Tracking the Chiral Recognition of Adsorbed Dipeptides at the Single‐Molecule Level

Lingenfelder, Magalí; Tomba, Giulia; Costantini, Giovanni; Ciacchi, Lucio Colombi; Vita, Alessandro De; Kern, Klaus

doi:10.1002/anie.200700194

Cited by 154 publications

(155 citation statements)

References 26 publications

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“…31 As already reported in ref 18, the XPS data are consistent with a zwitterionic charge state of the assembled Phe-Phe molecules. The NEXAFS spectra of the C1s edge (Figure 6a) show two broad σ* features and two π* resonances.…”

Section: Adsorbed Isolated Moleculessupporting

confidence: 81%

“…We followed the formation, growth, and dissociation dynamics of several Phe-Phe chains by acquiring consecutive STM images on the same surface region (videos V1-V3 in Supporting Information). The mutually induced, stereoselective formation of molecular dimers has been reported and discussed in ref 18. Starting from a pre-existing dimer (red circle in Figure 7(i)a), the interaction with a third molecule (indicated by a red arrow in Figure 7(i)) takes place initially with the formation of a metastable trimer structure (Figure 7(i)d-h).…”

Section: Adsorbed Isolated Moleculesmentioning

confidence: 72%

“…The choice of the periodically repeated cell used in the ab initio simulations is based on the periodicity and orientation of the molecular chains that form on Cu(110) after exposure to Phe-Phe molecules. 18 In the cell we used to model these molecular chains, two of the cell vectors are parallel to the [11 h2] and [11 h2 h] surface crystallographic directions, with dimensions of 8.89 and 22.24 Å, respectively. The third cell vector is perpendicular to the surface, and its length (11.13 Å) is chosen so that a vacuum layer corresponding to nine Cu layers separates the surface slab model from its periodically repeated images.…”

Section: Methodsmentioning

confidence: 99%

“…18 In particular, two molecules with C conformation would saturate their functionalities by forming a doubly bound molecular pair, while molecules with S conformation could assemble in linear structures of arbitrary length. Indeed, in a classical gas-phase MD simulation, we observed a series of nine L-Phe-L-Phe molecules bound to each other through the carboxylic and amino moieties, forming a stable, open-ended chain.…”

Section: Adsorbed Isolated Moleculesmentioning

confidence: 99%

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Structure and Energetics of Diphenylalanine Self-Assembling on Cu(110)

et al. 2007

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We investigate the dynamical features of the adsorption of diphenylalanine molecules on the Cu(110) surface and of their assembling into supramolecular structures by a combination of quantum and classical atomistic modeling with dynamic scanning tunneling microscopy and spectroscopic experiments. Our results reveal a self-assembling mechanism in which isolated adsorbed molecules change their conformation and adsorption mode as a consequence of their mutual interactions. In particular, the formation of zwitterions after proton transfer between initially neutral molecules is found to be the key event of the assembling process, which stabilizes the supramolecular structures. Because of the constraints on the intermolecular bonds exerted by the surface-molecule interactions, the assembly process is strictly stereoselective, and may suggest a general model for patterning and functionalization of bare metal surfaces with short chiral peptides.

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Section: Adsorbed Isolated Moleculessupporting

confidence: 81%

Section: Adsorbed Isolated Moleculesmentioning

confidence: 72%

Section: Methodsmentioning

confidence: 99%

Section: Adsorbed Isolated Moleculesmentioning

confidence: 99%

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Structure and Energetics of Diphenylalanine Self-Assembling on Cu(110)

et al. 2007

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“…The binding between Phe-Phe molecules, which results in the development of supramolecular chains, is most probably due to an interaction between the carboxylic group of one molecule and the amino group of the neighboring one. 7 On the other hand, a nonperfect matching of the chain structures with the underlying substrate might cause the frequent kink defects. The same mismatch could also generate a substrate-mediated repulsion among the chains and, similarly to what is observed in other systems, 8 result in their separation.…”

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confidence: 99%

Ordering of Dipeptide Chains on Cu Surfaces through 2D Cocrystallization

et al. 2007

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The fabrication of novel 2D 1a,b and 3D 1c molecular nanoarchitectures is attracting increasing attention in various research fields ranging from materials science to nanotechnology. Among biomolecules, peptides are very favorable building blocks, owing to the ease of their synthesis, relative stability, and chemical and biological functionalization. 2 They have been used for the design and construction of nanostructures for diverse applications, such as templates for the growth of functional networks, 3 biosensors for monitoring enzymatic reactions, 4 and organic catalysts for asymmetric aldol reactions. 5 A large amount of ordered peptide nanostructures with different geometries, 6 including nanotubes, nanospheres and nanofilaments, have been produced in solution or in vacuum. Peptide monolayer structures self-assembled on solid surfaces typically show a strong tendency to form chains. 6c-e Two-dimensional (2D) extended arrangements are difficult to produce due to a pronounced anisotropy in the intermolecular interactions.Here we report on the ordering and interconnection of 1D dipeptide nanostructures. Individual diphenylalanine molecules (Phe-Phe, Figure 1), only form short isolated chains with a broad length distribution when deposited on Cu substrates. By exploiting 2D cocrystallization with the organic linker terephthalic acid (TPA), we show that continuous and highly periodic dipeptide arrangements can be formed on both the anisotropic Cu(110) and the isotropic Cu(100) surface. This approach might be extended to the fabrication of similar peptide-based nanostructures with potential applications in biocompatible functional surfaces.Scanning tunneling microscopy (STM) measurements of L-Phe-L-Phe molecules deposited under ultrahigh vacuum on Cu surfaces reveal a preferential self-organization in the form of 1D chains. On the Cu(110) surface the Phe-Phe chains are typically isolated and characterized by a high density of kinks. On Cu(100) the chains show four possible orientations and are typically shorter, and their distribution is similarly dispersed (see Figure S1 in the Supporting Information).The formation of isolated chains suggests different intra-and interchain interactions. The binding between Phe-Phe molecules, which results in the development of supramolecular chains, is most probably due to an interaction between the carboxylic group of one molecule and the amino group of the neighboring one. 7 On the other hand, a nonperfect matching of the chain structures with the underlying substrate might cause the frequent kink defects. The same mismatch could also generate a substrate-mediated repulsion among the chains and, similarly to what is observed in other systems, 8 result in their separation. Chain-chain repulsion and kink defects are the reasons why extended and ordered structures are never formed, independently of the molecular coverage (see Figure S1).In order to overcome this limitation, we have co-deposited a molecular linker (TPA) with the aim of connecting the isolated Phe-Phe chains by ef...

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