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

Mohammad Abu-Laban, Raju R. Kumal, Jonathan Casey, Jeff Becca, Daniel LaMaster, Carlos N. Pacheco, Dan G. Sykes, Lasse Jensen, Louis H. Haber, Daniel J. Hayes

Research output: Contribution to journalArticle

2 Citations (Scopus)

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, 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.

Original languageEnglish (US)
Pages (from-to)312-321
Number of pages10
JournalJournal of Colloid And Interface Science
Volume526
DOIs
StatePublished - Sep 15 2018

Fingerprint

Nucleic acids
Thiophene
Nucleic Acids
Thiophenes
Pyrroles
Harmonic generation
Nanoparticles
Silver
Spectroscopy
Electrospray ionization
Energy barriers
Fluorescence spectroscopy
Biomolecules
Reaction kinetics
Mass spectrometry
Amines
Fluorescence
Nuclear magnetic resonance
Fluorescein
Sulfhydryl Compounds

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Biomaterials
  • Surfaces, Coatings and Films
  • Colloid and Surface Chemistry

Cite this

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. / Comparison of thermally actuated retro-diels-alder release groups for nanoparticle based nucleic acid delivery. In: Journal of Colloid And Interface Science. 2018 ; Vol. 526. pp. 312-321.
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Comparison of thermally actuated retro-diels-alder release groups for nanoparticle based nucleic acid delivery. / 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.

In: Journal of Colloid And Interface Science, Vol. 526, 15.09.2018, p. 312-321.

Research output: Contribution to journalArticle

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AU - Pacheco, Carlos N.

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