Alkyl and Aromatic Amines as Digestive Ripening/Size Focusing Agents for Gold Nanoparticles.

Both long chain alkyl thiols and alkyl amines behave as size focusing agents for gold nanoparticles, a process that is under thermodynamic control. However, amines do not oxidize surface gold atoms while thiols do oxidize surface gold to gold(I) with evolution of hydrogen gas. Therefore, alkyl amines participate in digestive ripening by a different mechanism.

Hydrogen generation from water/methanol under visible light using aerogel prepared strontium titanate (SrTiO3) nanomaterials doped with ruthenium and rhodium metals.

Nanostructured strontium titanate visible-light-driven photocatalysts containing rhodium and ruthenium were synthesized by a modified aerogel synthesis using ruthenium chloride and rhodium nitrate as dopant precursors, and titanium isopropoxide and strontium metal as the metal sources. The well-defined crystalline SrTiO(3) structure was confirmed by means of x-ray diffraction. After calcination at 500 °C, diffuse reflectance spectroscopy shows an increase in light absorption at 370 nm due to the presence of Rh(3 + ); however an increase of the calcination temperature to 600 °C led to a decrease in intensity, probably due to a loss of surface area.

Loss of hydrogen upon exposure of thiol to gold clusters at low temperature.

Gold-acetone-dodecanethiol and gold-acetone-phenylethanethiol colloids were prepared by the solvated metal atom dispersion method. Hydrogen evolution occurred at fairly low temperature, when the melting acetone-gold solvate encountered the thiol molecules, due to S-H bond scission. The gas inside the reactor was analyzed by gas chromatography, and the moles of H(2) was determined by calibration curves obtained from a series of known concentration samples.

Size Focusing of Nanoparticles by Thermodynamic Control through Ligand Interactions. Molecular Clusters Compared with Nanoparticles of Metals.

Ligand-capped metal entities come in two sizes, (1) molecular clusters of 10-200 metal atoms and (2) nanoparticles of 2000-10000 metal atoms. In numerous cases, certain "magic sizes" have been found to be most accessible and stable, clusters of 25, 38, 55, and 102 atoms and nanoparticles of 3500-5000 atoms or 4-5 nm. The most familiar and studied system is that of gold (metal) and thiol (ligand).

Solubility of gold nanoparticles as a function of ligand shell and alkane solvent.

The solubility of ca. 5.0 nm gold nanoparticles was studied systematically as a function of ligand shell and solvent.

Direct synthesis of aqueous quantum dots through 4,4'-bipyridine-based twin ligand strategy.

We report a new class of derivatized 4,4'-bipyridinium ligands for use in synthesizing highly fluorescent, extremely stable, water-soluble CdSe and CdTe quantum dots (QDs) for bioconjugation. We employed an evaporation-condensation technique, also known as solvated metal atom dispersion (SMAD), followed by a digestive ripening procedure. This method has been used to synthesize both metal nanoparticles and semiconductors in the gram scale with several stabilizing ligands in various solvents.

Transformation of indium nanoparticles to β-indium sulfide: digestive ripening and visible light-induced photocatalytic properties.

We report the transformation of polydispersed dodecanethiol stabilized indium nanoparticles, obtained from bulk indium shot by evaporation/condensation solvated metal atom dispersion (SMAD) technique, into highly monodispersed partially alkyl thiolate-capped β-indiumsulfide (In(2)S(3)) by a postpreparative digestive ripening in high boiling point t-butyltoluene (190 °C) solvent. Upon digestive ripening, the as-prepared polydispersed black indium nanoparticles showed a characteristic color transition from black to cream, pale yellow, yellow, and finally to brown, indicating the transformation of the indium metal nanoparticles into intermediates composed of indium thiolates, sulfides, and polysulfides, and finally into the product In(2)S(3) nanoparticles whose surfaces are partially capped with thiolates. The transformed product (In(2)S(3)) was characterized with UV-vis, XRD, EDX, SEM, XPS, and TEM.

Synthesis of indium nanoparticles: digestive ripening under mild conditions.

Here we report the synthesis of monodispersed indium nanoparticles by evaporation/condensation of indium shot using the solvated metal atom dispersion (SMAD) technique, followed by digestive ripening in low boiling point (BP 38 °C) methylene chloride and in a high boiling point (BP 110 °C) toluene solvent. The as-prepared SMAD indium nanoparticles are polydispersed with particle size ranging from 25 to 50 nm, but upon digestive ripening (heating of colloidal material at the boiling point of solvent in presence of excess surface active ligands) in methylene chloride, a remarkable reduction of particle size was achieved. In higher boiling solvent (toluene), where the indium nanoparticles at reflux temperature are probably melted, it does not allow the best result, and less monodispersity is achieved.

Biocidal properties of metal oxide nanoparticles and their halogen adducts.

Nanosized metal oxide halogen adducts possess high surface reactivities due to their unique surface morphologies. These adducts have been used as reactive materials against vegetative cells, such as Escherichia coli as well as bacterial endospores, including Bacillus subtilis and Bacillus anthracis (Delta Sterne strain). Here we report high biocidal activities against gram-positive bacteria, gram-negative bacteria, and endospores.

Virucidal properties of metal oxide nanoparticles and their halogen adducts.

Selected metal oxide nanoparticles are capable of strongly adsorbing large amounts of halogens (Cl(2), Br, I(2)) and mixed halogens. These solid adducts are relatively stable thermally, and they can be stored for long periods. However, in the open environment, they are potent biocides.

Novel dye-sensitized solar cell architecture using TiO2-coated vertically aligned carbon nanofiber arrays.

A novel dye-sensitized solar cell (DSSC) architecture based on vertically aligned carbon nanofibers coated with a thin nanoneedle-textured anatase TiO2 film is demonstrated. An encouraging overall conversion efficiency of approximately 1.09% and a rather high open-circuit voltage of approximately 0.

A multifunctional biocide/sporocide and photocatalyst based on titanium dioxide (TiO2) codoped with silver, carbon, and sulfur.

Composite nanostructured samples of Ag (0.5-20%)/(C, S)-TiO(2) were synthesized and characterized by EDX, XRD, FT-IR, UV-vis, BET, XPS, and zeta potential measurements. Photocatalytic and biocidal tests revealed that the amount of the codoped silver (Ag(+)) in (C, S)-TiO(2) played a crucial, distinctive role in the photodegradation of gas-phase acetaldehyde as well as in the inactivation of Escherichia coli cells and Bacillus subtilis spores.

Gold nanoparticle superlattices.

Ordered metal nanoparticle assemblies--superlattices--have captivated and stirred the imagination of scientists and engineers alike and promise great prospect for future technologies. This potential though will greatly be determined by the understanding and control that can be exerted on the assembling processes. This tutorial review presents a brief account of the factors that govern the formation of superlattices and then presents several examples of gold nanoparticle superlattices that are distinguished by the size of participating particles, chain length/functional group of the capping agent, the substrates on which they form etc.

Biocidal activity of nanocrystalline silver powders and particles.

While the activity of the SMAD powders is lower than that of pure silver nitrate, it has the ability to kill bacteria very effectively and over long periods of time.

Synthesis, characterization, and visible light activity of new nanoparticle photocatalysts based on silver, carbon, and sulfur-doped TiO2.

New nanoparticle photocatalysts based on silver, carbon, and sulfur-doped TiO2 having only the homogeneous anatase crystalline phase and high surface area were successfully synthesized by a modified sol-gel route. The catalysts were characterized by EDX, XRD, BET, UV-vis, IR, and Raman spectroscopy. The effects of the experimental parameters on the visible light reactivity of the catalysts were evaluated for the photodegradation of gaseous acetaldehyde as a model indoor pollutant.

Synthesis and characterization of a new Tiara Pd(II) thiolate complex, [Pd(SC12H25)2]6, and its solution-phase thermolysis to prepare nearly monodisperse palladium sulfide nanoparticles.

A new tiara Pd(II) thiolate complex, [Pd(SC12H25)2]6, has been synthesized and fully characterized by X-ray single crystal analysis, elemental analysis, MALDI, 1H NMR, powder XRD, IR, Raman, and UV/vis. It was found that, in each complex cluster, the six palladium atoms form a nearly planar hexagonal ring and the adjacent palladium atoms are bridged by sulfur atoms from both sides. Then the complex was further used as a single-source precursor to prepare nearly monodisperse palladium sulfide (PdS) nanoparticles through the high-temperature-induced decomposition in diphenyl ether.

Gram-scale synthesis of aqueous gold colloids stabilized by various ligands.

We have developed a method for the large-scale synthesis of gold nanoparticles (Au NPs) in an aqueous medium stabilized by various water-soluble ligands. Significantly, the narrow size-distribution of the particles is achieved without employing size-selective procedures. The versatility of the procedure is demonstrated for the preparation of three colloidal systems stabilized by different ligands.

First principles density functional study of the adsorption and dissociation of carbonyl compounds on magnesium oxide nanosurfaces.

The adsorption and dissociation of three carbonyl compounds, formaldehyde, acetaldehyde, and acetone, on the magnesium oxide nanosurface, consisting of four stacked (MgO)3 hexagons, is investigated by first principles density functional theory (DFT). In the case of formaldehyde, strongly chemisorbed species, with carboxylate-like structures, are initially formed. These may subsequently undergo heterolytic cleavage of an aldehyde C-H bond to form formate ions involving a surface oxide ion and a hydride ion adsorbed over the magnesium dication [(MgH+)(HCOO-)].

CF2Cl2 decomposition over nanocrystalline MgO: evidence for long induction periods.

CF(2)Cl(2) has been found to react with nanoscale MgO at 325 degrees C and higher temperatures. In excess of the halocarbon, the reaction results in the formation of MgF(2) as a predominant solid product, with CCl(4), and CO(2) formed as the main gaseous products. The kinetics of the process is characterized by a prolonged induction period, which is as long as 8.

Low-temperature metallic alloying of copper and silver nanoparticles with gold nanoparticles through digestive ripening.

We describe a remarkable and simple alloying procedure in which noble metal intermetallic nanoparticles are produced in gram quantities via digestive ripening. This process involves mixing of separately prepared colloids of pure Au and pure Ag or Cu particles and then heating in the presence of an alkanethiol under reflux. The result after 1 h is alloy nanoparticles.

Amphiphilic templating of magnesium hydroxide.

The synthesis of lamellar mesostructured Mg(OH)2 was achieved through a surfactant templating route. Amphiphilic compounds with different anionic headgroups (phosphate, sulfate, sulfonate, and carboxylate) were used as surfactants. Control of d spacing was achieved through the use of different alkyl carboxylate amphiphiles.

Superoxide radical anions on the surface of zirconia and sulfated zirconia: formation mechanisms, properties and structure.

In situ ESR spectroscopy has been used for direct comparison of different thermal and light-induced processes leading to generation of superoxide radical anions on the surface of various zirconia and sulfated zirconia materials. For materials of both types the magnetic resonance parameters of the radical anions were found to be practically independent of the generation method, except for oxygen coadsorption with NO that yields radicals with somewhat smaller gz values. The parameters appear to depend mostly on the state of the surface zirconia cations stabilizing the radical anions, so that the g tensor anisotropy is significantly smaller over sulfated zirconia.

Synthesis of spherical silver nanoparticles by digestive ripening, stabilization with various agents, and their 3-D and 2-D superlattice formation.

Capped nanoparticles of silver were synthesized via the solvated metal atom dispersion (SMAD) technique followed by a digestive ripening procedure producing gram quantities of monodisperse spherical nanoparticles. This shows for the first time that a digestive ripening protocol is possible for an element other than gold. The particle size and optical spectra were found to be dependent on the capping agent used.

Structural defects cause TiO2-based photocatalysts to be active in visible light.

Oxidation of TiO or Ti2O3 led to the formation of TiO2 with activity in visible light much higher than when TiN was used as a precursor, pointing out the importance of oxygen defects/vacancies for extension of activity of TiO2 into the visible region.