Ligand Exchange on Gold Nanorods: Going Back to the Future

Ligand exchange on gold nanorods (NRs) is still too often dismissed or not given the importance it should deserve. The many applications of gold NRs, mainly in plasmonics, biological imaging, and sensing, are made possible by fi nely tuning not only the optical properties of the metallic core but also the tethered functional groups. Gold NRs are mainly synthesized by using CTAB as the morphology-guiding surfactant, and an intimate relationship between the crystallographic facets of the rod and the CTAB bilayer exists. Because of this, it is imperative to fully understand the ligand exchange mechanisms that allow replacing CTAB with functional ligands, including the energetic contri- butions. Here, the major applications of gold NRs are briefly overviewed, and what is known about ligand exchange mechanisms is summarized, as well as why it is important to achieve complete removal of CTAB, including the techniques that are used to characterize the exchange reaction products. The concept of interface in gold NRs is briefly examined, and explained why the scientific community should focus more on understanding and characterizing it. Starting from the published literature, the reader is guided through the reasons why it is thought that ligand exchange on gold NRs is perhaps the next grand challenge in the nanoparticle field

Dimeric Gold Nanoparticle Assemblies as Tags for SERS- Based Cancer Detection

Herein, a new class of multifunctional materials combining a clustered nanoparticle-based probe is presented for surface enhanced Raman scattering (SERS)-based microscopy and surface functionalization for tissue targeting. Controlled assembly of spherical gold nanoparticles into dimers (DNP-REP) is engineered using a small, rigid Raman-active dithiolated linking reporter (REP) to yield narrow internanoparticle gaps and to strategically generate the “hot spot” while concurrently placing the reporter within the region of highest SERS enhancement. Peptide functionalized DNP-REP materials are highly stable even upon incubation with living cells and show controlled levels of binding and intracellular endocytosis. To demonstrate the functionality of such probes for disease detection, differentially targeted DNP-REPs are incubated over various time points with cultured human glioblastoma cells. Using human glioblastoma cells, the SERS maps of targeted tumor cells show the markedly enhanced signals of the DNP-REP, compared to conventional confocal fluorescence based approaches, especially at low incubation times. Even with as few as 40 internalized DNP-REP, a relatively intense SERS signal is measured, demonstrating the high signal to noise ratio and inherent biocompatibility of the materials. Thus, these Raman reporter-based nanoparticle cluster probes present a promising and versatile optical imaging tool for fast, reliable, selective, and ultrasensitive tissue targeting and disease detection and screening

Facile Solvothermal Preparation of Monodisperse Gold Nanoparticles and Their Engineered Assembly of Ferritin–Gold Nanoclusters

Herein, we report a quick and simple synthesis of water-soluble gold nanoparticles using a HAuCl4 and oleylamine mixture. Oleylamine serves as a reduction agent as well as a stabilizer for nanoparticle surfaces. The particle sizes can be adjusted by modulating reaction temperature and time. Solvothermal reduction of HAuCl4 with oleylamine can be confirmed by measuring the product in Fourier transform infrared (FTIR) spectroscopy. The plasmon band shifting from yellow to red confirms a nanosized particle formation. Amide bonds on the surface of the nanoparticles formed hydrogen bonds with one another, resulting in a hydrophobic monolayer. Particles dispersed well in nonpolar organic solvents, such as in hexane or toluene, by brief sonication. Next, we demonstrated the transfer of gold nanoparticles into water by lipid capsulation using 1-myristoyl-2-hydroxy-sn-glycero-3-phosphocholine (MHPC), 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-(methoxy polyethylene glycol)-2000 (DPPE-PEG2k), and 1,2-dioleoyl-sn-glycero-3-N-{5-amino-1-carboxypentyl}iminodiacetic acid succinyl nickel salt [DGS-NTA(Ni)]. The particle concentration can be obtained using an absorbance in ultraviolet–visible (UV–vis) spectra (at 420 nm). Instrumental analyses using transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) analysis, dynamic light scattering (DLS), and FTIR confirmed successful production of gold nanoparticles and fair solubility in water. Prepared gold particles were selectively clustered via engineered ferritin nanocages that provide multiple conjugation moieties. A total of 5–6 gold nanoparticles were clustered on a single ferritin nanocage confirmed in TEM. Reported solvothermal synthesis and preparation of gold nanoclusters may serve as an efficient, alternate way of preparing water-soluble gold nanoparticles, which can be used in a wide variety of biomedical applications