Mechanistic studies of a “Declick” reaction

Meadows, Margaret K.; Sun, Xiaolong; Kolesnichenko, Igor V.; Hinson, Caroline M.; Johnson, Kenneth A.; Anslyn, Eric V.

doi:10.1039/c9sc00690g

Title: Mechanistic studies of a “Declick” reaction

Journal Article · 12 August 2019 · Chemical Science

DOI: https://doi.org/10.1039/c9sc00690g · OSTI ID:1624973

Meadows, Margaret K. ^[1];

^[2];

^[3];

^[4]; Johnson, Kenneth A. ^[5];

^[4]

Mercer Univ., Macon, GA (United States). Dept. of Chemistry; DOE/OSTI
Xi'an Jiaotong Univ., Shaanxi (China). The Key Lab. of Biomedical Information Engineering of Ministry of Education, School of Life Science and Technology
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Photovoltaics & Materials Technology Dept.
Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
Univ. of Texas, Austin, TX (United States). Dept. of Molecular Biosciences, Inst. for Cellular and Molecular Biology

A kinetic analysis of a “declick” reaction is described. Compound 1, previously reported to couple an amine and a thiol (i.e. “click”) under mild aqueous conditions to create 2, undergoes release of the unaltered coupling partners upon triggering with dithiothreitol (DTT). In the study reported herein various aniline derivatives possessing para-electron donating and withdrawing groups were used as the amines. UV/vis spectroscopy of the declick reaction shows time-dependent spectra lacking isosbestic points, implying a multi-step mechanism. Global data fitting using numerical integration of rate equations and singular value decomposition afforded the spectra and time-dependence of each species, as well as rate constants for each step. The kinetic analysis reveals a multi-step process with an intermediate where both thiols of DTT have added prior to expulsion of the aniline leaving group, followed by rearrangement to the final product. Hammett plots show a negative rho value on two of the steps, indicating positive charge building (i.e. reduction of a negative charge) in the step leading to the intermediate and its ratedetermining breakdown. Overall, the kinetic study reported herein gives a complete mechanistic picture of the declick reaction.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC); Welch Foundation; Welch Regents Chair

Grant/Contract Number:: NA0003525

OSTI ID:: 1624973

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 38 Vol. 10; ISSN 2041-6520; ISSN CSHCBM

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (16)

An Auto‐Inductive Cascade for the Optical Sensing of Thiols in Aqueous Media: Application in the Detection of a VX Nerve Agent Mimic Sun, Xiaolong; Anslyn, Eric V. Angewandte Chemie, Vol. 129, Issue 32 https://doi.org/10.1002/ange.201704472	journal	July 2017
An Auto-Inductive Cascade for the Optical Sensing of Thiols in Aqueous Media: Application in the Detection of a VX Nerve Agent Mimic Sun, Xiaolong; Anslyn, Eric V. Angewandte Chemie International Edition, Vol. 56, Issue 32 https://doi.org/10.1002/anie.201704472	journal	July 2017
Singular value decomposition and least squares solutions Golub, G. H.; Reinsch, C. Numerische Mathematik, Vol. 14, Issue 5 https://doi.org/10.1007/BF02163027	journal	April 1970
[8] Singular value decomposition: Application to analysis of experimental data Henry, E. R.; Hofrichter, J. Methods in Enzymology https://doi.org/10.1016/0076-6879(92)10010-B	book	January 1992
Deconvolutions based on singular value decomposition and the pseudoinverse: a guide for beginners Hendler, Richard W.; Shrager, Richard I. Journal of Biochemical and Biophysical Methods, Vol. 28, Issue 1 https://doi.org/10.1016/0165-022X(94)90061-2	journal	January 1994
Global Kinetic Explorer: A new computer program for dynamic simulation and fitting of kinetic data Johnson, Kenneth A.; Simpson, Zachary B.; Blom, Thomas Analytical Biochemistry, Vol. 387, Issue 1 https://doi.org/10.1016/j.ab.2008.12.024	journal	April 2009
FitSpace Explorer: An algorithm to evaluate multidimensional parameter space in fitting kinetic data Johnson, Kenneth A.; Simpson, Zachary B.; Blom, Thomas Analytical Biochemistry, Vol. 387, Issue 1 https://doi.org/10.1016/j.ab.2008.12.025	journal	April 2009
A tetrahedral intermediate in the EPSP synthase reaction observed by rapid quench kinetics Anderson, Karen S.; Sikorski, James A.; Johnson, Kenneth A. Biochemistry, Vol. 27, Issue 19 https://doi.org/10.1021/bi00419a034	journal	September 1988
Kinetic and structural analysis of enzyme intermediates: lessons from EPSP synthase Anderson, Karen S.; Johnson, Kenneth A. Chemical Reviews, Vol. 90, Issue 7 https://doi.org/10.1021/cr00105a004	journal	November 1990
Substituent effects on dissociation of benzoic acids and heteroconjugation of benzoates with p-bromophenol in acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide. Intramolecular hydrogen bonding in o-hydroxybenzoic acids and their anions Kolthoff, I. M.; Chantooni, M. K. Journal of the American Chemical Society, Vol. 93, Issue 16 https://doi.org/10.1021/ja00745a001	journal	August 1971
Stopped-Flow Kinetic Analysis of the Interaction of Cyclo[8]pyrrole with Anions Karnas, Elizabeth; Kim, Sung Kuk; Johnson, Kenneth A. Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja107471x	journal	November 2010
Click and chemically triggered declick reactions through reversible amine and thiol coupling via a conjugate acceptor Diehl, Katharine L.; Kolesnichenko, Igor V.; Robotham, Scott A. Nature Chemistry, Vol. 8, Issue 10 https://doi.org/10.1038/nchem.2601	journal	September 2016
Singular value decomposition for genome-wide expression data processing and modeling Alter, O.; Brown, P. O.; Botstein, D. Proceedings of the National Academy of Sciences, Vol. 97, Issue 18, p. 10101-10106 https://doi.org/10.1073/pnas.97.18.10101	journal	August 2000
Missing value estimation methods for DNA microarrays Troyanskaya, O.; Cantor, M.; Sherlock, G. Bioinformatics, Vol. 17, Issue 6 https://doi.org/10.1093/bioinformatics/17.6.520	journal	June 2001
The singular value decomposition: Its computation and some applications Klema, V.; Laub, A. IEEE Transactions on Automatic Control, Vol. 25, Issue 2 https://doi.org/10.1109/TAC.1980.1102314	journal	April 1980
A Multilinear Singular Value Decomposition De Lathauwer, Lieven; De Moor, Bart; Vandewalle, Joos SIAM Journal on Matrix Analysis and Applications, Vol. 21, Issue 4 https://doi.org/10.1137/S0895479896305696	journal	January 2000

Similar Records

Elucidating the Mechanism for the Reaction of $o$-Phthalaldehyde with Primary Amines in the Presence of Thiols

Journal Article · 2023 · Journal of Physical Chemistry. B · OSTI ID:2293514

Rovelli, Grazia; Wilson, Kevin R.

Nicotinic cholinergic receptors in rat brain. Annual report No. 1, 1 May 83-30 Apr 84

Technical Report · 1984 · OSTI ID:5583593

Kellar, K J

Oxidation of aniline and other primary aromatic amines by manganese dioxide

Journal Article · 1990 · Environmental Science and Technology; (United States) · OSTI ID:5452506

Laha, S; Luthy, R G

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry

Title: Mechanistic studies of a “Declick” reaction

Citation Formats

References (16)

Similar Records

Related Subjects