The Structural Fate of Individual Multicomponent Metal‐Oxide Nanoparticles in Polymer Nanoreactors

Multicomponent nanoparticles can be synthesized with either homogeneous or phase‐segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal‐oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized by using scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co‐Ni‐O system forms a rock salt structure largely owing to the miscibility of CoO and NiO, while Cu‐Ni‐O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher‐ordered structure, Co‐Ni‐Cu‐O, was found to follow the behavior of lower ordered systems.     

Chemical synthesis of magnetic nanoparticles

Recent advances in the synthesis of various magnetic nanoparticles using colloidal chemical approaches are reviewed. Typically, these approaches involve either rapid injection of reagents into hot surfactant solution followed by aging at high temperature, or the mixing of reagents at a low temperature and slow heating under controlled conditions. Spherical cobalt nanoparticles with various crystal structures have been synthesized by thermally decomposing dicobalt octacarbonyl or by reducing cobalt salts. Nanoparticles of Fe-Pt and other related iron or cobalt containing alloys have been made by simultaneously reacting their constituent precursors. Many different ferrite nanoparticles have been synthesized by the thermal decomposition of organometallic precursors followed by oxidation or by low-temperature reactions inside reverse micelles. Rod-shaped iron nanoparticles have been synthesized from the oriented growth of spherical nanoparticles, and cobalt nanodisks were synthesized from the thermal decomposition of dicobalt octacarbonyl in the presence of a mixture of two surfactants.     

Direct synthesis of fct-structured FePt nanoparticles at low temperature with assistance of poly(N-vinyl-2-pyrrolidone)

Direct synthesis of fct-structured FePt nanoparticles was successfully achieved by using poly(N-vinyl-2-pyrrolidone) as a protective reagent at lower temperature than the case using low molecular weight ligands as a protective reagent. Experimental data suggest that a transformation of FePt nanoparticles from face-centered cubic to face-centered tetragonal (fct) structure takes place at reaction temperature of 261 degrees C. The results of XRD and the magnetic properties exhibit that the FePt nanoparticles synthesized at 261 degrees C have partially ordered fct-structure and a ferromagnetic behavior at room temperature.     

Nanostructured Materials Synthesis in a Mixed Surfactant Mesophase

The mixed surfactant system of bis (2-ethylhexyl) sodium sulfosuccinate (AOT) and α-phosphatidylcholine (lecithin) forms a rigid gel-like mesophase in the presence of equal volumes of water and a hydrocarbon (isooctane). Small angle neutron scattering (SANS) results indicate that these structures undergo transitions from columnar hexagonal geometries to lamellar geometries depending on the water content and/or the temperature. The system is used to synthesize nanostructured ceramics (silica) in the aqueous microphase. Interpenetrating networks of poly-(hydroxyethylmethacrylate) and poly(styrene) are also synthesized using the aqueous microphase to support the water soluble monomer (hydroxyethyl methacrylate) and the organic microphase (styrene). SANS results indicate that the template structure is maintained during materials synthesis.     

Temperature effect on the structure and characteristics of ZnS-based quantum dots

The synthesis of zinc sulfide (ZnS) quantum dots (QDs) by microwave heating in a water-ethanol medium is proposed. The effect of the synthesis temperature (80 °C, 100 °C, 120 °C, and 150 °C) on the QD characteristics is examined. Based on the analysis of X-ray diffraction profiles the conclusion is drawn that the hexagonal ZnS phase of wurtzite type with an average nanocrystal size of 2.6-3.7 nm forms in the synthesized QDs. The nanocrystallite size is found to increase with the QD synthesis heating temperature. The analysis of X-ray absorption spectra (XANES) at the zinc K-edge indicates a higher crystallinity of the QD samples prepared at higher synthesis temperatures. The combined analysis of X-ray diffraction profiles, optical diffuse reflectance spectra, and X-ray absorption spectra implies the following possible QD structure: the pure hexagonal ZnS phase of wurtzite type in the bulk of nanoparticles and the amorphous ZnO phase in the surface layer of nanoparticles.     

Positive and negative magnetodielectric effects in A-site ordered (BiMn3)Mn4O12 perovskite

A-site ordered perovskite (BiMn3)Mn4O12 was synthesized through a high-pressure synthesis route at 5 GPa and found to exhibit two magnetic transitions and to show either a positive or a negative magnetodielectric effect depending on the temperature range/magnetic state.     

Microwave-Assisted Green Synthesis of Non-Cytotoxic Silver Nanoparticles Using the Aqueous Extract of Rosa santana (rose) Petals and Their Antimicrobial Activity

Green methods using biological extracts, in particular plant-based solutions, have shown great potential for silver nanoparticle synthesis. A microwave-assisted single-step phytosynthesis of silver nanoparticles is described in the present study. The aqueous extract obtained from the Rosa santana (rose) petals was used for the first time in the synthesis. The synthesized nanoparticles obtained after optimized microwave conditions for time and temperature were analyzed by ultraviolet–visible spectroscopy (UV–Vis), Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), and Zeta-size analysis. The results obtained from the characterization studies showed that the synthesized nanoparticles were nearly spherical in shape with sizes from 6.52?nm to 25.24?nm with an average particle size of 14.48?nm with a face-centered cubic structure. The antibacterial activities of the synthesized nanoparticles were evaluated and revealed that the silver nanoparticles displayed good inhibition against both Gram-negative and Gram-positive bacteria. Also, the cytotoxic effect of the silver nanoparticles on a mouse fibroblast cell line (L929) was studied by a cell viability assay. The results showed that phytosynthesized silver nanoparticles were nontoxic to the healthy normal cell line at all tested concentrations.     

Amine‐Functionalized Polyglycidyl Methacrylate Microsphere as a Unified Template for the Synthesis of Gold Nanoparticles and Single‐Crystal Gold Plates

Polyglycidyl methacrylate (PGMA) microspheres, crosslinked and surface‐functionalized by amine, can be used as a solid‐state template for the synthesis of gold (Au) crystals in the forms of either nanoparticles (NPs) or plates. It is discovered that the polymer microsphere acts as an internal template to cultivate Au NPs inside the microsphere or an external template to generate the single‐crystal plates depending on the critical concentration (C_cr) of gold ions. The ion–dipole interaction and the structure‐dependent solubility of gold induce two distinct gold nanostructures in the presence of the functionalized polymer microspheres. The catalytic activity and long‐term storage of the developed gold nanostructures that can be easily scaled‐up for mass production through the developed novel methodology is demonstrated.     

A synthetic route to size-controlled fcc and fct FePt nanoparticles

We report here a new synthetic route to FePt nanoparticles using a stoichiometric mixture of Na2Fe(CO)4 and Pt(acac)2. The structure of FePt nanoparticles, their size, chemical composition, and magnetic property can be controlled by various synthetic parameters, such as the solvent type, nature, and molar ratio of surfactants and stabilizers, synthesis temperature, and purification process. Partially ordered fct (L10) nanoparticles with room temperature magnetic coercivity can be synthesized directly in tetracosane solution at 389 degrees C. The fcc FePt synthesized in nonadecane can be transformed into the magnetically important fct phase at 430 degrees C without significant particle sintering.     

Temperature effect on the synthesis of Au-Pt bimetallic nanoparticles

Pt-Au bimetallic nanoparticles have been synthesized by the polyol method and stabilized with poly(vinylpyrrolidone) (PVP), modifying the temperature of synthesis. Interesting structure changes were observed in the nanoparticles as the temperature was varied. At lower temperatures no bimetallic nanoparticles were detected, but as the temperature increased bimetallic nanoparticles started to appear, commonly obtaining core-shell nanoparticles, always covered by the polymer. This originates the modification of the optical response of the system in the UV-visible region. An absorption peak centered at 520 nm at low temperatures was observed (100-110 degrees C); at higher temperatures (130-170 degrees C) there were non detectable absorption peaks, and finally at the two highest temperatures (180-190 degrees C) the reappearance of an absorption feature centered at 510 nm was noticed. These UV-visible results indirectly imply the composition of the surface of the particle. The structure of the particles has been determined using transmission electron microscopy and high-angle annular dark field (HAADF), the latter being a powerful technique to determine the structural composition of the particles and allowing a direct correlation of the optical response with their structural composition. X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) studies were also performed on the samples and their results support the idea of a Pt(core)-Au(shell) structure with the elements segregated from each other. The combination of these experimental techniques with calculated UV-vis absorption spectra allowed, in a reliable way, the elucidation of the nanoparticles structure and elemental distribution.     

Ultraporous single phase iron oxide-silica nanostructured aerogels from ferrous precursors

Monoliths of iron oxide-silica aerogel nanocomposites have been synthesized using a novel synthesis route which consists of impregnating silica wet gels with anhydrous iron(II) precursors followed by ethanol supercritical drying of the gels. The process yields aerogels exhibiting high porosity, large surface areas (approximately 900 m2/g), rather low densities (approximately 0.6 g/cm3), and a homogeneous distribution of single-phase maghemite, gamma-Fe2O3, nanoparticles with average sizes in the 7-8 nm range. Remarkably, the gamma-Fe2O3 nanoparticles are obtained in the as-dried state without the need of postannealing. The nanoparticles are mostly superparamagnetic at room temperature but become blocked in a ferrimagnetic state at lower temperatures.     

Size-controllable synthesis of monodispersed colloidal silica nanoparticles via hydrolysis of elemental silicon

A new method is presented for preparing monodisperse and uniform-size silica nanoparticles using a two-stage hydrolysis of silicon powder in aqueous medium. The influence of synthesis conditions including solution composition and temperature on the formation of silica nanoparticles were systematically investigated. The structure and morphology of the silica particles were characterized via transmission electron microscopy (TEM) and dynamic light scattering (DLS). Various-sized particles in the range 10–100 nm were synthesized. The size of the nanoparticles can be precisely controlled by using a facile regrowth procedure in the same reaction media.     

Facile and ultra large scale synthesis of nearly monodispersed CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles by a low temperature sol–gel route

Nearly monodispersed cobalt ferrite nanoparticles were synthesized by a low temperature sol–gel route using propylene oxide as a gelation agent. The nanoparticles were obtained by the reaction of FeCl₂ and CoCl₂ in ethanol solution with propylene oxide to form the sol, followed by the boiling of the sol solution. The unique chemistry of this procedure allows the formation of highly homogeneous gel intermediate, resulting in the great reducing of crystallization temperature of ferrites to less than 100 °C without postannealing step. This guarantees the preparation of well defined and non-aggregated ferrite nanoparticles on an ultra-large scale of about 75 g in a single reaction. This large scale synthesis strategy offers important advantages over other conventional routes for the preparation of CoFe₂O₄ nanoparticles, showing the promising application of this route in the industrial production.     

Sequence Selective Michael Addition for Synthesis of Indeno‐Pyridine and Indeno‐Pyran Derivatives in One‐Pot Reaction Using CuO Nanoparticles in Water

The alternate synthesis of indeno‐pyridine and indeno‐pyran derivatives have been described by an unprecedented, green, one‐pot reaction of aromatic aldehydes, malononitrile, and indane 1,3‐dione. The formation of either indeno‐pyridine or indeno‐pyran derivatives based on a precise change in the Michael addition of indane 1,3‐dione or malononitrile on Knoevenagel product during the progress of reaction has been investigated. The reaction completed up to 30 min of time using CuO nanoparticles in water at an ambient temperature renders the protocol novel and environment friendly. All the synthesized compounds have been confirmed on the basis of their spectroscopic data. The CuO nanoparticles have been prepared by coprecipitation method and characterized by SEM, PXRD spectroscopy, and UV spectroscopy.     

Synthesis and characterization of stimuli‐responsive porous/hollow nanoparticles by self‐assembly of chitosan‐based graft copolymers and application in drug release

In this research, stimuli‐responsive porous/hollow nanoparticles were prepared by the self‐assembly method. First, chitosan‐graft‐poly(N‐isopropylacrylamide) (CS‐g‐PNIPAAm) copolymers were synthesized through polymerization of N‐isopropylacrylamide (NIPAAm) monomer in the presence of chitosan (CS) solution using ceric ammounium nitrate as the initiator. Then, the CS‐g‐PNIPAAm copolymers were dissolved in the acetic acid aqueous solution and heated to 40 °C to induce their self‐assembly. After CS‐g‐PNIPAAm assembled to form micelles, a cross‐linking agent was used to reinforce the structure to form nanoparticles. The molecular weight of grafted PNIPAAm on CS chains was changed to investigate its effect on the structure, morphology, thermo‐, and pH‐responsive properties of the nanoparticles. TEM images showed that a porous or hollow structure in the interior of nanoparticles was developed, depending on the medium temperature. The synthesized nanoparticles carried positive charges on the surface and exhibited stimuli‐responsive properties, and their mean diameter thus could be manipulated by changing the pH value and temperature of the environment. The nanoparticles showed a continuous release of the encapsulated doxycycline hyclate up to 10 days during an in vitro release experiment. These porous/hollow particles with environmentally sensitive properties are expected to be used in hydrophilic drug delivery system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2377–2387, 2010     

Discovery of the DNA "genetic code" for abiological gold nanoparticle morphologies

DNA is in control: Different combinations of DNA nucleotides can control the shape and surface roughness of gold nanoparticles during their synthesis. These nanoparticles were synthesized in the presence of either homogenous oligonucleotides or mixed-base oligonucleotides using gold nanoprisms as seeds. The effect of the individual DNA bases and their combinations on shape control are shown in the figure.     

Multistep solution-mediated formation of AuCuSn2: mechanistic insights for the guided design of intermetallic solid-state materials and complex multimetal nanocrystals

Understanding how solids form is a challenging task, and few strategies allow for the elucidation of reaction pathways that are useful for designing new solids. Here, we describe an unusual multistep reaction pathway that leads to the formation of AuCuSn(2), a new ternary intermetallic compound that was discovered as nanocrystals using a low-temperature solution route. The formation of AuCuSn(2) using a modified polyol process occurs through a multistep pathway that was elucidated by taking aliquots throughout the course of the reaction and studying the products using a variety of techniques. The reaction proceeds through four distinct steps: (a) formation of Au nanoparticles at or near room temperature, mediated by a galvanic reaction between Au(3+) and Sn(2+) (forming Au(0) and Sn(4+), precipitated as SnO(2) that forms a shell around the nanoparticles), (b) formation of NiAs-type AuSn nanoparticles, along with Cu and Sn, upon addition of NaBH(4), (c) aggregation and thermal interdiffusion to form AuCu(x)Sn(y) alloy nanoparticles, and (d) nucleation of intermetallic AuCuSn(2), which has an ordered NiAs-derived structure. The proposed mechanism was tested by starting the reaction with the AuSn intermediate. AuSn nanoparticles were synthesized separately and reacted with Cu and Sn nanoparticles, and ordered AuCuSn(2) formed as expected. Elucidation of this reaction pathway has important implications for guiding the design of new intermetallic solids, as well as for controlling the synthesis of complex multimetal nanocrystals.     

Synthesis and characterization of CdSe nanorods using a novel microemulsion method at moderate temperature

CdSe nanoparticles have been successfully synthesized using a novel microemulsion method at moderate temperature. It is found that with a combination of the surfactant AOT and hydrazine hydrate, it is possible to control the morphology of the nanoparticles. The hydrazine hydrate acts as both a reducing agent and a templating agent that favors the formation of a rodlike structure. The composition, morphology and optical properties of the CdSe nanoparticles were investigated using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption spectroscopy, photoluminescence (PL) spectroscopy, energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared (FT-IR) spectroscopy. The nucleation and growth mechanism for this system is also proposed based on a time-dependent study. This synthesis route provides a moderate temperature (100 degrees C) method for synthesizing rodlike CdSe, hence reducing the possibility of oxidation of this chalcogenide compound.     

Versatile biomimetic dendrimer templates used in the formation of TiO2 and GeO2

Biomimetic synthesis is emerging as an advantageous alternative to the harsh synthetic conditions traditionally used in metal oxide syntheses techniques. Silaffins, proteins from the C. fusiformis diatom, form silica in an aqueous environment under benign conditions. Amine terminated PAMAM and PPI dendrimers are effective mimics of silaffins and other silica precipitating polyamines. We have expanded the scope of dendrimer mediated metal oxide formation to include titanium dioxide, a photocatalyst, and germanium dioxide, a blue photoluminescent material. The nanoparticles were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (IR), and X-ray diffraction patterns (XRD). A variable temperature XRD analysis of TiO(2) nanoparticles was conducted to study the transition from anatase to rutile. TiO(2) nanoparticles synthesized in phosphate buffer showed a 200 degrees C decrease in the anatase to rutile transition temperature relative to TiO(2) templated in water. XRD analysis of GeO(2) nanoparticles in either water or phosphate buffer reveal crystalline alpha-phase germanium oxide. To our knowledge, this is the first report of the synthesis of crystalline GeO(2) under ambient conditions.     

Formation of gold@polymer core-shell particles and gold particle clusters on a template of thermoresponsive and pH-responsive coordination triblock copolymer

Template synthesis of various morphological gold colloidal nanoparticles using a thermoresponsive and pH-responsive coordination triblock copolymer of poly(ethylene glycol)-b-poly(4-vinylpyridine)-b-poly(N-isopropylacrylamide) is studied. The template morphology of the thermoresponsive and pH-responsive coordination triblock copolymer, which can be tuned by simply changing the pH or temperature of the triblock copolymer aqueous solution, ranges from single chains to core-corona micelles and further to micellar clusters. Various morphological gold colloidal nanoparticles such as discrete gold nanoparticles, gold@polymer core-shell nanoparticles, and gold nanoparticle clusters are synthesized on the corresponding template of the triblock copolymer by first coordination with gold ions and then reduction by NaBH4. All three resultant gold colloidal nanoparticles are stable in aqueous solution, and their sizes are 2, 10, and 7 nm, respectively. The gold@polymer core-shell nanoparticles are thermoresponsive. The gold nanoparticle cluster has a novel structure, and each one holds about 40 single gold nanoparticles.