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Halogenation of graphene triggered by heteroatom doping.

ABSTRACT: Halogenation is one of the most important ways to tailor the properties of graphene. We demonstrate for the first time that boron and nitrogen doping can effectively tune the interactions between halogen diatomic molecules and graphene from first principles calculations. Boron and nitrogen doping disrupt the regular pi-electron pattern and create spin density and orbital polarization. More interesting, nitrogen and boron doping not only significantly increases the binding energies of Cl₂, Br₂, and I₂ but also induces the spontaneous dissociation of F₂. The tunable effects from nitrogen and boron doping can adjust the interactions in a wide range. Overall, it is suggested that doping can be a very promising method for the facile halogenation of graphene.

SUBMITTER: Olanrele SO

PROVIDER: S-EPMC9075508 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Halogenation of graphene triggered by heteroatom doping.

Olanrele Samson O SO Lian Zan Z Si Chaowei C Li Bo B

RSC advances 20191118 64

Halogenation is one of the most important ways to tailor the properties of graphene. We demonstrate for the first time that boron and nitrogen doping can effectively tune the interactions between halogen diatomic molecules and graphene from first principles calculations. Boron and nitrogen doping disrupt the regular pi-electron pattern and create spin density and orbital polarization. More interesting, nitrogen and boron doping not only significantly increases the binding energies of Cl<sub>2</s ...[more]

PMID: 35542250

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Project description:Vanadium haloperoxidases (VHPOs) are unique enzymes in biology that catalyze a challenging halogen transfer reaction and convert a strong aromatic C-H bond into C-X (X = Cl, Br, I) with the use of a vanadium cofactor and H2O2. The VHPO catalytic cycle starts with the conversion of hydrogen peroxide and halide (X = Cl, Br, I) into hypohalide on the vanadate cofactor, and the hypohalide subsequently reacts with a substrate. However, it is unclear whether the hypohalide is released from the enzyme or otherwise trapped within the enzyme structure for the halogenation of organic substrates. A substrate-binding pocket has never been identified for the VHPO enzyme, which questions the role of the protein in the overall reaction mechanism. Probing its role in the halogenation of small molecules will enable further engineering of the enzyme and expand its substrate scope and selectivity further for use in biotechnological applications as an environmentally benign alternative to current organic chemistry synthesis. Using a combined experimental and computational approach, we elucidate the role of the vanadium haloperoxidase protein in substrate halogenation. Activity studies show that binding of the substrate to the enzyme is essential for the reaction of the hypohalide with substrate. Stopped-flow measurements demonstrate that the rate-determining step is not dependent on substrate binding but partially on hypohalide formation. Using a combination of molecular mechanics (MM) and molecular dynamics (MD) simulations, the substrate binding area in the protein is identified and even though the selected substrates (methylphenylindole and 2-phenylindole) have limited hydrogen-bonding abilities, they are found to bind relatively strongly and remain stable in a binding tunnel. A subsequent analysis of the MD snapshots characterizes two small tunnels leading from the vanadate active site to the surface that could fit small molecules such as hypohalide, halide, and hydrogen peroxide. Density functional theory studies using electric field effects show that a polarized environment in a specific direction can substantially lower barriers for halogen transfer. A further analysis of the protein structure indeed shows a large dipole orientation in the substrate-binding pocket that could enable halogen transfer through an applied local electric field. These findings highlight the importance of the enzyme in catalyzing substrate halogenation by providing an optimal environment to lower the energy barrier for this challenging aromatic halide insertion reaction.

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Halogenation of graphene triggered by heteroatom doping.

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Halogenation of graphene triggered by heteroatom doping.

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