T. Pradeep

Thermal conductivities of naked and monolayer protected metal nanoparticle based nanofluids: Manifestation of anomalous enhancement and chemical effects

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 volume). 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.

Luminescent Ag7 and Ag8 clusters by interfacial synthesis.

Molecular quantum clusters of noble metals are a fascinating area of contemporary interest in nanomaterials. While Au11, [1] Au13, [2] and Au55 [3] have been known for a few decades, several new clusters were discovered recently. These include Au8, [4] Au18, [5] Au25, [6] Au38, [7] and so on. Au11 has also been the subject of recent research. In view of their luminescence, several of these clusters are expected to be important in biolabeling and fluorescence resonance energy transfer as well as for creating luminescent patterns. There are many examples of template-assisted synthesis of water-soluble luminescent silver clusters with cores ranging from Ag2 to Ag8, having characteristic electronic transitions between 400–600 nm. However, unlike the case of gold, there are only limited examples of monolayer-protected silver analogues. Silver clusters protected with aryl, aliphatic, and chiral thiols have been reported, some of which have characteristic optical and mass spectrometric signatures. There is also a family of well-characterized metal-rich silver chalcogenide clusters. Besides single-crystal diffraction, mass spectrometry has also been used for detailed understanding of these clusters. Ag clusters with and without luminescence have also been reported. Herein we present gram-scale syntheses of two luminescent silver clusters, protected by small molecules containing thiol groups, with well-defined molecular formulas, by interfacial synthesis. This new synthetic approach has become promising in several other areas including semiconductor nanoparticles, two-dimensional superlattices, and 3D structures. A crude mixture of redand blue-green-emitting clusters Ag8(H2MSA)8 and Ag7(H2MSA)7 (H2MSA: mercaptosuccinic acid), respectively, was synthesized in gram quantities by an interfacial etching reaction conducted at an aqueous/ organic interface starting from H2MSA-protected silver nanoparticles (Ag@H2MSA) [19] as precursor (for details see the Experimental Section and Figure S1 in the Supporting Information). During the reaction, the optical absorption spectrum of the aqueous phase showed gradual disappearance of the surface plasmon resonance at 400 nm (Figure 1A) of metallic silver nanoparticles. The color of the aqueous phase gradually changed from brown to yellow and finally to orange. The particles of Ag@MSA are polydisperse (Figure 1Ca) and form smaller clusters in the aqueous phase upon etching (Figure 1Cb) with complete disappearance of the nanoparticles. The unetched particles move to the junction of the two phases and form a self-assembled film of monodisperse nanoparticles, resembling two-dimensional superlattices (Figure 1Cc), which appears blue in color. The smaller clusters formed in the reaction upon longer electron-beam irradiation coalesce to form nanoparticles (Figure S2). It is known that such clusters are unstable to high-energy electrons. The peak at 600 nm, which appears at shorter reaction time (60 min) and may be due to interplasmon coupling, disappears slowly, and a new feature is seen at 550 nm after 48 h of reaction (Figure 1A). In accordance with previous studies on silver clusters, we assign this peak to interband Figure 1. A) Time-dependent UV/Vis spectra of the clusters synthesized during interfacial etching at room temperature. B) UV/Vis absorption spectra of the clusters obtained from the two bands in PAGE. The inset shows a photograph of the wet gel after electrophoresis in UV light at room temperature, and the inset to the inset an image of the first band at 273 K. C) HRTEM images of a) assynthesized Ag@(H2MSA), b) the product obtained after interfacial etching, and c) particles in the blue layer at the interface. Individual clusters are not observable by TEM, but aggregates are seen faintly (b, shown in circles). Insets of (a) and (b) are photographs of Ag@MSA and crude cluster samples. d) Photographs of aqueous of cluster solutions of first (cluster 1) and second (cluster 2) PAGE bands at 273 K and room temperature, respectively. D) Luminescence emission of cluster 1 and cluster 2 in water, excited at 550 and 350 nm, respectively.

Reduced graphene oxide–metal/metal oxide composites: Facile synthesis and application in water purification

This paper describes a versatile, and simple synthetic route for the preparation of a range of reduced graphene oxide (RGO)-metal/metal oxide composites and their application in water purification. The inherent reduction ability of RGO has been utilized to produce the composite structure from the respective precursor ions. Various spectroscopic and microscopic techniques were employed to characterize the as-synthesized composites. The data reveal that the RGO-composites are formed through a redox-like reaction between RGO and the metal precursor. RGO is progressively oxidized primarily to graphene oxide (GO) and the formed metal nanoparticles are anchored onto the carbon sheets. Metal ion scavenging applications of RGO-MnO(2) and RGO-Ag were demonstrated by taking Hg(II) as the model pollutant. RGO and the composites give a high distribution coefficient (K(d)), greater than 10 L g(-1) for Hg(II) uptake. The K(d) values for the composites are found to be about an order of magnitude higher compared to parent RGO and GO for this application. A methodology was developed to immobilize RGO-composites on river sand (RS) using chitosan as the binder. The as-supported composites are found to be efficient adsorbent candidates for field application.

A micro-convection model for thermal conductivity of nanofluids

Increase in the specific surface area as well as Brownian motion are supposed to be the most significant reasons for the anomalous enhancement in thermal conductivity of nanofluids. This work presents a semi-empirical approach for the same by emphasizing the above two effects through micro-convection. A new way of modeling thermal conductivity of nanofluids has been explored which is found to agree excellently with a wide range of experimental data obtained by the present authors as well as the data published in literature

Molecular-receptor-specific, non-toxic, near-infrared-emitting Au cluster-protein nanoconjugates for targeted cancer imaging

Molecular-receptor-targeted imaging of folate receptor positive oral carcinoma cells using folic-acid-conjugated fluorescent Au(25) nanoclusters (Au NCs) is reported. Highly fluorescent Au(25) clusters were synthesized by controlled reduction of Au(+) ions, stabilized in bovine serum albumin (BSA), using a green-chemical reducing agent, ascorbic acid (vitamin-C). For targeted-imaging-based detection of cancer cells, the clusters were conjugated with folic acid (FA) through amide linkage with the BSA shell. The bioconjugated clusters show excellent stability over a wide range of pH from 4 to 14 and fluorescence efficiency of approximately 5.7% at pH 7.4 in phosphate buffer saline (PBS), indicating effective protection of nanoclusters by serum albumin during the bioconjugation reaction and cell-cluster interaction. The nanoclusters were characterized for their physico-chemical properties, toxicity and cancer targeting efficacy in vitro. X-ray photoelectron spectroscopy (XPS) suggests binding energies correlating to metal Au 4f(7/2) approximately 83.97 eV and Au 4f(5/2) approximately 87.768 eV. Transmission electron microscopy and atomic force microscopy revealed the formation of individual nanoclusters of size approximately 1 nm and protein cluster aggregates of size approximately 8 nm. Photoluminescence studies show bright fluorescence with peak maximum at approximately 674 nm with the spectral profile covering the near-infrared (NIR) region, making it possible to image clusters at the 700-800 nm emission window where the tissue absorption of light is minimum. The cell viability and reactive oxygen toxicity studies indicate the non-toxic nature of the Au clusters up to relatively higher concentrations of 500 microg ml(-1). Receptor-targeted cancer detection using Au clusters is demonstrated on FR(+ve) oral squamous cell carcinoma (KB) and breast adenocarcinoma cell MCF-7, where the FA-conjugated Au(25) clusters were found internalized in significantly higher concentrations compared to the negative control cell lines. This study demonstrates the potential of using non-toxic fluorescent Au nanoclusters for the targeted imaging of cancer.

Anisotropic nanomaterials: structure, growth, assembly, and functions.

Comprehensive knowledge over the shape of nanomaterials is a critical factor in designing devices with desired functions. Due to this reason, systematic efforts have been made to synthesize materials of diverse shape in the nanoscale regime. Anisotropic nanomaterials are a class of materials in which their properties are direction-dependent and more than one structural parameter is needed to describe them. Their unique and fine-tuned physical and chemical properties make them ideal candidates for devising new applications. In addition, the assembly of ordered one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) arrays of anisotropic nanoparticles brings novel properties into the resulting system, which would be entirely different from the properties of individual nanoparticles. This review presents an overview of current research in the area of anisotropic nanomaterials in general and noble metal nanoparticles in particular. We begin with an introduction to the advancements in this area followed by general aspects of the growth of anisotropic nanoparticles. Then we describe several important synthetic protocols for making anisotropic nanomaterials, followed by a summary of their assemblies, and conclude with major applications.

Copper Quantum Clusters in Protein Matrix: Potential Sensor of Pb2+ Ion

A one-pot synthesis of extremely stable, water-soluble Cu quantum clusters (QCs) capped with a model protein, bovine serum albumin (BSA), is reported. From matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, we assign the clusters to be composed of Cu(5) and Cu(13) cores. The QCs also show luminescence properties having excitation and emission maxima at 325 and 410 nm, respectively, with a quantum yield of 0.15, which are found to be different from that of protein alone in similar experimental conditions. The quenching of luminescence of the protein-capped Cu QCs in the presence of very low hydrogen peroxide concentration (approximately nanomolar, or less than part-per-billion) reflects the efficacy of the QCs as a potential sensing material in biological environments. Moreover, as-prepared Cu QCs can detect highly toxic Pb(2+) ions in water, even at the part-per-million level, without suffering any interference from other metal ions.

Ag9 Quantum Cluster through a Solid-State Route

A silver cluster having the composition Ag(9)(H(2)MSA)(7) (H(2)MSA = mercaptosuccinic acid) was synthesized in macroscopic quantities using a solid-state route. The clusters were purified by PAGE and characterized by UV-vis, FTIR, luminescence, and NMR spectroscopy, TEM, XPS, XRD, TG, SEM/EDAX, elemental analysis, and ESI MS. The solid-state route provides nearly pure Ag(9) clusters, and nanoparticle contamination was insignificant for routine studies. Formation of various clusters was observed by modifying the conditions. The effect of ligands on the synthesis was checked. The cluster decomposed slowly in water, and the decomposition followed first-order kinetics. However, it could be stabilized in solvent mixtures and in the solid state. Such materials may be important in cluster research because of their characteristic absorption profiles, which are similar to those of Au(25) and Au(38). The cluster showed luminescence with a quantum yield of 8 × 10(-3) at 5 °C.

Bright, NIR-Emitting Au23 from Au25: Characterization and Applications Including Biolabeling

A novel interfacial route has been developed for the synthesis of a bright-red-emitting new subnanocluster, Au(23), by the core etching of a widely explored and more stable cluster, Au(25)SG(18) (in which SG is glutathione thiolate). A slight modification of this procedure results in the formation of two other known subnanoclusters, Au(22) and Au(33). Whereas Au(22) and Au(23) are water soluble and brightly fluorescent with quantum yields of 2.5 and 1.3 %, respectively, Au(33) is organic soluble and less fluorescent, with a quantum yield of 0.1 %. Au(23) exhibits quenching of fluorescence selectively in the presence of Cu(2+) ions and it can therefore be used as a metal-ion sensor. Aqueous- to organic-phase transfer of Au(23) has been carried out with fluorescence enhancement. Solvent dependency on the fluorescence of Au(23) before and after phase transfer has been studied extensively and the quantum yield of the cluster varies with the solvent used. The temperature response of Au(23) emission has been demonstrated. The inherent fluorescence of Au(23) was used for imaging human hepatoma cells by employing the avidin-biotin interaction.

EFFECT OF NANOSCALE ZINC OXIDE PARTICLES ON THE GERMINATION, GROWTH AND YIELD OF PEANUT

An investigation was initiated to examine the effects of nanoscale zinc oxide particles on plant growth and development. In view of the widespread cultivation of peanut in India and in other parts of the globe and in view of the potential influence of zinc on its growth, this plant was chosen as the model system. Peanut seeds were separately treated with different concentrations of nanoscale zinc oxide (ZnO) and chelated bulk zinc sulfate (ZnSO4) suspensions (a common zinc supplement), respectively and the effect this treatment had on seed germination, seedling vigor, plant growth, flowering, chlorophyll content, pod yield and root growth were studied. Treatment of nanoscale ZnO (25 nm mean particle size) at 1000 ppm concentration promoted both seed germination and seedling vigor and in turn showed early establishment in soil manifested by early flowering and higher leaf chlorophyll content. These particles proved effective in increasing stem and root growth. Pod yield per plant was 34% higher compared to chelated bulk ZnSO4. Consequently, a field experiment was conducted during Rabi seasons of 2008–2009 and 2009–2010 with the foliar application of nanoscale ZnO particles at 15 times lower dose compared to the chelated ZnSO4 recommended and we recorded 29.5% and 26.3% higher pod yield, respectively, compared to chelated ZnSO4. The inhibitory effect with higher nanoparticle concentration (2000 ppm) reveals the need for judicious usage of these particles in such applications. This is the first report on the effect of nanoscale particles on peanut growth and yield.