Sitting Phases of Polymerizable Amphiphiles for Controlled Functionalization of Layered Materials

Abstract

Precisely tailoring surface chemistry of layered materials is a growing need for fields ranging from electronics to biology. For many applications, the need for noncovalently adsorbed ligands to simultaneously control interactions with a nonpolar substrate and a polar solvent is a particular challenge. However, biology routinely addresses a similar challenge in the context of the lipid bilayer. While conventional standing phases of phospholipids (such as those found in a bilayer) would not provide spatially ordered interactions with the substrate, here we demonstrate formation of a sitting phase of polymerizable phospholipids, in which the two alkyl chains extend along the surface and the two ionizable functionalities (a phosphate and an amine) sit adjacent to the substrate and project into the solvent, respectively. Interfacial ordering and polymerization are assessed by high-resolution scanning probe measurements. Water contact angle titrations demonstrate interfacial pKa shifts for the lipid phosphate but not for the amine, supporting localization of the phosphate near the nonpolar graphite surface.

Graphite and Graphene Fairy Circles: A Bottom-Up Approach for the Formation of Nanocorrals

“…Upon applying UV light to PCDA filled corrals, a topochemical polymerization reaction is induced. 57,58 The resulting polydiacetylene chains are readily distinguished in the STM images as very bright lines (Figure 9).…”

Highly Sensitive Polydiacetylene Ensembles for Biosensing and Bioimaging

“…In recent years, the preparation methods for PDA have been greatly advanced. PDA structures have been enriched from traditional films, micelles and vesicles to 3D-PDA structures, porous structures, hydrogels, macrocyclic structures, and single-layer nanosheets (Bang et al, 2016;Chae et al, 2016;Krishnan et al, 2016;Okaniwa et al, 2016;Jordan et al, 2017;Li et al, 2017a;Romera et al, 2017;Jeong et al, 2018;Takeuchi et al, 2018;Terada et al, 2018;Heo et al, 2019;Hu et al, 2019;Seo et al, 2019;Shin et al, 2020). Great progresses have also been made in the preparation of reversible and chiral PDA (Chen et al, 2016;He et al, 2020).…”

Self‐Assembly Behavior of Diacetylenic Acid Molecules upon Vapor Deposition: Odd–Even Effect on the Film Morphology

“…[1][2][3] As pecific packing distance and relative tilt angle between the neighboring diacetylene units are necessary for this 1,4-additionr eaction to proceed upon UV irradiation or heat treatment. [4][5][6] Owing to their unique electronic and opticalp roperties, the resultant polydiacetylenes have been much explored for their applicationsi nawide range of areas. [7][8][9][10][11][12] One potentiala pplication is in the area of organic electronics, wheret he conjugated polydiacetylene chainsa re used as semiconducting channel materials, [13,14] as the intra-chainc harge conduction is expected to be more facile than the charge-hopping process commonly involved in organic semiconductors.…”

“…It has long been known that certain types of diacetylenic molecules in their crystalline state can undergo “topochemical polymerization” reactions, from which a conjugated poly(ene‐yne) chain system is produced with little perturbation of the original crystal packing arrangement in the system [1–3] . A specific packing distance and relative tilt angle between the neighboring diacetylene units are necessary for this 1,4‐addition reaction to proceed upon UV irradiation or heat treatment [4–6] . Owing to their unique electronic and optical properties, the resultant polydiacetylenes have been much explored for their applications in a wide range of areas [7–12] .…”