Atomically precise pieces of matter of nanometer dimensions composed of noble metals are new categories of materials with many unusual properties. Over 100 molecules of this kind with formulas such as Au 25 (SR) 18 , Au 38 (SR) 24 , and Au 102 (SR) 44 as well as Ag 25 (SR) 18 , Ag 29 (S 2 R) 12 , and Ag 44 (SR) 30 (often with a few counterions to compensate charges) are known now. They can be made reproducibly with robust synthetic protocols, resulting in colored solutions, yielding powders or diffractable crystals. They are distinctly different from nanoparticles in their spectroscopic properties such as optical absorption and emission, showing well-defined features, just like molecules. They show isotopically resolved molecular ion peaks in mass spectra and provide diverse information when examined through multiple instrumental methods. Most important of these properties is luminescence, often in the visible−near-infrared window, useful in biological applications. Luminescence in the visible region, especially by clusters protected with proteins, with a large Stokes shift, has been used for various sensing applications, down to a few tens of molecules/ions, in air and water. Catalytic properties of clusters, especially oxidation of organic substrates, have been examined. Materials science of these systems presents numerous possibilities and is fast evolving. Computational insights have given reasons for their stability and unusual properties. The molecular nature of these materials is unequivocally manifested in a few recent studies such as intercluster reactions forming precise clusters. These systems manifest properties of the core, of the ligand shell, as well as that of the integrated system. They are better described as protected molecules or aspicules, where aspis means shield and cules refers to molecules, implying that they are "shielded molecules". In order to understand their diverse properties, a nomenclature has been introduced with which it is possible to draw their structures with positional labels on paper, with some training. Research in this area is captured here, based on the publications available up to December 2016.

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Silver nanoparticles can be coated on common polyurethane (PU) foams by overnight exposure of the foams to nanoparticle solutions. Repeated washing and air-drying yields uniformly coated PU foam, which can be used as a drinking water filter where bacterial contamination of the surface water is a health risk. Nanoparticles are stable on the foam and are not washed away by water. Morphology of the foam was retained after coating. The nanoparticle binding is due to its interaction with the nitrogen atom of the PU. Online tests were conducted with a prototypical water filter. At a flow rate of 0.5 L/min, in which contact time was of the order of a second, the output count of Escherichia coli was nil when the input water had a bacterial load of 10 5 colony-forming units (CFU) per mL. Combined with the low cost and effectiveness in its applications, the technology may have large implications to developing countries. B 2005 Wiley Periodicals, Inc.

Ligand exchange offers an effective way to modify the properties of the recently prepared quantum clusters of gold. To tune optical and photoluminescence properties of one of the most stable quantum clusters of gold, Au 25 SG 18 (SG-glutathione thiolate), we functionalized it by the exchange of -SG with functionalized -SG and with an altogether different ligand, namely, 3-mercapto-2-butanol (MB). The products were characterized by various techniques such as optical absorption (UV-vis), Fourier-transform infrared (FT-IR), nuclear magnetic resonance (NMR), X-ray photoelectron (XPS), and luminescence spectroscopies, mass spectrometry, and thermogravimetry (TG). Analyses of the TG data helped to establish the molecular composition of the products. Ligand exchange reaction was monitored by NMR spectroscopy, and it was found that the exchange reaction follows a first order kinetics. The XPS study showed that after the exchange reaction there was no change in the chemical nature of the metal core and binding energy values of Au 4f 7/2 and 4f 5/2 , which are similar in both the parent and the exchanged products. Photoluminescence studies of these clusters, done in the aerated conditions, showed that the excitation spectrum of the MB-exchanged product is entirely different from the acetyl-and formyl-glutathione exchanged products. The inherent fluorescence and solid-state emission of these clusters were observed. This intense emission allows optical imaging of the material in the solid state. The emission is strongly temperature dependent. The synthesis of a diverse variety of clusters and their chemical stability and intense luminescence offer numerous applications in areas such as energy transfer, sensors, biolabeling, and drug delivery.

Lactobacillus strains, common in buttermilk, assist the growth of gold, silver, and gold-silver alloy crystals of submicron dimensions upon exposure to the precursor ions. Several well-defined crystal morphologies are observed. Crystal growth occurs by the coalescence of clusters, and tens of crystals are found within the bacterial contour. Crystal growth does not affect the viability of the bacteria. Crystals are presumably nucleated through nanoclusters, which are formed within as well as transported into the bacteria. Biomass with the crystals can be harvested completely. Results point to potential applications in analytical chemistry, nanotechnology, medicine, and metal ion recovery. Coalescence appears to be a route by which surface area of the crystal is reduced so that it can be effectively protected to avoid biological damage.

Thermal conductivities of two kinds of Au nanoparticles were measured in water and toluene media. The water soluble particles, 10-20 nm in mean diameter, made with citrate stabilization showed thermal conductivity enhancement of 5%-21% in the temperature range of 30-60°C at a loading of 0.000 26 ͑by volume͒. The effect was 7%-14% for Au particles stabilized with a monolayer of octadecanethiol even for a loading of 0.011%. Comparatively lower thermal conductivity enhancement was observed for larger diameter Ag particles for significantly higher loading. Effective enhancement of 9%, even at vanishing concentrations, points to additional factors in the thermal conductivity mechanism in nanofluids. Results also point to important chemical factors such as the need for direct contact of the metal surface with the solvent medium to improve enhancement.

We show that the time-dependent biomineralization of Au(3+) by native lactoferrin (NLf) and bovine serum albumin (BSA) resulting in near-infrared (NIR) luminescent gold quantum clusters (QCs) occurs through a protein-bound Au(1+) intermediate and subsequent emergence of free protein. The evolution was probed by diverse tools, principally, using matrix-assisted laser desorption ionization mass spectrometry (MALDI MS), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The importance of alkaline pH in the formation of clusters was probed. At neutral pH, a Au(1+)-protein complex was formed (starting from Au(3+)) with the binding of 13-14 gold atoms per protein. When the pH was increased above 12, these bound gold ions were further reduced to Au(0) and nucleation and growth of cluster commenced, which was corroborated by the beginning of emission; at this point, the number of gold atoms per protein was ~25, suggesting the formation of Au(25). During the cluster evolution, at certain time intervals, for specific molar ratios of gold and protein, occurrence of free protein was noticed in the mass spectra, suggesting a mixture of products and gold ion redistribution. By providing gold ions at specific time of the reaction, monodispersed clusters with enhanced luminescence could be obtained, and the available quantity of free protein could be utilized efficiently. Monodispersed clusters would be useful in obtaining single crystals of protein-protected noble metal quantum clusters where homogeneity of the system is of primary concern.

We report the synthesis of highly luminescent, water soluble quantum clusters (QCs) of gold, which are stabilized by an iron binding transferrin family protein, lactoferrin (Lf). The synthesized AuQC@Lf clusters were characterized using UV-Visible spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), photoluminescence (PL), matrix assisted laser desorption ionization mass spectrometry (MALDI-MS), FTIR spectroscopy and circular dichroism (CD) spectroscopy along with picosecond-resolved lifetime measurements. Detailed investigations with FTIR and CD spectroscopy have revealed changes in the secondary structure of the protein in the cluster. We have also studied Förster resonance energy transfer (FRET) occurring between the protein and the cluster. The ability of the clusters to sense cupric ions selectively at ppm concentrations was tested. The stability of clusters in widely varying pH conditions and their continued luminescence make it feasible for them to be used for intracellular imaging and molecular delivery, particularly in view of Lf protection.