A highly efficient, reproducible,
and scalable approach for exfoliation
of MoS2 is critical for utilizing these emerging materials
from coatings and composites to printable devices. Additive-free techniques,
such as solvent-assisted exfoliation via sonication, are considered
to be the most viable approach, where N-methyl-2-pyrrolidone
(NMP) is the most effective solvent. However, understanding the mechanism
of exfoliation and the key role NMP plays during the process have
been elusive and challenges effective improvements in product yield
and quality. Here, we report systematic experiments to understand
the mechanism of solvent-assisted exfoliation by elucidating the sonolysis
chemistries associated with NMP. It is confirmed that in the presence
of O2(g) dissolved moisture in NMP plays a critical role
during sonication. The higher the moisture content, the more efficient
the exfoliation process is. Conversely, when exfoliations are carried
out with dried solvents with an inert atmosphere, reaction yields
decrease. This is due to redox-active species formed in situ through
an autoxidation pathway that converts NMP to N-methyl
succinimide by hydroperoxide intermediates. These highly reactive
species appear to aid exfoliation by oxidation at reactive edge sites;
the charging creates Coulombic repulsion between neighboring sheets
that disrupts interlayer basal plane bonding and enables electrostatic
stabilization of particles in high-dipole solvents. From these insights,
exfoliation in previously reported inactive solvents (e.g., acetonitrile),
as well as in the absence of probe sonication, is demonstrated. These
findings illustrate that exfoliation of MoS2, and possibly
TMD’s in general, can be mediated through understanding the
chemistry occurring at the surface–solvent interface.
Fibril motion improves peptide signaling
Artificial scaffolds that bear the peptide-signaling sequences of proteins for tissue regeneration often have limited effectiveness. Álvarez
et al
. synthesized supramolecular peptide fibril scaffolds bearing two peptide sequences that promote nerve regeneration, one that reduces glial scarring and another that promotes blood vessel formation (see the Perspective by Wojciechowski and Stevens). In a mouse model of paralyzing human spinal cord injury, mutations in a tetrapeptide domain outside of the signaling regions improved recovery by promoting intense supramolecular motion within the fibrils. The mutation with the most intense dynamics resulted in corticospinal axon regrowth and myelination, functional revascularization, and motor neuron survival. —PDS
Organic/inorganic core shell nanoparticles have been synthesized using high K TiO(2) as the core nanoparticle, and polystyrene as the shell. This material is easy to process and forms transparent continuous thin films, which exhibit a dielectric constant enhancement of over 3 times that of bulk polystyrene. This new dielectric material has been incorporated into capacitors and thin film transistors (TFTs). Mobilities approaching 0.2 cm(2)/V.s have been measured for pentacene TFTs incorporating the new TiO(2) polystyrene nanostructured gate dielectric, indicating good surface properties for pentacene film growth. This novel strategy for generating high K flexible gate dielectrics will be of value in improving organic and flexible electronic device performance.
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