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 excitation-dependent
emission in the visible region. Our data demonstrate that aromatic
groups improve the rigidity and piezoelectricity of organic self-assembled
materials for numerous applications.
Au/GaN and Pt/GaN contacts have been studied with XPS. According to XPS depth profiling, the N signal is weak in the region below the metal contact and the Pt or Au signal decreases much more slowly than expected for a sharp interface. Next, we have performed in situ studies of the formation of Au contacts on GaN. In contrast to the results from depth profiling, we observe 2D growth and little or no chemical interaction between Au and GaN. This suggests that conventional calculations of sputtering yields and ion-beam-induced mixing cannot be applied to the analysis of noble metal/GaN depth profiles. Heating during or after Au deposition results in strong clustering, observed by both XPS and AFM. The Schottky barrier height measured by XPS is 1.15 eV.
An aromatic dipeptide crystallizes into sandwich-like supramolecular semiconductors comprising alternating water and peptide layers, allowing doping and facilitating charge transfer.
Fe3O4–Au core–shell magnetic-plasmonic nanoparticles are expected to combine both magnetic and light responsivity into a single nanosystem, facilitating combined optical and magnetic-based nanotheranostic (therapeutic and diagnostic) applications, for example, photothermal therapy in conjunction with magnetic resonance imaging (MRI) imaging. To date, the effects of a plasmonic gold shell on an iron oxide nanoparticle core in magnetic-based applications remains largely unexplored. For this study, we quantified the efficacy of magnetic iron oxide cores with various gold shell thicknesses in a number of popular magnetic-based nanotheranostic applications; these included magnetic sorting and targeting (quantifying magnetic manipulability and magnetophoresis), MRI contrasting (quantifying benchtop nuclear magnetic resonance (NMR)-based T1 and T2 relaxivity), and magnetic hyperthermia therapy (quantifying alternating magnetic-field heating). We observed a general decrease in magnetic response and efficacy with an increase of the gold shell thickness, and herein we discuss possible reasons for this reduction. The magnetophoresis speed of iron oxide nanoparticles coated with the thickest gold shell tested here (ca. 42 nm) was only ca. 1% of the non-coated bare magnetic nanoparticle, demonstrating reduced magnetic manipulability. The T1 relaxivity, r1, of the thick gold-shelled magnetic particle was ca. 22% of the purely magnetic counterpart, whereas the T2 relaxivity, r2, was 42%, indicating a reduced MRI contrasting. Lastly, the magnetic hyperthermia heating efficiency (intrinsic loss power parameter) was reduced to ca. 14% for the thickest gold shell. For all applications, the efficiency decayed exponentially with increased gold shell thickness; therefore, if the primary application of the nanostructure is magnetic-based, this work suggests that it is preferable to use a thinner gold shell or higher levels of stimuli to compensate for losses associated with the addition of the gold shell. Moreover, as thinner gold shells have better magnetic properties, have previously demonstrated superior optical properties, and are more economical than thick gold shells, it can be said that “less is more”.
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