Succinimidyl Carbonate-Based Amine-Reactive Polymer Brushes: Facile Fabrication of Functional Interfaces

Abstract

Polymeric coatings that can undergo effective functionalization with ligands and (bio)­molecules necessary for intended applications are widely employed to engineer functional interfaces. Herein, amine-reactive polymer brushes are fabricated using a succinimidyl group-activated carbonate monomer, and their facile post-polymerization functionalization is demonstrated through ligand-mediated protein immobilization and detection. Copolymer brushes containing varying amounts of the reactive monomer and an ethylene glycol-based methacrylate comonomer were obtained using surface-mediated reversible addition fragmentation chain transfer polymerization. Post-polymerization functionalization of the thus-obtained copolymer brushes with a fluorine-containing amine, namely, 4-(trifluoromethyl)­benzylamine, demonstrated highly efficient functionalization at ambient temperature. To demonstrate possible applications, polymer brushes functionalized with a bioactive ligand, namely, biotin, were used to detect the target protein, streptavidin. The biotin–streptavidin interaction on brushes could also be employed to conjugate protein-coated quantum dots. Importantly, comparison of the attachment of 4-(trifluoromethyl)­benzylamine on activated carbonate group-containing brushes with reaction of the same molecule on traditional active ester-based brushes demonstrated higher extent of conjugation to carbonate brushes. Finally, orthogonal functionalization of the copolymer brushes with an amino-functionalized molecule and a maleimide-containing fluorescent dye in spatial control using microcontact printing was demonstrated. One can envision that the facile fabrication and efficient functionalization of succinimidyl carbonate-based amine-reactive brushes afford an attractive platform for applications using functional interfaces for diagnostic purposes.

Removal of uranium from wastewater through Ni–Al-layered double hydroxide@carbon nanotubes functionalized by polyethyleneimine

“…Adsorption has become one of the most commonly used methods [9][10][11][12] for removing uranyl ions from water, and efficient and fast adsorbents must be urgently obtained. [13][14][15] Metal organic frameworks (MOFs), 1,16 magnetic materials, 17,18 silica, 19 polyacrylonitriles, 20,21 hemp fiber, 14,15,22,23 and carbon materials [24][25][26][27] have been used in uranium adsorption.…”

“Clickable” Polymer Brush Interfaces: Tailoring Monovalent to Multivalent Ligand Display for Protein Immobilization and Sensing

“…Commonly used transformations include the Huisgen-type copper-catalyzed [3 + 2] azide–alkyne cycloaddition − and metal-free “click” reactions such as thiol–ene, thiol–yne, , thiol–maleimide, , and Diels–Alder cycloaddition . In particular, methods such as nitroxide-mediated polymerization (NMP), − atom-transfer radical polymerization (ATRP), − and reversible addition–fragmentation chain transfer (RAFT) polymerization − have been widely used for obtaining polymer brushes. There is an increasing interest in employing RAFT polymerization to fabricate polymeric brushes due to its metal-catalyst free nature, high compatibility with various functional groups, and efficient polymerization at moderate temperatures with a high level of oxygen tolerance.…”

Carbonate-based hyper-cross-linked polymers with pendant versatile electron-withdrawing functional groups for CO2adsorption and separation

“…31 It is worth noting that among these functionalities, the carbonyl group, as one of the Lewis basic sites present in polymers, can specically interact with CO 2 molecules, resulting in the swelling of the polymers, which is greatly benecial for increasing the overall degree of polymer swelling, CO 2 solubility in the polymer, and total CO 2 uptake performance of the polymers under adsorption pressure conditions. 43,44 Carbonates, as an intriguing class of small-molecule organic compounds in which the hydrogen atoms of two hydroxyl groups of carbonic acid molecules are partially or completely replaced by alkyl groups, 45 have been commonly employed as important industrial raw materials for the preparation of various polycarbonates with good solvent resistance, molding processability, and mechanical properties, which are widely applied in medical equipment, building material, automotive, aerospace, packaging, electronics, optical lens, and optical disc manufacturing industries. 46 Due to their reputation for being rich in carbonyl groups, carbonates, especially uorenylcontaining ones, are considered a new and big family of appropriate building blocks for fabricating functional HCPs with improved CO 2 uptake capacity and selective separation by strengthening the intermolecular interactions between the carbonyl groups in the polymer chains and CO 2 molecules.…”