A comprehensive overview is provided of oxidation conditions that induce a click reaction, and oxidation conditions are orthogonal to other click reactions so that sequential “click-oxidation-click” derivatization of molecules can be performed in one pot. Here, we review the various methods that can be used for such oxidation-induced “one-pot” click chemistry for the transformation of small molecules, materials, and biomolecules. These approaches have led to some of the fastest click reactions know to date. From the vast landscape of click reactions, approaches have emerged in the past decade centered around oxidative processes to generate in situ highly reactive synthons from dormant functionalities. Due to the rapid rates, clean conversions to the products, and compatibility of the reagents and reaction conditions even in complex settings, it has found applications in many molecule-oriented disciplines. Fluorescence intensity of proteins bound to spotted microarrays is used to enable a quantitative comparison between the different routes.Ĭlick chemistry has been established rapidly as one of the most valuable methods for the chemical transformation of complex molecules. The binding efficiency for different cyclooctyne‐azide‐based immobilization routes is assessed on azido‐functionalized antifouling polymer brushes via microchannel cantilever spotting. Strain‐promoted alkyne‐azide cycloaddition (SPAAC) is an eminent reaction for biorthogonal conjugation and surface immobilization. This work provides a reference for choosing appropriate cyclooctyne to couple with azides and can be useful for the design of biosensors or bio‐platforms for analyte detection, cell capture, and other biological applications. Both cyclooctynes demonstrate reliable binding performance with azide‐bearing diblock polymer brushes via μCS, but DBCO shows a higher surface density of molecular immobilization according to the protein binding assays. The assessment of binding efficiency is conducted on ordered arrays spotted by microchannel cantilever spotting (μCS) with a normal fluorescent microscope. The polymer brushes are composed of an antifouling bottom block and azide‐terminated top block. In the present work, different derivatives of dibenzocyclooctyne/bicyclononyne (DBCO/BCN) linked to either a fluorophore or a biotin‐moiety are patterned on ultra‐low fouling polymer brushes, which can avoid unspecific protein contamination without any prior blocking steps. While numerous studies have focused on enhancing the reactivity of cyclooctynes, a facile method to evaluate the binding efficiency for cyclooctyne‐azide‐based immobilization without any sophisticated facilities is still missing. Strain‐promoted alkyne‐azide cycloaddition (SPAAC) has become an indispensable tool in bioorthogonal conjugation and surface immobilization. The obtained results will help in obtaining a better understanding of the factors that affect the relative cycloaddition rates of norbornenes with tetrazines, which are crucial for selectively tuning their efficacy. The theoretical predictions were confirmed with the experimental data and analyzed with the use of the distortion/interaction model. The inverse electron-demand Diels Alder reaction of 3,6-dipyridin-2-yl-1,2,4,5-tetrazine with a series of norbornene derivatives was studied with quantum mechanical calculations at the M06-2X/6-311+G(d,p) level of theory. Among the different types of dienophiles used in the IEDDA reactions, norbornenes have been widely used given their high stability and fast reaction rates. In this regard, the inverse electron demand Diels-Alder (IEDDA) reaction represents a promising metal-free alternative with enhanced reaction rates compared to other reactions of the click chemistry toolbox. The study of the reaction rates and mechanism of click chemistry reactions still remains an interesting challenge in organic chemistry.
0 Comments
Leave a Reply. |
AuthorWrite something about yourself. No need to be fancy, just an overview. ArchivesCategories |