Nucleic acid structural engineering using pyrene-functionalized 2'-amino-alpha-L-LNA monomers and abasic sites

J Org Chem. 2008 Sep 19;73(18):7060-6. doi: 10.1021/jo800551j. Epub 2008 Aug 19.

Abstract

Oligonucleotides (ONs) modified with a 2'-N-(pyren-1-yl)acetyl-2'-amino-alpha-L-LNA thymine monomer Y flanked on the 3'-side by an abasic site Phi (i.e., YPhi-unit) exhibit unprecedented increases in thermal affinity (DeltaT(m) values) toward target strands containing abasic sites (DeltaT(m) per YPhi unit >+33.0 degrees C in 9-mer duplexes relative to unmodified ONs). Biophysical studies along with force field calculations suggest that the conformationally locked 2-oxo-5-azabicyclo[2.2.1]heptane skeleton of monomer Y, in concert with the short rigid acetyl linker, efficiently forces the thymine and pyrene moieties to adopt an interplanar distance of approximately 3.4 A. This precisely positions the pyrene moiety in the duplex core void formed by abasic sites (Phi:Phi pair) for optimal pi-pi overlap. Duplexes with multiple YPhi: APhi units separated by one base pair are tolerated extraordinarily well, as exemplified by a 13-mer duplex containing four separated YPhi: APhi units (8 abasic sites distributed over 13 "base pairs"), which exhibit a thermal denaturation temperature of 60.5 degrees C. The YPhi probes display up to 16-fold increases in fluorescence intensity at 380 nm upon hybridization with abasic target strands, whereby self-assembly of these complex architectures can be easily monitored. This study underlines the potential of N2'-functionalized 2'-amino-alpha-L-LNA as building blocks in nucleic acid based diagnostics and nanomaterial engineering.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Base Pairing
  • Bridged Bicyclo Compounds, Heterocyclic / chemistry
  • Circular Dichroism
  • Molecular Conformation
  • Nucleic Acid Denaturation
  • Nucleic Acids / chemistry*
  • Oligonucleotides / chemical synthesis
  • Oligonucleotides / chemistry*
  • Spectrometry, Fluorescence
  • Spectrophotometry, Ultraviolet
  • Temperature
  • Thymidine Monophosphate / analogs & derivatives*
  • Thymidine Monophosphate / chemistry
  • Thymine / analogs & derivatives
  • Thymine / chemistry*

Substances

  • 2'-N-(pyren-1-yl)acetyl-2'-amino-alpha-L-LNA
  • 2-oxo-5-azabicyclo(2.2.1)heptane
  • Bridged Bicyclo Compounds, Heterocyclic
  • Nucleic Acids
  • Oligonucleotides
  • Thymidine Monophosphate
  • Thymine