016/j.trac.2015.07.008
9. Feng L, Zhang S, Liu Z. Graphene based gene transfection. Nanoscale 2011; 3 (3): 1252-7. doi: 10.1039/C0NR00680G
10. Zhang L, Xia J, Zhao Q, Liu L, Zhang Z. Functional graphene oxide as a nanocarrier for controlled loading and targeted delivery of mixed anticancer drugs. Small 2010; 6 (4): 537-44. doi: 10.1002/smll.200901680
11. Yang K, Zhang S, Zhang G, Sun X, Lee S-T et al. Graphene in mice: ultrahigh in vivo tumor uptake and efficient photothermal therapy. Nano Letters 2010; 10 (9): 3318-23. doi: 10.1021/nl100996u
12. Kantheti S, Gaddam RR, Narayan R, Raju KVSN. Hyperbranched polyol decorated carbon nanotube by click chemistry for functional polyurethane urea hybrid composites. RSC Adv 2014; 4 (47): 24420-7. doi: 10.1039/c4ra02442g
13. Bagri A, Mattevi C, Acik M, Chabal YJ, Chhowalla M et al. Structural evolution during the reduction of chemically derived graphene oxide. Nature Chemistry 2010; 2 (7): 581-7. doi: 10.1038/nchem.686
14. Shim G, Kim M-G, Park JY, Oh Y-K. Graphene-based nanosheets for delivery of chemotherapeutics and biological drugs. Advanced Drug Delivery Reviews 2016; 105: 205-27. doi: 10.1016/j.addr.2016.04.004
15. Jaleel JA, Sruthi S, Pramod K. Reinforcing nanomedicine using graphene family nanomaterials. Journal of Controlled Release 2017; 255: 218-30. doi: 10.1016/j.jconrel.2017.04.041
16. Ting SRS, Chen G, Stenzel MH. Synthesis of glycopolymers and their multivalent recognitions with lectins. Polymer Chemistry 2010; 1 (9): 1392-412. doi: 10.1039/C0PY00141D
17. Pramudya I, Chung H. Recent progress of glycopolymer synthesis for biomedical applications. Biomaterials Science 2019; 7 (12): 4848-72. doi: 10.1039/C9BM01385G
18. Abdouni Y, Yilmaz G, Becer CR. Sequence and architectural control in glycopolymer synthesis. Macromol Rapid Commun 2017; 38 (24). doi: 10.1002/marc.201700212
19. Bhattacharya K, Banerjee SL, Kundu M, Mandal M, Singha NK. Glycopolymer ornamented octa-arm POSS based organic-inorganic hybrid star block copolymer as a lectin binding ligand. Materials Science and Engineering: C 2020; 116:111210. doi: 10.1016/j.msec.2020.111210
20. Wilkins LE, Badi N, Du Prez F, Gibson MI. Double-Modified Glycopolymers from Thiolactones to Modulate Lectin Selectivity and Affinity. ACS Macro Letters 2018; 7 (12): 1498-502. doi: 10.1021/acsmacrolett.8b00825
21. Kursun TT, Cimen D, Caykara T. Glycopolymer brushes with specific protein recognition property. Journal of Applied Polymer Science 2017; 134 (36). doi: 10.1002/app.45238
22. Gou Y, Geng J, Richards SJ, Burns J, Remzi Becer C et al. A Detailed Study on Understanding Glycopolymer Library and Con A Interactions. Journal of Polymer Science Part A Polymer Chemistry 2013; 51 (12): 2588-97. doi: 10.1002/pola.26646
23. Oz Y, Abdouni Y, Yilmaz G, Becer CR, Sanyal A. Magnetic glyconanoparticles for selective lectin separation and purification. Polymer Chemistry 2019; 10 (24): 3351-61. doi: 10.1039/C8PY01748D
24. Hartweg M, Jiang Y, Yilmaz G, Jarvis CM, Nguyen HVT, Primo GA et al. Synthetic glycomacromolecules of defined valency, absolute configuration, and topology distinguish between human lectins. JACS Au. 2021. doi: 10.1021/jacsau.1c00255
25. Bandaru NM, Voelcker NH. Glycoconjugate-functionalized carbon nanotubes in biomedicine. Journal of Materials Chemistry 2012; 22 (18): 8748-58. doi: 10.1039/C2JM16636D
26. Omurtag Ozgen PS, Atasoy S, Zengin Kurt B, Durmus Z, Yigit G et al. Glycopolymer decorated multiwalled carbon nanotubes for dual targeted breast cancer therapy. Journal of Materials Chemistry B 2020; 8 (15): 3123-37. doi: 10.1039/c9tb02711d
27. Zhao J, Babiuch K, Lu H, Dag A, Gottschaldt M et al. Fructose-coated nanoparticles: a promising drug nanocarrier for triple-negative breast cancer therapy. Chemical Communications 2014; 50 (100): 15928-31. doi: 10.1039/c4cc06651k
28. Dag A, Cakilkaya E, Omurtag Ozgen PS, Atasoy S, Yigit Erdem G et al. Phthalocyanine-conjugated glyconanoparticles for chemophotodynamic combination therapy. Biomacromolecules 2021; 22 (4): 1555-67. doi: 10.1021/acs.biomac.0c01811
29. Hummers WS, Offeman RE. Preparation of Graphitic Oxide. Journal of the American Chemical Society. 1958; 80 (6): 1339. doi: 10.1021/ ja01539a017
30. Durmus Z, Durmus A, Kavas H. Synthesis and characterization of structural and magnetic properties of graphene/hard ferrite nanocomposites as microwave-absorbing material. Journal of Materials Science 2014; 50 (3): 1201-13. doi: 10.1007/s10853-014-8676-3
31. Liu J, Yang W, Tao L, Li D, Boyer C et al. Thermosensitive graphene nanocomposites formed using pyrene-terminal polymers made by RAFT polymerization. 2010; 48 (2): 425-33. doi: 10.1002/pola.23802
32. Dag A, Omurtag Ozgen PS, Atasoy S. Glyconanoparticles for targeted tumor therapy of platinum anticancer drug. Biomacromolecules 2019; 20 (8): 2962-72. doi: 10.1021/acs.biomac.9b00528
33. Cakir N, Hizal G, Becer CR. Supramolecular glycopolymers with thermo-responsive self-assembly and lectin binding. Polymer Chemistry 2015; 6 (37): 6623-31. doi: 10.1039/c5py00939a
34. Dag A, Lu H, Stenzel M. Controlling the morphology of glyco-nanoparticles in water using block copolymer mixtures: the effect on cellular uptake. Polymer Chemistry 2015; 6 (45): 7812-20. doi: 10.1039/c5py01360g
35. Yilmaz G, Becer CR. Glyconanoparticles and their interactions with lectins. Polymer Chemistry 2015; 6 (31): 5503-14. doi: 10.1039/ c5py00089k