Mechanistic Investigation on Copper–Arylacetylide Polymerization and Sensing Applications

Abstract

Exploration of new polymerization reactions is very intriguing in fundamental and practical research, whichw ill advance reaction theories and produce various functional materials.H erein, we report an ew polymerization method based on the reaction of Cu I and arylacetylide,which generates linear polymers with high molecular weight and low polydispersity index of molecular weight. The Cu-arylacetylide polymerization exhibits different characteristics with traditional polymerizations such as mild reaction temperature,a ir atmosphere reaction, high molecular weight, fast polymerization rate,and imprecise molar ratio between monomers.The bond formation path and activation energy of each step was investigated by density functional theory calculations to understand the reaction mechanism. The poly(Cu-arylacetylide)s exhibit strong fluorescence emission and inherent semiconductive properties,w hich have been used to fabricate an electronic device for streptavidin sensing.

Unusual design strategy for a stable and soluble high-molecular-weight copper(i) arylacetylide polymer

“…Recently, we and Zhang et al have reported that soluble CAA polymer with biotin segment can be fabricated into thin film as protein sensor. 9 In this communication, we systematically studied the design and preparation of soluble CAA polymers. It was found that the electronic nature of substituents affects the stability of In general, the CAA compounds are prepared by yne ligands and Cu(I) salts using weak base as proton absorbent.…”

Intrinsically Electron Conductive, Antibacterial, and Anti‐swelling Hydrogels as Implantable Sensors for Bioelectronics

“…Based on the poly(Cu‐M2) structure, the structures of poly(Cu‐M1) and hydrogels have been proposed and shown in Figure 1a and Figure S10 (Supporting Information). [ 37 ]…”

“…We proposed the reaction mechanism of Cu‐arylacetylide polymerization and illuminated bond formation path and activation energy of each step. [ 37 ] The Cu‐arylacetylide polymerization can occur at room temperature and air atmosphere generating linear polymers with M n of >5.96 × 10 4 g mol −1 . Although the poly(Cu‐arylacetylide)s exhibit intriguing characteristics and some breakthroughs have been achieved, the poly(Cu‐arylacetylide)s‐based hydrogels have yet to be reported.…”

Computational mechanistic studies on persulfate assisted p‐phenylenediamine polymerization

“…Radical mediated cyclization [3 + 2] based allyl radical polymerization reaction mechanism was studied with DFT 19 . The Cu–arylacetylide polymerization reaction mechanism was investigated theoretically 20 . The phenylenediamine polymerization mechanism attracted scientists decades ago: Lakard et al investigated the p‐PDA polymerization mechanisms with voltammetry and ab initio studies.…”