Oxidation of iso‐propanol and n‐butanol by catalase encapsulated within macroporous polyampholyte cryogel matrix

Abstract

Iso‐propanol and n‐butanol were oxidized using catalase encapsulated within monolithic polyampholyte cryogel, p(APTAC‐co‐AMPS), derived from an anionic monomer, 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid sodium salt (AMPS), and a cationic monomer, (3‐acrylamidopropyl) trimethylammonium chloride (APTAC). Macroporous polyampholyte cryogels containing various amounts of catalase were synthesized in situ under cryo‐polymerization conditions at a molar ratio of monomers [APTAC]:[AMPS] = 75:25 mol.% in the presence of 10 mol.% cross‐linking agent, N,N‐methylenebisacrylamide (MBAA). The oxidation of alcohols was carried out inside of a monolithic macroporous sample by passing the mixture of alcohol and hydrogen peroxide through at a fixed flow‐rate. Analysis using gas–liquid chromatography and gas chromatography–mass spectrometry showed that iso‐propanol is converted to acetone at a yield of 87.6%, whereas n‐butanol is converted to butyraldehyde at a yield of 80% at 20°C and atmospheric pressure. The influence of pH, temperature, and ratios of substrate to hydrogen peroxide on the degree of conversion of iso‐propanol was evaluated. SEM images of cryogel‐encapsulated catalase before and after several cycles of oxidation of iso‐propanol show collapsing, among other alterations, in the morphology of the cryogel matrix. The oxidation mechanism of iso‐propanol and n‐butanol using cryogel‐encapsulated catalase was suggested.

In Situ Entrapment of Catalase within Macroporous Cryogel Matrix for Ethanol Oxidation: Flow-through Mode versus Batch Reactor

“…It was selected for oxidation of ethanol because it becomes inactivated only after the decomposition of 50 mL of H 2 O 2 . The activity of catalase immobilized within the monolithic cryogel matrix in the decomposition of hydrogen peroxide was calculated in previous work [35]. The initial activities of catalase immobilized in cryogel samples (diameter 10 mm and height 10 mm) were 89.6, 200 and 221 U•mL −1 for 1, 5 and 10 mg of the amount of immobilized catalase that correspond to an immobilization yield of 40.32%, 90.0%, and 99.45%, respectively.…”

“…The monolithic p(APTAC-co-AMPS) cryogel containing various amounts of catalase was synthesized under cryoconditions (T = −12 • C) according to the literature [35]. For this goal, an initial molar ratio of monomers [APTAC]:[AMPS] was 75:25 mol.%.…”

“…As an initiator, ammonium persulfate (APS) was used and N,N,N',N'tetramethylethylenediamine (TEMED) was employed as an accelerator (Figure 1). The present manuscript deals with the study of the biocatalyst composed of catalase immobilized within a polyampholyte cryogel in ethanol oxidation, because the previous article [35] was focused on the study of iso-propanol and n-butanol oxidation in a flowthrough catalytic reactor. The aim of this work is a comparative study of the catalytic properties of catalase immobilized within a monolithic polyampholyte cryogel in oxidation of ethanol to acetaldehyde under mild conditions (ambient temperature, atmospheric pressure) using the flow-through and batch catalytic reactors.…”

“…The present work was inspired by our previous research reports on the aerobic oxidation of alcohols mediated by a biocatalyst composed of catalase immobilized within the polyampholyte cryogel p(APTAC-co-AMPS) [35]. The one-stage immobilization of metal nanoparticles into a matrix of amphoteric cryogels was developed by our research group [36][37][38] and furthermore, was successfully used for the selective hydrogenation of various substrates in a flow-through reactor.…”

Synthesis and Characterization of a New Cryogel Matrix for Covalent Immobilization of Catalase

“…Catalase is a well-known enzyme that catalyzes the breakdown reaction of hydrogen peroxide or, in other words, a protein molecule which breaks down 5 × 10 6 hydrogen peroxide molecules per minute [ 15 ]. There are also many industrial applications where catalase is used, for example, in the removal of hydrogen peroxide from dairy processing or bleaching in the textile industry for dyeing [ 16 , 17 , 18 ].…”