PtAu nanoparticles (NPs) were shown to strongly enhance the kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Li-O(2) cells. Li-O(2) cells with PtAu/C were found to exhibit the highest round-trip efficiency reported to date. During ORR via xLi(+) + O(2) + xe(-) --> Li(x)O(2), the discharge voltage with PtAu/C was considerably higher than that of pure carbon and comparable to that of Au/C. During OER via Li(x)O(2) --> xLi(+) + O(2) + xe(-), the charge voltages with PtAu/C fell in the range from 3.4 to 3.8 V(Li), which is slightly lower than obtained with Pt. It is hypothesized that PtAu NPs exhibit bifunctional catalytic activity, having surface Au and Pt atoms primarily responsible for ORR and OER kinetics in Li-O(2) cells, respectively.
Combination therapy, or the use of multiple drugs, has been proven to be effective for complex diseases, but the differences in chemical properties and pharmacokinetics can be challenging in term of the loading, delivering, and releasing multiple drugs. Here we demonstrate that we can load and selectively release two different DNA oligonucleotides from two different gold nanorods. DNA was loaded on the nanorods via thiol conjugation. Selective releases were induced by selective melting of gold nanorods via ultrafast laser irradiation at the nanorods' longitudinal surface plasmon resonance peaks. Excitation at one wavelength could selectively melt one type of gold nanorods and selectively release one type
Increasingly detailed structural and dynamic studies are highlighting the precision with which biomolecules execute often complex tasks at the molecular scale. The efficiency and versatility of these processes have inspired many attempts to mimic or harness them. To date, biomolecules have been used to perform computational operations and actuation, to construct artificial transcriptional loops that behave like simple circuit elements and to direct the assembly of nanocrystals. Further development of these approaches requires new tools for the physical and chemical manipulation of biological systems. Biomolecular activity has been triggered optically through the use of chromophores, but direct electronic control over biomolecular 'machinery' in a specific and fully reversible manner has not yet been achieved. Here we demonstrate remote electronic control over the hybridization behaviour of DNA molecules, by inductive coupling of a radio-frequency magnetic field to a metal nanocrystal covalently linked to DNA. Inductive coupling to the nanocrystal increases the local temperature of the bound DNA, thereby inducing denaturation while leaving surrounding molecules relatively unaffected. Moreover, because dissolved biomolecules dissipate heat in less than 50 picoseconds (ref. 16), the switching is fully reversible. Inductive heating of macroscopic samples is widely used, but the present approach should allow extension of this concept to the control of hybridization and thus of a broad range of biological functions on the molecular scale.
The ability to direct bimetallic nanoparticles to express desirable surface composition is a crucial step toward effective heterogeneous catalysis, sensing, and bionanotechnology applications. Here we report surface composition tuning of bimetallic Au-Pt electrocatalysts for carbon monoxide and methanol oxidation reactions. We establish a direct correlation between the surface composition of Au-Pt nanoparticles and their catalytic activities. We find that the intrinsic activities of Au-Pt nanoparticles with the same bulk composition of Au0.5Pt0.5 can be enhanced by orders of magnitude by simply controlling the surface composition. We attribute this enhancement to the weakened CO binding on Pt in discrete Pt or Pt-rich clusters surrounded by surface Au atoms. Our finding demonstrates the importance of surface composition control at the nanoscale in harnessing the true electrocatalytic potential of bimetallic nanoparticles and opens up strategies for the development of highly active bimetallic nanoparticles for electrochemical energy conversion.
Conjugation of proteins to nanoparticles has numerous applications in sensing, imaging, delivery, catalysis, therapy and control of protein structure and activity. Therefore, characterizing the nanoparticle-protein interface is of great importance. A variety of covalent and non-covalent linking chemistries have been reported for nanoparticle attachment. Site-specific labeling is desirable in order to control the protein orientation on the nanoparticle, which is crucial in many applications such as fluorescence resonance energy transfer. We evaluate methods for successful site-specific attachment. Typically, a specific protein residue is linked directly to the nanoparticle core or to the ligand. As conjugation often affects the protein structure and function, techniques to probe structure and activity are assessed. We also examine how molecular dynamics simulations of conjugates would complete those experimental techniques in order to provide atomistic details on the effect of nanoparticle attachment. Characterization studies of nanoparticle-protein complexes show that the structure and function are influenced by the chemistry of the nanoparticle ligand, the nanoparticle size, the nanoparticle material, the stoichiometry of the conjugates, the labeling site on the protein and the nature of the linkage (covalent versus non-covalent).
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