Critical Analysis of Rate Constants and Turnover Frequency in Nucleic Acid-Templated Reactions: Reaching Terminal Velocity. 2017

Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
Department of Organic Chemistry, NCCR Chemical Biology, Faculty of Science, University of Geneva , 30 quai Ernest-Ansermet, 1205 Geneva, Switzerland.

Nucleic acid-templated reactions have attracted significant attention for nucleic acid sensing and imaging. The level of signal amplification obtained from templated reactions is a function of the template turnover, wherein the template acts as the catalyst. Herein, we report the application of a pyridinium linker that immolates upon photocatalytic reduction with a ruthenium complex to yield the fastest nucleic acid templated reaction reported to date. We show that the templated reaction turnover is limited by the duplex dissociation kinetics beyond probes longer than a 6-mer and proceeded fastest for a 5-mer PNA probe. Using a beacon architecture that masks the catalytic template, we show that this methodology can be used for nucleic acid sensing extending the analyte recognition beyond a 5-mer. The system proceeds with a catalytic efficiency of 105 M-1 s-1 and achieves turnover frequency of >100 h-1.

UI MeSH Term Description Entries
D009696 Nucleic Acids High molecular weight polymers containing a mixture of purine and pyrimidine nucleotides chained together by ribose or deoxyribose linkages. Nucleic Acid,Acid, Nucleic,Acids, Nucleic
D009942 Organometallic Compounds A class of compounds of the type R-M, where a C atom is joined directly to any other element except H, C, N, O, F, Cl, Br, I, or At. (Grant & Hackh's Chemical Dictionary, 5th ed) Metallo-Organic Compound,Metallo-Organic Compounds,Metalloorganic Compound,Organometallic Compound,Metalloorganic Compounds,Compound, Metallo-Organic,Compound, Metalloorganic,Compound, Organometallic,Compounds, Metallo-Organic,Compounds, Metalloorganic,Compounds, Organometallic,Metallo Organic Compound,Metallo Organic Compounds
D011726 Pyridinium Compounds Derivatives of PYRIDINE containing a cation C5H5NH or radical C5H6N. Compounds, Pyridinium
D012428 Ruthenium A hard, brittle, grayish-white rare earth metal with an atomic symbol Ru, atomic number 44, and atomic weight 101.07. It is used as a catalyst and hardener for PLATINUM and PALLADIUM.
D015394 Molecular Structure The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds. Structure, Molecular,Molecular Structures,Structures, Molecular

Related Publications

Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
May 2014, Organic & biomolecular chemistry,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
December 2014, Journal of the American Chemical Society,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
June 2017, ChemMedChem,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
November 2013, Chembiochem : a European journal of chemical biology,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
March 2021, Biosensors & bioelectronics,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
September 2008, Chembiochem : a European journal of chemical biology,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
November 2010, Chemical communications (Cambridge, England),
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
April 2015, ACS chemical biology,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
August 2014, Bioorganic & medicinal chemistry,
Dalu Chang, and Eric Lindberg, and Nicolas Winssinger
July 2009, Chemistry (Weinheim an der Bergstrasse, Germany),
Copied contents to your clipboard!