Polydopamine Meets Solid-State Nanopores: A Bioinspired Integrative Surface Chemistry Approach To Tailor the Functional Properties of Nanofluidic Diodes

Abstract

The ability to modulate the surface chemical characteristics of solid-state nanopores is of great interest as it provides the means to control the macroscopic response of nanofluidic devices. For instance, controlling surface charge and polarity of the pore walls is one of the most important applications of surface modification that is very relevant to attain accurate control over the transport of ions through the nanofluidic architecture. In this work, we describe a new integrative chemical approach to fabricate nanofluidic diodes based on the self-polymerization of dopamine (PDOPA) on asymmetric track-etched nanopores. Our results demonstrate that PDOPA coating is not only a simple and effective method to modify the inner surface of polymer nanopores fully compatible with the fabrication of nanofluidic devices but also a versatile platform for further integration of more complex molecules through different covalent chemistries and self-assembly processes. We adjusted the chemical modification strategy to obtain various configurations of the pore surface: (i) PDOPA layer was used as primer, precursor, or even responsive functional coating; (ii) PDOPA layer was used as a platform for anchoring chemical functions via the Michael addition reaction; and (iii) PDOPA was used as a reactive layer inducing the metallization of the pore walls through the in situ reduction of metallic precursors present in solution. We believe that the transversal concept of integrative surface chemistry offered by polydopamine in combination with the remarkable physical characteristics of asymmetric nanopores constitutes a new framework to design multifunctional nanofluidic devices employing soft chemistry-based nanofunctionalization techniques.

Phosphate‐Responsive Biomimetic Nanofluidic Diodes Regulated by Polyamine–Phosphate Interactions: Insights into Their Functional Behavior from Theory and Experiment

“…Chemical Etching : Polyethylene terephthalate (PET) foils irradiated with one single heavy ion were chemically etched creating a “bullet‐like” shaped open channel. Details of the surfactant‐assisted etching process performed in a two‐chamber electrolytic cell are explained elsewhere . Before the etching process, the ion‐track containing foils were exposed on one side to UV light for 6 h only on the side exposed to the etchant without surfactant.…”

Graphene-based microfluidics for serial crystallography

“…Following assembly of the COC fluidic layer to the adhesive bottom layer containing a PMMA/graphene film, both the top and bottom halves of the device were coated with poly(dopamine) (PDA) to create a hydrophilic surface and facilitate channel wetting. 105,106 …”

“…A 2 mg/mL solution of dopamine hydrochloride (Sigma) in 10 mM Tris buffer pH 8.5 105,106 (Fisher, Molecular Biology grade) was freshly prepared and then carefully dropped onto the PMMA/graphene films to cover the entire channel surface (Figure 2 and † ESI Figures S8, S9). The surfaces were allowed to incubate for at least 5 hours at room temperature (23°C) in a sealed Petri dish.…”

Bioinspired integrated nanosystems based on solid-state nanopores: “iontronic” transduction of biological, chemical and physical stimuli

“…80–82 If we consider that the degree of rectification is highly dependent on the surface charge density, the use of a responsive polymer layer can provide a simple means to sensitively increase the number of fixed charges on the nanopore walls.…”