Self-assembled nanostructures of peptide amphiphiles (PAs) with molecular structures C 16 K 2 and C 16 K 3 (where C indicates the number of carbon atoms in the alkyl chain and K is the lysine in the head group) were studied by a combination of theoretical modeling, transmission electron and atomic force microscopes, and acid−base titration experiments. The supramolecular morphology of the PAs (micelles, fibers, or lamellas) was dependent on the pH and ionic strength of the solution. Theoretical modeling was performed using a molecular theory that allows determining the equilibrium morphology, the size, and the charge of the soft nanoassemblies as a function of the molecular structure of the PA, and the pH and salt concentration of the solution. Theoretical predictions showed good agreement with experimental data for the pH-dependent morphology and size of the nanoassemblies and their apparent pK a s. Two interesting effects associated with charge regulation mechanisms were found: first, ionic strength plays a dual role in the modulation of the electrostatic interactions in the system, which leads to complex dependencies of the aggregation numbers with salt concentration; second, the aggregation number of the nanostructures decreases upon increasing the charge per PA. The second mechanism, charge regulation by size regulation, tunes the net charge of the assemblies to decrease the electrostatic repulsions. A remarkable consequence of this behavior is that adding an extra lysine residue to the charged region of the PAs can lead to an unexpected decrease in the total charge of the micelles. 59 Antimicrobial properties are also highly dependent on the 60 charge of the PAs: a recent study has shown that cationic PAs 61 can inhibit the formation of bacterial films, while anionic ones 62 show no antimicrobial activity at all. 25 In a related biomedical 63 application, the performance of vaccines prepared from PA 64 nanostructures was found to be strongly dependent on their 65 morphology, size, and charge. 26 The importance of nanostruc-66 ture morphology and charge transcends the biological uses of 67 PAs and spans nanotechnology applications as well. For 68 example, Stupp's group has developed a biomineralization 69 strategy for PA nanofibers that requires a negative surface
A dual
optimization approach to nanoparticle catalysis is reported
in which both the composition of a bimetallic nanoparticle and the
electronic properties of the supporting polystyrene-based polymer
can be varied to optimize reactivity and chemoselectivity in nitroarene
reductions. Ruthenium–cobalt nanoparticles supported on polystyrene
are shown to catalyze nitroarene reductions at room temperature with
exceptional activity, as compared with monometallic ruthenium catalysts.
Both the identity of the second metal and the M1/M2 ratio show a profound effect on the chemoselectivity of nitroarene
reductions. These polymer-supported bimetallic catalysts are shown
to react with nearly complete chemoselectivity for nitro group reduction
over a variety of easily reducible functional groups. The electronic
properties of the supporting polymer also have a significant impact
on catalysis, in which electron-deficient polystyrenes enable 100%
conversion to the aniline product in just 20 min at room temperature.
Polymer effects are also shown to influence the mechanism of the reduction
reaction, in addition to accelerating the rate, confirming the impact
of the polymer structure on catalytic efficiency. These catalysts
are easily prepared in a single step from commercial materials and
can be readily recycled without loss of activity.
The ability of antibodies to bind a wide variety of analytes with high specificity and high affinity make them ideal candidates for therapeutic and diagnostic applications. However, the poor stability and high production cost of antibodies has prompted exploration of a variety of synthetic materials capable of specific molecular recognition. Unfortunately, it remains a fundamental challenge to create a chemically-diverse population of protein-like, folded synthetic nanostructures with defined molecular conformations in water. Here we report the synthesis and screening of
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.