Environmentally friendly synthesis and formation mechanism of copper nanowires with controlled aspect ratios from aqueous solution with ascorbic acid.

Copper (Cu) nanowires (NWs) were synthesized by the reduction of Cu-chloride complexes using ascorbic acid (AA) as a mild reducing agent, polyvinylpyrrolidone (PVP) as a capping agent, and NaCl as an additive under atmospheric conditions at 80 °C. Surface analyses revealed that both Cl ions and PVP were required for the synthesis of Cu NWs. Together, the Cl ions and PVP capped the Cu (1 0 0) side faces, leading to anisotropic growth of Cu NWs along the [1 1 0] direction. To obtain Cu NWs with high aspect ratios, we evaluated the synthetic mechanism under different reaction conditions. The results indicated that the presence of dissolved oxygen (DO) was the dominant factor affecting aspect ratio of Cu NWs. DO and hydrogen peroxide resulting from the reaction between DO and AA oxidized the surfaces of the growing Cu NWs, preventing further growth. Decreasing the amount of oxides on the Cu NW surfaces and removing DO increased the aspect ratios of the Cu NWs. The results indicated that DO should be removed from the reaction solution to obtain high-aspect-ratio Cu NWs in aqueous solutions containing AA.

Aqueous Phase Synthesis of CuIn Alloy Nanoparticles and Their Application for a CIS (CuInSe2)-Based Printable Solar Battery.

To apply CuInSe2 (CIS)-based printable solar batteries; an aqueous phase synthesis method of Cu-In (CI) alloy nanoparticles is studied. Metal complexes in the original solution are restricted to homogenized species by utilizing calculations. For example; [(Cu2+)(ASP2-)2] [ASP: the "body (C4H5O4N)" of aspartic acid (C4H7O4N)] is predominant in the pH 6-13 region (CASP/CCu > 6); while In complexes can be restricted to [(In3+)(OH-)(EDTA4-)] (pH 10-12; CEDTA/CIn = 2) and/or [(In3+)(ASP2-)2] (pH 7-9; CASP/CIn = 5). These results indicate that the added amount of complex reagents should be determined by calculations and not the stoichiometric ratio. The reduction potential of homogenized metal complex is measured by cyclic voltammetry (CV) measurements and evaluated by Nernst's equation using the overall stability constants. CuIn alloy nanoparticles with a small amount of byproduct (In nanoparticles) are successfully synthesized. The CI precursor films are spin-coated onto the substrate using a 2-propanol dispersion. Then the films are converted into CIS solar cells; which show a maximum conversion efficiency of 2.30%. The relationship between the open circuit potential; short circuit current density; and fill factor indicate that smoothing of the CIS films and improving the crystallinity and thickness increase the solar cell conversion efficiency.

Significant stabilization of palladium by gold in the bimetallic nanocatalyst leading to an enhanced activity in the hydrodechlorination of aryl chlorides.

The stabilization effect of Au towards Pd changed the reactivity of Pd in Au/Pd bimetallic nanoclusters, altering the reaction mechanism from homogeneous to heterogeneous in dechlorination reaction of aryl chlorides. This phenomenon was illustrated by the observed enhancement of the rate of reaction by in situ generated Au-rich bimetallic Au/Pd nanoclusters.

Plannar light source using a phosphor screen with single-walled carbon nanotubes as field emitters.

We developed and successfully fabricated a plannar light source device using a phosphor screen with single-walled carbon nanotubes (SWCNTs) as field emitters in a simple diode structure composed of the cathode containing the highly purified and crystalline SWCNTs dispersed into an organic In2O3-SnO2 precursor solution and a non-ionic surfactant. The cathode was activated by scratching process with sandpaper to obtain a large field emission current with low power consumption. The nicks by scratching were treated with Fourier analysis to determine the periodicity of the surface morphology and designed with controlling the count number of sandpapers. The anode, on the other hand, was made with phosphor deliberately optimized by coverage of ITO nanoparticles and assembled together with the cathode by the new stable assembling process resulting to stand-alone flat plane-emission panel. The device in a diode structure has a low driving voltage and good brightness homogeneity in that plane. Furthermore, field emission current fluctuation, which is an important factor in comparing luminance devices too, has a good stability in a simple diode panel. The flat plane-emission device employing the highly purified and crystalline SWCNTs has the potential to provide a new approach to lighting in our life style.

Long-term biopersistence of tangled oxidized carbon nanotubes inside and outside macrophages in rat subcutaneous tissue.

Because of their mechanical strength, chemical stability, and low molecular weight, carbon nanotubes (CNTs) are attractive biological implant materials. Biomaterials are typically implanted into subcutaneous tissue or bone; however, the long-term biopersistence of CNTs in these tissues is unknown. Here, tangled oxidized multi-walled CNTs (t-ox-MWCNTs) were implanted into rat subcutaneous tissues and structural changes in the t-ox-MWCNTs located inside and outside of macrophages were studied for 2 years post-implantation. The majority of the large agglomerates were present in the intercellular space, maintained a layered structure, and did not undergo degradation. By contrast, small agglomerates were found inside macrophages, where they were gradually degraded in lysosomes. None of the rats displayed symptoms of cancer or severe inflammatory reactions such as necrosis. These results indicate that t-ox-MWCNTs have high biopersistence and do not evoke adverse events in rat subcutaneous tissue in vivo, demonstrating their potential utility as implantable biomaterials.

Helicity-selective photoreaction of single-walled carbon nanotubes with organosulfur compounds in the presence of oxygen.

This report describes a helicity-selective photoreaction of single-walled carbon nanotubes (SWNTs) with disulfide in the presence of oxygen. The SWNTs were characterized using absorption, photoluminescence (PL), Raman, and X-ray photoelectron spectroscopy, scanning electron microscopy, and current-voltage (I-V) measurements. Results showed remarkable helicity-selective (metallic SWNTs/semiconducting SWNTs and diameter) functionalization of SWNTs. The reaction rate decreases in the order of metallic SWNTs > semiconducting SWNTs and small-diameter SWNTs > large-diameter SWNTs. Control experiments conducted under various experimental conditions and ESR and femtosecond laser flash photolysis measurements revealed that the helicity-selective reaction proceeds via a photoinduced electron transfer reaction. The PL and I-V measurements showed that the photoreaction is effective not only to control SWNT conductivity but also for the band gap modulation of semiconducting SWNTs.

Boron-assisted transformation to rod-like graphitic carbons from multi-walled carbon nanotubes in boron-mixed multi-walled carbon nanotube solids.

We produced boron-mixed multi-walled carbon nanotube solids (B-mixed MWCNT solids) by heating and pressing the powder of purified MWCNTs mixed with 1, 5, and 10 wt % boron in the temperature range 1400-1800 °C every 200 °C under a constant pressure of 20 MPa in vacuo, and investigated the influence of boron addition on nanotube structure and the mechanical and electrical properties of the resulting B-mixed MWCNT solids. The structure of the prepared material was characterized by scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy-electron energy loss spectroscopy, Raman scattering spectroscopy, and X-ray diffraction, and their mechanical properties and conductivity were measured using a mechanical and Vickers indentation tester and an electric resistor, respectively. It is notable that part of the nanotubes in the B-mixed MWCNT solids solidified at 1800 °C had dramatically changed into rod-like graphitic carbons (RLGCs). The occupancy distribution of RLGCs increased with increasing boron contents. However, boron was not detected in the energy-loss near-edge structure spectrum of RLGCs. Furthermore, RLGCs were not observed in the boron-unmixed sample treated with the same solidified condition, indicating that adding boron causes a remarkable ability to transform the phase of MWCNT. Transformation from MWCNTs to RLGCs resulted in increased specific bending strength and modulus, Vickers hardness, and electrical conductivity of B-mixed MWCNT solids with increasing boron content and solidified temperature.

Toxicity evaluations of various carbon nanomaterials.

After the discovery of fullerene and carbon nanotubes, various carbon nanomaterials were discovered or synthesized. The carbon nanomaterials have remarkable properties, different from bulk materials with the same chemical composition, and are therefore useful for industrial applications. However, the toxicity of nanomaterials may also differ from that of the bulk materials; this difference poses a concern. The physical similarity of nanomaterials to asbestos has led to evaluations for toxicity by many researchers using various methods. In this review, we compile and compare the toxicity evaluations of each carbon nanomaterial.

Oxidation of unsaturated carboxylic acids under hydrothermal conditions.

Hydrothermal oxidation pathways of high molecular weight unsaturated carboxylic acids were investigated for the potential use of chemoselectivity to improve the efficiency of the desired products from biomasses directly containing or easily producing unsaturated carboxylic acids. Hock cleavage, which frequently occur at general chemical, was observed in the absence of any acid catalyst and may be a potential major oxidation cleavage mechanism, which leads to the cleavage at both the carbon-carbon double bond and the single bond near a double bond. The addition of a peroxyl radical to the double bond may be also a potential major oxidation mechanism, which leads to the oxidation cleavage mainly at the carbon-carbon double bond. Cleavage at the carbon-carbon bond near the double bond by the addition of a peroxyl radical to the double bond may also occur. However, oxidation at either alpha-, beta-, or gamma-carbon to the -COOH group hardly occurred. These results may help to selectively produce desired products from biomasses, such as lignin and oils.

Synthesis of monodispersed nanoparticles functionalized carbon nanotubes in plasma-ionic liquid interfacial fields.

Metal nanoparticles intercalated into and encapsulated inside single-walled (SWNTs) and double-walled (DWNTs) carbon nanotubes are synthesized using a plasma technique combined with the introduction of ionic liquids under low gas pressures. Owing to the synthesis in nano-spaces of the SWNTs and DWNTs as a template, high-density and monodispersed metal nanoparticles are realized, which could be applied to specific composite-nanodevices based on carbon nanotubes.

Biodistribution imaging of magnetic particles in mice: X-ray scanning analytical microscopy and magnetic resonance imaging.

Nano-sized particles have received much attention in view of their varied application in a wide range of fields. For example, magnetite (Fe(3)O(4)) nanoparticles have been investigated for various medical applications. In this study, we visualized the distribution of administered magnetic nanoparticles in mice using both X-ray scanning analytical microscopy (XSAM) and magnetic resonance imaging (MRI). After administration, the nanoparticles were rapidly dispersed via the blood circulation, and reached the liver, kidney and spleen. Using the XSAM and MRI methods in a complementary fashion, the biodistribution of nano-sized magnetite particles was successfully visualized.

Material nanosizing effect on living organisms: non-specific, biointeractive, physical size effects.

Nanosizing effects of materials on biological organisms was investigated by biochemical cell functional tests, cell proliferation and animal implantation testing. The increase in specific surface area causes the enhancement of ionic dissolution and serious toxicity for soluble, stimulative materials. This effect originates solely from materials and enhances the same functions as those in a macroscopic size as a catalyst. There are other effects that become prominent, especially for non-soluble, biocompatible materials such as Ti. Particle size dependence showed the critical size for the transition of behaviour is at approximately 100 microm, 10 microm and 200 nm. This effect has its origin in the biological interaction process between both particles and cells/tissue. Expression of superoxide anions, cytokines tumour necrosis factor-alpha and interleukin-1 beta from neutrophils was increased with the decrease in particle size and especially pronounced below 10 microm, inducing phagocytosis to cells and inflammation of tissue, although inductively coupled plasma chemical analysis showed no dissolution from Ti particles. Below 200 nm, stimulus decreases, then particles invade into the internal body through the respiratory or digestive systems and diffuse inside the body. Although macroscopic hydroxyapatite, which exhibits excellent osteoconductivity, is not replaced with natural bone, nanoapatite composites induce both phagocytosis of composites by osteoclasts and new bone formation by osteoblasts when implanted in bone defects. The progress of this bioreaction results in the conversion of functions to bone substitution. Although macroscopic graphite is non-cell adhesive, carbon nanotubes (CNTs) are cell adhesive. The adsorption of proteins and nano-meshwork structure contribute to the excellent cell adhesion and growth on CNTs. Non-actuation of the immune system except for a few innate immunity processes gives the non-specific nature to the particle bioreaction and restricts reaction to the size-sensitive phagocytosis. Materials larger than cell size, approximately 10 microm, behave inertly, but those smaller become biointeractive and induce the intrinsic functions of living organisms. This bioreaction process causes the conversion of functions such as from biocompatibility to stimulus in Ti-abraded particles, from non-bone substitutional to bone substitutional in nanoapatite and from non-cell adhesive to cell adhesive CNTs. The insensitive nature permits nanoparticles that are less than 200 nm to slip through body defence systems and invade directly into the internal body.

Super-robust, lightweight, conducting carbon nanotube blocks cross-linked by de-fluorination.

We produced large binder-free multi-walled carbon nanotube (MWNT) blocks from fluorinated MWNTs using thermal heating and a compressing method in vacuo. This technique resulted in the formation of covalent MWNT networks generated by the introduction of sp(3)-hybridized carbon atoms that cross-link between nanotubes upon de-fluorination. The resulting carbon nanotube blocks are lighter than graphite, can be machined and polished, and possess average bending strengths of 102.2 MPa, a bending modulus of 15.4 GPa, and an electrical conductivity of 2.1 x 10(2) S/cm. Although each nanotube exhibits a random structure in these blocks, the mechanical properties are 3 times higher than those obtained for commercial graphite. On the basis of theoretical molecular dynamics simulations, a model is presented for the nanotube interconnecting mechanism upon de-fluorination.

Concentrated colloids of silica-encapsulated gold nanoparticles: colloidal stability, cytotoxicity, and X-ray absorption.

As an effort to develop a new, effective, nontoxic X-ray contrast agent, the concentrated colloids of silica-encapsulated gold nanoparticles (Au@SiO2 NPs) were fabricated and their colloidal stability, cytotoxicity, and X-ray absorption were investigated. The concentrated colloidal NPs were manufactured by forming a 4 nm-thick silica shell on the surface of each Au NP with 15 nm diameter, followed by enrichment to [Au] = 100 mM. They were very stable in water: the NPs were well separated each other without forming agglomerates and their optical property was very similar to that before enrichment. The colloidal stability of the NPs in biological environment was strongly dependent on their previous morphology in water. The NPs with minor shell damage were stable in phosphate buffered saline (PBS) solution: both in water and in PBS solution, they showed very similar morphology and optical property. However, the NPs with profound shell damage formed big agglomerates in PBS solution, resulting in the red-shift and broadening of the Au surface plasmon resonance peak. Cell viability and proliferation assessments revealed the biocompatibility of the Au@SiO2 NPs: no apparent cytotoxicity was observed even at 100 ppm NPs. The concentrated colloidal NPs showed very strong X-ray absorption. Their relative X-ray transmittance to water was comparable to that of a commercial agent. Considering these, the concentrated colloids of the Au@SiO2 NPs are suitable for an X-ray contrast agent.

Relation of the number of cross-links and mechanical properties of multi-walled carbon nanotube films formed by a dehydration condensation reaction.

Multi-walled carbon nanotube (MWCNT) films were prepared by employing a condensation reaction utilizing 1,3-dicyclohexylcarbodiimide (DCC) to cross-link each MWCNT with carboxylic acid and hydroxyl groups. Morphological changes in the resultant MWCNT films were monitored using scanning electron microscopy and showed that the MWCNTs were randomly intertwined in the films. The prepared MWCNT films were 17 mm in diameter and 20 microm in thickness, and the apparent density was 0.59 g/cm(3). Fourier transform-infrared spectroscopy confirmed that each MWCNT modified with carboxylic acid and hydroxyl groups was cross-linked through the ester bond. It was found that the ratio of the number of ester cross-links and carbon atoms of the nanotubes per unit apparent volume (cm(3)) of condensed-MWCNT films was 5.27 x 10(-3) using thermogravimetric analysis (TGA). The tensile strength and Vickers hardness of condensed-MWCNT films achieved an average of 15 and 9.2 MPa, respectively, and were greater than those of free-standing MWCNT films without ester bond.

Biological behavior of hat-stacked carbon nanofibers in the subcutaneous tissue in rats.

The tissue response to hat-stacked carbon nanofibers (H-CNFs) was evaluated. H-CNFs were implanted in the subcutaneous tissue of rats. Histological and ultrastructural investigations were carried out by transmission electron microscopy. Although many macrophages and foreign body giant cells were seen around H-CNFs, no severe inflammatory response such as necrosis was observed. Some H-CNFs were observed in lysosomal vacuoles of phagocytes. These results showed that H-CNFs were not strong prophlogistic substances and were englobed in vivo.

Strict preparation and evaluation of water-soluble hat-stacked carbon nanofibers for biomedical application and their high biocompatibility: influence of nanofiber-surface functional groups on cytotoxicity.

Water-soluble H-CNFs modified with a carboxyl group possessed the ability to induce TNF-alpha, whereas CHAPS-treated H-CNFs possessed significantly greater activity and were also found to activate NF-kappaB reporter activity, to a significantly greater level than H-CNFs; furthermore the functional group modified or coated on the surface of H-CNFs was a significant cytotoxic factor that affected cell activation.

Influence of length on cytotoxicity of multi-walled carbon nanotubes against human acute monocytic leukemia cell line THP-1 in vitro and subcutaneous tissue of rats in vivo.

Carbon nanotubes (CNTs) are single- or multi-cylindrical graphene structures that possess diameters of a few nanometers, while the length can be up to a few micrometers. These could have unusual toxicological properties, in that they share intermediate morphological characteristics of both fibers and nanoparticles. To date, no detailed study has been carried out to determine the effect of length on CNT cytotoxicity. In this paper, we investigated the activation of the human acute monocytic leukemia cell line THP-1 in vitro and the response in subcutaneous tissue in vivo to CNTs of different lengths. We used 220 nm and 825 nm-long CNT samples for testing, referred to as "220-CNTs" and "825-CNTs", respectively. 220-CNTs and 825-CNTs induced human monocytes in vitro, although the activity was significantly lower than that of microbial lipopeptide and lipopolysaccharide, and no activity appeared following variation in the length of CNTs. On the other hand, the degree of inflammatory response in subcutaneous tissue in rats around the 220-CNTs was slight in comparison with that around the 825-CNTs. These results indicated that the degree of inflammation around 825-CNTs was stronger than that around 220-CNTs since macrophages could envelop 220-CNTs more readily than 825-CNTs. However, no severe inflammatory response such as necrosis, degeneration or neutrophil infiltration in vivo was observed around both CNTs examined throughout the experimental period.

Ultra-stable nanoparticles of CdSe revealed from mass spectrometry.

Nanoparticles under a few nanometres in size have structures and material functions that differ from the bulk because of their distinct geometrical shapes and strong quantum confinement. These qualities could lead to unique device applications. Our mass spectral analysis of CdSe nanoparticles reveals that (CdSe)(33) and (CdSe)(34) are extremely stable: with a simple solution method, they grow in preference to any other chemical compositions to produce macroscopic quantities. First-principles calculations predict that these are puckered (CdSe)(28)-cages, with four- and six-membered rings based on the highly symmetric octahedral analogues of fullerenes, accommodating either (CdSe)(5) or (CdSe)(6) inside to form a three-dimensional network with essentially heteropolar sp(3)-bonding. This is in accordance with our X-ray and optical analyses. We have found similar mass spectra and atomic structures in CdS, CdTe, ZnS and ZnSe, demonstrating that mass-specified and macroscopically produced nanoparticles, which have been practically limited so far to elemental carbon, can now be extended to a vast variety of compound systems.