<scp>l</scp>-Cysteine on Ag(111): A Combined STM and X-ray Spectroscopy Study of Anchorage and Deprotonation

Fischer, Sybille; Papageorgiou, Anthoula C.; Marschall, Matthias; Reichert, Joachim; Diller, Katharina; Klappenberger, Florian; Allegretti, Francesco; Nefedov, Alexei; Wöll, Christof; Barth, Johannes V.

doi:10.1021/jp305270h

Cited by 78 publications

(82 citation statements)

References 57 publications

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“…This might be attributed to either of the following reasons concerning over layer formation: 1) weakening the interaction of L-cysteine with Ag(111) reduces the amount of charge transfer, therefore the strength of the interface dipole can be decreased, 2) change of the adsorption orientation affects the intrinsic dipole moment of cysteine; parallel to the metal surface reduces the intrinsic dipole moment contribution to the interface dipole, and 3) a combination of these two phenomena. Fischer, et al [20] addressed evaporated L-cysteine on Ag(111) and reported that L-cysteine forms a dense-packed layer on Ag(111). In this case, the monolayer coverage is chemosorbed to Ag(111) forming silver-sulfur bonding, and L-cysteine exists mainly as a zwitterion for all the layers.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, an understanding of the interaction of L-cysteine with metal surfaces is necessary. There have been experimental and theoretical research studies that examined the behavior of L-cysteine adsorbed on different faces of gold [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19], silver [20][21][22][23], and copper [24][25][26] metallic single crystals as model systems for understanding the interaction of L-cysteine with metal surfaces and also L-cysteine adsorbed on some other surfaces considering technological interests [27][28][29][30][31][32][33][34][35]. In the experimental studies, the L-cysteine sample for investigation was formed using either the self-assembly or evaporation method.…”

Section: Introductionmentioning

confidence: 99%

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Interface Electronic Structures of the L-Cysteine on Noble Metal Surfaces Studied by Ultraviolet Photoelectron Spectroscopy

Koswattage

Kinjo

Nakayama

et al. 2015

e-J. Surf. Sci. Nanotech.

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L-cysteine, one of amino acids, is well known in the bioelectronics field as a linker between proteins and metal electrodes. The interface electronic structures between L-cysteine and metals are therefore very crucial because they dominate the charge carrier injection characteristics into such biological systems. However the interface electronic structures of L-cysteine and metals have been not well understood. In this study, the electronic structures at the interfaces of sequentially deposited L-cysteine layers on the metal surfaces of Au(111), Ag(111), and Cu (111) were investigated by thickness-dependent ultraviolet photoelectron spectroscopy (UPS). At the contact regions, the electronic structures of L-cysteine revealed modification with respect to its bulk phase and significant variation depending on the substrate. The electronic structure at the interfaces including work function, secondary electron cutoff (SECO), highest occupied molecular orbital (HOMO) onset, position of an interface state, charge injection barrier, and ionization energy were estimated for each case.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Interface Electronic Structures of the L-Cysteine on Noble Metal Surfaces Studied by Ultraviolet Photoelectron Spectroscopy

Koswattage

Kinjo

Nakayama

et al. 2015

e-J. Surf. Sci. Nanotech.

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“…On the contrary, three different adsorption regimes are identified for Cys/Ag(111) [44]: 1) the multilayer, in which Cys zwitterions physisorb on top of an already present monolayer of molecules and maintain their SH-group intact; 2) the  phase, consisting of a single layer of zwitterionic molecules chemisorbed through their deprotonated S-group; 3) the  phase, produced upon annealing the  phase to T > 393 K and consisting in a mixture of anionic and neutral molecules. While many amino acids adsorb in an anionic form upon deposition [175], thermally activated deprotonation of the ammonium group was previously reported only for Met on Cu(111) [62].…”

Section: Adsorption State Of Aa At Ag Surfacesmentioning

confidence: 95%

“…In addition, the availability of a tunable X-ray source offers the possibility to perform also edge spectroscopies, in particular Near Edge X-ray Absorption Fine Structure (NEXAFS). Providing significant information on the molecular bonds orientation, this technique is very helpful for the characterisation of the structural conformation of the adsorbed molecules [44][45][46].…”

Section: Spectroscopic Techniquesmentioning

confidence: 99%

Adsorption and self-assembly of bio-organic molecules at model surfaces: A route towards increased complexity

Costa

Pradier

Tielens

et al. 2015

Surface Science Reports

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Understanding the bio-physical-chemical interactions at nanostructured biointerfaces and the assembling mechanisms of so-called hybrid nano-composites is nowadays a keyissue for nanoscience in view of the many possible applications foreseen. The contribution of surface science in this field is noteworthy since, using a bottom-up approach, it allows the investigation of the fundamental processes at the basis of complex interfacial phenomena and thus it helps to unravelthe elementary mechanisms governing them. Nowadays it is well demonstrated that a wide variety of different molecular assemblies can form upon adsorption of small biomolecules at surfaces. The geometry of such self-organized structures can often be tuned by a careful control of the experimental conditions during the deposition process. Indeed an impressive number of studies exist (both experimental and -to a lesser extendtheoretical), which demonstrate the ability of molecular self-assembly to create different structural motifs in a more or less predictable manner, by tuning the molecular building blocks as well as the metallic substrate. In this frame, amino acidsand small peptides at surfaces are key, basic, systems to be studied. The amino acidsstructure is simple enough to serve as a model for the chemisorption of biofunctional molecules, but their adsorption at surfaces has applications in surface functionalization, in enantiospecific catalysis, biosensing, nanoparticles shape control or in emerging fields such as "green" corrosion inhibition. In this paper we review the most recent advancements in this field. We will start from amino acids adsorption at metal surfaces and we will evolve then in the direction of more complex systems, in thelight of the latest improvements of surface science techniques and of computational methods. On one side, we will focus on amino acids adsorption at oxide surfaces, on the other on peptide adsorption both at metal and oxide substrates. Particular attention will be drawn to the added value provided by the combination of several experimental surface science techniques and to the precious contribution of advanced complementary computational methods to resolve the details of systems of increased complexity. Finally, some hints into experiments performed in the presence of water and then characterized in UHV and in the related theoretical work will be presented. This is a further step towards abetter approximation of real biological systems. However, since the methods employed are often not typical of surface science, this topic is not developed in details.2

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“…1-3 Thiols adsorption has also been studied on the other coinage metals [4][5][6][7] . Thiols 4,[8][9][10][11][12][13][14][15] , disulfides [16][17][18][19] , methionines [20][21][22][23][24] , cysteines [25][26][27][28][29][30][31][32][33] , etc. have been studied experimentally and theoretically.…”

Section: Introductionmentioning

confidence: 99%

Dibenzyl disulfide adsorption on Cu(111) surface: a DFT study

2015

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The adsorption of dibenzyl disulfide (DBDS) on a Cu(111) surface model was investigated by using density functional (DFT) calculations, considering energetic and electronic aspects. Several complexes were generated, where the bridge, hollow hcp, hollow fcc and top adsorption sites were considered. The results show that the Cu-S interaction guides the final complexes, and a secondary π-Cu weak interaction confers an extra stability. The complexes were grouped as physi-or chemi-sorption according to their adsorption energy applying a distortion decomposition model, with a preference by a double interaction of S with Cu (i.e. hollow hcp, and bridge sites). A degree of disulfide bond dissociation was observed in the complexes, being correlated with adsorption energies. From an electronic aspect, it was found that the electronic flow from copper to DBDS occurs in the most stables complexes, checked with charge analysis.These results are agreed with experimental revelations of copper corrosion on power transformers.

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l-Cysteine on Ag(111): A Combined STM and X-ray Spectroscopy Study of Anchorage and Deprotonation

Cited by 78 publications

References 57 publications

Interface Electronic Structures of the L-Cysteine on Noble Metal Surfaces Studied by Ultraviolet Photoelectron Spectroscopy

Interface Electronic Structures of the L-Cysteine on Noble Metal Surfaces Studied by Ultraviolet Photoelectron Spectroscopy

Adsorption and self-assembly of bio-organic molecules at model surfaces: A route towards increased complexity

Dibenzyl disulfide adsorption on Cu(111) surface: a DFT study

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