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The structure and electric properties of peptide composite layers with gold nanoparticles


A.I. Loskutov - Ph.D. (Chem.), Associate Professor, Moscow State Technological University STANKIN
A.M. Mandel - Ph.D. (Phys.-Math.), Associate Professor, Moscow State Technological University STANKIN
V.B. Oshurko - Dr.Sc. (Phys.-Math.), Professor, Head of Department, Moscow State Technological University STANKIN
S.A. Egorov - Student, Moscow State Technological University STANKIN
V.A. Romanov - Student, Moscow State Technological University STANKIN
K.G. Solomakho - Post-graduate Student, Moscow State Technological University STANKIN

The processes of formation of thin layers of a composite based on the peptide hexamethylenediamide bis-monosuccinylglutamyl-lysine), {HOOC-(CH2)2-CO-Glu-Lys-NH-(CH2)3}2, and gold nanoparticles (NP) were studied by AFM and STM-STS probe microscopy. Upon crystallization from aqueous colloidal solutions at pH = 7,4. The composite solutions were deposited on the surface of gold films and a freshly prepared surface of single-crystal graphite by drop casting, or spin-coating. Gold NPs have the shape of very thin discs. The average size is ≈ 50 nm, and the height ≤ 4 nm. On the surface of gold, disordered multilayer structures consisting of separate flat particles of different sizes are formed. On the graphite surface the growth of thin filaments and stepped structures with smooth (≤ 0,5 nm) terraces begins. The electrical characteristics of the peptide layers, which were determined by measuring the local tunnel current-voltage characteristics (LTCVC), differ significantly on gold and graphite surfaces. A hysteresis on the CVC is observed on the gold substrate. In this case, all CVC pass through 0 only at negative values of the applied voltage. In addition, current minima appears on them: the region of negative differential conductivity (NDC), on the forward and reverse course, which are never observed at the LTCVC of the PT at pH = 4,2 (isoelectronic point). The distance between the current minima is about 1 eV. Unlike LTCVC of PT-Au composite on gold, it passes through 0 on graphite similarly to the PT at pH = 4,2. Minima of the tunnel current also arise. Depending on the thickness of the layer and the coordinates of the CVC measurement point on the surface of the sample, the relative magnitude of these minima and their position can vary. The obtained results show a strong dependence of the morphology and electrical properties of the composite layers on the nature of the substrate and the state of its surface. This indicates the significant role of interface interactions in the processes of layer growth. It is assumed that such features of crystallization of peptide composites are due to the zwitterionic nature of its molecule. The magnitude and sign of the total charge of peptide molecule can be controlled by changing the pH of the solution. Thus, when pH is raised to 7 and higher, the PT anion is formed. Potassium and gold ions may be the cations. The hysteresis at LTCVC at pH ≥ 7 composite PT-Au shows that the formulated PT salt is a ferroelectric in contrast to the crystallization of neutral PT molecules at pH = 4,2. In the PT salt and the PT-Au composite, the appearance of ferroelectric properties may be occur due to the ordering of the hydrogen bonds in the peptide anion. In the case of a composite layer on the graphite surface, exactly the opposite patterns are observed, and the shape of LTCVC is similar to the LTCVC of the initial PT at pH = 4,2 except for the presence of NDC regions. Of all the substrate materials studied by us (mica, glass, gold, graphite), the latter is the most inert to the interaction with PT. Therefore, it can be concluded that the nature of the interaction of PT with the substrate in the adsorption layer determines not only the architectonics of poly-layers with a thickness of several hundred nanometers, but also their electronic structure and properties. The emergence of NDP regions at LTCVC may be due to several reasons, including the occurrence of oxidation-reduction reactions in the PT-Au layers. The structural and electrical properties of crystallized peptide composite layers layers depend not only on the chemical structure of the peptide molecule, but also on its conformation in the PT-substrate interface. Peptide nanocomposite can be considered as a perspective material of organic electronics.

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