Nanoplasmonics tuned “click chemistry”

Abstract

Nanoplasmonics is a growing field of optical condensed matter science dedicated to optical phenomena at the nanoscale level in metal systems. Extensive research on noble metallic nanoparticles (NPs) has emerged within the last two decades due to their ability to keep the optical energy concentrated in the vicinity of NPs, in particular, the ability to create optical near-field enhancement followed by heat generation. We have exploited these properties in order to induce a localised "click" reaction in the vicinity of gold nanostructures under unfavourable experimental conditions. We demonstrate that this reaction can be controlled by the plasmonic properties of the nanostructures and we propose two physical mechanisms to interpret the observed plasmonic tuning of the "click" chemistry.

Plasmon-Mediated Surface Functionalization: New Horizons for the Control of Surface Chemistry on the Nanoscale

“…The temperature increase can be high enough to cross the potential energy barrier and activate surface reactions (Fig. 2f), such as thiol-ene click chemistry in the vicinity of gold nanostructures [27] .…”

“…Aside from directing the grafting of molecular entities on nanoscale regions of bare uncoated nanostructures, as described in the previous section, plasmon excitation can also be used to modify and post-functionalize the surface chemistry of molecular entities already grafted on the surface. For example, plasmonic properties were exploited to induce localized thiol-ene "click" chemistry reactions on gold nanostructures functionalized with allyl mercaptan self-assembled monolayers (SAMs) [27] . The "click" reaction was based on the addition of the thiol end groups of thiophenol to the alkene groups of SAMs.…”

Kinetics of Plasmon-Driven Hydrosilylation of Silicon Surfaces: Photogenerated Charges Drive Silicon- Carbon Bond Formation

“…10 Depending on the size and other properties of the metallic nanostructures, illumination with the resonant optical wavelength to excite LSPR modes can be used to drive surface chemical reactions. Published examples include silicon-carbon bond formation on silicon surfaces via hydrosilylation of alkenes and alkynes, [11][12][13] aryl monolayer formation on gold through organic iodide cleavage, 14 thiol-ene Click chemistry on gold surfaces , 15 several examples of localized polymerization , [16][17][18][19][20][21] and spatially selective activation of light-sensitive monolayers in close proximity to gold colloids, 22 among others. The mechanisms for the plasmon-driven surface chemistry appear to vary, and have been proposed to result from the strong and confined electromagnetic field, local generation of heat, or hot carriers, although it is very challenging to parse out the precise roles of the LSPR.…”

Protection of silver and gold LSPR biosensors in corrosive NaCl environment by short alkanethiol molecules; characterized by extinction spectrum, helium ion microscopy and SERS

“…It is rather common that one noble metal platform can be used for different plasmonic applications. 16,41,42,67,68 Adsorption processes of sulfur compounds have been observed with SERS measurements before. 69,70 It is possible to learn about cleavage of the S-H bond, crystallinity of the adsorbed layer and semiquantitative evaluation of the amount of adsorbed molecules.…”