Comparison of thermally actuated retro-diels-alder release groups for nanoparticle based nucleic acid delivery

[Display omitted] The present study explores alternate pericyclic chemistries for tethering amine-terminal biomolecules onto silver nanoparticles. Employing the versatile tool of the retro-Diels-Alder (rDA) reaction, three thermally-labile cycloadducts are constructed that cleave at variable tempera...

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Bibliographic Details
Published in:Journal of colloid and interface science 2018-09, Vol.526, p.312-321
Main Authors: Abu-Laban, Mohammad, Kumal, Raju R., Casey, Jonathan, Becca, Jeff, LaMaster, Daniel, Pacheco, Carlos N., Sykes, Dan G., Jensen, Lasse, Haber, Louis H., Hayes, Daniel J.
Format: Article
Language:English
Subjects:
Delivery
Furan
Gene Transfer Techniques
Maleimide
Metal Nanoparticles - chemistry
Models, Chemical
Nanoparticle
Pyrrole
retro-Diels-Alder
RNA, Small Interfering - chemistry
Second Harmonic Generation (SHG)
Silver - chemistry
Thiophene
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Summary:[Display omitted] The present study explores alternate pericyclic chemistries for tethering amine-terminal biomolecules onto silver nanoparticles. Employing the versatile tool of the retro-Diels-Alder (rDA) reaction, three thermally-labile cycloadducts are constructed that cleave at variable temperature ranges. While the reaction between furan and maleimide has widely been reported, the current study also evaluates the reverse reaction kinetics between thiophene-maleimide, and pyrrole-maleimide cycloadducts. Density Functional Theorem (DFT) calculations used to model and plan the experiments, predict energy barriers for the thiophene-maleimide reverse reaction to be greatest, and the pyrrole-maleimide barriers the lowest. Based on the computational analyses, it is projected that the cycloreversion rate would occur slowest with the thiophene, followed by furan, and finally pyrrole would yield the promptest release. These thermally-responsive linkers, characterized by Electrospray Ionization Mass Spectrometry, 1H and 13C NMR, are thiol-linked to silver nanoparticles and conjugate single stranded siRNA mimics with 5′ fluorescein tag. Second harmonic generation spectroscopy (SHG) and fluorescence spectroscopy are used to measure release and rate of release. The SHG decay constants and fluorescence release profiles obtained for the three rDA reactions confirm the trends obtained from the DFT computations.
ISSN:0021-9797
1095-7103
DOI:10.1016/j.jcis.2018.04.085