Organic Electrochemistry and a Role Reversal: Using Synthesis To Optimize Electrochemical Methods

Abstract

Diblock copolymers are excellent coatings for microelectrode arrays because they provide a stable surface that can support both synthetic and analytical electrochemistry. However, the surfaces that are optimal for synthetic studies are not the same as the surfaces that are optimal for analytical studies. Hence, no one surface provides an ideal platform for both building and analyzing a molecular library. Fortunately, the synthetic chemistry available on a microelectrode array allows a surface that is ideal for synthesis can be converted into one that is ideal for signaling studies; a scenario that allows for the use of an optimized synthetic and analytical surface on a single microelectrode array.

Rapidly sequence-controlled electrosynthesis of organometallic polymers

“…Though the liquid-phase and solid-phase synthesis can theoretically be extended to many kinds of monomers, this approach remains extremely difficult in making complex molecular architectures and tuning functional versatility, and precludes itself for synthesis and applications of materials. Making the connection in opposite direction between organic synthesis and electrochemistry has been realized to hold significant potential in both areas 18 . For example, the oxidative and reductive reactions in general organic synthesis are incompatible in identical solution, but electrochemical stimuli can enable switchable oxidative and reductive reactions to take place at the interface of identical electrode.…”

Electroorganic Synthesis and the Construction of Addressable Molecular Surfaces

“…Since arylborate esters can be made from arylbromides, it appeared possible to utilize the arylbromide based surface for the synthesis of the addressable surface and then convert it into the arylborate ester surface for the subsequent signaling experiments. Such an approach would satisfy the standards for synthetic stability and analytical capabilities required for construction of the addressable surface by taking advantage of both of the “ideal” polymer reaction layers on the same array . With this in mind, a 12 K‐array coated with the bromide ester based polymer was treated with a solution containing a diborate ester substrate, triphenylphosphine ligand, tetrabutylammonium bromide as an electrolyte, and either a Pd(II) or Cu(II) precatalyst for the desired reaction.…”

“…The change to the borate ester surface also dramatically improved the performance of the arrays in analytical experiments. [23,24] Shown in Figure 5 are two CV waves measured for a ferrocyanide/ferricyanide redox mediator on an array using either the bromide surface or the borate ester surface. The medium for the study was water in a manner consistent with the use of an array for studying small molecule protein interactions.…”

“…Such an approach would satisfy the standards for synthetic stability and analytical capabilities required for construction of the addressable surface by taking advantage of both of the "ideal" polymer reaction layers on the same array. [24] With this in mind, a 12 K-array coated with the bromide ester based polymer was treated with a solution containing a diborate ester substrate, triphenylphosphine ligand, tetrabutylammonium bromide as an electrolyte, and either a Pd(II) or Cu(II) precatalyst for the desired reaction. For the reaction with Pd(0), the solution also included allylacetate as a confining agent to scavenge any Pd(0) that escaped from the electrode selected for the reduction reaction and potassium acetate to neutralize any acid generated at the anode.…”

“…The change to the borate ester surface also dramatically improved the performance of the arrays in analytical experiments . Shown in Figure are two CV waves measured for a ferrocyanide/ferricyanide redox mediator on an array using either the bromide surface or the borate ester surface.…”