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Growth mechanism of penniform BaWO4 nanostructures in catanionic reverse micelles involving polymers.

The formation of penniform BaWO4 nanostructures made of nanowires or nanobelts under the direction of a block copolymer in catanionic reverse micelles has been studied in detail. On the basis of the experimental results obtained from the BaWO4 crystallization in aqueous polymer solutions and careful transmission electron microscopy (TEM) observations of BaWO4 nanostructures formed in reverse micelles containing polymers, a detailed two-stage growth mechanism has been proposed for the formation of the penniform nanostructures in reverse micelles, which involves the polymer-controlled shaft formation (Stage 1) and the mixed surfactants-controlled barb growth (Stage 2). During Stage 1, poly(ethylene glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) induced the formation of c-axis-oriented shuttle-like nanocrystals and the subsequent oriented attachment of these shuttle-like nanocrystals resulted in the formation of [100]-oriented shafts with many parallel [001]-oriented pricks. During Stage 2, [001]-oriented nanowires or nanobelts grew gradually from the pricks into barbs, leading to the formation of well-defined penniform BaWO4 nanostructures with the barb morphology essentially determined by the mixing ratio r of the anionic to cationic surfactants (i.e., nanowires were formed at r=1 while nanobelts were formed at r deviating from 1). The current understanding of the growth mechanism of penniform BaWO4 nanostructures in catanionic reverse micelles involving polymers may be potentially applied for designing a new synthesis system for the controlled synthesis of other hierarchical 1D nanostructures with desired architectures.

Journal Article↗

Nanostructured ceramics for biomedical implants.

Recent progress in the synthesis, characterization, and biological compatibility of nanostructured ceramics for biomedical implants is reviewed. A major goal is to develop ceramic coating technology that can reduce the friction and wear in mating total joint replacement components, thus contributing to their significantly improved function and longer life span. Particular attention is focused on the enhancement of mechanical properties such as hardness, toughness, and friction coefficient and on the bioactivity as they pertain to the nanostructure of the material. The development of three nanostructured implant coatings is discussed: diamond, hydroxyapatite, and functionally graded metalloceramics based on the Cr-Ti-N ternary system. Nanostructured diamond produced by chemical vapor deposition (CVD) techniques and composed of nano-size diamond grains have particular promise because of the combination of ultrahigh hardness, improved toughness over conventional microcrystalline diamond, low friction, and good adhesion to titanium alloys. Nanostructured processing applied to hydroxyapatite coatings is used to achieve the desired mechanical characteristics and enhanced surface reactivity and has been found to increase osteoblast adhesion, proliferation, and mineralization. Finally, nanostructured metalloceramic coatings provide continuous variation from a nanocrystalline metallic bond at the interface to the hard ceramic bond on the surface and have the ability to overcome adhesion problems associated with ceramic hard coatings on metallic substrates.

Animals↗

Nanostructured surfaces for bone biotemplating applications.

A major goal of orthopedic biomaterials research is to design better surface chemistries and configurations to control behavior of bone cells such as osteoblasts. Nanostructured architecture significantly affects the response of several cell lines. In this work, nanostructured surfaces were prepared by vapor liquid solid growth of silicon nanowires from size-controlled gold colloid catalysts deposited on fused silica substrates. The lengths and surface densities of the nanowires were varied to assess the effect of these parameters on bone cell response. Osteoblasts were seeded on nanowire surfaces to investigate both short-term adhesion and proliferation and long-term functionality and matrix production. Cell adhesion and proliferation were characterized using a standard 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide assay and cell counting for up to 4 days of culture. The total protein content, alkaline phosphatase activity, and matrix production were quantified using standard colorimetric assays for up to 4 weeks of culture. Matrix production was also characterized by measuring surface concentrations of calcium and phosphorus using X-ray photoelectron spectroscopy. Further, scanning electron microscopy was used to investigate osteoblast morphology on nanostructured surfaces. Over the 4-week study, the nanostructured surfaces demonstrated improved osteoblast adhesion and proliferation and increased alkaline phosphatase activity and matrix production compared to non-nanostructured control surfaces.

Alkaline Phosphatase↗

Rational synthesis, self-assembly, and optical properties of PbS-Au heterogeneous nanostructures via preferential deposition.

High-quality, monodisperse PbS-Au(1), PbS-Au(4), and PbS-Au(n) nanostructures have been synthesized via a facile and convenient solution chemistry approach. HRTEM images of these nanostructures showed good selectivity of gold deposition on the semiconductor in several spatially correlated directions. The formation of these regular nanostructures can be explained by the difference in polarity of crystal facets that led to the selective growth of metal on the semiconductor surface. Owing to their narrow size distribution and intrinsic high-symmetry, the resulting PbS-Au(4) and PbS-Au(n) heterogeneous nanostructures could spontaneously self-assemble into ordered arrays with different symmetries. From the results of the pump-probe measurements, the presence of Au in PbS-Au(4) nanostructures has substantially altered the nonlinear optical response of PbS nanocrystals.

Gold↗

Growth and characterization of highly branched nanostructures of magnetic nanoparticles.

Magnetite nanoparticles of Fe(3)O(4) have been found to grow into large highly branched nanostructures including nanochains and highly branched nanotrees in the solid state through a postannealing process. By varying the preparation conditions such as annealing time and temperature, the nanostructures could be easily manipulated. Changing the starting concentration of the magnetic nanoparticle solution also caused significant changes of the nanoarchitectures. When the magnetic nanoparticle concentration is low, the nanoparticles formed straight rods mainly with an average diameter of 80 nm and a length of several microns. With increasing concentration of the nanoparticles, treelike structures began to form. With further increase of the concentration, well-ordered nanostructures with the appearance of snowflakes were generated. The driving force for the formation of the highly ordered nanostructures includes interaction between the nanoparticles and interaction through surface-capping molecules. This experiment demonstrates that novel nanostructures can be generated by self-assembly of magnetic nanoparticles under the solid state.

Chemistry, Physical↗

Supported lipid bilayer self-spreading on a nanostructured silicon surface.

We report on the self-spreading behavior of a supported lipid bilayer (SLB) on a silicon surface with various 100 nm nanostructures. SLBs have been successfully grown from a small spot of a lipid molecule source both on a flat surface and uneven surfaces with 100 nm up-and-down nanostructures. After an hour, the self-spreading SLB forms a large circle or an ellipse depending on the nanostructure pattern. The results are explained by a model that shows that a single-layer SLB grows along the nanostructured surfaces. The model is further supported by a quantitative analyses of our data. We also discuss the stability of the SLB on nanostructured surfaces in terms of the balance between its bending and adhesion energies.

Animals↗

Evaporated nanostructured Y2O3:Eu thin films.

Europium-doped yttrium oxide (Y2O3:Eu) is a well-known luminescent material that in recent years has been studied in thin-film form. However, to date there has not been a great effort put into altering the nanostructure of these films. A thin-film deposition technique called glancing angle deposition allows for a high degree of control over the nanostructure of the thin film, resulting in thin films with nanostructure geometries ranging from chevron and post to helix. Glancing-angle deposition was used to make europium-doped yttrium oxide thin films with slanted-post nanostructures. Portions of the films were annealed in air at 850 degrees C for 10 hours following deposition. Scanning electron microscopy was used to characterize the nanostructures of the films, while UV laser excitation was used to characterize the photoluminescence properties of the films. The annealed samples exhibited increased photoluminescent responses compared to unannealed samples; however, the porous nanoscale geometry of the films was unaffected. In order to optimize the photoluminescence properties of the films, both the partial pressure of oxygen during film deposition and the level of europium doping in the source material used were varied. Films fabricated from the source material with a greater amount of europium doping had larger photoluminescent responses, while the optimal partial pressure of oxygen during electron-beam evaporation was found to be less than 1.0 x 10(-4) torr.

Europium↗

Nanotopography: cellular responses to nanostructured materials.

Several in vitro and in vivo experiments have shown that nanostructured materials, which mimic the nanometer topography of the native tissues, improve biocompatible responses, and result in better tissue integration in medical implants. Understanding various aspects of nanotopography is extremely important for better designs of these devices. In this review paper, recent progress in the fabrication, characterization, biological responses, and application of nanostructured materials are discussed. Specifically, materials such as ceramics and polymers used to manufacture nanostructured surfaces are briefly introduced. Techniques for fabrication and characterization of nanostructured materials are also explored. Cellular responses such as morphology, alignment, adhesion, proliferation, and profiles of gene expression of various cell types after their exposure to nanofeatured materials are particularly reviewed. Finally, the paper briefly discusses some application of nanostructured materials including those in biosensor and tissue engineering fields.

Biocompatible Materials↗

Large-scale synthesis of a novel tri(8-hydroxyquioline) aluminum nanostructure.

A novel tri(8-hydroxyquioline) aluminum (AlQ3) nanostructure was prepared on large scale at low cost by low-temperature physical vapor deposition (PVD). The morphologies, the chemical bondings, and photoluminescence of the AlQ3 nanostructure were investigated by environmental scanning electronic microscopy (ESEM), Fourier transform infrared spectrum (FT-IR), and photoluminescence (PL) spectra, respectively. The AlQ3 nanostructure was composed of micro-sphere with nanowire-cluster growing on the surface. The diameter of micro-sphere and nanowire were about 5 microm and 80 nm, respectively. FT-IR results indicated that the AlQ3 molecule had a strong thermal stability under research conditions. The growth mechanism of the novel nanostructure was discussed. The novel organic nanostructure would be believed to attractive building field-emission devices and other optical devices.

Aluminum↗

Reproducible lateral force microscopy measurements for quantitative comparisons of the frictional and chemical properties of nanostructures.

Atomic force microscopy (AFM) is a widely used technique for characterizing the topography and frictional properties of nanostructures. Inherent misalignments between the AFM cantilever and the feedback hardware lead to crosstalk between topography data and lateral force microscopy (LFM) data. Because the degree of crosstalk depends on the positioning of the cantilever, LFM and topography data of the same structure can vary from one experiment to the next. For nanostructures with large LFM contrast, errors as large as 50% in topography and LFM can be observed. This paper describes an empirical strategy for correcting this alignment error. The technique is used to characterize the frictional properties of scanning probe-induced oxide nanostructures and the hydrogen-terminated Si(111) surfaces on which they are patterned. Reproducible differences in the frictional properties of the oxide nanostructures patterned on HF-treated and NH4F-treated Si(111) surfaces are observed and attributed to the mixed-hydride versus monohydride termination of each surface. The observed frictional contrast is consistent with known differences in surface reactivity and demonstrates how LFM measurements can provide insight into the frictional and chemical properties of nanostructures

Journal Article↗

Nanostructured carbon fiber disk electrodes for sensitive determinations of adenosine and uric acid

Nanostructured carbon fiber microdisk electrodes were prepared by a combination of mechanical polishing and electrolytic treatment, where the latter involved moderate oxidation of the surface, followed by a reduction. A high density of surface defects contributed to a high capacitance of the nanostructured electrodes. Facilitated proton transfer was observed at the nanostructured surface and was associated with cation-exchanged oxide defects. The nanostructured surfaces intercalated uric acid and adenosine and engaged in fast electron/proton transfer in the oxidation of both analytes. As a result, electrolytic treatment followed by fast-scan voltammetry determinations led to a sensitive response to both analytes in physiological buffers. The nanostructured electrodes showed remarkable stability and could be easily regenerated and reused. With long use, electrode activity decreased. Kinetic discrimination of the surface-mediated reaction of ascorbate was achieved at high scan rates.

Journal Article↗

Mechanistic study on the replacement reaction between silver nanostructures and chloroauric acid in aqueous medium.

The replacement reaction between silver nanostructures and an aqueous HAuCl(4) solution has recently been demonstrated as a versatile method for generating metal nanostructures with hollow interiors. Here we describe the results of a systematic study detailing the morphological, structural, compositional, and spectral changes involved in such a heterogeneous reaction on the nanoscale. Two distinctive steps have been resolved through a combination of microscopic and spectroscopic methods. In the first step, silver nanostructure (i.e., the template) is dissolved to generate gold atoms that are deposited epitaxially on the surface of each template. Silver atoms also diffuse into the gold shell (or sheath) to form a seamless, hollow nanostructure with its wall made of Au-Ag alloys. The second step involves dealloying, a process that selectively removes silver atoms from the alloyed wall, induces morphological reconstruction, and finally leads to the formation of pinholes in the walls. Reaction temperature was found to play an important role in the replacement reaction because the solubility constant of AgCl and the diffusion coefficients of Ag and Au atoms were both strongly dependent on this parameter. This work has enabled us to prepare metal nanostructures with controllable geometric shapes and structures, and thus optical properties (for example, the surface plasmon resonance peaks could be readily shifted from 500 to 1200 nm by controlling the ratio between Ag and HAuCl(4)).

Journal Article↗

Synthesis and synchrotron light-induced luminescence of ZnO nanostructures: nanowires, nanoneedles, nanoflowers, and tubular whiskers.

ZnO nanostructures, including single-crystal nanowires, nanoneedles, nanoflowers, and tubular whiskers, have been fabricated at a modestly low temperature of 550 degrees C via the oxidation of metallic Zn powder without a metal catalyst. Specific ZnO nanostructures can be obtained at a specific temperature zone in the furnace depending on the temperature and the pressure of oxygen. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD) studies show that ZnO nanostructures thus prepared are single crystals with a wurtzite structure. X-ray excited optical luminescence (XEOL) from the ZnO nanostructures show noticeable morphology-dependent luminescence. Specifically, ZnO nanowires of around 15 nm in diameter emit the strongest green light. The morphology of these nanostructures, their XEOL, and the implication of the results will be discussed.

Light↗

Ribbon- and boardlike nanostructures of nickel hydroxide: synthesis, characterization, and electrochemical properties.

We report the synthesis, characterization, and electrochemistry properties of ribbon- and boardlike nanostructures of nickel hydroxide, which crystallize in different phases. The ribbonlike nanostructures (nanoribbons) of nickel hydroxide were synthesized by treating amorphous alpha-Ni(OH)2 with high concentrations of nickel sulfate. These nanoribbons crystallized in a new phase had typical widths of 5-25 nm, thicknesses of 3-9 nm, and lengths of up to a few micrometers. After further treatment in alkali at 60 degrees C, the nanoribbons converted to boardlike nanostructures (nanoboards), which crystallized in the beta-phase with the average length-width-thickness ratio of 20:6:1. The crystal structures, Raman spectra, and electrochemical properties of these nanostructures of nickel hydroxide are described in this paper. For comparison, the amorphous alpha-Ni(OH)2 has also been investigated. Moreover, the intermediate product between the nanoribbons and the nanoboards displays a unique structure, which implied an interesting transformation process. The nanoribbons with the new phase show some unique features in Raman spectra, two new peaks located at 3534 and 3592 cm(-1) in the OH stretching region, indicating the new chemical environment of the hydroxyl groups. The nanoboards exhibit the highest specific capacity, which is close to the theoretical capacity of beta-Ni(OH)2. It suggests that the boardlike nanostructure is helpful in improving the electrochemical performance of nickel hydroxide. Because of their unique structures and properties, the nanoribbons and nanoboards of nickel hydroxide may give a new perspective for applications in the areas of catalysts and rechargeable batteries.

Journal Article↗

Stimulated emission in ZnO nanostructures: A time-resolved study.

Stimulated emission was studied using time-integrated and time-resolved photoluminescence in ZnO comb, tetrapod, and rod nanostructures. All the measurements were performed on ensembles of the nanostructures. The nanostructures were fabricated by vapor deposition (combs, tetrapods) and hydrothermal methods (rods). While stimulated emission was detected in all of the nanostructures, significant differences in the behavior of the stimulated emission, as well as the lasing threshold power, were found for different morphologies. The differences in the time evolution of the lasing spectra were particularly pronounced. The observed differences in the stimulated emission spectra of the three types of nanostructures in both exciton-exciton scattering and electron-hole plasma regimes are discussed.

Journal Article↗

Synthesis and growth mechanism of titanate and titania one-dimensional nanostructures self-assembled into hollow micrometer-scale spherical aggregates.

Three-dimensional, dendritic micrometer-scale spheres of alkali metal hydrogen titanate 1D nanostructures (i.e., nanowires and nanotubes) have been generated using a modified hydrothermal technique in the presence of hydrogen peroxide and an alkali metal hydroxide solution. Sea-urchin-like assemblies of these 1D nanostructures have been transformed into their hydrogen titanate analogues (lepidocrocite HxTi2-x/4squarex/4O4 (x approximately 0.7, square: vacancy)) by neutralization as well as into their corresponding anatase TiO2 nanostructured counterparts through a moderate high-temperature annealing dehydration process without destroying the 3D hierarchical structural motif. The as-prepared hollow spheres of titanate and titania 1D nanostructures have overall diameters, ranging from 0.8 to 1.2 microm, while the interior of these aggregates are vacuous with a diameter range of 100 to 200 nm. The constituent, component titanate and TiO2 1D nanostructures have a diameter range of 7+/-2 nm and lengths of up to several hundred nanometers. A proposed two-stage growth mechanism of these hollow micrometer-scale spheres was supported by time-dependent scanning electron microscopy, atomic force microscopy, and inductively coupled plasma atomic emission spectrometry data. We have also demonstrated that these assemblies are active photocatalysts for the degradation of synthetic Procion Red dye under UV light illumination.

Journal Article↗

Mg-catalyzed autoclave synthesis of aligned silicon carbide nanostructures.

In this article, a novel magnesium-catalyzed co-reduction route was developed for the large-scale synthesis of aligned beta-SiC one-dimensional (1D) nanostructures at relative lower temperature (600 degrees C). By carefully controlling the reagent concentrations, we could synthesize beta-SiC rodlike and needlelike nanostructures. The possible growth mechanism of the as-synthesized beta-SiC 1D nanostructures has been investigated. The structure and morphology of the as-synthesized beta-SiC nanostructures are characterized using X-ray diffraction, Fourier transform infrared absorption, and scanning and transmission electron microscopes. Raman and photoluminescence properties are also investigated at room temperature. The as-synthesized beta-SiC nanostructures exhibit strong shape-dependent field emission properties. Corresponding to their shapes, the as-synthesized nanorods and nanoneedles display the turn-on fields of 12, 8.4, and 1.8 V/microm, respectively.

Journal Article↗

Asymmetric ZnO nanostructures with an interior cavity.

As a next level of nanofabrication of inorganic materials, free-standing asymmetric nanostructures with an interior space are highly desirable for new applications. In this work, we demonstrate a wet synthesis scheme for bullet-head-like nanostructures of wurtzite zinc oxide (ZnO). The synthesized asymmetric nanostructures are single crystalline, and each has an interior space. In addition to the exterior geometric anisotropy, it is found that the interior space is located at the upper part of the ZnO nanostructures; a new type of structural anisotropy has thus been revealed. On the basis of the present findings, in principle, this synthetic architecture should be applicable to other II-VI compound semiconductors through stabilizing two or more sets of crystallographic planes in solution media. The possibility of dimerization and higher ordered coupling/growth of the ZnO nanostructures has also been addressed.

Journal Article↗