Nanosized molecular clusters (MCs) composed of PbBr2 and neutral ligand butylamine (BTYA) with unique optical properties in solution and solid states have been synthesized using ligand-assisted reprecipitation and spin-coating, separately. The studies of their optical properties using ultraviolet–visible (UV−vis) absorption and photoluminescence (PL) show the first electronic absorption and PL band of the MCs at 401 and 411 nm, respectively, for the solution and solid state samples that exhibit good stability under ambient conditions. Low-temperature PL spectra below 30 K show vibronic peaks indicative of a single size or a very narrow size distribution of the MCs. On the basis of Raman, X-ray diffraction, and transmission electron microscopy measurements, a layered structural model is proposed for the MCs with a BTYA ligand capping on the surface of the corner-shared tilted [PbBr6]4– octahedral framework. The stable and retained structure of MCs in the solid state is promising for photonics applications.

Methylammonium lead bromide perovskite magic-sized clusters and quantum dots were synthesized using a new heated ligand assisted reprecipitation (HLARP) technique using organic amines and acids as capping ligands. The optical properties of these nanoparticles were analyzed using UV−vis electronic absorption and photoluminescent spectroscopy. Varying the temperature of the precursor solution while keeping the antisolvent temperature consistent allows for tuning between perovskite magic-sized clusters (MSCs) and quantum dots (PQDs) without the need to use excessive concentrations of capping ligand. Higher precursor solution temperatures favor MSCs, while lower temperatures favor PQDs. Furthermore, increasing the temperature of the system shifts the original emission band from 436 to 453 nm, by increasing the size and potentially through the introduction of surface defects. Low frequency Raman spectroscopy reveals that MSCs have vibrational frequencies that are similar to those of bulk perovskite. Electrospray mass spectrometry and infrared spectroscopy were used to probe the ligands on the surface of the MSCs, indicating that amine is the primary capping ligand and the surface is presumably cation rich.

Metal halide perovskites, such as methylammonium lead bromide, have recently attracted considerable attention due to their interesting and useful photoelectric properties. Here, two types of methylammonium lead bromide magic-sized clusters (MSCs), passivated with oleylamine and oleic acid, were synthesized using ligand-assisted reprecipitation (LARP) and heated LARP (HLARP) methods. The optical properties of these MSCs were characterized using UV−vis electronic absorption and photoluminescence (PL) spectroscopies. The HLARP synthesis resulted in a two-fold increase in the PL quantum yield of the MSCs to 76%. The stability of the MSCs was tested using timedependent PL spectroscopy. LARP MSCs in solution degraded completely after 14 days under ambient conditions, while HLARP MSCs lasted for 26 days. To stabilize them, the MSCs were added to a non-coordinating matrix, paraffin. Both MSCs showed significantly improved resistance to water with the addition of paraffin. Solid LARP MSCs lost all luminescence with and without the addition of paraffin by about 3 h. Solid HLARP MSCs without paraffin started to aggregate after 3 h, but paraffin stabilized HLARP MSC films were stable for 8 days. This improved stability in solid state form allowed for accurate, nonaggregated analysis using Raman spectroscopy, X-ray diffraction, and transmission electron microscopy. Raman spectroscopy revealed that the HLARP MSCs show an additional peak at 147 cm −1 compared to LARP MSCs, which is attributed to methylammonium. X-ray diffraction and transmission electron microscopy confirm that MSCs have a quasi-crystalline orthorhombic structure.

Hollow gold nanospheres (HGNs) have been used as the template for seed-mediated growth of multibranched hollow gold nanostars (HNS). The HGNs were synthesized via anerobic reduction of cobalt chloride to cobalt nanoparticles and then formation of a gold shell via galvanic replacement followed by the oxidation of the cobalt core. We obtained control of the inner core size of the HGNs by increasing the size of the sacrificial cobalt core and by varying the ratio of B­(OH)3/BH4 using boric acid rather than 48 h aged borohydride. We synthesized the HNS by reducing Au3+ ions in the presence of Ag+ ions using ascorbic acid, creating a spiky morphology that varied with the Au3+/Ag+ ratio. A broadly tunable localized surface plasmon resonance was achieved through control of both the inner core and the spike length. Amyloid beta (Aβ) was conjugated to the HNS by using a heterobifunctional PEG linker and identified by the vibrational modes associated with the conjugated ring phenylalanine side chain. A bicinchoninic acid assay was used to determine the concentration of Aβ conjugated to HNS as 20 nM, which is below the level of Aβ that negatively affects long-term potentiation. Both the core size and spike length were shown to affect the optical properties of the resulting nanostructures. This HGN templated method introduced a new parameter for enhancing the plasmonic properties of gold nanostars, namely, the addition of a hollow core. Hollow gold nanostars are highly desirable for a wide range of applications, including high sensitivity disease detection and monitoring.

Hollow gold nanospheres (HGNs) are core/shell structures with a dielectric material core, usually composed of solvent, and a gold metal shell. Such structures have two metal/dielectric interfaces to allow interaction between the gold metal with the interior and external dielectric environment. Upon illumination by light, HGNs exhibit unique surface plasmon resonance (SPR) properties compared to solid gold nanoparticles. Their SPR absorption/scattering can be tuned by changing their diameter, shell thicknesses, and surface morphologies. In addition to the low toxicity, easy functionalization, resistance to photobleaching, and sensitivity to changes in surrounding medium of gold, the enhanced surface‐to‐volume ratio and tunable SPR of HGNs make them highly attractive for different applications in the fields of sensing, therapy, and theranostics. In this article, we review recent progress on the synthesis and structural control of HGNs and applications of their SPR properties in biomedical sensing and theranostics. This article is categorized under: Diagnostic Tools > Biosensing Diagnostic Tools > in vitro Nanoparticle‐Based Sensing Diagnostic Tools > in vivo Nanodiagnostics and Imaging