title: Nanosized reactors based on polyethyleneimines: from microheterogeneous systems to immobilized catalysts.
abstract: Effective nanoreactors based on polyethyleneimines (PEIs) for the hydrolytic cleavage of O-alkyl O-p-nitrophenyl chloromethylphosphonates (alkyl = ethyl, hexyl) and di(p-nitrophenyl)phosphate were developed in conformity with the idea of modeling the polyfunctional catalytic mechanism of enzymes. A step-by-step modification of the single PEI solution by additives with their own catalytic activities (sodium dodecyl sulfate and lanthanum salt) gave rise to a marked improvement in the reaction efficiency. A 104-106-fold acceleration of the reaction compared to the aqueous basic hydrolysis of the substrates was achieved in the sodium dodecyl sulfate-polyethyleneimine-La(III) ternary system. This system can be considered to be metallomicelles immobilized on a hydrophilic polymer matrix. When the PEI immobilized on silica gel was used as a catalyst, the full completion of the reaction was achieved for 100 min under mild conditions, while the half-life of the reaction in a comparable homogeneous regime exceeds 100 h.
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul. Akad. Arbuzov, Kazan 420088, Russia. lucia@iopc.knc.ru
authors.forename: Lucia Ya
authors.initials: LY
authors.lastname: Zakharova
authors.forename: Alsu R
authors.initials: AR
authors.lastname: Ibragimova
authors.forename: Farida G
authors.initials: FG
authors.lastname: Valeeva
authors.forename: Andrey V
authors.initials: AV
authors.lastname: Zakharov
authors.forename: Asiya R
authors.initials: AR
authors.lastname: Mustafina
authors.forename: Lyudmila A
authors.initials: LA
authors.lastname: Kudryavtseva
authors.forename: Harlampy E
authors.initials: HE
authors.lastname: Harlampidi
authors.forename: Alexander I
authors.initials: AI
authors.lastname: Konovalov
mesh_terms: D002384:Catalysis; D004798:Enzymes / Q000737:chemistry; D006868:Hydrolysis; D007811:Lanthanum / Q000737:chemistry; D008823:Micelles; D008956:Models, Chemical; D053758:Nanoparticles; D010316:Particle Size; D011094:Polyethyleneimine / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry; D011199:Potentiometry; D012492:Salts / Q000737:chemistry; D012967:Sodium Dodecyl Sulfate / Q000737:chemistry; D013501:Surface-Active Agents / Q000737:chemistry; D013696:Temperature
chemical_list: D004798:Enzymes; D008823:Micelles; D011108:Polymers; D012492:Salts; D013501:Surface-Active Agents; D012967:Sodium Dodecyl Sulfate; D007811:Lanthanum; D011094:Polyethyleneimine