Conformational Impact on Amino Acid-Surface π-π Interactions on a (7,7) Single-Walled Carbon Nanotube: A Molecular Mechanics Approach.

A study of π-π interactions between a (7,7) single-walled carbon nanotube (SWNT) and three different aromatic amino acids (AAA), namely l-tyrosine (Tyr), l-tryptophan (Trp), and l-phenylalanine (Phe) was conducted with a molecular mechanics (MM) approach. For each of the amino acids we investigated the behavior of six different conformers. We examined the impact of the so-called edge effects by testing the parameters of the built-in switching function in MM. We found the optimal SWNT length to be approximately 80 Å for the size of the molecules in our conformational studies. The positional effect of electron withdrawing groups with respect to the aromatic tail was studied to understand the influence of this interaction specific to adsorption strength and geometry. We decomposed the aromatic amino acid-surface interactions into three components: overall energy, aromatic ring, and amino acid head adsorption energies. We found that the ability of the amino acid's head to interact with the surface π-densities had a greater impact on the overall energy than the amino acid head interaction with its substituent's aromatic ring's π-electrons.

Atomic Charge Dependency of Spiropyran/Merocyanine Adsorption as a Precursor to Surface Isomerization Reactions.

This computational study investigates the adsorption of various spiropyran and merocyanine isomers on a NaCl substrate using a combination of density functional theory (DFT) and molecular mechanics (MM) calculations. Four different charge methods were used to determine the partial atomic charges for the adsorbate molecules, including Mulliken population analysis and three electrostatic potential (ESP) methods (Merz-Kollman, ChelpG, and Hu-Lu-Yang), while three different force fields (AMBER 3, CHARMM 27, and MM+) were employed for the MM calculations. The results show that the various DFT charge methods produced similar outcomes for the molecules' partial atomic charges, with some exceptions for individual atoms and methods. Additionally, it was found that the ESP charge methods were more sensitive to the conformer orientation than the Mulliken approach. The adsorption behavior of merocyanine conformers with the central bond in trans orientation (T-conformers) was similar for various configurations, with the molecule adsorbing mostly flat with its aromatic rings almost parallel to the substrate. However, C-conformers (with their central bond in cis orientation) and spiropyran isomers exhibited inconsistent adsorption behavior, mostly because only some of the aromatic rings contributed to the adsorption behavior. Due to additional van der Waals interactions of more aromatic rings, the adsorption energies for T-conformers are consistently 0.2-0.3 eV higher than for C-conformers and for spiropyran. The study found that the adsorption geometries and energies of stable T-conformers were independent of the partial atomic charge scheme and force field used, and C-conformers show parameter-dependent behavior upon adsorption, leading to metastable configurations. These findings indicate viable pathways during the spiropyran-merocyanine isomerization reactions. Therefore, the results provide initial insights into the possibility of switching spiropyran isomers into merocyanine isomers and vice versa after adsorption onto substrates.

Combined DFT and Molecular Mechanics Modeling of the Adsorption of Semiconducting Molecules on an Ionic Substrate: PTCDA and CuPc on NaCl.

Experimental results suggest that molecular geometry and energies can be influenced by the presence of thin film substrates as well as surrounding molecules. It is imperative that computational models take this influence into account. The accurate computational modeling of these molecules is an efficient way of carrying out chemistry calculations and reinforcing experimental findings. In our study, density functional theory (DFT) and molecular mechanics (MM) are used to model the configurations of the organic semiconducting materials, 3,4,9,10-perylene tetracarboxylic dianhydride, C24H8O6 (PTCDA), and copper(II) phthalocyanine, C32H16CuN8 (CuPc), as adsorbed on single- and double-layer NaCl substrates of various dimensions and charge settings. After a geometry and charge optimization of the molecules using DFT, the molecular geometries are optimized under different environments using computational calculations with specific force-field settings in HyperChem Professional 8.0(TM) software using MM. Energies and geometries of the molecules are then recorded, and our data are compared to experimental results of similar systems. We find that, with the appropriate choice of substrate properties, the calculated molecular configurations directly reflect those found experimentally. Our results support the idea that this method of simulation can produce reliable models in the field of physical chemistry.

Molecular wires self-assembled on a graphite surface.

We report a scanning tunneling microscopy study of the amino acid l-methionine on highly ordered pyrolytic graphite deposited under ambient conditions. Our experiments demonstrate the ability of l-methionine to form highly regular structures on the surface of the graphite template. By means of self-assembly, the amino acid arranges itself into an array of molecular wires, i.e., well-ordered stripes of uniform width and separation. The spacing of these wires can be controlled with the deposition amount of the amino acid, whereas the width stays constant. The width of the wires is determined by two methionine molecules arranged with their carboxyl group facing each other. The regular separation of individual wires suggest a long-range interaction among them. Molecular mechanics calculations are used to compare the experimental results with a basic model for the methionine configuration on the surface. A model for the adsorption geometry of methionine on graphite is presented.

Controlled metalation of self-assembled porphyrin nanoarrays in two dimensions.

We report a bottom-up approach for the fabrication of metallo-porphyrin compounds and nanoarchitectures in two dimensions. Scanning tunneling microscopy and tunneling spectroscopy observations elucidate the interaction of highly regular porphyrin layers self-assembled on a Ag(111) surface with iron monomers supplied by an atomic beam. The Fe is shown to be incorporated selectively in the porphyrin macrocycle whereby the template structure is strictly preserved. The immobilization of the molecular reactants allows the identification of single metalation events in a novel reaction scheme. Because the template layers provide extended arrays of reaction sites, superlattices of coordinatively unsaturated and magnetically active metal centers are obtained. This approach offers novel pathways to realize metallo-porphyrin compounds, low-dimensional metal-organic architectures and patterned surfaces which cannot be achieved by conventional means.

Conformational adaptation and selective adatom capturing of tetrapyridyl-porphyrin molecules on a copper (111) surface.

We present a combined low-temperature scanning tunneling microscopy and near-edge X-ray adsorption fine structure study on the interaction of tetrapyridyl-porphyrin (TPyP) molecules with a Cu(111) surface. A novel approach using data from complementary experimental techniques and charge density calculations allows us to determine the adsorption geometry of TPyP on Cu(111). The molecules are centered on "bridge" sites of the substrate lattice and exhibit a strong deformation involving a saddle-shaped macrocycle distortion as well as considerable rotation and tilting of the meso-substituents. We propose a bonding mechanism based on the pyridyl-surface interaction, which mediates the molecular deformation upon adsorption. Accordingly, a functionalization by pyridyl groups opens up pathways to control the anchoring of large organic molecules on metal surfaces and tune their conformational state. Furthermore, we demonstrate that the affinity of the terminal groups for metal centers permits the selective capture of individual iron atoms at low temperature.

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.