Noncovalent Interactions between Dopamine and Regular and Defective Graphene

Fernández, Ana Cecilia Rossi; Castellani, Norberto J.

doi:10.1002/cphc.201700252

Cited by 31 publications

(17 citation statements)

References 63 publications

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“…From the values summarized in Table , we can observe that the first contribution is in the range of −1.206 eV to −1.478 eV, while the second contribution is in the range of +0.071 eV to −2.678 eV, for the three values of applied electric field; i. e., the latter exhibits a much broader variability, according to the strength of molecule‐substrate bonding. E GGA always makes a stabilizing contribution in almost all cases, as was obtained for ZDA/Ag; however, for NDA/Ag(111), with E =0 V/Å, it is destabilizing, similarly as it was obtained previously for DA/graphene . The E GGA contribution to E ads is prevailing for PDA/Ag(111) (more than 60%) and minority for NDA/Ag(111) (less than 15%), while it is intermediate for DPDA/Ag(111) and ZDA/Ag(111).…”

Section: Resultssupporting

confidence: 76%

Electric Field Effects on the Adsorption of Dopamine Species on Ag(111): DFT Investigation of Interaction Mechanism

et al. 2020

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The study of interactions between dopamine (DA) and noble metal surfaces as Ag, is envisaged as a fundamental factor to attain more efficient electrochemical sensor materials. We describe, in the framework of Density Functional Theory, the adsorption of four dopamine species, neutral (NDA), zwitterionic (ZDA), protonated (PDA) and deprotonated (DPDA) species on Ag (111), upon the application of an external electric field (E), a fact of pertinence for electrochemistry tests. The ZDA and PDA species show relatively large binding energies of about 2.9 eV to 4.6 eV and suffer a significant flatting upon adsorption, compared with DPDA and NDA. The adsorbates binding energy is an increasing function of the applied E for ZDA and PDA species, showing a great change when the results for positive and negative E are compared. An electron transfer is produced from NDA, ZDA and PDA species to Ag, while in the case of DPDA an opposite behavior is obtained. As the sign of E is modified, an increase of charge values in all DA species is observed. The theoretical results obtained here show that ZDA and PDA species are the most affected DA species upon adsorption on Ag(111) and when non-zero electric fields are applied.

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Section: Resultssupporting

confidence: 76%

Electric Field Effects on the Adsorption of Dopamine Species on Ag(111): DFT Investigation of Interaction Mechanism

et al. 2020

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“…Therefore, the electronic contribution is repulsive and NDA to Ag binding is mainly due to attractive dispersive interactions. This remark was outlined before for NDA adsorption on graphene [53] and for adenine on graphene, [54] which was attributed to the fact that at adsorbate-substrate distances less than 3 Å, the kinetic energy contribution to the energy of single-particle Kohn-Sham orbitals is more relevant than the attractive contribution due to electronic exchange and correlation effects. Conversely, the presence of attractive interactions in the non-vdW contribution cannot be discarded for the NDA/Ag system, as it was explained for the case of adenine adsorption on Cu(110), where the binding was attributed to an ionic interaction between adsorbate and substrate.…”

Section: The Free Neutral Dopamine and Zwitterionic Dopamine Speciesmentioning

confidence: 80%

Neutral and zwitterionic dopamine species adsorbed on silver surfaces: A DFT investigation of interaction mechanism

Fernández

Meier

Castellani

2018

Int J of Quantum Chemistry

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Biomolecules nondissociative adsorption on noble metals is a key process in metallic biosensors implying several questions related to the stability and orientation of such molecules. Here, the neurotransmitter dopamine (DA) adsorption on silver surface is investigated in the context of density functional theory (DFT). Two different dopamine isomers, the neutral (NDA) and zwitterionic (ZDA) species, and two different silver surfaces, Ag (110) and Ag(111), were considered. NDA shows relatively large binding energies, compared to previously studied π‐π bonded systems. ZDA adsorbs even much more strongly although this species is less stable than NDA in vacuum. To elucidate the nature of the interaction between adsorbate and substrate, an electronic structure analysis was performed. Adsorbed NDA species suffers the loss of electronic charge, accompanied by a downshift of its molecular levels and the appearance of an attractive interaction of coulombic nature between adsorbate and substrate. The significant ZDA binding can be related to larger electron transfer and coupling between ZDA and Ag orbitals. Moreover, for both species, an important contribution of attractive noncovalent interactions of different degrees can be observed. The Ag substrate produces several modifications on NDA and ZDA vibrational frequencies. Noticeably relevant are the large red/blue shifts undergone by the N‐H/O‐H stretching bands of zwitterionic species, of up to −670/+430 cm−1.

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“…level (see details in SI) using the model graphene structures presented in Figure 7. While graphene and N-graphene with vacancies have been studied theoretically, [22][23] to our knowledge this is the first time that DFT calculations have been used to evaluate the interaction of DA with graphitic edges, and the first to take into account the entropic contributions to the adsorption by computing the Gibbs free energy of adsorption, G ads. We started our computational analysis by optimising the structures of the isolated DA molecule and the graphitic model surfaces shown in Figure 7, followed by the adsorption of DA on the different surfaces taking into account all the possible orientations and adsorption sites.…”

Section: Computational Studies Of Da Adsorption On Graphene Modelsmentioning

confidence: 99%

“…[19][20] Recently, catechol has been shown to adsorb on graphene nanoplatelets 21 and the adsorption of DA on graphene, in particular, has been investigated by means of theoretical calculations. [22][23] Due to its biological relevance as an important neurotransmitter, DA has also been intensely studied in the context of electroanalysis and simultaneous detection in the presence of co-analytes such as ascorbic acid. [24][25][26] DA also has relevance to the nitrogenated amorphous carbon literature in this context, [26][27][28] because these carbons may be engineered to have low background currents and wide potential windows.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Study of Dopamine as an Electrochemical Probe of the Surface Nanostructure of Graphitized N-Doped Carbon

et al. 2018

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N-doped carbon nanomaterials have received increased attention from electrochemists due to their applications in the metal-free electrocatalysis of important redox processes. In this work, a series of graphitized undoped and nitrogen-doped carbon electrodes prepared by thermal annealing of sputtered amorphous carbon films were prepared and characterized using a combination of X-ray photoelectron spectroscopy and Raman spectroscopy. Adsorption of the surface-sensitive redox probe dopamine at each electrode surface was then studied using cyclic voltammetry and the results correlated to the physico-chemical characterisation. Results indicate that dopamine adsorption is influenced by both the nitrogen surface chemistry and the degree of graphitization of the carbon scaffold. N-doping, with predominantly graphitic-N sites, was found to increase adsorption of dopamine more than 6 fold on carbon surfaces when the introduction of N atoms did not result in substantial alterations to the sp 2 network. However, when an identical type and level of N-doping is accompanied by a significant increase in disorder in the carbon scaffold, adsorption is limited to levels comparable to those of nitrogen-free carbon. Density functional theory studies of dopamine adsorption on graphene and N-doped graphene model surfaces showed that dopamine interacts via π-stacking at the graphene surface. The Gibbs free energy of adsorption on N-doped graphenes were estimated at 12-13 kcal mol-1 , and found to be approximately twice that of undoped graphenes. Results suggest that chemical changes resulting from N-doping enhance adsorption; however, high coverage values depend on the availability of sites for π-stacking. Therefore, the structurally disruptive effects of N-incorporation can significantly depress the dopamine response by limiting the availability of basal sites, ultimately dominating the overall electrochemical response of the carbon electrode.

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Noncovalent Interactions between Dopamine and Regular and Defective Graphene

Cited by 31 publications

References 63 publications

Electric Field Effects on the Adsorption of Dopamine Species on Ag(111): DFT Investigation of Interaction Mechanism

Electric Field Effects on the Adsorption of Dopamine Species on Ag(111): DFT Investigation of Interaction Mechanism

Neutral and zwitterionic dopamine species adsorbed on silver surfaces: A DFT investigation of interaction mechanism

Experimental and Computational Study of Dopamine as an Electrochemical Probe of the Surface Nanostructure of Graphitized N-Doped Carbon

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