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.

Recent Progress in the Development of Composite Membranes Based on Polybenzimidazole for High Temperature Proton Exchange Membrane (PEM) Fuel Cell Applications

“…Chemical modification of PBI by means of click chemistry reactions [ 90 ] and by the alternative and enviromental friendly metal-free click chemistry reactions [ 91 ], such as the strain-promoted azide–alkyne cycloaddition (SPAAC) [ 92 ], the thiol-ene [ 93 , 94 ] and thiol-yne coupling [ 95 , 96 ], the inverse electron−demand Diels−Alder (IEDDA) reaction [ 97 ], the strain-promoted alkyne−nitrone cycloaddition (SPANC) [ 98 , 99 ], and the strain-promoted oxidation-controlled cyclooctyne–1,2–quinone cycloaddition (SPOCQ) [ 100 , 101 , 102 ], can afford an interesting variety of PBI structures with potential applications in PEM for fuel cell applications. The main advantages of these reactions include their fast reaction kinetics, versatililty and regiospecificity, high product yields, and easy purification of the products.…”

Orthogonal, dual protein labelling by tandem cycloaddition of strained alkenes and alkynes to ortho-quinones and azides

“…Specifically, we demonstrated that strain-promoted oxidation-controlled ortho-quinone cycloaddition (SPOCQ) with cyclooctyne, 14 can be successfully applied for the site-specific conjugation of a cyclooctyne-functionalized fluorophore or a toxic payload to tyrosine-engineered proteins, including the monoclonal antibody trastuzumab, 12 as well as for highly efficient and complete surface modification. 15 Interestingly, with these developments, tyrosine is emerging as a very versatile amino acid for various peptide 16 and protein 17 derivatization strategies. With the present study, we have expanded the arsenal of SPOCQ chemistry by demonstrating that besides cyclooctynes strained alkenes also display high reactivity for ortho-quinones.…”

Strain‐Promoted Cycloaddition of Cyclopropenes with o‐Quinones: A Rapid Click Reaction

“…Herein, we report a novel click reaction between strained alkenes, namely 1‐methyl‐3‐substituted cyclopropenes, and o ‐quinones. We determine the rate constants for the reaction in solution using UV spectroscopy and on a surface using DART‐HRMS . Furthermore, we also demonstrate the quantitative nature of the reaction on surfaces and demonstrate its versatility using anti‐fouling polymer brush functionalization.…”

“…An additional feature of this reaction is that quinone formation can be triggered by enzymatic or electrochemical oxidation, thus providing an inducible click handle. In addition, when used for surface functionalization, SPOCQ achieves a rarely obtained quantitative conversion within 4 h with high surface‐bound rates ( k 2 =33±2 m −1 s −1 ) . A distinct feature of this reaction is, however, the use of a relatively large, hydrophobic eight‐membered ring, which in itself is not necessary for bio‐conjugations and typically disadvantageous in sterically crowded environments such as polymers and surfaces.…”

“…400.7 eV) signals from narrow scan analysis (Figures S4.19 and S4.23). With a BCN‐C 4 F 9 analog, the reaction yielded a 30 % yield, while the sterically advantageous cyclopropene provided 60 % conversion (each averaged over 6 samples). This further shows the wide applicability of this approach for polymer modification.…”