Biocatalytic metal nanopatterning through enzyme-modified microelectrodes
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ORIGINAL PAPER
Biocatalytic metal nanopatterning through enzyme-modified microelectrodes Esteban Malel 1 & Daniel Mandler 1 Received: 29 March 2020 / Revised: 15 June 2020 / Accepted: 16 June 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract The formation of narrow-size distribution nanomaterials on surfaces in defined patterns is a research area of great interest due to its relevance in many applications such as catalysis, optoelectronics, and sensing devices. Patterning surface with nanostructures has been achieved by numerous techniques including electron-beam lithography, microcontact printing, constructive lithography, and different scanning probe microscopy techniques. Here, we present a different approach by which gold patterns are formed by an enzyme-catalyzed reaction followed by a surface-catalyzed process. Our study takes the advantage of scanning electrochemical microscopy (SECM) where the tip is modified with an enzyme and generates a reductant. The latter participates in an electroless deposition reaction, where AuCl4− is reduced catalyzed by a Pd surface. The result is local deposition of gold patterns made of nanoparticles as soon as the reductant generated by the tip, i.e., hydroquinone, approaches the Pd surface. Two enzymes were used: glucose oxidase (GOx) and alkaline phosphatase (ALP). The entire process was carefully studied and optimized, which enabled a good control of the patterns formed. Keywords Glucose oxidase . Alkaline phosphatase . Gold nanoparticles . Biocatalyzed deposition . Scanning electrochemical microscopy
Introduction During the last years, the synthesis of narrow-size distribution nanomaterials in defined patterns is a research area of great interest due to its relevance in many applications such as catalysis, optoelectronics, and sensing devices [1–7]. Patterning nanostructures has been demonstrated by a large number of techniques including electron-beam lithography [8], microcontact printing [9], constructive lithography [10], and different scanning probe–based techniques [11–14]. All these techniques have their advantages and disadvantages. For example, microcontact printing allows patterning on almost every surface, but with low nanometric resolution; electronbeam lithography has a higher nanometric resolution; however, molecular patterning with organic molecules is limited. Sagiv and coworkers [13, 15–17] used AFM microscopy to produce metallic patterns by constructive nanolithography. * Daniel Mandler [email protected] 1
Institute of Chemistry, The Hebrew University of Jerusalem, 9190401 Jerusalem, Israel
This technique uses a conductive AFM tip to form patterns on self-assembled monolayers (SAM), by oxidation of the end group of the carboxylic chain. Then, the modified molecule acts as an anchor for further modifications and metal patterning using metallic salts. In a more recent work, Zeira et al. [10] used a new approach for constructive nanolithography called contact electrochemical transfer (CET). In this technique, a meta
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