Noncovalent Functionalization Of Graphene Research Articles

Theoretical investigation on graphene induced self-alignment of donor-acceptor structures

Non-covalent functionalization of graphene (Gr) with conducting polymers (CPs) improves the electrical and mechanical properties of both materials owing to the noncovalent π-π stacking interaction between the surface and the aromatic rings in CPs. However, a comprehensive understanding of the self-organization and chain orientation of CPs on the Gr surface remains lacking, which may limit the engineering of CP-Gr complexes with optimized morphology for optoelectronic applications. This study focuses on the Density Functional Theory (DFT) calculations and homemade Python programming code to investigate the self-organization of donor (D)-acceptor (A) type molecules on the Gr surface, aiming to elucidate factors governing the direction of self-alignment. Specifically, basic structural parameters characterizing the aromatic D-A molecules, such as the intramolecular aromatic ring distances, are explored to determine the rules for the preferred alignment direction of the CP monomers on the Gr surface, either in armchair or zigzag paths. Additionally, the influence of Gr on the morphological properties of aromatic molecules, variations in interaction energies between Gr and D-A-D systems with changing A units, and the impact of Gr size on molecular fitting characteristics are examined. The accurate determination of chain alignment direction, which can be applied for all conjugated small molecules and polymers at 2D material interfaces is crucial for guiding experimental studies aimed at tailoring structures and enhanced properties, such as promoting the crystalline domains with high electrical conductivity.

Graphene nanocomposites for real-time electrochemical sensing of nitric oxide in biological systems.

Nitric oxide (NO) signaling plays many pivotal roles impacting almost every organ function in mammalian physiology, most notably in cardiovascular homeostasis, inflammation, and neurological regulation. Consequently, the ability to make real-time and continuous measurements of NO is a prerequisite research tool to understand fundamental biology in health and disease. Despite considerable success in the electrochemical sensing of NO, challenges remain to optimize rapid and highly sensitive detection, without interference from other species, in both cultured cells and in vivo. Achieving these goals depends on the choice of electrode material and the electrode surface modification, with graphene nanostructures recently reported to enhance the electrocatalytic detection of NO. Due to its single-atom thickness, high specific surface area, and highest electron mobility, graphene holds promise for electrochemical sensing of NO with unprecedented sensitivity and specificity even at sub-nanomolar concentrations. The non-covalent functionalization of graphene through supermolecular interactions, including π-π stacking and electrostatic interaction, facilitates the successful immobilization of other high electrolytic materials and heme biomolecules on graphene while maintaining the structural integrity and morphology of graphene sheets. Such nanocomposites have been optimized for the highly sensitive and specific detection of NO under physiologically relevant conditions. In this review, we examine the building blocks of these graphene-based electrochemical sensors, including the conjugation of different electrolytic materials and biomolecules on graphene, and sensing mechanisms, by reflecting on the recent developments in materials and engineering for real-time detection of NO in biological systems.

Characterizing the Non-Covalent Binding of a Pyrene-Derived Linker for DNA Immobilization on Graphene Field-Effect Transistors

Graphene field-effect transistors (G-FETs) constitute an emerging platform for biosensing applications. Most genomic applications with G-FETs use single-stranded DNA (ssDNA) as probes in order to capture a specific target DNA sequence and to detect the corresponding change in the electrical response of the sensor1. Controlling the distribution of DNA probes on the graphene surface is crucial to the sensitivity, selectivity and reproducibility of the sensors1. The most popular immobilization approach uses a non-covalent linker molecule named 1-pyrenebutanoic acid succinimidyl ester (PBASE)1. This bifunctional molecule binds to the graphene surface through non-covalent π-π interactions via its aromatic pyrene group, and on the other end, its succinimidyl ester group can form a covalent bond with amine groups added to the terminal end of ssDNA probes. However, the adsorption process of PBASE molecules is not well controlled, which represents a limitation in the optimization of G-FET biosensors.Here, we present an investigation of the kinetics of the non-covalent adsorption of PBASE on graphene, in order to control the density of ssDNA probes for biosensing applications with G-FETs. We fabricated G-FET sensor arrays using CVD-grown graphene and photolithography techniques, as described previously2. First, we investigated the effect of incubation time on PBASE coverage on graphene, using electrical curves as well as Raman hyperspectral imaging (RIMA). We report a significative and reproducible electrical signature for the PBASE compared to the control without PBASE. We find that this electrical signature appears and saturates quickly compared to the timescales usually reported in the literature. Corroborating results were obtained with RIMA spectroscopy, showing a rapid response of the graphene modes following PBASE incubation. Next, we studied the effect of PBASE accumulation on the assembly of ssDNA probes. We will discuss the combined effect of PBASE accumulation and screening effects in saline buffer on the electrical signature of ssDNA probes. Our results will enable a better control on the non-covalent functionalization of graphene with PBASE for the assembly of various biomolecular probes for biosensing applications.1. Béraud A, Sauvage M, Bazan CM, Tie M, Bencherif A, Bouilly D. Graphene field-effect transistors as bioanalytical sensors: design, operation and performance. Analyst. 2021;(146):403-428.2.Bazan CM, Béraud A, Nguyen M, Bencherif A, Martel R and Bouilly D. Dynamic Gate controlled of Aryldiazonium chemistry on Graphene field-effect transistors. Nano Lett. 2022;22(7):2635-2642.

Fabrication of BP2T functionalized graphene via non-covalent π-π stacking interactions for enhanced ammonia detection.

Graphene has stimulated great enthusiasm in a variety of fields, while its chemically inert surface still remains challenging for functionalization towards various applications. Herein, we report an approach to fabricate non-covalently functionalized graphene by employing π–π stacking interactions, which has potentialities for enhanced ammonia detection. 5,5′-Di(4-biphenylyl)-2,2′-bithiophene (BP2T) molecules are used in our work for the non-covalent functionalization through strong π–π interactions of aromatic structures with graphene, and systematic investigations by employing various spectroscopic and microscopic characterization methods confirm the successful non-covalent attachment of the BP2T on the top of graphene. From our gas sensing experiments, the BP2T functionalized graphene is promising for ammonia sensing with a 3-fold higher sensitivity comparing to that of the pristine graphene, which is mainly attributed to the enhanced binding energy between the ammonia and BP2T molecules derived by employing the Langmuir isotherm model. This work provides essential evidence of the π–π stacking interactions between graphene and aromatic molecules, and the reported approach also has the potential to be widely employed in a variety of graphene functionalizations for chemical detection.

Self-assembly of the surfactant mixtures on graphene in the presence of electrolyte: a molecular simulation study

The insolubility of graphene nanosheets in aqueous media has been a limitation for the practical applications of this unique material. The non-covalent functionalization of graphene with mixed surfactants is an effective procedure for preparation of stable graphene dispersions. Physical adsorption of surfactants onto graphene surfaces is a significant stage in the dispersion of graphene nanosheets in the aqueous environment. Studies have shown that the presence of electrolyte greatly affects the adsorption process of pure surfactants on solid surfaces. Examination of mixed surfactants adsorption on graphene in the presence of electrolyte will help to better understand the mechanism of molecular interactions between the graphene nanosheets and mixed surfactants. Therefore, in this study, we used molecular dynamics simulations to investigate the adsorption of mixed surfactants on graphene in the presence of electrolyte and to study the morphology of assemblies formed from mixed surfactants on graphene. We investigate the effects of electrolyte concentration and surface coverage of surfactants' mixture on the adsorption process and structural changes in the assemblies formed on graphene nanosheets. We have found that increasing the ionic strength of electrolyte reinforces stretching of surfactants adsorbed on graphene toward the aqueous phase, and this leads to a clear volume expansion in the structure of graphene-surfactant mixture hemi-spherical micelles. In fact, screening effect of electrolyte ions on electrostatic repulsion between charged head-groups made molecules approach each other, leading to a more compact assembly of surfactants on graphene surface. As hemi-spherical micelles of mixed surfactants-graphene expanded, the steric repulsion between these micelles also increased, which in turn, inhibited the re-aggregation of graphene sheets covered with surfactants.

Noncovalent functionalization of graphene through physisorption of 1,1-diamino-2,2-dinitroethene: Impacts of and cooperativity between hydrogen bond and π···π interaction

The rich π-electrons region of graphene enables it to be a good material which can interact with many organic molecules. As a low-sensitivity and high-energy explosive, 1,1-diamino-2,2-dinitroethene and its dimer possess unique characters including hydrogen bonds and π bond which can adsorb on graphene through physisorption. The results suggest that the adsorption energies have a very small difference on the different adsorption sites. Due to the physisorption, the geometrical and electronic properties of 1,1-diamino-2,2-dinitroethene and its dimer vary significantly. The intramolecular as well as intermolecular hydrogen bond strengths are considerably affected due to the π···π interaction of 1,1-diamino-2,2-dinitroethene or its dimer with graphene. The cooperativity between intermolecular hydrogen bonds and π···π interactions is observed which causes wax of intermolecular hydrogen bonds and wane of π···π interactions. The physisorption of 1,1-diamino-2,2-dinitroethene or its dimer also leads to the variation of electronic property of graphene.

1-nm-Wide Hydrated Dipole Arrays Regulate AuNW Assembly on Striped Monolayers in Nonpolar Solvent

Summary We show that striped phases of horizontally oriented phospholipids presenting 1-nm-wide orientable dipole arrays can order and straighten flexible 2-nm-diameter gold nanowires (AuNWs) with lengths (up to 1 μm) that greatly exceed the template pitch (∼7.5 nm). AuNW ordering can extend over areas > 100 μm2. Whereas wires bundle in solution, with contact between ligand shells, wires adsorbing to the template separate to much larger center-to-center distances (e.g., 12–30 nm) near multiples of the template pitch, consistent with repulsive interactions between wires emerging during interactions with dipole arrays in the template. AuNW assembly was carried out in cyclohexane, a nonpolar solvent. Interestingly, we found that wire ordering was contingent on the extent of phospholipid headgroup hydration and the presence of excess oleylamine, which assembled into hemicylindrical micelles around the hydrated headgroups. Together, these components generated a protected polar environment that enabled the phospholipid headgroups to function collectively to regulate AuNW assembly.

Noncovalent functionalization of graphene via π-hole···π and σ-hole···π interactions

Physisorption of bromopentafluorobenzene (C6F5Br) on graphene can occur due to the unique σ-hole and π-hole characters of C6F5Br and the rich π-electrons region of graphene, leading to the formation of three types of π-hole···π and σ-hole···π interactions. The π-hole···π interactions are even stronger than the σ-hole···π interactions. The property of graphene was significantly affected by such physisorption.

Graphene induced molecular flattening of meso -5,10,15,20-tetraphenyl porphyrin: DFT calculations and molecular dynamics simulations

Abstract Noncovalent functionalization of graphene with porhyrins that possess a large conjugated π-system of bonds can extend the range of practical applications of this nanomaterial. In this work the structures of hybrids formed by porphin and meso-5,10,15,20-tetraphenyl porphyrin (TPP) with graphene and the corresponding intermolecular interaction energies are studied with the DFT and molecular dynamics (MD) calculations. The influence of the peripheral rings arranged around the porphyrin core in the TPP structure on its interaction energy with graphene upon the TPP adsorption on graphene is analyzed. The flattening of the TPP structure occurring due to the adsorption is observed. The interaction of TPP with graphene also leads to distortion of the flat structure of the porphyrin core and to some twisting of its side rings, so the dihedral angle between the planes of the porphyrin core and the side residues decreases from 64° to 50°. In spite of the flattening and the larger size of the TPP structure compared to the porphin structure their interaction energies with graphene are similar (about 20 kcal/mol). It is also shown that TPP alters the uniform distribution of the electrostatic potential on graphene by reducing the zone of small negative potential of graphene located under the porphyrin molecule. The MD simulation performed in this work describes the process of the adsorption of porphin and TPP on graphene in water environment and reveals significant mobility of this molecule on the graphene surface.

On the optoelectronic properties of non-covalently functionalized graphene for solar cell application

In this study, we report a simple approach toward the non-covalent functionalization of graphene by anthracene and thiophene molecules in different configurations, depending on the direction of the molecules approach to the surface of graphene. We examined structural, optoelectronic and vibrational properties of graphene before and after interaction with anthracene and thiophene. The density functional theory at B3LYP with 6-311G(d,p), 6-31G(d,p) and 6-31G(d) was employed to choose appropriate basis set that provides a more accurate molecular–properties description. This is important to compare and understand the deep relationship between the chemical structure of these heterostructures and their related properties to be chosen as an active layer in electronic devices. The device-based thiophene–graphene with perpendicular configuration film as an active layer in CdTe/CdS solar cell shows the best performance with a power conversion efficiency of $$9.58\%$$ , an open-circuit voltage of $$0.7\,\hbox {V}$$ , a short-circuit current density of $$24.47\,\hbox {mA}\,\hbox {cm}^{2}$$ and a fill factor of $$55.92\%$$ under simulated AM1.5 conditions at $$1000\,\hbox {W}\,\hbox {m}^{2}$$ .

On the role of substituent in noncovalent functionalization of graphene and organophosphor recognition: IQA and SAPT perspective

AbstractDespite importance of integrating organic molecules with graphene to fabricate graphene‐based electronic devices, the role of substituents and interface stabilizing forces are poorly understood. In this work, the interactions of 7,7,8,8‐tetracyanoquinodimethane (TCNQ), 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ), hydroquinone (Q), and tetrafluorohydroquinone (TFQ) with graphene have been investigated by means of interacting quantum atoms and SAPT(DFT). In addition, in context of potential design of a graphene‐based sensor for detection of the nerve agent sarin, we studied the interaction of graphene and the organic molecules with the dimethyl methylphosphonate (DMMP)—the molecule that mimics sarin. The results show that the organic molecules attach to graphene via C(sp2)⋯C(sp2), C(sp2)⋯C(sp) and H⋯π bonds. In addition, they trap DMMP via various linkages such as hydrogen, lonepair⋯π and H⋯π. The quantum effects play a significant role. The Pauli repulsion is responsible for p‐doping of graphene. The substituents are stabilized on graphene by the exchange‐correlation energy. The fluorination of the benzenoid ring raises the electron‐sharing. The through space and through bond effects of the fluorine atoms (‐F) increase the classical attraction of the cyano groups and benzenoid ring with graphene, respectively. When comparing performance of the ab initio and DFT methods, MP2 predicts too much attraction due to well‐known overestimation of the dispersion energy by the uncoupled dispersion component for benzene rings, while ωB97xD functional and SAPT(DFT) provide weaker interaction energies, in good agreement with each other.

Structures of single, double and triple layers of lipids adsorbed on graphene: Insights from all-atom molecular dynamics simulations

Non-covalent functionalization of graphene with phospholipids is a promising technique for biosensing applications and intracellular delivery of analytical probes and drugs. However, molecular details of the self-assembly of lipids on graphene surface is still poorly understood and hard to control. There is a clear lack of understanding of why various kinds of lipid aggregates can form on graphene. In the current work, we address this question by investigating equilibrium and dynamical properties of lipid layers adsorbed on graphene in water environment and in vacuum using all-atom Molecular Dynamics simulations. It is shown that a variety of lipid aggregates can form on top of graphene depending on initial orientation, number of adsorbed lipid layers and the presence of water. The lipid layers self-organize and reorient in order to minimize hydrophobic mismatch on graphene-lipid, lipid-lipid and water-lipid interfaces. Obtained structures range from homogeneous layers to the networks of inverted micelle-like structures and weakly bound cylindrical micelles on top of monolayers. Our results are in excellent agreement with recent experimental findings. Another pronounced effect of graphene is the strong ordering of the lipid atoms which are in direct contact with it. In all studied systems at least two well-structured atomic shells are formed above the graphene surface at the distances of 0.35 and 0.85 nm.

Non-covalent functionalization of graphene with a hydrophilic self-limiting monolayer for macro-molecule immobilization

Two different pyrene-substituted ions were used to render the surface of graphene hydrophilic. Self-limiting monolayers of ammonium and sulfonate substituted pyrenes were used to give, respectively, an overall positive and negative charge to the surface. Both pyrenes gave a stable hydrophilic surface and were used to selectively immobilise negatively or positively charged macro-molecules. This simple and versatile non-covalent approach can be used on graphene on a variety of substrates (e.g. copper, SiO2), suspended graphene, and also for graphite.

Thermodynamics study of the noncovalent functionalization of surfactant suspended graphene nanosheets with porphyrin molecules

AbstractWe report on the noncovalent functionalization of graphene with hydrophobic tetraphenyl porphyrin (TPP) molecules in micellar aqueous suspensions. We study the thermodynamical parameters of the reaction using optical spectroscopy, and measure its Gibbs energy. We show that a total reaction can be achieved, leading to a high functionalization yield, despite the ‐stacking noncovalent binding.Side view of a graphene nanosheet covered with porphyrins.

Noncovalent Functionalization of Graphene and Graphene Oxide for Energy Materials, Biosensing, Catalytic, and Biomedical Applications

This Review focuses on noncovalent functionalization of graphene and graphene oxide with various species involving biomolecules, polymers, drugs, metals and metal oxide-based nanoparticles, quantum dots, magnetic nanostructures, other carbon allotropes (fullerenes, nanodiamonds, and carbon nanotubes), and graphene analogues (MoS2, WS2). A brief description of π-π interactions, van der Waals forces, ionic interactions, and hydrogen bonding allowing noncovalent modification of graphene and graphene oxide is first given. The main part of this Review is devoted to tailored functionalization for applications in drug delivery, energy materials, solar cells, water splitting, biosensing, bioimaging, environmental, catalytic, photocatalytic, and biomedical technologies. A significant part of this Review explores the possibilities of graphene/graphene oxide-based 3D superstructures and their use in lithium-ion batteries. This Review ends with a look at challenges and future prospects of noncovalently modified graphene and graphene oxide.

Noncovalent Interaction of Graphene with Heterocyclic Compounds: Benzene, Imidazole, Tetracene, and Imidazophenazines.

Noncovalent functionalization of graphene with organic molecules offers a direct route to multifunctional modification of this nanomaterial, leading to its various possible practical applications. In this work, the structures of hybrids formed by linear heterocyclic compounds such as imidazophenazine (F1) and its derivatives (F2-F4) with graphene and the corresponding interaction energies are studied by using the DFT method. Special attention is paid to the hybrids where the attached molecule is located along the graphene zigzag (GZZ ) and armchair (GAC ) directions. The interaction energies corresponding to the graphene hybrids of the F1-F4 compounds for the two directions are found to be distinct, while tetracene (being a symmetrical molecule) shows a small difference between these binding energies. It is found that the back-side CH3 and CF3 groups have an important influence on the arrangements of F1 derivatives on graphene and on their binding energies. The contribution of the CF3 group to the total binding energy of the F3 molecule with graphene is the largest (3.4 kcal mol(-1) ) (the GZZ direction) while the CH3 group increases this energy of F2 only by 2.0 kcal mol(-1) (the GAC direction). It is shown that replacing the carbons with other atoms or adding a back-side group enables one to vary the polarizability of graphene.

Understanding Defect‐Stabilized Noncovalent Functionalization of Graphene

The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high‐resolution interfacial X‐ray scattering, and ab initio density functional theory calculations. The findings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. The structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogen bonding with terminal hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton‐coupled‐electron‐transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. These results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.

A versatile strategy towards non-covalent functionalization of graphene by surface-confined supramolecular self-assembly of Janus tectons.

Two-dimensional (2D), supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D) building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2)-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications.

Non‐Covalent Functionalization of Graphene with Bisphenol A for High‐Performance Supercapacitors

AbstractThe reduced graphene oxide (RGO)/bisphenol A (BPA) composites were prepared by an adsorption‐reduction method. The composites are characterized by X‐ray diffraction (XRD), UV‐vis, thermogravimetric (TG) analysis, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM). The results confirm that BPA is adsorbed on the basal plane of RGO by π‐π stacking interaction. Furthermore, the electrochemical behaviors were evaluated by cyclic voltammetry, galvanostatic charge/discharge techniques and electrochemical impedance spectroscopy (EIS). The results show that the RGO/BPA nanocomposites exhibit ultrahigh specific capacitance of 466 F·g−1 at a current density of 1 A·g−1, excellent rate capability (more than 81% retention at 10 A·g−1 relative to 1 A·g−1) and superior cycling stability (90% capacitance decay after 4000 cycles). Consequently, the RGO/BPA nanocomposites can be regarded as promising electrode materials for supercapacitor applications.

Noncovalent functionalization of graphene with pyrene-terminated liquid crystalline polymer

Pyrene-terminated liquid crystalline polymers (poly [8-(4-cyano-4′-biphenyl)-1-octanoylacrylate] and poly [6-(4-cyano-4′-biphenyl)-1-hexanoylacrylate]) were synthesized and used to functionalize graphene sheets via π–π interactions. The resulting liquid crystalline polymers functionalized graphene sheets were characterized by UV–vis spectroscopy, fluorescence spectroscopy, thermal gravimetric analysis, Fourier transform infrared spectroscopy, X-ray diffraction, atomic force microscopy and Raman spectroscopy. It was found that an intercalated layer structure was formed when polymer was grafted onto graphene sheets. The liquid crystalline polymers were able to effectively disperse graphene in N,N-dimethylformamide that were stable for months. Additionally, a remarkable smaller distance of adjacent mesogenic units was observed, which is attributed to the confinement of the polymer chains between 2D reduced graphene oxide sheets.