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Rapid and Complete Surface Modification with Strain-Promoted Oxidation-Controlled Cyclooctyne-1,2-Quinone Cycloaddition (SPOCQ).

ABSTRACT: Strain-promoted oxidation-controlled cyclooctyne-1,2-quinone cycloaddition (SPOCQ) between functionalized bicyclo[6.1.0]non-4-yne (BCN) and surface-bound quinones revealed an unprecedented 100?% conjugation efficiency. In addition, monitoring by direct analysis in real time mass spectrometry (DART-MS) revealed the underlying kinetics and activation parameters of this immobilization process in dependence on its microenvironment.

SUBMITTER: Sen R

PROVIDER: S-EPMC5363232 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature

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Rapid and Complete Surface Modification with Strain-Promoted Oxidation-Controlled Cyclooctyne-1,2-Quinone Cycloaddition (SPOCQ).

Sen Rickdeb R Escorihuela Jorge J van Delft Floris F Zuilhof Han H

Angewandte Chemie (International ed. in English) 20170215 12

Strain-promoted oxidation-controlled cyclooctyne-1,2-quinone cycloaddition (SPOCQ) between functionalized bicyclo[6.1.0]non-4-yne (BCN) and surface-bound quinones revealed an unprecedented 100 % conjugation efficiency. In addition, monitoring by direct analysis in real time mass spectrometry (DART-MS) revealed the underlying kinetics and activation parameters of this immobilization process in dependence on its microenvironment. ...[more]

PMID: 28198134

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Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies.

Project description:Stimulated by its success in both bioconjugation and surface modification, we studied the strain-promoted oxidation-controlled cycloalkyne-1,2-quinone cycloaddition (SPOCQ) in three ways. First, the second-order rate constants and activation parameters (ΔH⧧) were determined of various cyclooctynes reacting with 4-tert-butyl-1,2-quinone in a SPOCQ reaction, yielding values for ΔH⧧ of 4.5, 7.3, and 12.1 kcal/mol, for bicyclo[6.1.0]non-4-yne (BCN), cyclooctyne (OCT), and dibenzoazacyclooctyne (DIBAC), respectively. Second, their reaction paths were investigated in detail by a range of quantum mechanical calculations. Single-configuration theoretical methods, like various DFT and a range of MP2-based methods, typically overestimate this barrier by 3-8 kcal/mol (after inclusion of zero-point energy, thermal, and solvation corrections), whereas MP2 itself underestimates the barrier significantly. Only dispersion-corrected DFT methods like B97D (yielding 4.9, 6.4, and 12.1 kcal/mol for these three reactions) and high-level CCSD(T) and multireference multiconfiguration AQCC ab initio approaches (both yielding 8.2 kcal/mol for BCN) give good approximations of experimental data. Finally, the multireference methods show that the radical character in the TS is rather small, thus rationalizing the use of single-reference methods like B97D and SCS-MP2 as intrinsically valid approaches.

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