Vertical Alignment of Size-Controlled Self-Assembled Diphenylalanine Peptide Nanotubes Using Polyethersulfone Hollow Fiber Membranes On Silicon (original) (raw)
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Nanomaterials
The structures and properties of the diphenylalanine (FF) peptide nanotubes (PNTs), both L-chiral and D-chiral (L-FF and D-FF) and empty and filled with water/ice clusters, are presented and analyzed. DFT (VASP) and semi-empirical calculations (HyperChem) to study these structural and physical properties of PNTs (including ferroelectric) were used. The results obtained show that after optimization the dipole moment and polarization of both chiral type L-FF and D-FF PNT and embedded water/ice cluster are enhanced; the water/ice cluster acquire the helix-like structure similar as L-FF and D-FF PNT. Ferroelectric properties of tubular water/ice helix-like cluster, obtained after optimization inside L-FF and D-FF PNT, as well of the total L-FF and D-FF PNT with embedded water/ice cluster, are discussed.
Self-assembled arrays of peptide nanotubes by vapour deposition
Nature Nanotechnology, 2009
The use of bionanostructures in real-world applications will require precise control over biomolecular self-assembly and the ability to scale up production of these materials 1 . A significant challenge is to control the formation of large, homogeneous arrays of bionanostructures on macroscopic surfaces 2-4 . Previously, bionanostructure formation has been based on the spontaneous growth of heterogenic populations in bulk solution 1 . Here, we demonstrate the self-assembly of large arrays of aromatic peptide nanotubes using vapour deposition methods. This approach allows the length and density of the nanotubes to be fine-tuned by carefully controlling the supply of the building blocks from the gas phase. Furthermore, we show that the nanotube arrays can be used to develop high-surface-area electrodes for energy storage applications, highly hydrophobic self-cleaning surfaces and microfluidic chips.
Stability of diphenylalanine peptide nanotubes in solution
Nanoscale, 2011
Over the last couple of years, self-organizing nanotubes based on the dipeptide diphenylalanine have received much attention, mainly as possible building blocks for the next generation of biosensors and as drug delivery systems. One of the main reasons for this large interest is that these peptide nanotubes are believed to be very stable both thermally and chemically. Previously, the chemical and thermal stability of self-organizing structures has been investigated after the evaporation of the solvent. However, it was recently discovered that the stability of the structures differed significantly when the tubes were in solution. It has been shown that, in solution, the peptide nanotubes can easily be dissolved in several solvents including water. It is therefore of critical importance that the stability of the nanotubes in solution and not after solvent evaporation be investigated prior to applications in which the nanotube will be submerged in liquid. The present article reports results demonstrating the instability and suggests a possible approach to a stabilization procedure, which drastically improves the stability of the formed structures. The results presented herein provide new information regarding the stability of selforganizing diphenylalanine nanotubes in solution.
Langmuir, 2006
The diphenylalanine peptide, the core recognition motif of the -amyloid polypeptide, efficiently self-assembles into discrete, well-ordered nanotubes. Here, we describe the notable thermal and chemical stability of these tubular structures both in aqueous solution and under dry conditions. Scanning and transmission electron microscopy (SEM and TEM) as well as atomic force microscopy (AFM) revealed the stability of the nanotubes in aqueous solution at temperatures above the boiling point of water upon autoclave treatment. The nanotubes preserved their secondary structure at temperatures up to 90°C, as shown by circular dichroism (CD) spectra. Cold field emission gun (CFEG) high-resolution scanning electron microscope (HRSEM) and thermogravimetric analysis (TGA) of the peptide nanotubes after dry heat revealed durability at higher temperature. It was shown that the thermal stability of diphenylalanine peptide nanotubes is significantly higher than that of a nonassembling dipeptide, dialanine. In addition to thermal stability, the peptide nanotubes were chemically stable in organic solvents such as ethanol, methanol, 2-propanol, acetone, and acetonitrile, as shown by SEM analysis. Moreover, the acetone environment enabled AFM imaging of the nanotubes in solution. The significant thermal and chemical stability of the peptide nanotubes demonstrated here points toward their possible use in conventional microelectronic and microelectromechanics processes and fabrication into functional nanotechnological devices.
Temperature-driven phase transformation in self-assembled diphenylalanine peptide nanotubes
Journal of Physics D: Applied Physics, 2010
Diphenylalanine (FF) peptide nanotubes (PNTs) represent a unique class of self-assembled functional biomaterials owing to a wide range of useful properties including nanostructural variability, mechanical rigidity and chemical stability. In addition, strong piezoelectric activity has recently been observed paving the way to their use as nanoscale sensors and actuators. In this work, we fabricated both horizontal and vertical FF PNTs and examined their optical second harmonic generation and local piezoresponse as a function of temperature. The measurements show a gradual decrease in polarization with increasing temperature accompanied by an irreversible phase transition into another crystalline phase at about 140-150 • C. The results are corroborated by the molecular dynamic simulations predicting an order-disorder phase transition into a centrosymmetric (possibly, orthorhombic) phase with antiparallel polarization orientation in neighbouring FF rings. Partial piezoresponse hysteresis indicates incomplete polarization switching due to the high coercive field in FF PNTs.
Peptide Nanotube-Modified Electrodes for Enzyme−Biosensor Applications
Analytical Chemistry, 2005
The fabrication and notably improved performance of composite electrodes based on modified self-assembled diphenylalanine peptide nanotubes is described. Peptide nanotubes were attached to gold electrodes, and we studied the resulting electrochemical behavior using cyclic voltammetry and chronoamperometry. The peptide nanotube-based electrodes demonstrated a direct and unmediated response to hydrogen peroxide and NADH at a potential of +0.4 V (vs SCE). This biosensor enables a sensitive determination of glucose by monitoring the hydrogen peroxide produced by an enzymatic reaction between the glucose oxidase attached to the peptide nanotubes and glucose. In addition, the marked electrocatalytic activity toward NADH enabled a sensitive detection of ethanol using ethanol dehydrogenase and NAD + .
Bioinspired peptide nanotubes: deposition technology, basic physics and nanotechnology applications
Journal of Peptide Science, 2011
Synthetic peptide monomers can self-assemble into PNM such as nanotubes, nanospheres, hydrogels, etc. which represent a novel class of nanomaterials. Molecular recognition processes lead to the formation of supramolecular PNM ensembles containing crystalline building blocks. Such low-dimensional highly ordered regions create a new physical situation and provide unique physical properties based on electron-hole QC phenomena. In the case of asymmetrical crystalline structure, basic physical phenomena such as linear electro-optic, piezoelectric, and nonlinear optical effects, described by tensors of the odd rank, should be explored. Some of the PNM crystalline structures permit the existence of spontaneous electrical polarization and observation of ferroelectricity. The PNM crystalline arrangement creates highly porous nanotubes when various residues are packed into structural network with specific wettability and electrochemical properties.
Diphenylalanine (FF) represents the simplest peptide building block that self-assembles into ordered nanostructures with interesting physical properties. Among self-assembled peptide structures, FF nanotubes display notable stiffness and piezoelectric parameters (Young's modulus = 19−27 GPa, strain coefficient d 33 = 18 pC/N). Yet, inorganic alternatives remain the major materials of choice for many applications due to higher stiffness and piezoelectricity. Here, aiming to broaden the applications of the FF motif in materials chemistry, we designed three phenyl-rich dipeptides based on the β,β-diphenyl-Ala-OH (Dip) unit: Dip-Dip, cyclo-Dip-Dip, and tert-butyloxycarbonyl (Boc)-Dip-Dip. The doubled number of aromatic groups per unit, compared to FF, produced a dense aromatic zipper network with a dramatically improved Young's modulus of ∼70 GPa, which is comparable to aluminum. The piezoelectric strain coefficient d 33 of ∼73 pC/N of such assembly exceeds that of poled polyvinylidene-fluoride (PVDF) polymers and compares well to that of lead zirconium titanate (PZT) thin films and ribbons. The rationally designed π−π assemblies show a voltage coefficient of 2−3 Vm/N, an order of magnitude higher than PVDF, improved thermal stability up to 360°C (∼60°C higher than FF), and useful photoluminescence with wide-range excitationdependent emission in the visible region. Our data demonstrate that aromatic groups improve the rigidity and piezoelectricity of organic self-assembled materials for numerous applications.