Abstract
Graphene oxide (GO)–gelatin (G) aerogels were synthesized by covalent and noncovalent methods, changing on the synthesis the GO:G ratio and the pH of the GO suspension, evaluating the physical, chemical, and functional properties of these materials. Comparatively, low GO:G ratios with alkali GO suspension promoted GO–G interactions for covalent aerogels. In contrast, high GO:G ratios under acidic conditions promoted noncovalent interactions. Scanning electron microscopy showed heterogeneous structures with pore sizes of 53.26 ± 25.53 µm and 25.31 ± 10.38 µm for covalent and noncovalent aerogels, respectively. The synthesis method did not influence the surface charge; however, differences were depending on the GO content and their chemical activation, shifting from 15.63 ± 0.55 mV to − 20.53 ± 1.07 mV. Noncovalent aerogels presented higher absorption ratios in phosphate-buffered saline (PBS) solution (35.5 ± 2.4 gPBS/gaerogel–49.6 ± 3.8 gPBS/gaerogel) than covalent aerogels. Therefore, due to these properties, noncovalent aerogels could be more useful than covalent aerogels for absorption potential applications, as biomedicine or water-treatment, where the promotion of surface interactions and high absorption capability is desired.
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References
N. Hsing, U. Schubert, Aerogels-airy materials: chemistry, structure, and properties. Angew. Chem. Int. Ed. 37, 22–45 (1998)
S.K.H. Gulrez, S. Al-Assaf, G.O. Phillips, Hydrogels: methods of preparation, characterisation and applications, in Progress in Molecular and Environmental Bioengineering—From Analysis and Modeling to Technology Applications, ed. by A. Carpi (InTech, Croatia, 2011)
S. Plazzotta, S. Calligaris, L. Manzocco, Innovative bioaerogel-like materials from fresh-cut salad waste via supercritical-CO2-drying. Innov. Food Sci. Emerg. Technol. 47, 485–492 (2018). https://doi.org/10.1016/j.ifset.2018.04.022
J. Siepmann, R.A. Siegel, M.J. Rathbone, Controlled Release Society, eds., Fundamentals and Applications of Controlled Release Drug Delivery. Springer : Controlled Release Society, New York, 2012
H. Nassira, A. Sánchez-Ferrer, J. Adamcik, S. Handschin, H. Mahdavi, N. Taheri Qazvini, R. Mezzenga, Gelatin-graphene nanocomposites with ultralow electrical percolation threshold. Adv. Mater. 28, 6914–6920 (2016). https://doi.org/10.1002/adma.201601115
S. Gorgieva, V. Kokol, Collagen- vs. gelatine-based biomaterials and their biocompatibility: review and perspectives, in Biomaterials Applications for Nanomedicine, ed. by R. Pignatello (InTech, Croatia, 2011)
B. Mohanty, H.B. Bohidar, Microscopic structure of gelatin coacervates. Int. J. Biol. Macromol. 36, 39–46 (2005). https://doi.org/10.1016/j.ijbiomac.2005.03.012
L. Baldino, S. Concilio, S. Cardea, E. Reverchon, Interpenetration of natural polymer aerogels by supercritical drying. Polymers. 8, 106 (2016). https://doi.org/10.3390/polym8040106
G. Shim, M.-G. Kim, J.Y. Park, Y.-K. Oh, Graphene-based nanosheets for delivery of chemotherapeutics and biological drugs. Adv. Drug Deliv. Rev. 105, 205–227 (2016). https://doi.org/10.1016/j.addr.2016.04.004
J. Lin, X. Chen, P. Huang, Graphene-based nanomaterials for bioimaging. Adv. Drug Deliv. Rev. 105, 242–254 (2016). https://doi.org/10.1016/j.addr.2016.05.013
S.-H. Lee, M. Kotal, J.-H. Oh, P. Sennu, S.-H. Park, Y.-S. Lee, I.-K. Oh, Nanohole-structured, iron oxide-decorated and gelatin-functionalized graphene for high rate and high capacity Li-Ion anode. Carbon 119, 355–364 (2017). https://doi.org/10.1016/j.carbon.2017.04.031
C. Liu, H. Liu, A. Xu, K. Tang, Y. Huang, C. Lu, In situ reduced and assembled three-dimensional graphene aerogel for efficient dye removal. J. Alloy. Compd. 714, 522–529 (2017). https://doi.org/10.1016/j.jallcom.2017.04.245
J. An, Y. Gou, C. Yang, F. Hu, C. Wang, Synthesis of a biocompatible gelatin functionalized graphene nanosheets and its application for drug delivery. Mater. Sci. Eng. C 33, 2827–2837 (2013). https://doi.org/10.1016/j.msec.2013.03.008
G. Chen, C. Qiao, Y. Wang, J. Yao, Synthesis of biocompatible gelatin-functionalised graphene nanosheets for drug delivery applications. Aust. J. Chem. 67, 1532 (2014). https://doi.org/10.1071/CH13678
Y. Piao, B. Chen, Self-assembled graphene oxide-gelatin nanocomposite hydrogels: characterization, formation mechanisms, and pH-sensitive drug release behavior. J. Polym. Sci. Part B Polym. Phys. 53, 356–367 (2015). https://doi.org/10.1002/polb.23636
H. Liu, J. Cheng, F. Chen, D. Bai, C. Shao, J. Wang, P. Xi, Z. Zeng, Gelatin functionalized graphene oxide for mineralization of hydroxyapatite: biomimetic and in vitro evaluation. Nanoscale. 6, 5315 (2014). https://doi.org/10.1039/c4nr00355a
Y. Piao, B. Chen, One-pot synthesis and characterization of reduced graphene oxide–gelatin nanocomposite hydrogels. RSC Advances. 6, 6171–6181 (2016). https://doi.org/10.1039/C5RA20674J
D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L.B. Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide. ACS Nano 4, 4806–4814 (2010). https://doi.org/10.1021/nn1006368
A.B. Bourlinos, D. Gournis, D. Petridis, T. Szabó, A. Szeri, I. Dékány, Graphite oxide: chemical reduction to graphite and surface modification with primary aliphatic amines and amino acids. Langmuir 19, 6050–6055 (2003). https://doi.org/10.1021/la026525h
B. Boeckx, G. Maes, Experimental and theoretical observation of different intramolecular H-bonds in lysine conformations. J. Phys. Chem. B. 116, 12441–12449 (2012). https://doi.org/10.1021/jp306916e
E. Garand, M.Z. Kamrath, P.A. Jordan, A.B. Wolk, C.M. Leavitt, A.B. McCoy, S.J. Miller, M.A. Johnson, Determination of noncovalent docking by infrared spectroscopy of cold gas-phase complexes. Science 335, 694–698 (2012). https://doi.org/10.1126/science.1214948
N.A. Kumar, H.-J. Choi, Y.R. Shin, D.W. Chang, L. Dai, J.-B. Baek, Polyaniline-grafted reduced graphene oxide for efficient electrochemical supercapacitors. ACS Nano 6, 1715–1723 (2012). https://doi.org/10.1021/nn204688c
S. Bose, T. Kuila, MdE Uddin, N.H. Kim, A.K.T. Lau, J.H. Lee, In-situ synthesis and characterization of electrically conductive polypyrrole/graphene nanocomposites. Polymer 51, 5921–5928 (2010). https://doi.org/10.1016/j.polymer.2010.10.014
K.N. Kudin, B. Ozbas, H.C. Schniepp, R.K. Prudhomme, I.A. Aksay, R. Car, Raman Spectra of Graphite Oxide and Functionalized Graphene Sheets. Nano Letters. 8, 36–41 (2008). https://doi.org/10.1021/nl071822y
V.K. Rana, M.-C. Choi, J.-Y. Kong, G.Y. Kim, M.J. Kim, S.-H. Kim, S. Mishra, R.P. Singh, C.-S. Ha, Synthesis and drug-delivery behavior of chitosan-functionalized graphene oxide hybrid nanosheets. Macromol. Mater. Eng. 296, 131–140 (2011). https://doi.org/10.1002/mame.201000307
S. Makharza, O. Vittorio, G. Cirillo, S. Oswald, E. Hinde, M. Kavallaris, B. Büchner, M. Mertig, S. Hampel, Graphene oxide–gelatin nanohybrids as functional tools for enhanced carboplatin activity in neuroblastoma cells. Pharm. Res. 32, 2132–2143 (2015). https://doi.org/10.1007/s11095-014-1604-z
C. Wan, M. Frydrych, B. Chen, Strong and bioactive gelatin–graphene oxide nanocomposites. Soft Matter 7, 6159 (2011). https://doi.org/10.1039/c1sm05321c
C. Su, M. Acik, K. Takai, J. Lu, S. Hao, Y. Zheng, P. Wu, Q. Bao, T. Enoki, Y.J. Chabal, K. Ping Loh, Probing the catalytic activity of porous graphene oxide and the origin of this behaviour. Nat Commun. 3, 1298 (2012). https://doi.org/10.1038/ncomms2315
B. Chen, L. Wang, S. Gao, Recent advances in aerobic oxidation of alcohols and amines to imines. ACS Catal. 5, 5851–5876 (2015). https://doi.org/10.1021/acscatal.5b01479
W. Wang, Z. Wang, Y. Liu, N. Li, W. Wang, J. Gao, Preparation of reduced graphene oxide/gelatin composite films with reinforced mechanical strength. Mater. Res. Bull. 47, 2245–2251 (2012). https://doi.org/10.1016/j.materresbull.2012.05.060
E.M. Zadeh, A. Yu, L. Fu, M. Dehghan, I. Sbarski, I. Harding, Physical and thermal characterization of graphene oxide modified gelatin-based thin films. Polym. Compos. 35, 2043–2049 (2014). https://doi.org/10.1002/pc.22865
K. Min, T.H. Han, J. Kim, J. Jung, C. Jung, S.M. Hong, C.M. Koo, A facile route to fabricate stable reduced graphene oxide dispersions in various media and their transparent conductive thin films. J. Colloid Interface Sci. 383, 36–42 (2012). https://doi.org/10.1016/j.jcis.2012.06.021
Z. Lei, N. Christov, X.S. Zhao, Intercalation of mesoporous carbon spheres between reduced graphene oxide sheets for preparing high-rate supercapacitor electrodes. Energy Environ. Sci. 4, 1866 (2011). https://doi.org/10.1039/c1ee01094h
K. Krishnamoorthy, M. Veerapandian, K. Yun, S.-J. Kim, The chemical and structural analysis of graphene oxide with different degrees of oxidation. Carbon 53, 38–49 (2013). https://doi.org/10.1016/j.carbon.2012.10.013
S.M. Ahsan, C.M. Rao, The role of surface charge in the desolvation process of gelatin: implications in nanoparticle synthesis and modulation of drug release. Int. J. Nanomed. 12, 795–808 (2017). https://doi.org/10.2147/IJN.S124938
C. Bastioli, Rapra Technology Limited, eds., Handbook of Biodegradable Polymers, Rapra Technology, Shrewsbury, 2005
M. Ramos, A. Valdés, A. Beltrán, M. Garrigós, Gelatin-Based Films and Coatings for Food Packaging Applications. Coatings. 6, 41 (2016). https://doi.org/10.3390/coatings6040041
S. Mohammadi, H. Keshvari, M. Eskandari, S. Faghihi, Graphene oxide–enriched double network hydrogel with tunable physico-mechanical properties and performance. React. Funct. Polym. 106, 120–131 (2016). https://doi.org/10.1016/j.reactfunctpolym.2016.07.015
H. Fan, W. Shen, Gelatin-based microporous carbon nanosheets as high performance supercapacitor electrodes. ACS Sustain. Chem. Eng. 4, 1328–1337 (2016). https://doi.org/10.1021/acssuschemeng.5b01354
S.R. Shin, C. Zihlmann, M. Akbari, P. Assawes, L. Cheung, K. Zhang, V. Manoharan, Y.S. Zhang, M. Yüksekkaya, K. Wan, M. Nikkhah, M.R. Dokmeci, X.S. Tang, A. Khademhosseini, Reduced graphene oxide-GelMA hybrid hydrogels as scaffolds for cardiac tissue engineering. Small 12, 3677–3689 (2016). https://doi.org/10.1002/smll.201600178
C. Cha, S.R. Shin, X. Gao, N. Annabi, M.R. Dokmeci, X.S. Tang, A. Khademhosseini, Controlling mechanical properties of cell-laden hydrogels by covalent incorporation of graphene oxide. Small 10, 514–523 (2014). https://doi.org/10.1002/smll.201302182
J.H. Lee, Y. Lee, Y.C. Shin, M.J. Kim, J.H. Park, S.W. Hong, B. Kim, J.-W. Oh, K.D. Park, D.-W. Han, In situ forming gelatin/graphene oxide hydrogels for facilitated C2C12 myoblast differentiation. Appl. Spectrosc. Rev. 51, 527–539 (2016). https://doi.org/10.1080/05704928.2016.1165686
Y. Piao, B. Chen, Synthesis and mechanical properties of double cross-linked gelatin-graphene oxide hydrogels. Int. J. Biol. Macromol. 101, 791–798 (2017). https://doi.org/10.1016/j.ijbiomac.2017.03.155
E.-P. Ng, S. Mintova, Nanoporous materials with enhanced hydrophilicity and high water sorption capacity. Microporous Mesoporous Mater. 114, 1–26 (2008). https://doi.org/10.1016/j.micromeso.2007.12.022
G. Horvat, M. Pantić, Ž. Knez, Z. Novak, Encapsulation and drug release of poorly water soluble nifedipine from bio-carriers. J. Non-Cryst. Solids 481, 486–493 (2018). https://doi.org/10.1016/j.jnoncrysol.2017.11.037
M. Salgado, F. Santos, S. Rodríguez-Rojo, R.L. Reis, A.R.C. Duarte, M.J. Cocero, Development of barley and yeast β-glucan aerogels for drug delivery by supercritical fluids. J. CO2 Utiliz. 22, 262–269 (2017). https://doi.org/10.1016/j.jcou.2017.10.006
M. Martins, A.A. Barros, S. Quraishi, P. Gurikov, S.P. Raman, I. Smirnova, A.R.C. Duarte, R.L. Reis, Preparation of macroporous alginate-based aerogels for biomedical applications. J. Supercritic. Fluids. 106, 152–159 (2015). https://doi.org/10.1016/j.supflu.2015.05.010
S. Quraishi, M. Martins, A.A. Barros, P. Gurikov, S.P. Raman, I. Smirnova, A.R.C. Duarte, R.L. Reis, Novel non-cytotoxic alginate–lignin hybrid aerogels as scaffolds for tissue engineering. J. Supercritic. Fluids. 105, 1–8 (2015). https://doi.org/10.1016/j.supflu.2014.12.026
G. Santos-López, W. Argüelles-Monal, E. Carvajal-Millan, Y. López-Franco, M. Recillas-Mota, J. Lizardi-Mendoza, Aerogels from chitosan solutions in ionic liquids. Polymers. 9, 722 (2017). https://doi.org/10.3390/polym9120722
Acknowledgements
We thank the FONDECYT-Chile for their financial support of this investigation, Project No. 1170681. The authors are grateful to the FONDEQUIP, Project No. EQM150139. The authors are grateful to the contribution of the Scientific Equipment Unit – MAINI, Catholic University of the North, Chile; for the assessment of the sample preparation, analysis and data generated through the CONICYT Equipment Program FONDEQUIP XPS EQM140044, 2014-2016.
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Sebastián Guajardo: Conceptualization, Methodology, Formal analysis, Investigation, Writing – Original draft preparation, Visualization. Katherina Fernández: Conceptualization, Methodology, Validation, Supervision, Writing – Review & editing, Project administration. Toribio Figueroa: Investigation, Visualization. Jessica Borges: Investigation, Visualization. Manuel Meléndrez: Visualization, Writing- Reviewing and Editing.
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Guajardo, S., Figueroa, T., Borges, J. et al. Comparative Study of Graphene Oxide-Gelatin Aerogel Synthesis: Chemical Characterization, Morphologies and Functional Properties. J Inorg Organomet Polym 31, 1517–1526 (2021). https://doi.org/10.1007/s10904-020-01770-9
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DOI: https://doi.org/10.1007/s10904-020-01770-9