"Comparison of thermally actuated retro-diels-alder release groups for " by Mohammad Abu-Laban, Raju R. Kumal et al.

Faculty Publications

Title

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

Authors

Mohammad Abu-Laban, The Department of Biomedical Engineering, The Pennsylvania State University, University Park, PA 16802, United States. Electronic address: mua323@psu.edu.
Raju R. Kumal, The Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803, United States. Electronic address: rkumal1@lsu.edu.
Jonathan Casey, The Department of Biomedical Engineering, The Pennsylvania State University, University Park, PA 16802, United States. Electronic address: jsc49@psu.edu.
Jeff Becca, The Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, United States. Electronic address: jbb5516@psu.edu.
Daniel LaMaster, The Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803, United States. Electronic address: dlamas1@lsu.edu.
Carlos N. Pacheco, The Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, United States; The NMR Facility, The Pennsylvania State University, University Park, PA 16802, United States. Electronic address: cpacheco223@gmail.com.
Dan G. Sykes, The Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, United States. Electronic address: djs12@psu.edu.

Document Type

Article

Publication Date

9-15-2018

Abstract

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, H and C 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.

Publication Source (Journal or Book title)

Journal of colloid and interface science

First Page

312

Last Page

321

Recommended Citation

Abu-Laban, M., Kumal, R. R., Casey, J., Becca, J., LaMaster, D., Pacheco, C. N., & Sykes, D. G. (2018). Comparison of thermally actuated retro-diels-alder release groups for nanoparticle based nucleic acid delivery. Journal of colloid and interface science, 526, 312-321. https://doi.org/10.1016/j.jcis.2018.04.085

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