Deciphering the Adsorption Mechanisms of RGD Subunits: <scp>l</scp>-Aspartic Acid on Cu(110)

Totani, Roberta; Méthivier, Christophe; Cruguel, Hervé; Pradier, Claire‐Marie; Humblot, Vincent

doi:10.1021/acs.jpcc.7b04948

Cited by 10 publications

(23 citation statements)

References 45 publications

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“…10,[13][14][15]18,19 The decomposition mechanism of Asp on chiral Cu(643) R&S and achiral Cu(110) surfaces has been studied recently. 10,16,19 Amino acid monomers such as Asp exist in one of three possible chemical forms: neutral (HO 2 CCH(NH 2 )-CH 2 CO 2 H), zwitterionic ( − O 2 CCH(NH 3 + )CH 2 CO 2 H), or anionic ( − O 2 CCH(NH 2 )CH 2 CO 2 H). Because it has two carboxylate groups, Asp can also exist as a di-anion ( − O 2 CCH(NH 2 )CH 2 CO 2 − ).…”

Section: ■ Introductionmentioning

confidence: 99%

Kinetics and Mechanism of Aspartic Acid Adsorption and Its Explosive Decomposition on Cu(100)

2019

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The mechanism and kinetics of aspartic acid (Asp, HO2CCH(NH2)CH2CO2H) decomposition on Cu(100) have been studied using X-ray photoemission spectroscopy and temperature-programmed reaction spectroscopy. We investigate the Asp decomposition mechanism in detail using unlabeled d-Asp and isotopically labeled l-Asp-4-13C (HO2CCH(NH2)CH2 13CO2H), l-Asp-d 7 (DO2CCD(ND2)CD2CO2D), l-Asp-2,3,3-d 3 (HO2CCD(NH2)CD2CO2H), and l-Asp-15N-2,3,3-d 3 (HO2CCD(15NH2)CD2CO2H). The monolayer of Asp adsorbed on the Cu(100) surface is in a doubly deprotonated bi-aspartate form (−O2CCH(NH2)CH2CO2−). During heating, Asp decomposes on Cu(100) with kinetics consistent with a vacancy-mediated explosion mechanism. The mechanistic steps yield CO2 by sequential cleavage of the C3–C4 and C1–C2 bonds, and NCCH3 and H2 via decomposition of the remaining CH(NH2)CH2 intermediate. Deuterium labeling has been used to demonstrate that scrambling of H(D) occurs during the decomposition to acetonitrile of the CD(NH2)CD2 intermediate formed by decarboxylation of l-Asp-2,3,3-d 3 and l-Asp-15N-2,3,3-d 3.

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Section: ■ Introductionmentioning

confidence: 99%

Kinetics and Mechanism of Aspartic Acid Adsorption and Its Explosive Decomposition on Cu(100)

2019

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“…Studying adsorption of ARG is thus part of a project aiming at the comprehensive knowledge of the RGD adsorption mechanism. Adsorption of aspartic acid, which occupies the other end of RGD with respect to ARG, has been recently investigated on several copper surfaces, showing quite complex adsorption modes and 2D structures [19][20][21][22]. As for ARG which shows great similarities with lysine or methionine, it is frequently employed in nanotechnologies as corrosion inhibitor [23] and metal nanoparticle stabilizer [24] and plays a potential key role in biological interfaces [25].…”

Section: -Introductionmentioning

confidence: 99%

“…The O 1s and N 1s peaks prove that ARG adsorbs on the investigated surface. The estimated average thickness of the so-obtained ARG film is 0.3 nm, indicating a submonolayer coverage.The O 1s spectrum,Figure 2(a), displays only one component, centred at a Binding Energy (BE) of 531.6 ± 0.1 eV, due to the contribution from O atoms in the carboxylate groups (COO -)[19,38]. This allows us to conclude that ARG molecules, once adsorbed on the surface, have deprotonated carboxylic acid groups.…”

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confidence: 96%

Binding and 2D organization of arginine on Cu(1 1 0)

Totani

Méthivier

Costa

et al. 2020

Applied Surface Science

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In this work we present a detailed surface science characterization of L-arginine adsorption on the Cu(110) surface in a submonolayer regime. Arginine (ARG) is one of the main components of the tripeptide RGD (arginine-glycine-aspartic acid) commonly used as a linker/binder when engineering biomedical devices such as integrin receptors. We replaced the traditional Knusden cell sublimation method to obtain molecular films by dosing arginine directly from an aqueous solution through an electrospray ionization device (ESI). X-ray Photoelectron Spectroscopy (XPS) evidenced the coexistence of different adsorbed molecular species. In addition, Scanning Tunneling Microscopy (STM) data show that the arginine molecules form short and well-separated lines, constituted of dimers of molecules on the surface. DFT calculations helped clarifying these experimental findings, bringing strong evidences that ARG molecules adsorb in an ionic and a neutral form, with varied binding modes between N atoms and Cu atoms from the surface. These different N-Cu bonds lead to the establishment of intermolecular H-bonds, responsible for the dimerization process.

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“…Numerous experimental studies (e.g. [2][3][4][5][6][7] ) have contributed in the past few decades to our understanding of these elements, utilizing a range of surface-sensitive spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), Infrared spectroscopy techniques, and time-of-flight secondary mass spectrometry (ToF-SIMS). Although these are extremely powerful tools, these techniques do not provide real-space information on the buildup of coatings.…”

Section: Introductionmentioning

confidence: 99%

In Situ EC-STM Study and DFT Modeling of the Adsorption of Glycerol on Cu(111) in NaOH Solution

et al. 2019

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Organic coatings are often required for the protection of metals against environmental degradation. Despite their extensive use, only limited information is available on the initial stages of adsorption and formation of protective films, especially at the molecular and atomic level. As a model system for coating formation, this study investigates the adsorption of glycerol molecules on the single-crystalline Cu(111) surface. A combined electrochemical and scanning tunneling microscopy (EC-STM) study in NaOH aqueous solution enabled following the adsorption process in detail, providing molecular information on the glycerol film structure. A potential-driven adsorption of glycerol was observed, suppressing the adsorption of hydroxyl molecules and copper oxidation. The adsorbed species assembled in a nearest neighbor arrangement fitting a (√3 × √3) R30° hexagonal structure with respect to the Cu(111) lattice. This experimentally observed configuration was confirmed by density functional theory (DFT) calculations. DFT modeling indicates that a mixed adsorption mode involving the two primary alcohol groups adsorbed at different z-positions relative to the surface is the most favorable. This mixed configuration enabled the formation of an extended network of hydrogen bonds that aids to stabilize the glycerol film. This implies that interactions between glycerol molecules play a non-negligible effect in the growth process of such an organic film, allowing the formation of organic layers in the absence of strong interfacial interactions.

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Deciphering the Adsorption Mechanisms of RGD Subunits: l-Aspartic Acid on Cu(110)

Cited by 10 publications

References 45 publications

Kinetics and Mechanism of Aspartic Acid Adsorption and Its Explosive Decomposition on Cu(100)

Kinetics and Mechanism of Aspartic Acid Adsorption and Its Explosive Decomposition on Cu(100)

Binding and 2D organization of arginine on Cu(1 1 0)

In Situ EC-STM Study and DFT Modeling of the Adsorption of Glycerol on Cu(111) in NaOH Solution

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