Supramolecular Polymer/Surfactant Complexes as Catalysts for Phosphate Transfer Reactions

Abstract

Designing artificial enzymes with tailored molecular interactions between the substrate and active site is of major intellectual and practical significance. We report the improved catalytic efficiency of a supramolecular polymer/surfactant complex comprised of PAIM − , a poly(acrylic acid) derivative with imidazole groups attached to the polymer by amide bonds, and the cationic surfactant cetyltrimethylammonium bromide (CTAB). Supramolecular complex formation, at concentrations below the respective CMC values, provides convenient hydrophobic pockets for the reactants close to the multiple catalytic centers, where imidazole and carboxylate groups act as nucleophiles for the degradation of a model phosphate triester, delivering the highly efficient performance of the supramolecular catalysts. Catalytic effects are on the order of thousands for nucleophilic catalysis and are higher by 2 orders of magnitude for the supramolecular polymer/surfactant complex at pH 9. The reported supramolecular catalytic complexes allow important changes in polarity and, given the presence of functional groups common to a variety of hydrolytic enzymes, could be of general applicability in such reactions.

Phosphotungstate-Functionalized Mesoporous Janus Silica Nanosheets for Reaction-Controlled Pickering Interfacial Catalysis

“…1−4 However, they often suffer from low catalytic efficiency because of the huge mass transfer resistance at a limited oil/ water interfacial area. 5,6 Pickering interfacial catalysis (PIC) has recently aroused increasing interest for the oil/water biphasic catalysis. In these systems, the solid nanoparticle (NP) acts both as an emulsifier and a interfacial catalyst at the oil/water interface, which provides a large reaction interfacial area for mass transport, hence enhancing catalytic efficiency.…”

Cu(II)‐catalyzed hydrolysis of tris‐2‐pyridyl phosphate assisted by sodium dodecyl sulfate micelles

“…The results show a very special micellar effect, which combines the exploitation of some of the primary driving forces important for the efficiency of enzyme catalysis, such as approximation of the reactants by hydrophobic and electrostatic components, as well as by acid‐base complexation. The results can aid the planning of novel biomimetic systems with enhanced catalytic activity for the targeted detoxification of phosphotriesters …”

Simple and highly active strontium-based catalyst for detoxification of an organophosphorus chemical warfare agent simulant

“…Sarin itself is categorized as an organophosphorus (OP) chemical warfare agent, a class of compounds that attacks the nervous system through the inhibition of acetylcholinesterase, a process that can be irreversible and lead to death depending on the degree of intoxication and the time taken to administer an antidote (Delfino et al 2009;Mercey et al 2012;Chen et al 2018;Costanzi et al 2018). In this context, several research groups worldwide have directed efforts toward the investigation of homogeneous and heterogeneous catalytic systems for the destruction of organophosphorus biocides and related compounds (Pavez et al 2016;Trotochaud et al 2017;Balow et al 2017Balow et al , 2018Gerola et al 2017;Fonsaca et al 2017;Amaya Vargas et al 2018;Wanderlind et al 2014Wanderlind et al , 2018Wanderlind et al , 2019Ryu et al 2019;Santos et al 2016), looking for safe and low-cost systems able to detoxify these compounds through highly efficient processes.…”