Bio-nanotechnology has become a widespread exciting field of research as the basic biological structure of bio-inspired materials and nanotechnology share the common length scale. Bio-nanotechnology, which is mainly based on bio-inspired nanostructured materials, has potential applications in nanomedicine, drug delivery, bio-sensors, and bio-degradable electronic devices. The nanostructures obtained from biomolecules are attractive due to their biocompatibility for molecular recognition, ease of chemical modification, and the ability to scaffold other organic and inorganic materials. Peptide nanostructures formed through the self-assembly process of the basic building block of diphenylalanine show promising applications in biodegradable electronic devices, drug delivery, catalysis agent, waveguide, and frequency converter. This research focusses on the self-assembly process in a dipeptide, L, L diphenylalanine (FF) and exploring its electronic, optical, and magnetic properties. The role of solvents in the self-assembly process of FF is explored by combining density functional theory (DFT) along with experimental characterization techniques such as electron microscopy, Raman scattering, and x-ray diffraction (XRD). One of the objectives of this work was to explore the nonlinear optical (NLO) properties of FF nanostructures via second harmonic generation (SHG). The ratio of the nonlinear optical coefficients was obtained from individual FF nanotubes as a function of the tube diameter and thermal annealing conditions. The ratio of the shear to the longitudinal component (d15/d33) of the NLO coefficient increases with the diameter of the tubes. One of the transverse components, d31, of the NLO coefficient is found to be negative, and its magnitude with respect to the longitudinal component (d33) increases with the tube diameter. Thermal treatment of individual FF tubes has a similar effect as increasing the diameter of the tubes in SHG polarimetry. The functionalization of FF micro-nanostructures (FF-MNS) with nanomaterials was studied. FF-MNS with Ag or Au nanoparticles were explored in surface-enhanced Raman scattering (SERS). Such self-assembled nanostructures provide a natural template for tethering Au and Ag nanoparticles (Nps) due to its fractal surface. The FF-MNS undergo an irreversible phase transition from hexagonal packing (hex) to an orthorhombic (ort) structure at [about] 150 [degree]C. The metal Nps form chains on hex FF-MNS as inferred from transmission electron microscopy images and a uniform non-aggregated distribution in the ort phase. The SERS spectra obtained from R6G bound to FF-MNSs with AuNps show a higher enhancement for the ort phase compared with the hex phase. The experimental results agree well with our calculated Raman spectra of model systems using DFT. Our results indicate that FF-MNS both in the hex and ort phase can be used as substrates for SERS analysis with different metal Nps, opening up a novel class of optically active bio-based substrates. The use of magnetic nanoparticles with biomolecules offers a versatile path for tuning the functionality of the composite material for several applications. The functionalization of FF-MNS with cobalt ferrite (CFO) magnetic nanoparticles was achieved. The interaction between CFO nanoparticles and FF-MNS was investigated by optical spectroscopy, x-ray photoelectron spectroscopy (XPS), and magnetization measurements. The changes in the XPS data from pristine FF-MNS and CFO:FF-MNS are indicative of a charge transfer process from CFO to FF-MNS, changing the electronic states of the Fe2+ and Co2+ ions. A comparison of the magnetic characterization from CFO nanoparticles and CFO:FF-MNS shows a higher saturation magnetization from the nanocomposite sample, which is attributed to a change in the cationic distribution in CFO upon binding with the peptide. We were further successful in demonstrating the application of FF-MNS as a bio-degradable active layer in an organic light emitting diode (OLED). FF-MNS were functionalized with two blue-emitting conducting polymers: di-octyl-substituted polyfluorene (PF8) and ethyl-hexyl polyfluorene (PF2/6), and used as an active layer in an OLED architecture. A combination of molecular dynamics and experimental characterization techniques reveals a stronger binding mechanism for PF8 compared to PF2/6 with FF-MNS. Biodegradability tests from FF-MNS:PF8 nanocomposite films show more than 80% weight loss in 2 h by enzymatic action compared to PF8 pristine films, which do not degrade. Self-assembled FF-MNS with organic semiconductors open up a new generation of biocompatible and biodegradable materials in organic electronics.
2D Self-assembled molecular networks and on-surface reactivity under nanoscale lateral confinement
