Microscale patterning of hydrophobic/hydrophilic surfaces by spatially controlled galvanic displacement reactions.

In this letter, we report the design and fabrication of different metal patterns for the realization of spatially controlled hydrophobic/hydrophilic regions with micrometer resolution. The fabrication procedure, based on a combination of lithographic techniques and wet-chemistry reactions (namely, spontaneous Galvanic displacement reactions) is reliable, undemanding, and highly versatile, allowing the achievement of precise spatial control along with the use of a wide variety of different materials.

Micro/nanoscale patterning of nanostructured metal substrates for plasmonic applications.

The ability to precisely control the pattern of different metals at the micro- and nanoscale, along with their topology, has been demonstrated to be essential for many applications, ranging from material science to biomedical devices, electronics, and photonics. In this work, we show a novel approach, based on a combination of lithographic techniques and galvanic displacement reactions, to fabricate micro- and nanoscale patterns of different metals, with highly controlled surface roughness, onto a number of suitable substrates. We demonstrate the possibility to exploit such metal films to achieve significant fluorescence enhancement of nearby fluorophores, while maintaining accurate spatial control of the process, from submicron resolution to centimeter-sized features. These patterns may be also exploited for a wide range of applications, including SERS, solar cells, DNA microarray technology, hydrophobic/hydrophilic substrates, and magnetic devices.

Synthesis of gold nanospheres and nanotriangles by the Turkevich approach.

Gold nanoparticles of triangular morphology possess interesting optical properties with potential application in medicine and infrared absorbing coatings, however, little is known about conditions that favor their growth. In this paper, we have reinvestigated a time-tested recipe for the formation of gold nanospheres by citrate reduction of aqueous gold ions under boiling conditions (Turkevich recipe). Our principle findings are that gold nanotriangle formation is kinetically controlled and is highly favored at low temperatures. Furthermore, the presence of chloride ions from the precursor chloroaurate ions plays a major role in promoting the growth of <111> oriented triangular/truncated triangular particles. The presence of bromide and iodide ions that possess the ability to replace surface-bound chloride ions inhibits triangle formation to varying degrees.

Liquid foam as a template for the synthesis of iron oxyhydroxide nanoparticles.

Liquid foams have been used as a template to prepare iron oxyhydroxide nanoparticles. This is achieved by a process of electrostatic entrapment of Fe2+/Fe3+ ions in the foam stabilized by the surfactant sodium dodecyl sulfate followed by the in situ hydrolysis of the metal ions. Infrared and selected area electron diffraction measurements suggest the formation of a mixture of beta-FeO(OH) and gamma-FeO(OH) crystallographic phases after the in situ hydrolysis of the metal ions in the foam template. Transmission electron microscopy analysis of the powders obtained from the foam indicates that the particles are fairly monodisperse with an average size of around 50 nm. Scanning electron microscopy pictures reveal that the particles form loosely bound aggregates of around 300 nm. After the powders obtained in the foam are annealed at 400 degrees C, X-ray diffraction measurements show that the FeO(OH) particles are converted to alpha-Fe2O3. The mechanistic aspects of metal ion hydrolysis in a foam are discussed, and some of the advantages of this method vis-à-vis the normal solution-based methods are outlined.

Rapid synthesis of Au, Ag, and bimetallic Au core-Ag shell nanoparticles using Neem (Azadirachta indica) leaf broth.

We report on the use of Neem (Azadirachta indica) leaf broth in the extracellular synthesis of pure metallic silver and gold nanoparticles and bimetallic Au/Ag nanoparticles. On treatment of aqueous solutions of silver nitrate and chloroauric acid with Neem leaf extract, the rapid formation of stable silver and gold nanoparticles at high concentrations is observed to occur. The silver and gold nanoparticles are polydisperse, with a large percentage of gold particles exhibiting an interesting flat, platelike morphology. Competitive reduction of Au3+ and Ag+ ions present simultaneously in solution during exposure to Neem leaf extract leads to the synthesis of bimetallic Au core-Ag shell nanoparticles in solution. Transmission electron microscopy revealed that the silver nanoparticles are adsorbed onto the gold nanoparticles, forming a core-shell structure. The rates of reduction of the metal ions by Neem leaf extract are much faster than those observed by us in our earlier studies using microorganisms such as fungi, highlighting the possibility that nanoparticle biological synthesis methodologies will achieve rates of synthesis comparable to those of chemical methods.

Biological synthesis of triangular gold nanoprisms.

The optoelectronic and physicochemical properties of nanoscale matter are a strong function of particle size. Nanoparticle shape also contributes significantly to modulating their electronic properties. Several shapes ranging from rods to wires to plates to teardrop structures may be obtained by chemical methods; triangular nanoparticles have been synthesized by using a seeded growth process. Here, we report the discovery that the extract from the lemongrass plant, when reacted with aqueous chloroaurate ions, yields a high percentage of thin, flat, single-crystalline gold nanotriangles. The nanotriangles seem to grow by a process involving rapid reduction, assembly and room-temperature sintering of 'liquid-like' spherical gold nanoparticles. The anisotropy in nanoparticle shape results in large near-infrared absorption by the particles, and highly anisotropic electron transport in films of the nanotriangles.

Immobilization of biogenic gold nanoparticles in thermally evaporated fatty acid and amine thin films.

We have recently demonstrated the biological synthesis of gold nanoparticles by the reduction of aqueous chloroaurate ions by the fungus Fusarium oxysporum and with extract of geranium (Pelargonium graveolens) leaf. In this paper, we demonstrate the immobilization of biogenic gold nanoparticles in lipid thin films deposited by thermal evaporation. The charge on the gold nanoparticles synthesized by both the fungus and the geranium plant extract is used to facilitate their immobilization in both anionic and cationic lipid thin films. A rough estimate of the isoelectric point of the proteins capping the gold nanoparticles synthesized using the fungus could be made by pH-dependent microgravimetry studies of the immobilization process. An interesting size and shape selectivity in the immobilized gold nanoparticles is observed in the lipid thin films. The biogenic gold nanoparticle-lipid composite films were characterized using quartz crystal microgravimetry, UV-vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy.

A low-temperature, soft chemistry method for the synthesis of zirconia nanoparticles in thermally evaporated fatty amine thin films.

We demonstrate the synthesis of zirconia nanoparticles in a lipid matrix by a simple, low temperature beaker-based process. This is accomplished by electrostatic entrapment of ZrF6(2-) ions within thermally evaporated octadecylamine (ODA) thin films followed by the low-temperature in situ hydrolysis of the entrapped metal ion complexes. The zirconia particles thus formed were of the monoclinic phase and were fairly monodisperse with particles of average size 40 nm. The zirconia crystallites appeared to exhibit preferred orientation indicating epitaxial growth of the crystals within the lipid matrix. The formation of zirconia nanoparticles in the lipid matrix was investigated using quartz crystal microgravimetry (QCM), optical absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray diffraction (XRD) techniques.

Geranium leaf assisted biosynthesis of silver nanoparticles.

Development of biologically inspired experimental processes for the synthesis of nanoparticles is evolving into an important branch of nanotechnology. In this paper, we report on the use of Geranium (Pelargonium graveolens) leaf extract in the extracellular synthesis of silver nanoparticles. On treating aqueous silver nitrate solution with geranium leaf extract, rapid reduction of the silver ions is observed leading to the formation of highly stable, crystalline silver nanoparticles in solution. Transmission electron microscopy analysis of the silver particles indicated that they ranged in size from 16 to 40 nm and were assembled in solution into quasilinear superstructures. The rate of reduction of the silver ions by the geranium leaf extract is faster than that observed by us in an earlier study using a fungus, Fusarium oxysporum, thus highlighting the possibility that nanoparticle biosynthesis methodologies will achieve rates of synthesis comparable to those of chemical methods. This study also represents an important advance in the use of plants over microorganisms in the biosynthesis of metal nanoparticles.