Make Conjugation Simple: A Facile Approach to Integrated Nanostructures

We report a facile approach to the conjugation of protein-encapsulated gold fluorescent nanoclusters to the iron oxide nanoparticles through catechol reaction. This method eliminates the use of chemical linkers and can be readily extended to the conjugation of biological molecules and other nanomaterials onto nanoparticle surfaces. The key to the success was producing water-soluble iron oxide nanoparticles with active catechol groups. Further, advanced electron microscopy analysis of the integrated gold nanoclusters and iron oxide nanoparticles provided direct evidence of the presence of a single fluorescent nanocluster per protein template. Interestingly, the integrated nanoparticles exhibited enhanced fluorescent emission in biological media. These studies will provide significantly practical value in chemical conjugation, the development of multifunctional nanostructures, and exploration of multifunctional nanoparticles for biological applications

Layer-Structured Copper Antimony Chalcogenides (CuSbSe_<i>x</i>S_2–<i>x</i>): Stable Electrode Materials for Supercapacitors

The ever-growing need for energy generation and storage applications demands development of materials with high performance and long-term stability. A sizable number of chalcogenide-based materials have been investigated for supercapacitor applications. Layer-structured chalcogenides are advantageous in terms of providing large surface area with good ionic conductivity and ability to host a variety of atoms or ions between the layers. CuSbS₂ is a ternary layered chalcogenide material that is composed of earth abundant and less-toxic elements. For the first time, we have developed a simple colloidal method for the synthesis of CuSbSe_<i>x</i>S_2–<i>x</i> mesocrystals over the whole composition range (0 ≤ <i>x</i> ≤ 2) by substitution of S with Se. Our approach yields mesocrystals with belt-like morphology for all the compositions. X-ray diffraction results show that substitution of sulfur with selenium in CuSbS₂ enables tuning the width of the interlayer gap between the layers. To investigate the suitability of CuSbSe_<i>x</i>S_2–<i>x</i> mesocrystals for supercapacitor applications, we have carried out electrochemical measurements by cyclic voltammetry and galvanostatic charge–discharge measurements in 3 M KOH, NaOH and LiOH electrolytes. Our investigations reveal that the mesocrystals exhibit promising specific capacitance values with excellent cyclic stability. The unique properties of CuSbSe_<i>x</i>S_2–<i>x</i> mesocrystals make them attractive both for solar energy conversion and energy storage applications

Pathways for Gold Nucleation and Growth over Protein Cages

Proteins are widely utilized as templates in biomimetic synthesis of gold nanocrystals. However, the role of proteins in mediating the pathways for gold nucleation and growth is not well understood, in part because of the lack of spatial resolution in probing the complicated biomimetic mineralization process. Self-assembled protein cages, with larger size and symmetry, can facilitate in the visualization of both biological and inorganic components. We have utilized bacteriophage P22 protein cages of ∼60 nm diameter for investigating the nucleation and growth of gold nanocrystals. By adding a gold precursor into the solution with preexisting protein cages and a reducing agent, gold nuclei/prenucleation clusters form in solution, which then locate and attach to specific binding sites on protein cages and further grow to form gold nanocrystals. By contrast, addition of the reducing agent into the solution with incubated gold precursor and protein cages leads to the formation of gold nuclei/prenucleation clusters both in solution and on the surface of protein cages that then grow into gold nanocrystals. Because of the presence of cysteine (Cys) with strong gold-binding affinity, gold nanocrystals tend to bind at specific sites of Cys, irrespective of the binding sites of gold ions. Analyzing the results obtained using these alternate routes provide important insights into the pathways of protein-mediated biomimetic nucleation of gold that challenge the importance of incubation, which is widely utilized in the biotemplated synthesis of inorganic nanocrystals