Pristine graphene covalent functionalization with aromatic aziridines and their application in the sensing of volatile amines – an <i>ab initio</i> investigation

Baachaoui, Sabrine; Aldulaijan, Sarah; Raouafi, F.; Besbes, Rafâa; Sementa, Luca; Fortunelli, Alessandro; Raouafi, Noureddine; Dhouib, Adnene

doi:10.1039/d0ra09964c

Cited by 13 publications

(42 citation statements)

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“…−0.2 eV at all the examined positions, namely, two parallel, atop, bridge, and hollow positions, which is consistent with previous findings. 19 3.3. Chemical Reaction of the Activated Carbenes with Graphene.…”

Section: Resultsmentioning

confidence: 99%

“…The energy cutoffs for the plane-wave functions and the charge density were set at 49.14 and 442.32 Ry, respectively. 19 A graphene supercell was used, consisting of 6 × 6 unit cells (72 carbon atoms), with different modifiers physically or chemically adsorbed on it. Smaller and larger supercells were examined for comparison to validate convergence of results.…”

Section: Computational Detailsmentioning

confidence: 99%

“…A projector-augmented wave basis set, periodic boundary conditions, and the Perdew–Burke–Ernzerhof exchange–correlation functional were used in all the calculations, and a semi-empirical Grimme’s DFT-D3 (version 4) van der Waals correction was applied consistently. The energy cutoffs for the plane-wave functions and the charge density were set at 49.14 and 442.32 Ry, respectively …”

Section: Computational Detailsmentioning

confidence: 99%

“…7,8,17,18 This process was investigated theoretically and experimentally to design new nanomaterials for sensing applications. 10,19 Recently, several authors reported the use of dihalo-(dichloro, dibromo, or diiodo)carbene to manipulate the band gap of graphene through functionalization and used it for the removal of Pb(II) from wastewater. 9,10,16,20 Moreover, Sun et al generated diarylcarbenes from diaromatic ketones and used them to modify graphene oxide to improve its solubility in water.…”

Section: Introductionmentioning

confidence: 99%

“…This leads to changes in the electronic structure of graphene that can transform it from a zero-gap anomalous conductor to a non-zero-gap semiconducting material. − Furthermore, the functionalizing groups can bear organic groups such as carboxylic acid, amine, alcohols, and so forth that can serve for further (bio)functionalization. Haloforms (i.e., chloroform, bromoform, and iodoform) and diazirines are among the most used precursors to generate carbenes upon activation with a strong base and light irradiation, respectively. − Functionalized diazirine-derived carbenes were used to modify carbon nanotubes, diamond, fullerene, and graphene. , Similarly, aromatic azides can be cleaved to yield aromatic nitrenes, which can readily react with a carbon–carbon double bond from the graphene to yield the corresponding aziridine appendages linked to graphene. ,,, This process was investigated theoretically and experimentally to design new nanomaterials for sensing applications. , …”

Section: Introductionmentioning

confidence: 99%

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Density Functional Theory Investigation of Graphene Functionalization with Activated Carbenes and Its Application in the Sensing of Heavy Metallic Cations

et al. 2021

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Anthropogenic activities presently generate undesirable industrial and house waste byproducts such as heavy metallic cations (HMCs), which are then often released into the environment, despite being harmful to human beings. Developing new materials that can detect and capture HMCs is therefore highly desirable for wastewater remediation, especially if using cheap starting raw materials such as carbon. To shed theoretical light in this direction, we use density functional theory simulations to study the functionalization of pristine graphene with prototypical carbenes, RC(O)CH, with R = −OCH 3 (2a), −OH (2b), −ONa (2c), and −Ph (2d), and explore their use in sensing and capturing toxic HMCs (here, we focus on the most common and harmful ones: Cd 2+ , Hg 2+ , and Pb 2+ ). We first demonstrate that, starting from activated diazomethanes, RC(O)CHN 2 (1a−d), and graphene as precursors, it is possible to yield substituted cyclopropanes tethered to graphene, here modeled as a 6 × 6 supercell (g6×6), via a [2 + 1]cycloaddition reaction. Projected density of states and band structure calculations show that the cycloaddition reaction induces a band gap opening of the graphene, which can be used to tune it for electronic sensing devices. These nanomaterials (g6×6/3a−d) favorably interact with the metallic cations through coordination bonds with interaction energies varying from −1.18 to −2.75 eV. Differences in the electronic charge density following HMC adsorption reveal regions of electron depletion or gain induced by these interactions. Based on energetic and electronic structure analysis, we suggest that g6×6/3b−d are good candidates to detect HMCs. All the four nanomaterials show a higher affinity toward Pb 2+ , as rationalized by a synergic interaction with the graphene substrate, suggesting that they can be used for Pb 2+ sensing and removal. Notably, we demonstrate that once and only once the proper computational approach is employed, the accuracy of our predictions of a larger interaction strength of Pb 2+ with respect to Cd 2+ is validated via the agreement with available experimental data on g6×6/3b. Finally, we predict that by varying the pH, the g6×6/3b,c pair can be employed to differentially sense Cd 2+ and Hg 2+ cations.

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Section: Resultsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Density Functional Theory Investigation of Graphene Functionalization with Activated Carbenes and Its Application in the Sensing of Heavy Metallic Cations

et al. 2021

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σ‐Hole intermolecular interactions between carbon oxides and dihalogens: Ab‐initio investigations

Rahali¹,

Zouaghi²,

Sanz

et al. 2023

J Comput Chem

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Recently, halogen bonding (XB) has received increased attention as a new type of non‐covalent interaction widely present in nature. In this work, quantum chemical calculations at DFT level have been carried out to investigate halogen bonding interactions between COn(n = 1 or 2) and dihalogen molecules XY (X = F, Cl, Br, I and Y = Cl, Br, I). Highly accurate all‐electron data, estimated by CCSD(T) calculations, were used to benchmark the different levels of computational methods with the objective of finding the best accuracy/computational cost. Molecular electrostatic potential, interaction energy values, charge transfer, UV spectra, and natural bond orbital (NBO) analysis were determined to better understand the nature of the XB interaction. Density of states (DOS) and projected DOS were also computed. Hence, according to these results, the magnitude of the halogen bonding is affected by the halogen polarizability and electronegativity, where for the more polarizable and less electronegative halogen atoms, the σ‐hole is bigger. Furthermore, for the halogen‐bonded complexes involving CO and XY, the OC∙∙∙XY interaction is stronger than the CO∙∙∙XY interaction. Thus, the results presented here can establish fundamental characteristics of halogen bonding in media, which would be very helpful for applying this noncovalent interaction for the sustainable capture of carbon oxides.

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Detection of Ochratoxin A Mycotoxin with Graphene Nanosheets Functionalized with Selective Peptides Using Molecular Dynamics

Algethami,

Mastouri,

Rabti

et al. 2024

Arab J Sci Eng

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Pristine graphene covalent functionalization with aromatic aziridines and their application in the sensing of volatile amines – an ab initio investigation

Abstract: Simulations show that the total volatile basic amines (TVB) from spoiled fish can be sensed by aziridine-functionalized graphene nanomaterials to induce substantial changes in the physical properties.

Cited by 13 publications

References 50 publications

Density Functional Theory Investigation of Graphene Functionalization with Activated Carbenes and Its Application in the Sensing of Heavy Metallic Cations

Density Functional Theory Investigation of Graphene Functionalization with Activated Carbenes and Its Application in the Sensing of Heavy Metallic Cations

σ‐Hole intermolecular interactions between carbon oxides and dihalogens: Ab‐initio investigations

Detection of Ochratoxin A Mycotoxin with Graphene Nanosheets Functionalized with Selective Peptides Using Molecular Dynamics

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