Nanosized reactors based on polyethyleneimines: from microheterogeneous systems to immobilized catalysts.
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.
Zakharova
Lucia Ya
LY
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
Ibragimova
Alsu R
AR
Valeeva
Farida G
FG
Zakharov
Andrey V
AV
Mustafina
Asiya R
AR
Kudryavtseva
Lyudmila A
LA
Harlampidi
Harlampy E
HE
Konovalov
Alexander I
AI
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
D004798:Enzymes; D008823:Micelles; D011108:Polymers; D012492:Salts; D013501:Surface-Active Agents; D012967:Sodium Dodecyl Sulfate; D007811:Lanthanum; D011094:Polyethyleneimine