Functional noble metal nanoparticle superlattices grown at interfaces

Nanoparticle crystals or superlattices (SLs) are three dimensional arrangements of nanoparticles in the micrometre regime. In SLs, the particles are periodically arranged in a coherent long range order and hence they show collective properties. Various spectroscopic, scattering and imaging techniques have been used to understand the structure of self-assembled SLs. Extensive interest in particle SLs is due to the collective properties of the building blocks, which help us to understand the evolution in properties of organized structures. Controlling the assembly of such organized solids may open up new opportunities for fundamental studies as well as for engineering advanced materials with useful attributes. This review presents our efforts in creating SLs of noble metal nanoparticles and studies performed with those materials

Mesoflowers: a new class of highly efficient surface-enhanced Raman active and infrared-absorbing materials

A method for the synthesis of a new class of anisotropic mesostructured gold material, which we call "mesoflowers", is demonstrated. The mesoflowers, unsymmetrical at the single particle level, resemble several natural objects and are made up of a large number of stems with unusual pentagonal symmetry. The mesostructured material has a high degree of structural purity with star-shaped, nano-structured stems. The mesoflowers were obtained in high yield, without any contaminating structures and their size could be tuned from nano- to meso-dimensions. The dependence of various properties of the mesoflowers on their conditions of formation was studied. The near-infrared-infrared (NIR-IR) absorption exhibited by the mesoflowers has been used for the development of infrared filters. Using a prototypical device, we demonstrated the utility of the gold mesoflowers in reducing the temperature rise in an enclosure exposed to daylight in peak summer. These structures showed a high degree of surface-enhanced Raman scattering (SERS) activity compared to spherical analogues. SERS-based imaging of a single mesoflower is demonstrated. The high SERS activity and NIR-IR absorption property open up a number of exciting applications in diverse areas

Aqueous to organic phase transfer of Au<SUB>25</SUB> clusters

Aqueous to organic phase transfer of water soluble sub-nanocluster, Au25SG18 (-SG, glutathione thiolate) is demonstrated using the phase transfer reagent, tetraoctylammonium bromide. The phase transfer occurred by the electrostatic attraction between the hydrophilic carboxylate anion of the glutathione ligand on the cluster surface in the aqueous phase and the hydrophobic tetraoctylammonium cation in the toluene phase. Detailed spectroscopic characterization of the phase transferred cluster using optical absorption, photoluminescence and X-ray photoelectron spectroscopy showed that the cluster retains its integrity during the phase transfer. The interaction of the cluster with the phase transfer reagent can be studied with infrared spectroscopy. The phase transferred cluster can be dried and redissolved in an organic medium, just as the original cluster. This is the first report of the phase transfer of a sub-nanocluster, keeping the cluster core intact. The effect of dilution and pH on phase transfer of this cluster is studied in detail. This method promises several possibilities to explore the properties, reactivity and applications of sub-nanoclusters both in the aqueous and organic phases

Molecular precursor-mediated tuning of gold mesostructures: synthesis and SERRS studies

This article describes the high yield synthesis of a range of anisotropic gold mesostructures such as flowers, cubes, plates, and quasispherical mesostructures using a seed-mediated approach. These structures were formed from precursor seed nanoparticles of gold stabilized by the template, 1,2-phenylenediamine (1,2-PDA). We demonstrated that control of the morphologies from mesoflowers to quasispherical structures is possible with the molecular precursors used in the synthesis of seeds. It was found that concentration of the template, 1,2-PDA added during seed preparation played an important role in the conversion of mesoflowers to quasispherical and cube-like structures. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectroscopy and energy dispersive analysis of X-rays (EDAX) were used for the determination of physical and chemical composition of the nano/mesostructures formed. The seed nanoparticles responsible for the formation of these various anisotropic structures were further characterized and analyzed using laser desorption ionization mass spectrometry (LDI MS) and TEM. We demonstrated high surface-enhanced resonance Raman scattering (SERRS) activity of the mesoflowers using crystal violet (CV) as the analyte molecule. The shape-dependent SERRS activity of various meso/nanostructures was also studied. A ~0.8&#215;102 decrease in the SERRS intensity was observed in quasispherical structures compared to mesoflowers. The increased SERRS activity is attributed to the unique shape and nanofeatures present on the mesoflowers, which were absent in the quasispherical mesostructures. We believe that the high SERRS activity exhibited by the mesoflowers may be utilized for developing novel sensors

Supported quantum clusters of silver as enhanced catalysts for reduction

Quantum clusters (QCs) of silver such as Ag7(H2MSA)7, Ag8(H2MSA)8 (H2MSA, mercaptosuccinic acid) were synthesized by the interfacial etching of Ag nanoparticle precursors and were loaded on metal oxide supports to prepare active catalysts. The supported clusters were characterized using high resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and laser desorption ionization mass spectrometry. We used the conversion of nitro group to amino group as a model reaction to study the catalytic reduction activity of the QCs. Various aromatic nitro compounds, namely, 3-nitrophenol (3-np), 4-nitrophenol (4-np), 3-nitroaniline (3-na), and 4-nitroaniline (4-na) were used as substrates. Products were confirmed using UV-visible spectroscopy and electrospray ionization mass spectrometry. The supported QCs remained active and were reused several times after separation. The rate constant suggested that the reaction followed pseudo-first-order kinetics. The turn-over frequency was 1.87 s-1 per cluster for the reduction of 4-np at 35°C. Among the substrates investigated, the kinetics followed the order, SiO2 > TiO2 > Fe2O3 > Al2O3

Gold nanoparticle superlattices as functional solids for concomitant conductivity and SERS tuning

Mercaptosuccinic acid protected gold nanoparticles (Au@MSA) self assemble to form superlattice (SL) crystals at the air-water interface. These have been used for gas adsorption. The current-voltage (I-V) characteristics of the SL film with embedded SL crystals, obtained by four probe measurements, show Ohmic conduction. The conductance observed was proportional to the polarizability of the adsorbed gases. The current through the SL decreases on adsorption of the gas along with decrease in the SERS intensity of a probe molecule from the crystals. We rationalise our observation of the linear dependence of the conductance on the polarizability of the adsorbed gas using a simple model calculation. Variation of the conductance may be useful in designing electrical switches operating at the nanometre length scales

Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience

Noble metal quantum clusters (NMQCs) are the missing link between isolated noble metal atoms and nanoparticles. NMQCs are sub-nanometer core sized clusters composed of a group of atoms, most often luminescent in the visible region, and possess intriguing photo-physical and chemical properties. A trend is observed in the use of ligands, ranging from phosphines to functional proteins, for the synthesis of NMQCs in the liquid phase. In this review, we briefly overview recent advancements in the synthesis of protein protected NMQCs with special emphasis on their structural and photo-physical properties. In view of the protein protection, coupled with direct synthesis and easy functionalization, this hybrid QC-protein system is expected to have numerous optical and bioimaging applications in the future, pointers in this direction are visible in the literature

Luminescent quantum clusters of gold in transferrin family protein, lactoferrin exhibiting FRET

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 Forster 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

Two distinct fluorescent quantum clusters of gold starting from metallic nanoparticles by pH-dependent ligand etching

Two fluorescent quantum clusters of gold, namely Au25 and Au8, have been synthesized from mercaptosuccinic acid-protected gold nanoparticles of 4-5 nm core diameter by etching with excess glutathione. While etching at pH ~3 yielded Au25, that at pH 7-8 yielded Au8. This is the first report of the synthesis of two quantum clusters starting from a single precursor. This simple method makes it possible to synthesize well-defined clusters in gram quantities. Since these clusters are highly fluorescent and are highly biocompatible due to their low metallic content, they can be used for diagnostic applications

Size tuning of Au nanoparticles formed by electron beam irradiation of Au<SUB>25</SUB> quantum clusters anchored within and outside of dipeptide nanotubes

Glutathione protected Au25 quantum clusters, exhibiting characteristic fluorescence, have been uniformly coated inside and outside of &#946;-Ala-L-Ile dipeptide nanotubes. These coated structures have been imaged using the inherent fluorescence of Au25. Upon exposure to an electron beam, in a transmission electron microscope, the quantum clusters gradually transform to gold nanoparticles, of the metallic size regime. The nanoparticles grow to a size of 4.5 nm and thereafter the particle size is unaffected by electron beam exposure. The nanotubes are intact and this template is shown to control the uniformity of the size of the nanoparticles grown. The quantum clusters can be loaded selectively inside the tubes using capillarity of the nanotubes. The sizes of the nanoparticles grown are tuned using electron beam exposure