To date, numerous inorganic nanocarriers have been explored for drug delivery systems (DDSs). However, the clinical application of inorganic formulations has often been hindered by their toxicity and failure to biodegrade. We describe here a transformable liquid-metal nanomedicine, based on a core–shell nanosphere composed of a liquid-phase eutectic gallium-indium core and a thiolated polymeric shell. This formulation can be simply produced through a sonication-mediated method with bioconjugation flexibility. The resulting nanoparticles loaded with doxorubicin (Dox) have an average diameter of 107 nm and demonstrate the capability to fuse and subsequently degrade under a mildly acidic condition, which facilitates release of Dox in acidic endosomes after cellular internalization. Equipped with hyaluronic acid, a tumour-targeting ligand, this formulation displays enhanced chemotherapeutic inhibition towards the xenograft tumour-bearing mice. This liquid metal-based DDS with fusible and degradable behaviour under physiological conditions provides a new strategy for engineering theranostic agents with low toxicity.
Here we report on the biomimetic synthesis of Pd nanoparticles for use as models of green catalytic systems. The nanomaterials are synthesized using peptides isolated via phage-display techniques that are specific to Pd surfaces. Using this synthetic strategy, peptide-functionalized Pd nanoparticles of 1.9 +/- 0.3 nm in diameter are produced, which are soluble and stable in aqueous solutions. Once characterized, these biobased materials were then used as catalysts to drive the formation of C-C bonds using the Stille coupling reaction. Under the conditions of an aqueous solvent at room temperature, quantitative product yields were achieved within 24.0 h employing catalyst loadings of > or = 0.005 mol % of Pd. Additionally, high TOF values of 3207 +/- 269 mol product x (mol Pd x h)(-1) have been determined for these materials. The catalytic reactivity was then examined over a set of substrates with substitutions for both functional group and halide substituents, demonstrating that the peptide-based Pd nanoparticles are reactive toward a variety of functionalities. Taken together, these bioinspired materials represent unique model systems for catalytic studies to elucidate ecologically friendly reactive species and conditions.
Diverse classes of metallic nanostructures have been explored recently for a variety of applications, including energy efficient catalytic transformations. The morphology, size, and local chemical environment of the catalytic nanomaterials can have dramatic effects on their reactivity. Herein, we demonstrate a peptide-template-based approach for the synthesis of Pd and Pt nanostructures of varying morphologies under ambient conditions. In this report, we examine the effect of the metal/peptide ratio over an expansive range to demonstrate the stepwise production of materials ranging from nanospheres to nanoparticle networks for the Pd structures. Interestingly, when the metallic composition was changed to Pt, only spherical materials were generated, indicating that the metallic composition of the nanostructures plays a key role in the final morphology. The hydrogenation of allyl alcohol was then employed as a model reaction to examine the catalytic reactivity of these metallic nanomaterials. Under environmentally benign reaction conditions, high turnover frequency values were observed for the metallic Pd and Pt nanocatalysts that was independent of the material morphology. Given their high degree of reactivity and facile synthetic preparation, these materials could prove to be versatile and efficient catalysts for a variety of industrially and environmentally important reactions.
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