Polyethylenimine (PEI) is a cationic polymer widely used in non-viral gene delivery systems and other polymer technologies. PEI with a MW of 25 kD was cross-linked in aqueous solution by the aromatic di-aldehyde isophthalaldehyde. This di-aldehyde cross-links PEI by forming stable imines with the primary amine groups in branched PEI. Cross-linking was evaluated at different concentrations of PEI using NMR, dynamic light scattering (DLS or QELS) and solvent extraction. It is demonstrated that isophthalaldehyde was able to cross-link PEI intramolecularly in solution near physiological pH resulting in the formation of unimolecular cross-linked nanoparticles. Proton NMR was used to examine the cross-linking reaction in-situ. The aldehyde resonance of isophthalaldehyde became broadened as cross-linking occurred. Organic-aqueous liquid-liquid extraction studies supported both that the cross-linking was intramolecular and that the cross-linked structures were stable to hydrolysis in water at neutral pH. As cross-linking occurred, the percentage of isophthalaldehyde that could be extracted from the solution was reduced. The molecular radii and aggregation behavior was monitored by QELS. The particle size of the polymer molecules in solution decreased with increased cross-linking, indicating the intra-molecular cross-linking between the PEI branches. These results clearly show that cross-linking of PEI with isophthalaldehyde creates soluble unimolecular polymer nanoparticles. These materials hold promise for a variety of applications in biotechnology.
| Published in | American Journal of Polymer Science and Technology (Volume 7, Issue 4) |
| DOI | 10.11648/j.ajpst.20210704.11 |
| Page(s) | 50-56 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
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Copyright © The Author(s), 2021. Published by Science Publishing Group |
Nanoparticles, Cross-Linking, Polyethylenimine
| [1] | De Araújo Santos, J.; Liarte, D. B.; Ribeiro, A. B.; dos Santos Rizzo, M.; da Costa, M. Osajima, J. A.; Silva-Filho, E. C. Biopolymeric Materials Used as Nonviral Vectors: A Review, Polysaccharides 2021, 2, 100–109. DOI: 10.3390/polysaccharides2010007. |
| [2] | Baker, A.; Saltik, M.; Lehrmann, H.; Killisch, I.; Mautner, V.; Lamm, G.; Christofori, G.; Cotton, M. “Polyethylenimine (PEI) is a simple, inexpensive and effective reagent for condensing and linking plasmid DNA to adenovirus for gene delivery” Gene Therapy 1997, 4, 773–782. |
| [3] | Varga, C. M.; Tedford, N. C.; Thomas, M.; Klibanov, A. M., Griffith, L. G.; Lauffenburger, D. A. “Quantitative comparison of polyethylenimine formulations and adenoviral vectors in terms of intracellular gene delivery processes” Gene Therapy 2005 12, 1023–1032. |
| [4] | Longo, P. A.; Kavran, J. M.; Kim, M. S. Leahy, D. J. “Transient Mammalian Cell Transfection with Polyethylenimine (PEI)” Methods Enzymol. 2013; 529: 227–240. DOI: 10.1016/B978-0-12-418687-3.00018-5. |
| [5] | Li, S.; Hanson, J. E.; “Cross-linking of Polyethylenimine with Isophthalaldehyde: A Model for Soluble Imprinted Polymers” Polym. Mat. Sci. Eng., 2003, 89, 559. |
| [6] | Liu, Bao, H.; Liu, C.; Wu, F.; Gao, F. “‘Turn-on’ Fluorescence Determination of b-Glucosidase Activity Using Fluorescent Polymer Nanoparticles Formed from Polyethylenimine Cross-Linked with Hydroquinone” ACS Appl. Polym. Mater. 2019, 1, 3057-3063. |
| [7] | Liu, J.; Jiang, X.; Xu, L.; Wang, X.; Hennink, W. E.; Zhuo, R. “Novel Reduction-Responsive Cross-Linked Polyethylenimine Derivatives by Click Chemistry for Nonviral Gene Delivery” Bioconjugate Chem. 2010, 21, 1827-1835. |
| [8] | Cordes, E. H.; Jencks, W. P. “The Mechanism of Hydrolysis of Schiff Bases Derived from Aliphatic Imines” J. Am. Chem. Soc. 1963, 85 (18), 2843-2848. |
| [9] | https://ww2.epa.gov/tsca-screening-tools |
| [10] | Reiser, A; Pitts, E. J. Photogr. Sci. 1981, 29, 187-191. |
| [11] | Mirau, P. A. “A Practical Guide to Understanding the NMR of Polymers” Wiley-Interscience, Hoboken NJ, 2005. |
| [12] | Minton, A. P. Anal. Biochem. 2016, 501, 4-22. |
| [13] | ter Huurne, G. M.; Voets, I. K.; Palmans, A. R. A.; Meijer, E. W. “Effect of Intra- versus Intermolecular Cross-Linking on the Supramolecular Folding of a Polymer Chain” Macromolecules 2018, 51, 8853−8861. DOI: 10.1021/acs.macromol. |
| [14] | Schweins, R.; Lindner, P.; Huber, K. “Calcium Induced Shrinkage of NaPA Chains: A SANS Investigation of Single Chain Behavior” Macromolecules, 2003, 36, 9564-9573. |
| [15] | Mann, S. K.; Pham, T. N.; McQueen, L. L.; Lewandowksi, J. R.; Brown, S. P. Mol. Pharmaceutics, 2020, 17, 622-631. |
| [16] | Mukherji, D.; Marques, C. M.; Kremer, K. “Depleted depletion drives polymer swelling in poor solvent mixtures” Nature Communications 2017, 8, Article 1374. |
| [17] | Braco, L.; Dabulis, K.; Klibanov, A. M. Proc. Nat. Acad. Sci. USA, 1990, 87, 274-277. |
APA Style
Sueyuan Li, James Edward Hanson. (2021). Soluble Unimolecular Polymer Nanoparticles by Crosslinking of Polyethylenimine with Isophthalaldehyde. American Journal of Polymer Science and Technology, 7(4), 50-56. https://doi.org/10.11648/j.ajpst.20210704.11
ACS Style
Sueyuan Li; James Edward Hanson. Soluble Unimolecular Polymer Nanoparticles by Crosslinking of Polyethylenimine with Isophthalaldehyde. Am. J. Polym. Sci. Technol. 2021, 7(4), 50-56. doi: 10.11648/j.ajpst.20210704.11
AMA Style
Sueyuan Li, James Edward Hanson. Soluble Unimolecular Polymer Nanoparticles by Crosslinking of Polyethylenimine with Isophthalaldehyde. Am J Polym Sci Technol. 2021;7(4):50-56. doi: 10.11648/j.ajpst.20210704.11
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Download@article{10.11648/j.ajpst.20210704.11,
author = {Sueyuan Li and James Edward Hanson},
title = {Soluble Unimolecular Polymer Nanoparticles by Crosslinking of Polyethylenimine with Isophthalaldehyde},
journal = {American Journal of Polymer Science and Technology},
volume = {7},
number = {4},
pages = {50-56},
doi = {10.11648/j.ajpst.20210704.11},
url = {https://doi.org/10.11648/j.ajpst.20210704.11},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpst.20210704.11},
abstract = {Polyethylenimine (PEI) is a cationic polymer widely used in non-viral gene delivery systems and other polymer technologies. PEI with a MW of 25 kD was cross-linked in aqueous solution by the aromatic di-aldehyde isophthalaldehyde. This di-aldehyde cross-links PEI by forming stable imines with the primary amine groups in branched PEI. Cross-linking was evaluated at different concentrations of PEI using NMR, dynamic light scattering (DLS or QELS) and solvent extraction. It is demonstrated that isophthalaldehyde was able to cross-link PEI intramolecularly in solution near physiological pH resulting in the formation of unimolecular cross-linked nanoparticles. Proton NMR was used to examine the cross-linking reaction in-situ. The aldehyde resonance of isophthalaldehyde became broadened as cross-linking occurred. Organic-aqueous liquid-liquid extraction studies supported both that the cross-linking was intramolecular and that the cross-linked structures were stable to hydrolysis in water at neutral pH. As cross-linking occurred, the percentage of isophthalaldehyde that could be extracted from the solution was reduced. The molecular radii and aggregation behavior was monitored by QELS. The particle size of the polymer molecules in solution decreased with increased cross-linking, indicating the intra-molecular cross-linking between the PEI branches. These results clearly show that cross-linking of PEI with isophthalaldehyde creates soluble unimolecular polymer nanoparticles. These materials hold promise for a variety of applications in biotechnology.},
year = {2021}
}
TY - JOUR T1 - Soluble Unimolecular Polymer Nanoparticles by Crosslinking of Polyethylenimine with Isophthalaldehyde AU - Sueyuan Li AU - James Edward Hanson Y1 - 2021/11/19 PY - 2021 N1 - https://doi.org/10.11648/j.ajpst.20210704.11 DO - 10.11648/j.ajpst.20210704.11 T2 - American Journal of Polymer Science and Technology JF - American Journal of Polymer Science and Technology JO - American Journal of Polymer Science and Technology SP - 50 EP - 56 PB - Science Publishing Group SN - 2575-5986 UR - https://doi.org/10.11648/j.ajpst.20210704.11 AB - Polyethylenimine (PEI) is a cationic polymer widely used in non-viral gene delivery systems and other polymer technologies. PEI with a MW of 25 kD was cross-linked in aqueous solution by the aromatic di-aldehyde isophthalaldehyde. This di-aldehyde cross-links PEI by forming stable imines with the primary amine groups in branched PEI. Cross-linking was evaluated at different concentrations of PEI using NMR, dynamic light scattering (DLS or QELS) and solvent extraction. It is demonstrated that isophthalaldehyde was able to cross-link PEI intramolecularly in solution near physiological pH resulting in the formation of unimolecular cross-linked nanoparticles. Proton NMR was used to examine the cross-linking reaction in-situ. The aldehyde resonance of isophthalaldehyde became broadened as cross-linking occurred. Organic-aqueous liquid-liquid extraction studies supported both that the cross-linking was intramolecular and that the cross-linked structures were stable to hydrolysis in water at neutral pH. As cross-linking occurred, the percentage of isophthalaldehyde that could be extracted from the solution was reduced. The molecular radii and aggregation behavior was monitored by QELS. The particle size of the polymer molecules in solution decreased with increased cross-linking, indicating the intra-molecular cross-linking between the PEI branches. These results clearly show that cross-linking of PEI with isophthalaldehyde creates soluble unimolecular polymer nanoparticles. These materials hold promise for a variety of applications in biotechnology. VL - 7 IS - 4 ER -
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