Self-assembled peptide nanostructures for electrical, optical, and magnetic applications

Field of study: Physics.Dr. Suchismita Guha, Dissertation Supervisor.Includes vita."May 2018."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.Includes bibliographical references (pages 131-139)

Enhanced Piezoresponse and Nonlinear Optical Properties of Fluorinated Self-Assembled Peptide Nanotubes

Self-assembled L,L-diphenylalanine (FF) nanostructures offer an attractive platform for photonics and nonlinear optics. The nonlinear optical (NLO) coefficients of FF nanotubes depend on the diameter of the tube [S. Khanra et al. Phys. Chem. Chem. Phys. 19(4), 3084-3093 (2017)]. To further enhance the NLO properties of FF, we search for structural modifications. Here, we report on the synthesis of fluorinated FF dipeptides by replacing one ortho-hydrogen atom in each of the phenyl groups of FF by a fluorine atom. Density-functional theoretical calculations yield insights into minimum energy conformers of fluorinated FF (Fl-FF). Fl-FF self-assembles akin to FF into micron-length tubes. The effects of fluorination are evaluated on the piezoelectric response and nonlinear optical properties. The piezoelectric d15 coefficient of Fl-FF is found to be more than 10 times higher than that of FF nanotubes, and the intensity of second harmonic generation (SHG) polarimetry from individual Fl-FF nanotubes is more than 20 times that of individual FF nanotubes. Furthermore, we obtain SHG images to compare the intensities of FF and Fl-FF tubes. This work demonstrates the potential of fluorine substitution in other self-assembled biomimetic peptides for enhancing nonlinear optical response and piezoelectricity

Electrical and Magnetic Properties of Molybdenum Doped Yttrium Ion Garnet for Spintronic Applications

Yttrium iron garnet (YIG) is a synthetic garnet and ferrimagnetic with chemical formula Y3Fe5O12. In YIG, five iron (III) ions occupy two octahedral and three tetrahedral sites, with the yttrium (III) ions coordinated by eight oxygen ions in an irregular cube. The iron ions in the two coordination sites exhibit different spins, resulting in ferrimagnetic behavior. YIG is used in microwave, optical, and magneto-optical applications, e.g. microwave YIG filters, solid-state lasers, and data storage. In view of these interesting properties and important applications, YIG and Mo doped YIG have been synthesized systematically using solid state reaction method. The phase purity and structural details were confirmed using X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. XRD study shows that all samples exhibit a cubic structure with a lattice constant of about 12 angstrom. Room temperature dielectric measurements indicate that the YIG shows the usual dielectric dispersion. Molybdenum(x=0.02, 0.05, 0.1) has been used to dope and thereby change the magnetic and electrical properties of yttrium iron garnet. Electrical and optical data show that the electrical conductivity increases and the band gap decreases with Mo doping. It is found that band gap engineering is possible through Mo doping. Magnetization data shows that saturation magnetization increases at low values and then decreases with additional Mo doping. It is found that the coercive field of Mo doped YIG can be tuned through Mo doping. All the results indicate that Mo-doping may provide suitable YIG spintronic materials for future spin electronic devices

New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties

Interactions between well-mixed fine powders of As2O3, P2O5, MoO3, WO3 and Nb2O5 at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N2 and air atmosphere, and single crystals electrical conductivity studies. The results evidenced the formation of new complex solids of previously unknown compositions and structures. Three out of four compounds crystallized in non-centrosymmetric space groups and represent layered 2D polymeric puckered structures that being stacked on each other form 3D lattices. All new solids exhibit strong second-harmonic-generation (SHG effect; based on YAG 1064 nm tests with detection of 532 nm photons), and a rare photosalient effect when crystals physically move in the laser beam. Single crystals’ electrical conductivity of the four new synthesized compounds was measured, and the results showed their semiconductor behavior. Values of band gaps of these new solids were determined using diffusion reflectance spectroscopy in the visible region. Aspects of new solids’ practical usefulness are discussed

Hybrid ZnO-organic semiconductor interfaces in photodetectors: A comparison of two near-infrared donor-acceptor copolymers

Hybrid organic-inorganic photodiode interfaces have gained significant interest due to their unique physical properties such as mechanical flexibility and high photosensitivity. Two diketopyrrolopyrrole (DPP)-based donor-acceptor copolymers with different backbone conformations are characterized in an inverted non-fullerene photodiode architecture using ZnO nano-patterned films as the electron transport layer. The DPP copolymer with a thienothiophene unit (PBDT-TIDPP) is more planar and rigid compared to the DPP system with a thiophene unit connecting the donor and acceptor moieties within the monomer (PBDT-TDPP). The hybrid interfaces were optimized by using poly(3-hexylthiophene) (P3HT) as the p-type layer for monitoring the critical thickness and morphology of the ZnO layer. The maximum photoresponsivity from a P3HT:ZnO photodiode was found to be 56 mA/W. The photoresponsivity of PBDT-TTDPP:ZnO photodiodes were found to be more than two orders of magnitude higher than PBDT-TDPP:ZnO photodiodes, which is attributed to an enhanced transport of carriers due to the planar backbone conformation of the PBDT-TTDPP copolymer. Capacitance-voltage measurements from hybrid Schottky barrier interfaces further shed light into the nature of photocarriers and device parameters. First-principles time-dependent density-functional theoretical calculations yield a higher absorptivity for the PBDT-TTDPP dimer compared to PBDT-TDPP. (C) 2017 Elsevier B.V. All rights reserved

Probing nonlinear optical coefficients in self-assembled peptide nanotubes

Self-assembled L,L-diphenylalanine (FF) peptide micro/nanotubes represent a class of biomimetic materials with a non-centrosymmetric crystal structure and strong piezoelectricity. The peptide nanotubes synthesized by a liquid phase method yield tube lengths in the hundreds of micron range, inner diameters in the few hundred nanometer range, and outer diameters in the 5-15 μm range. Second harmonic generation (SHG) polarimetry from individual self-assembled FF nanotubes is used to obtain the nonlinear (NLO) optical coefficients as a function of the tube diameter and thermal treatment. 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 of the nonlinear coefficient is found to be negative, and its magnitude with respect to the longitudinal component increases with the tube diameter. Thermal treatment of individual FF tubes has a similar effect upon increasing the diameter of the tubes in SHG polarimetry. Concurrent Raman scattering measurements from individual FF tubes show a distinct change in the low frequency (100 cm−1) region with the diameter of the tubes reflecting subtle effects of water