Two-dimensional polymers with versatile functionalities via gemini monomers

Abstract

Two-dimensional synthetic polymers (2DSPs) are sheet-like macromolecules consisting of covalently linked repeat units in two directions. Access to 2DSPs with controlled size and shape and diverse functionality has been limited because of the need for monomers to retain their crystallinity throughout polymerization. Here, we describe a synthetic strategy for 2DSPs that obviates the need for crystallinity, via the free radical copolymerization of amphiphilic gemini monomers and their monomeric derivatives arranged in a bilayer at solid-liquid interfaces. The ease of this strategy allowed the preparation of 2DSPs with well-controlled size and shape and diverse functionality on solid templates composed of various materials with wide-ranging surface curvatures and dimensions. The resulting 2DSPs showed remarkable mechanical strength and have multiple applications, such as nanolithographic resist and antibacterial agent. The broad scope of this approach markedly expands the chemistry, morphology, and functionality of 2DSPs accessible for practical applications.

Online determination of mercury isotopic compositions at ultratrace levels by automated purge and trap coupled with multicollector inductively coupled plasma-mass spectrometry

“…The coal standards (NIST 1632e) were pretreated by the double-stage thermal combustion-trapping method, 43 and Hg was finally oxidized to Hg( ii ) in a solution of a 40% (v/v) mixture of HNO 3 and HCl (2 : 1, v/v). Biota standards (NRC DORM-4) were treated with microwave digestion in a mixture of HNO 3 and H 2 O 2 .…”

Polymerization-Induced Reassembly of Gemini Molecules toward Generating Porous Two-Dimensional Polymers

“…Very recently, our group reported a freestanding film of 2DPs via the in situ free-radical polymerization of the 2D assemblies of an amphiphilic Gemini monomer and its derivatives to expand this method. 20 In this system, our dissipative particle dynamics (DPD) simulations and rotating-frame Overhauser effect spectroscopy (ROESY) studies unveiled a polymerization-induced self-assembly effect (PISA) that contributes to the improved regularity of 2DPs. This PISA effect was also recognized as an entropy-directed interfacial self-assembly, which has been intensely investigated in the field of nanoparticle interfacial organization.…”

“…Inspired by the pioneering works of spatially confined linear polymerizations, the in situ polymerization of preorganized amphipathic monomers (e.g., phosphocholine monomers) has proven to be another efficient strategy for preparing 2DPs on various solid–liquid interfaces. − However, these reported strategies can not easily produce freestanding monolayers of 2DPs, posing a limitation to the further exploration of reliable functions for this new class of 2D organic materials. Very recently, our group reported a freestanding film of 2DPs via the in situ free-radical polymerization of the 2D assemblies of an amphiphilic Gemini monomer and its derivatives to expand this method . In this system, our dissipative particle dynamics (DPD) simulations and rotating-frame Overhauser effect spectroscopy (ROESY) studies unveiled a polymerization-induced self-assembly effect (PISA) that contributes to the improved regularity of 2DPs.…”

“…Overview of the Formation Process of Porous 2D Polymer Membranes (P-2DPs) . Our previous experimental and computational research had shown that highly cross-linked nonporous 2D polymer membranes (NP-2DPs) could be produced by the polymerization-induced self-assembly of Gemini MA-11-2-11-MA monomers ( P -5-0-5- P , Figure a). The high consistency between the experimental and computational results inspired us to explore the possibility of and new design principles for the generation of porous 2DPs (P-2DPs) via systematic computational research.…”

Nanoconfinement Approaches to Two-Dimensional Polymeric Materials

“…To improve mechanical stability, Liu et al recently synthesized a highly cross-linked membrane from a gemini monomer and monomeric derivatives (Figure b) . The bilayer membrane was prepared on a supportive solid substrate, and the methacrylate group condensed in the middle of the bilayer exhibited a high conversion ratio of up to 99%.…”