Self-Catalyzed Sensitization of CuO Nanowires via a Solvent-free Click Reaction

Abstract

Recent advances in organic surface sensitization of metal oxide nanomaterials focused on two-step approaches with the first step providing a convenient functionalized chemical “hook”, such as an alkyne functionality connected to a carboxylic group in prop-2-ynoic acid. The second step then took advantage of copper-catalyzed click chemistry to deliver the desired structure (such as benzyl or perylene) attached to an azide to react with the surface-bound alkyne. The use of this approach on CuO not only resulted in a successful morphology preserving chemical modification but also has demonstrated that surface Cu­(I) can be obtained during the process and promote a surface-catalyzed click reaction without additional copper catalyst. Here, it is demonstrated that this surface-catalyzed chemistry can be performed on a surface of the CuO nanomaterial without a solvent, as a “dry click” reaction, as confirmed with spectroscopic and microscopic investigations with X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, solid-state nuclear magnetic resonance, and scanning electron microscopy. Computational studies provided instructive information on the interaction between the surface prop-2-yonate and azide functional group to better understand the mechanism of this surface-catalyzed click reaction.

Click Chemistry-Mediated Particle Counting Sensing via Cu(II)-Polyglutamic Acid Coordination Chemistry and Enzymatic Reaction

“…The SEM images display that the CuAAC reaction results in the azido-MBs gathering around the surface of the alkyne-PS microspheres (Figure E,F). The coupling of functional molecules to MBs and PS microspheres was assessed by Fourier transform infrared spectroscopy. , The absorption bands at approximately 2120 and 2200 cm –1 mainly derived from the NNN band of azido molecules and the CC band of alkyne molecules, respectively (Figure S2). Dynamic light scattering was also employed to characterize the MBs, PS microspheres, and their conjugates.…”

On-Surface Azide–Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?

“…In 2001, Sharpless and co-workers developed “click” chemistry that enables the formation of 1,2,3-triazole compounds, and since then, the method has been widely used for synthetic chemistry. − The reaction has two product possibilities: 1,4-disubstituted and 1,5-disubstituted triazoles. Different catalysts can yield either regioisomers or a mixture of both. − The two isomers possess completely different chemical properties in solution and thus have different applications. − …”

Uniform wrapping of copper(i) oxide nanocubes by self-controlled copper-catalyzed azide–alkyne cycloaddition toward selective carbon dioxide electrocatalysis

“…[38][39][40] Whether the reaction proceeds on the surface or tentatively leached Cu(I) species from the apparently heterogeneous Cu catalyst is under active debate, because both monomeric and oligomeric organometallic species can be involved. 35 Single-molecule detection of CuAAC, 41 facet-dependent activity and retention of Cu 2 O shape after catalysis, 42,43 and computational analysis 44 indicate that CuAAC occurs on the solid surface at room temperature. Our present results of layer formation corroborate the heterogeneous CuAAC process at room temperature, but it easily becomes a solution process at elevated temperatures.…”