Structural localisation of catalytic H2O2 oxidation sites in starch

Onno Broekman; Ciaran W. Lahive; Warner Piersma; Johanna Thomann; André Heeres; Thomas Wielema; Madeleine J. Bussemaker; Jelle Brinksma; Peter Deuss

doi:10.1016/j.carbpol.2025.123528

Structural localisation of catalytic H2O2 oxidation sites in starch

Onno Broekman (First author), Ciaran W. Lahive, Warner Piersma, Johanna Thomann, André Heeres, Thomas Wielema, Madeleine J. Bussemaker, Jelle Brinksma, Peter Deuss

Biobased Chemistry & Refinery

Research output: Contribution to journal › Article › Academic › peer-review

3 Downloads (Pure)

Abstract

The catalytic oxidation of potato starch by [MnIV2 (μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn =1,4,7-trimethyl-1,4,7-triazacyclononane) with H2O2, was recently introduced as a promising alternative to ubiquitous sodium hypochlorite (NaOCl). Here, we report an in-depth investigation into interactions of the catalyst with the starch granule. Pitted starches obtained by pre-treatment with high-frequency ultrasound (HFUS) were shown to result in a uniquely homogeneous oxidation. To study this further, fractionation of oxidised potato starch was done which showed a preference for the oxidation of smaller granules with a higher
relative surface area. This result was corroborated by chemical surface gelatinisation of fractionated granules.
These studies showed that the inside of the granules was oxidised, but that Mncat had a moderate preference for oxidation of the periphery. Together, these results allow for a better understanding of oxidation of starch by Mncat and how it differs from NaOCl oxidation making further optimisation of the process possible.

Original language	English
Article number	123528
Journal	Carbohydrate Polymers
Volume	358
DOIs	https://doi.org/10.1016/j.carbpol.2025.123528
Publication status	Published - 15 Jun 2025

Keywords

chemical surface gelatinisation
high-frequency ultrasound
homogeneous catalysis
hydrogen peroxide
mechanical pre-treatmen
starch oxidation

Access to Document

10.1016/j.carbpol.2025.123528Licence: CC BY

1-s2.0-S0144861725003091-mainFinal published version, 5.29 MBLicence: CC BY

Cite this

@article{0cea067282bd415bb780dcbb0173de02,

title = "Structural localisation of catalytic H2O2 oxidation sites in starch",

abstract = "The catalytic oxidation of potato starch by [MnIV2 (μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn =1,4,7-trimethyl-1,4,7-triazacyclononane) with H2O2, was recently introduced as a promising alternative to ubiquitous sodium hypochlorite (NaOCl). Here, we report an in-depth investigation into interactions of the catalyst with the starch granule. Pitted starches obtained by pre-treatment with high-frequency ultrasound (HFUS) were shown to result in a uniquely homogeneous oxidation. To study this further, fractionation of oxidised potato starch was done which showed a preference for the oxidation of smaller granules with a higher relative surface area. This result was corroborated by chemical surface gelatinisation of fractionated granules. These studies showed that the inside of the granules was oxidised, but that Mncat had a moderate preference for oxidation of the periphery. Together, these results allow for a better understanding of oxidation of starch by Mncat and how it differs from NaOCl oxidation making further optimisation of the process possible.",

keywords = "chemical surface gelatinisation, high-frequency ultrasound, homogeneous catalysis, hydrogen peroxide, mechanical pre-treatmen, starch oxidation, chemische oppervlakte verdikking, hoge frequentie echografie, homegene katalyse, waterstof peroxide, mechanische voorbehandeling, oxidatie van zetmeel",

author = "Onno Broekman and Lahive, {Ciaran W.} and Warner Piersma and Johanna Thomann and Andr{\'e} Heeres and Thomas Wielema and Bussemaker, {Madeleine J.} and Jelle Brinksma and Peter Deuss",

year = "2025",

month = jun,

day = "15",

doi = "10.1016/j.carbpol.2025.123528",

language = "English",

volume = "358",

journal = "Carbohydrate Polymers",

issn = "0144-8617",

publisher = "Elsevier Science",

}

TY - JOUR

T1 - Structural localisation of catalytic H2O2 oxidation sites in starch

AU - Broekman, Onno

AU - Lahive, Ciaran W.

AU - Piersma, Warner

AU - Thomann, Johanna

AU - Heeres, André

AU - Wielema, Thomas

AU - Bussemaker, Madeleine J.

AU - Brinksma, Jelle

AU - Deuss, Peter

PY - 2025/6/15

Y1 - 2025/6/15

N2 - The catalytic oxidation of potato starch by [MnIV2 (μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn =1,4,7-trimethyl-1,4,7-triazacyclononane) with H2O2, was recently introduced as a promising alternative to ubiquitous sodium hypochlorite (NaOCl). Here, we report an in-depth investigation into interactions of the catalyst with the starch granule. Pitted starches obtained by pre-treatment with high-frequency ultrasound (HFUS) were shown to result in a uniquely homogeneous oxidation. To study this further, fractionation of oxidised potato starch was done which showed a preference for the oxidation of smaller granules with a higher relative surface area. This result was corroborated by chemical surface gelatinisation of fractionated granules. These studies showed that the inside of the granules was oxidised, but that Mncat had a moderate preference for oxidation of the periphery. Together, these results allow for a better understanding of oxidation of starch by Mncat and how it differs from NaOCl oxidation making further optimisation of the process possible.

AB - The catalytic oxidation of potato starch by [MnIV2 (μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn =1,4,7-trimethyl-1,4,7-triazacyclononane) with H2O2, was recently introduced as a promising alternative to ubiquitous sodium hypochlorite (NaOCl). Here, we report an in-depth investigation into interactions of the catalyst with the starch granule. Pitted starches obtained by pre-treatment with high-frequency ultrasound (HFUS) were shown to result in a uniquely homogeneous oxidation. To study this further, fractionation of oxidised potato starch was done which showed a preference for the oxidation of smaller granules with a higher relative surface area. This result was corroborated by chemical surface gelatinisation of fractionated granules. These studies showed that the inside of the granules was oxidised, but that Mncat had a moderate preference for oxidation of the periphery. Together, these results allow for a better understanding of oxidation of starch by Mncat and how it differs from NaOCl oxidation making further optimisation of the process possible.

KW - chemical surface gelatinisation

KW - high-frequency ultrasound

KW - homogeneous catalysis

KW - hydrogen peroxide

KW - mechanical pre-treatmen

KW - starch oxidation

KW - chemische oppervlakte verdikking

KW - hoge frequentie echografie

KW - homegene katalyse

KW - waterstof peroxide

KW - mechanische voorbehandeling

KW - oxidatie van zetmeel

U2 - 10.1016/j.carbpol.2025.123528

DO - 10.1016/j.carbpol.2025.123528

M3 - Article

SN - 0144-8617

VL - 358

JO - Carbohydrate Polymers

JF - Carbohydrate Polymers

M1 - 123528

ER -

Structural localisation of catalytic H2O2 oxidation sites in starch

Abstract

Keywords

Access to Document

Fingerprint

Cite this