Zwitterionic self-assembly of l-methionine nanogratings on the Ag(111) surface

The engineering of complex architectures from functional molecules on surfaces provides new pathways to control matter at the nanoscale. In this article, we present a combined study addressing the self-assembly of the amino acid l-methionine on Ag(111). Scanning tunneling microscopy data reveal spontaneous ordering in extended molecular chains oriented along high-symmetry substrate directions. At intermediate coverages, regular biomolecular gratings evolve whose periodicity can be tuned at the nanometer scale by varying the methionine surface concentration. Their characteristics and stability were confirmed by helium atomic scattering. X-ray photoemission spectroscopy and high-resolution scanning tunneling microscopy data reveal that the l-methionine chaining is mediated by zwitterionic coupling, accounting for both lateral links and molecular dimerization. This methionine molecular recognition scheme is reminiscent of sheet structures in amino acid crystals and was corroborated by molecular mechanics calculations. Our findings suggest that zwitterionic assembly of amino acids represents a general construction motif to achieve biomolecular nanoarchitectures on surfaces.

[1]  K. Kelly,et al.  Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces. , 2003, Accounts of chemical research.

[2]  T. Osaka,et al.  Enantioselective crystal growth of leucine on a self-assembled monolayer with covalently attached leucine molecules. , 2004, Journal of the American Chemical Society.

[3]  A Riemann,et al.  Supramolecular gratings for tuneable confinement of electrons on metal surfaces. , 2007, Nature nanotechnology.

[4]  K. Kern,et al.  Engineering atomic and molecular nanostructures at surfaces , 2005, Nature.

[5]  M. Canepa,et al.  High resolution X-ray photoelectron spectroscopy of L-cysteine self-assembled films , 2004 .

[6]  J. Barth,et al.  Molecular architectonic on metal surfaces. , 2007, Annual review of physical chemistry.

[7]  B. Hammer,et al.  Growth of unidirectional molecular rows of cysteine on Au(110)-(1 x 2) driven by adsorbate-induced surface rearrangements. , 2004, Physical review letters.

[8]  Giampiero Naletto,et al.  Performance of the grating-crystal monochromator of the ALOISA beamline at the Elettra Synchrotron , 1999 .

[9]  S. Baroni,et al.  Monitoring two-dimensional coordination reactions: directed assembly of co-terephthalate nanosystems on Au(111). , 2006, The journal of physical chemistry. B.

[10]  K. Schulten,et al.  Molecular biomimetics: nanotechnology through biology , 2003, Nature materials.

[11]  B. Hammer,et al.  Chiral switching by spontaneous conformational change in adsorbed organic molecules , 2006, Nature Materials.

[12]  Markus Antonietti,et al.  Ionic Self‐Assembly: Facile Synthesis of Supramolecular Materials , 2003 .

[13]  K. Fichthorn,et al.  Substrate-mediated interactions on solid surfaces: theory, experiment, and consequences for thin-film morphology , 2003 .

[14]  N. Oxtoby,et al.  Controlling molecular deposition and layer structure with supramolecular surface assemblies , 2003, Nature.

[15]  Shiyoshi Yokoyama,et al.  Selective assembly on a surface of supramolecular aggregates with controlled size and shape , 2001, Nature.

[16]  Bengt Herbert Kasemo,et al.  Biological surface science , 1998 .

[17]  B. Schade,et al.  Amino acid networks , 1998 .

[18]  B. Dalhus,et al.  Crystal structures of hydrophobic amino acids: interaction energies of hydrogen-bonded layers revealed by ab initio calculations , 2004 .

[19]  K. Kern,et al.  Deprotonation-Driven Phase Transformations in Terephthalic Acid Self-Assembly on Cu(100) , 2004 .

[20]  M. Canepa,et al.  High resolution XPS of the S?2p core level region of the L-cysteine/gold interface , 2004 .

[21]  N. V. Richardson,et al.  Enantiomeric interactions between nucleic acid bases and amino acids on solid surfaces , 2003, Nature materials.

[22]  Klaus Kern,et al.  Supramolecular Assemblies of Trimesic Acid on a Cu(100) Surface , 2002 .

[23]  S. M. Barlow,et al.  Complex organic molecules at metal surfaces: bonding, organisation and chirality , 2003 .

[24]  W. Schneider,et al.  Creation of an atomic superlattice by immersing metallic adatoms in a two-dimensional electron sea. , 2004, Physical review letters.

[25]  R. Car,et al.  Two-Dimensional Self-Assembly of Supramolecular Clusters and Chains , 1999 .

[26]  M. Preuss,et al.  Coulombic amino group-metal bonding: adsorption of adenine on Cu110. , 2005, Physical review letters.

[27]  M. Graetzel,et al.  Adsorbed .omega.-hydroxy thiol monolayers on gold electrodes: evidence for electron tunneling to redox species in solution , 1991 .

[28]  E. Schmich,et al.  Strong Temperature Dependence of Irradiation Effects in Organic Layers , 2004 .

[29]  G. Meyer.  A simple low‐temperature ultrahigh‐vacuum scanning tunneling microscope capable of atomic manipulation , 1996 .

[30]  M. Canepa,et al.  Electronic and geometric characterization of the L-cysteine paired-row phase on Au(110). , 2006, Langmuir : the ACS journal of surfaces and colloids.

[31]  T. Kawai,et al.  Low dimensional self-organization of DNA-base molecules on Cu(111) surfaces , 1997 .

[32]  P. Günter,et al.  Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111). , 2002, Journal of the American Chemical Society.

[33]  K. Kern,et al.  Steering molecular organization and host–guest interactions using two-dimensional nanoporous coordination systems , 2004, Nature materials.

[34]  A. De Vita,et al.  Mesoscopic correlation of supramolecular chirality in one-dimensional hydrogen-bonded assemblies. , 2001, Physical review letters.

[35]  B. Kasemo,et al.  Glycine on Pt(111): a TDS and XPS study , 1997 .

[36]  M. Canepa,et al.  Ultrahigh vacuum deposition of L-cysteine on Au(110) studied by high-resolution X-ray photoemission: from early stages of adsorption to molecular organization. , 2005, The journal of physical chemistry. B.

[37]  Günter,et al.  Building Supramolecular Nanostructures at Surfaces by Hydrogen Bonding Fruitful discussions with A. de Vita, B. Müller, and H. Brune are acknowleged. , 2000, Angewandte Chemie.

[38]  L. Kantorovich,et al.  Planar nucleic acid base super-structures , 2006 .

[39]  B. Hammer,et al.  Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy , 2002, Nature.

[40]  K. Kern,et al.  Mesoscopic metallosupramolecular texturing by hierarchic assembly. , 2005, Angewandte Chemie.

[41]  S. Mashiko,et al.  Conformation selective assembly of carboxyphenyl substituted porphyrins on Au (111). , 2004, The Journal of chemical physics.

[42]  I. Stensgaard,et al.  One-dimensional assembly and selective orientation of Lander molecules on an O-Cu template. , 2004, Angewandte Chemie.