The influence of anionic vesicles on the oligomerization of p-aminodiphenylamine catalyzed by horseradish peroxidase and hydrogen peroxide

Luginbühl, Sandra; Milojević-Rakić, Maja; Junker, Katja; Bajuk–Bogdanović, Danica; Pašti, Igor A.; Kissner, Reinhard; Ćirić‐Marjanović, Gordana; Walde, Peter

doi:10.1016/j.synthmet.2017.01.011

Cited by 22 publications

(116 citation statements)

References 47 publications

(156 reference statements)

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“…Fifthly, the template may act as counterion (dopant) for PANI‐ES type molecules (A − in Fig. ), and may force these molecules to adopt optimal average chain conformations . In the work we present now, we show that the templates may even play an additional role .…”

Section: Introductionmentioning

confidence: 68%

“…. In at least two examples, the template‐assisted enzymatic formation of a PANI‐ES type product from 2 was proven undoubtedly . This product was obtained in suspensions of 80 – 100 nm‐sized AOT vesicles with either Trametes versicolor laccase (TvL) and dissolved dioxygen (O 2 ) from air at pH = 3.5, or with horseradish peroxidase isoenzyme C (HRPC) and added hydrogen peroxide (H 2 O 2 ) at pH = 4.3 .…”

Section: Introductionmentioning

confidence: 99%

“…In at least two examples, the template‐assisted enzymatic formation of a PANI‐ES type product from 2 was proven undoubtedly . This product was obtained in suspensions of 80 – 100 nm‐sized AOT vesicles with either Trametes versicolor laccase (TvL) and dissolved dioxygen (O 2 ) from air at pH = 3.5, or with horseradish peroxidase isoenzyme C (HRPC) and added hydrogen peroxide (H 2 O 2 ) at pH = 4.3 . In the case of the laccase system, the PANI‐ES type product was found to be the linear N‐C‐ para coupled PADPA dimer as emeraldine salt (in about 50% yield), i.e., the protonated half‐oxidized and half‐reduced linear tetraaniline, which is the shortest possible PANI‐ES type molecule.…”

Section: Introductionmentioning

confidence: 99%

“…Other products were formed in lower abundance, e.g., phenazine containing oligomers . In the case of the HRPC/H 2 O 2 /AOT vesicle system, the PADPA dimer was also obtained as emeraldine salt, but in much lower yield than in the case of the laccase . Although the template‐assisted enzymatic oxidation and oligo‐ or polymerization reactions mentioned above are complex and the products – probably always – are mixtures of different compounds, it became clear from many studies that the templates may play not only one particular role for ‘guiding’ the reactions, but several roles simultaneously as summarized in Fig.…”

Section: Introductionmentioning

confidence: 99%

“…Well‐studied activators of cyt c are suspensions of cardiolipin‐containing lipid vesicles . We questioned whether through the interaction of cyt c with anionic AOT vesicles, this heme protein is activated as well and therefore can be used as alternative biocatalyst for the oxidation and oligomerization of PADPA with H 2 O 2 , in a similar way as in the case of HRPC/H 2 O 2 . Since this was indeed found to be the case, an additional role of AOT vesicles as templates could be demonstrated, namely the role as activator of the enzyme (cyt c ), see Fig.…”

Section: Introductionmentioning

confidence: 99%

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A Novel Role of Vesicles as Templates for the Oxidation and Oligomerization of p‐Aminodiphenylamine by Cytochrome c

Luginbühl

Iwasaki

Varkey

et al. 2017

Helvetica Chimica Acta

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The oxidation and subsequent oligo‐ or polymerization of aniline or the N‐C‐para coupled aniline dimer p‐aminodiphenylamine (N‐phenyl‐1,4‐phenylenediamine) with H2O2‐dependent heme peroxidases in aqueous medium at pH = 4.3 is strongly influenced in a positive way by the presence of anionic polymers, micelles or vesicles as soft ‘templates’ (macromolecular or polymolecular additives), to yield products which resemble the emeraldine salt form of polyaniline (PANI‐ES). The positive effect the templates exert on the reaction mainly originates from interactions between the templates and the monomers, reaction intermediates and products, whereby the reaction occurs localized in the vicinity of the templates, suppressing undesired side reactions. As shown in the present work, the templates may even play an additional role, depending on the type of catalyst. Through interactions between the heme protein cytochrome c and anionic vesicles, cytochrome c gains increased peroxidase activity. In this way, the templates not only serve for hosting the oxidation and oligo‐ or polymerization reactions for obtaining PANI‐ES type products, but also simultaneously activate the catalyst in order to trigger the reaction.

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Section: Introductionmentioning

confidence: 68%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A Novel Role of Vesicles as Templates for the Oxidation and Oligomerization of p‐Aminodiphenylamine by Cytochrome c

Luginbühl

Iwasaki

Varkey

et al. 2017

Helvetica Chimica Acta

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Pluronic‐Conjugated Enzyme Cascade for In Situ Oxidation in Biphasic Media

Wang

et al. 2018

ChemCatChem

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AP luronic-conjugated enzymec ascade was synthesized for catalyzing oxidation reactionsu sing hydrogen peroxide (H 2 O 2 ) as the oxidant. The synthesis started with encapsulating enzymes in the micelles of aldehyde-functionalized Pluronic (PL) containing bovine serum albumin (BSA). Schiff-base bonds formed betweent he amine groups of proteins and the aldehyde groups of the PL, which werer educed to am ore stable form, resulting in enzyme-PLc onjugates. The effects of operation parameters on the conjugatey ield were examined using glucoseo xidase( GOx) and horseradish peroxidase (HRP) as examples. The co-localization of GOx and HRP was confirmed by Fçrster resonance energy transfer (FRET), from which the average distance between GOx and HRPw as interpreted as 6.1 nm. The proximity effect was confirmed by adding ah igh concentration of catalase (CAT) to as olution of GOx-HRP-PL to catalyze the oxidation of ABTS. The GOx-HRP-PL conjugate was readily solubilized in organic solvents such as dimethyl sulfoxide, methanolo rc hloroform. Phenol oxidation with GOx-HRP-PL in dimethyl sulfoxide/water biphasic media was conducted using glucose as the substrate to generate H 2 O 2 in situ. The multiple enzyme conjugate provided a1 .3-fold higherr emoval rate compared to their native counterparts in free form. The GOx-HRP-PL conjugate could be readily recovered by centrifugation at 4 8Ca nd 90 %o ft he initial activity remained after 10 cycles.Chemical engineering practicei soften concernedw iths afe and high-efficient ways to conducto xidationr eactions. One prominente xample is the oxidation by hydrogen peroxide, a powerful and environmentally friendly oxidantr esponsible for the industrial production of variousc hemicals such as propylene oxide, [1] epoxy oleic acid, [2] cyclopentanone, [3] polystyrene, [4] and 2-methylcyclohexanone. [5] Because of its high activity and intrinsic instability,t he storageo fH 2 O 2 is inconvenient in engineering practices.T oc ompensatef or its decomposition, an overloading of H 2 O 2 is often appliedt ot he feedstock, which reduces the processing economics. [6] It would be of great interest to develop novel reactions ystemsc apable of in situ generation of H 2 O 2 for concomitant oxidations. Considering the highe fficiency and mildness of enzymatic catalysis, we intend to develope nzymatic oxidation systems which are able to simultaneously generate and utilize H 2 O 2 as an oxidant.Horseradish peroxidase (HRP) is an enzyme utilizing H 2 O 2 for variouso xidation processes. [7] For example, HRP is used in the treatment of wastewater containing phenolic compounds. [8] The contaminants are oxidized into phenoxy radicals by H 2 O 2 , [9] followed by polymerization to form insoluble compounds.D eactivation of HRP by H 2 O 2 is observed in the oxidation processes. [9a, 10] An enzymatic system is much desirable that is capable of in situ generating H 2 O 2 for concomitant oxidation catalyzed by HRP.A mong variousm ethods of in situ H 2 O 2 generation, [11] glucose oxidase( GOx) is attractiv...

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Application of an enzymatic cascade reaction for the synthesis of the emeraldine salt form of polyaniline

et al. 2021

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The synthesis of the emeraldine salt form of polyaniline (PANI-ES) from aniline with Aspergillus sp. glucose oxidase (GOD), d-glucose, dissolved O2, and horseradish peroxidase isoenzyme C (HRPC) in the presence of large unilamellar vesicles of AOT (sodium bis-(2-ethylhexyl)sulfosuccinate) as templates at pH = 4.3 and T ~ 25 °C was investigated in a systematic way. In this cascade reaction mixture, the oxidation of aniline is catalyzed by HRPC with H2O2 that is formed in situ as byproduct of the GOD-catalyzed oxidation of d-glucose with O2. Under the elaborated experimental conditions which we considered ideal, the formation of PANI-ES products is evident, as judged by UV/Vis/NIR and EPR measurements. Comparison was made with a reference reaction, which was run under similar conditions with added H2O2 instead of GOD and d-glucose. Although the reference reaction was found to be superior, with the cascade reaction, PANI-ES products can still be obtained with high aniline conversion (> 90%) within 24 h as stable dark green PANI-ES/AOT vesicle dispersion. Our results show that the in situ formation of H2O2 does not prevent the inactivation of HRPC known to occur in the reference reaction. Moreover, the GOD used in the cascade reaction is inactivated as well by polymerization intermediates.

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The influence of anionic vesicles on the oligomerization of p-aminodiphenylamine catalyzed by horseradish peroxidase and hydrogen peroxide

Cited by 22 publications

References 47 publications

A Novel Role of Vesicles as Templates for the Oxidation and Oligomerization of p‐Aminodiphenylamine by Cytochrome c

A Novel Role of Vesicles as Templates for the Oxidation and Oligomerization of p‐Aminodiphenylamine by Cytochrome c

Pluronic‐Conjugated Enzyme Cascade for In Situ Oxidation in Biphasic Media

Application of an enzymatic cascade reaction for the synthesis of the emeraldine salt form of polyaniline

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