Biomedical Applications of Advanced Multifunctional Magnetic Nanoparticles.

In this review, we have presented the latest results and highlights on biomedical applications of a class of noble metal nanoparticles, such as gold, silver and platinum, and a class of magnetic nanoparticles, such as cobalt, nickel and iron. Their most important related compounds are also discussed for biomedical applications for treating various diseases, typically as cancers. At present, both physical and chemical methods have been proved very successful to synthesize, shape, control, and produce metal- and oxide-based homogeneous particle systems, e.g., nanoparticles and microparticles. Therefore, we have mainly focused on functional magnetic nanoparticles for nanomedicine because of their high bioadaptability to the organs inside human body. Here, bioconjugation techniques are very crucial to link nanoparticles with conventional drugs, nanodrugs, biomolecules or polymers for biomedical applications. Biofunctionalization of engineered nanoparticles for biomedicine is shown respective to in vitro and in vivo analysis protocols that typically include drug delivery, hyperthermia therapy, magnetic resonance imaging (MRI), and recent outstanding progress in sweep imaging technique with Fourier transformation (SWIFT) MRI. The latter can be especially applied using magnetic nanoparticles, such as Co-, Fe-, Ni-based nanoparticles, α-Fe2O3, and Fe3O4 oxide nanoparticles for analysis and treatment of malignancies. Therefore, this review focuses on recent results of scientists, and related research on diagnosis and treatment methods of common and dangerous diseases by biomedical engineered nanoparticles. Importantly, nanosysems (nanoparticles) or microsystems (microparticles) or hybrid micronano systems are shortly introduced into nanomedicine. Here, Fe oxide nanoparticles ultimately enable potential and applicable technologies for tumor-targeted imaging and therapy. Finally, we have shown the latest aspects of the most important Fe-based particle systems, such as Fe, α-Fe2O3, Fe3O4, Fe-Fe(x)O(y) oxide core-shell nanoparticles, and CoFe2O4-MnFe2O4 core-shell nanoparticles for nanomedicine in the efficient treatment of large tumors at low cost in near future.

Controlled synthesis of porous platinum nanostructures for catalytic applications.

Porous platinum, that has outstanding catalytic and electrical properties and superior resistant characteristics to corrosion, has been widely applied in chemical, petrochemical, pharmaceutical, electronic, and automotive industries. As the catalytic activity and selectivity depend on the size, shape and structure of nanomaterials, the strategies for controlling these factors of platinum nanomaterials to get excellent catalytic properties are discussed. Here, recent advances in the design and preparation of various porous platinum nanostructures are reviewed, including wet-chemical synthesis, electro-deposition, galvanic replacement reaction and de-alloying technology. The applications of various platinum nanostructures are also discussed, especially in fuel cells.

Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next PEMFCs, and DMFCs.

A concerted migration mechanism of mixed oxide ion and electron conduction in reduced ceria studied by first-principles density functional theory.

Ceria based oxides are regarded as key oxide materials for energy and environmental applications, such as solid oxide fuel cells, oxygen permeation membranes, fuel cell electrodes, oxygen storage, or heterogeneous catalysis. This great versatility in applications is rendered possible by the fact that rare earth-doped ceria is a pure oxygen ion conductor while undoped ceria, CeO(2-δ), is a mixed oxygen ion-electron conductor. To get deeper insight into the mixed conduction mechanism of oxygen ions and electrons from atomistic and electronic level viewpoints we have applied first-principles density functional theory (DFT + U method). The calculation results show that oxygen vacancies strongly attract localized electrons, forming associates between them. The migration energy of an oxygen vacancy in such an associate is substantially lowered compared to the unassociated case due to the simultaneous positional rearrangement of localized electrons during the ionic jump process. Accordingly, we propose a concerted migration mechanism of oxygen vacancies and localized electrons in reduced ceria; this mechanism results in an increased diffusivity of oxygen vacancies supported by localized electrons compared with that in pure oxide ion conductors.

Global minimum structure search in Li(x)CoO2 composition using a hybrid evolutionary algorithm.

The global minimum structures for Li(x)CoO(2) compositions where 0 ≤ x ≤ 1 were probed by using a hybrid evolutionary algorithm with an underlying ab initio structural relaxation scheme. The method successfully predicted experimentally observed variants of layered configurations at various degrees of lithiation and the spinel (Fd3[combining macron]m) phase at x = 1/2. New low-energy non-layered host structures at x < 1/2 were also revealed. These structures can be formed from the usual layered configuration through coherent stacking faults along the c-axis and the migration of Co ions into the Li-poor intercalation layer.

First-principles density functional calculation of electrochemical stability of fast Li ion conducting garnet-type oxides.

The research and development of rechargeable all-ceramic lithium batteries are vital to realize their considerable advantages over existing commercial lithium ion batteries in terms of size, energy density, and safety. A key part of such effort is the development of solid-state electrolyte materials with high Li(+) conductivity and good electrochemical stability; lithium-containing oxides with a garnet-type structure are known to satisfy the requirements to achieve both features. Using first-principles density functional theory (DFT), we investigated the electrochemical stability of garnet-type Li(x)La(3)M(2)O(12) (M = Ti, Zr, Nb, Ta, Sb, Bi; x = 5 or 7) materials against Li metal. We found that the electrochemical stability of such materials depends on their composition and structure. The electrochemical stability against Li metal was improved when a cation M was chosen with a low effective nuclear charge, that is, with a high screening constant for an unoccupied orbital. In fact, both our computational and experimental results show that Li(7)La(3)Zr(2)O(12) and Li(5)La(3)Ta(2)O(12) are inert to Li metal. In addition, the linkage of MO(6) octahedra in the crystal structure affects the electrochemical stability. For example, perovskite-type La(1/3)TaO(3) was found, both experimentally and computationally, to react with Li metal owing to the corner-sharing MO(6) octahedral network of La(1/3)TaO(3), even though it has the same constituent elements as garnet-type Li(5)La(3)Ta(2)O(12) (which is inert to Li metal and features isolated TaO(6) octahedra).

Tuned longitudinal surface plasmon resonance and third-order nonlinear optical properties of gold nanorods.

In order to elucidate the relationship for third-order nonlinear optical properties of anisotropic metal nanoparticles between the incident laser wavelength and surface plasmon resonance (SPR) wavelength, gold nanorods (GNRs) with a tuned longitudinal SPR mode in frequency were prepared by seed-mediated methods with two different surfactants, cetyltrimethylammonium bromide (CTAB) and benzyldimethylammonium chloride (BDAC). The real and imaginary parts of the third-order nonlinear optical susceptibilities χ(3) were examined by near-infrared (800 nm) femtosecond Z-scan and I-scan techniques for various gold sols with SPR wavelengths of 530 nm (spheres), 800 nm (nanorods) and 1000 nm (nanorods), named as 530GNSs, 800GNRs and 1000GNRs, respectively. All the samples showed intrinsically third-order nonlinear optical refractive responses. However, as for the real part of χ(3) for one particle, 800GNRs whose plasmon peak was tuned to the incident laser wavelength exhibited a Reχ(3) value 45 times stronger than 530GNSs. More interestingly, the imaginary part of χ(3) was more greatly influenced at the tuned SPR wavelength. Here we first demonstrate that 800GNRs showed plasmon-enhanced saturable absorption (SA) due to a longitudinal SPR tuned to the incident laser wavelength.

A novel proton conductor of imidazole-aluminium phosphate hybrids in the solid state.

Anhydrous proton transport at temperatures above 100 °C has attracted considerable attention in the development of fuel cells that operate at intermediate temperatures. Liquid-state imidazole (ImH) is known to be a fast anhydrous proton conductor above 100 °C; however, evaporation and severe conductivity drops above and below its melting point (∼90 °C), respectively, are major drawbacks to ImH. In this paper, we report a novel solid-state anhydrous ImH-Al(H(2)PO(4))(3) (AlP) hybrid material prepared via a simple synthesis using mechanical milling. This solid-state hybrid exhibits relatively a high ionic conductivity of ∼0.1 mS cm(-1) at 100 °C and remarkably a small activation energy of 0.23 eV. In addition, the ImH-AlP hybrid material provides a means of overcoming both temperature-dependent drawbacks to pure ImH: (1) the ImH-AlP hybrid is thermally stable up to 130 °C, and (2) the hybrid material maintains high ionic conductivity below the melting point of ImH.

Preparation of gold nano-cones as surface-enhanced Raman scattering sensors for molecule detection.

Surface-enhanced Raman spectroscopy (SERS) is a powerful novel analytical tool which integrates high levels of sensitivity for trace analysis of chemical and biomolecular species due to the massive enhancement of Raman signals by using nanometre-sized metal particles. However, SERS can be envisaged as an analytical tool only if substrates with strong, predictable and reproducible SERS enhancement can be produced. Here we have developed one simple Ar+ ions sputtering technology to prepare gold nano-cones array on silicon substrates as surface-enhanced Raman scattering (SERS)-active substrates. The tip of the gold cone-structures exhibited an extremely sharp curvature with an apex diameter of 20 nm and the interior apex angle of the nanocones was around 20 degrees. These samples were evaluated as potential SERS substrates using Rhodamine 6G molecules as molecule probe and exhibited SERS enhancement factor of greater than 10, originated from the localized electron field enhancement around the apex of cones and the surface plasmon coupling of periodic structures.

The synthesis and characterization of platinum nanoparticles: a method of controlling the size and morphology.

In this paper, Pt nanoparticles with good shapes of nanocubes and nano-octahedra and well-controlled sizes in the range 5-7 and 8-12 nm, respectively, have been successfully synthesized. The modified polyol method by adding silver nitrate and varying the molar ratio of the solutions of silver nitrate and H(2)PtCl(6) has been used to produce Pt nanoparticles of the size and shape to be controlled. The size and morphology of Pt nanoparticles have been studied by transmission electron microscopy (TEM) and high resolution TEM (HRTEM). The results have shown that their very sharp and good shapes exist in the main forms of cubic, cuboctahedral, octahedral and tetrahedral shapes directly related to the crystal nucleation along various directions of the [100] cubic, [111] octahedral and [111] tetrahedral facets during synthesis. In particular, various irregular and new shapes of Pt nanoparticles have been found. Here, it is concluded that the role of silver ions has to be considered as an important factor for promoting and controlling the development of Pt nanoparticles of [100] cubic, [111] octahedral and [111] tetrahedral facets, and also directly orienting the growth and formation of Pt nanoparticles.

Aligned gold nanoneedle arrays for surface-enhanced Raman scattering.

A simple Ar(+)-ion irradiation route has been developed to prepare gold nanoneedle arrays on glass substrates for surface-enhanced Raman scattering (SERS)-active substrates. The nanoneedles exhibited very sharp tips with an apex diameter of 20 nm. These arrays were evaluated as potential SERS substrates using malachite green molecules and exhibited a SERS enhancement factor of greater than 10(8), which is attributed to the localized electron field enhancement around the apex of the needle and the surface plasmon coupling originating from the periodic structure. This work demonstrates a new technique for producing controllable and reproducible SERS substrates potentially applicable for chemical and biological assays.

Reduction Mechanisms of Cu2+-Doped Na2O-Al2O3-SiO2 Glasses during Heating in H2 Gas.

Controlling valence state of metal ions that are doped in materials has been widely applied for turning optical properties. Even though hydrogen has been proven effective to reduce metal ions because of its strong reducing capability, few comprehensive studies focus on practical applications because of the low diffusion rate of hydrogen in solids and the limited reaction near sample surfaces. Here, we investigated the reactions of hydrogen with Cu2+-doped Na2O-Al2O3-SiO2 glass and found that a completely different reduction from results reported so far occurs, which is dominated by the Al/Na concentration ratio. For Al/Na < 1, Cu2+ ions were reduced via hydrogen to metallic Cu, distributing in glass body. For Al/Na > 1, on the other hand, the reduction of Cu2+ ions occurred simultaneously with the formation of OH bonds, whereas the reduced Cu metal moved outward and formed a metallic film on glass surface. The NMR and Fourier transform infrared results indicated that the Cu2+ ions were surrounded by Al3+ ions that formed AlO4, distorted AlO4, and AlO5 units. The diffused H2 gas reacted with the Al-O-···Cu+ units, forming Al-OH and metallic Cu, the latter of which moved freely toward glass surface and in return enhanced H2 diffusion.

Optical properties and valence change of europium ions in a sol-gel Al2O3-B2O3-SiO2 glass by femtosecond laser pulses.

The Al2O3-B2O3-SiO2 glass containing europium ions was prepared by a sol-gel method. Fluorescence line-narrowing spectra (FLN) indicate two different environments of the Eu 3+ ions. The calculated second crystal-field parameters exhibit the opposite behaviors of the two different environments. The FLN excitation and emission spectra before and after irradiation show that the change of the emission mainly comes from the Eu 3+ ions at site I, revealing that the concentration ratio of the Eu 3+ ions at site I to site II was decreased. The emission spectra confirmed that some Eu 3+ ions were reduced into Eu 2+ ions. The excitation spectra indicate that the Eu 3+ ions at the sites with higher covalence degree can be easily reduced, implying that the Eu 3+ ions are more easily reduced at site I than at site II. The absorption spectra before and after irradiation exhibit that the absorption of Eu 2+ ions increases and that the positive hole centers appear. These results suggest a mechanism of the formation of the Eu 2+ ions by femtosecond laser irradiation.

Enhancement of third-order optical nonlinearities in 3-dimensional films of dielectric shell capped Au composite nanoparticles.

The composite nanoparticles of Au-core capped by CdS shells of different thickness were prepared and assembled into densely packed 3-dimensional films by the layer-by-layer self-assembly (LBL) technique. These films exhibited the 3-dimensional structure of densely packed Au@CdS composite nanoparticles and the shell thickness was tunable by changing the concentration of Cd2+-thiourea complexes. These multilayer films exhibited enhanced third-order optical nonlinear responses and ultrafast response times (several picoseconds). The third-order nonlinear optical susceptibility of the film with the CdS shell thickness of 4.4 nm was estimated to be 1.48 x 10(-9) esu and the value decreases with the increase of the CdS shell thickness. The enhancement of the optical nonlinearity was explained based on the calculation according to the electrostatic approximation by the solution of Laplace's equation under the boundary conditions appropriate to the model of core-shell nanoparticles, and mainly attributed to localized electric field effects in the CdS shell region. Additionally, the nonlinearity was optimized by determination of the values of the dielectric constant and thickness of the different shell.

Template guided self-assembling two-dimensional array of Au@SiO2 core-shell nanoparticles for room-temperature single electron transistors.

The composite nanoparticles of a gold core capped by a SiO2 shell with well-controlled thickness have been synthesized and fabricated into two-dimensional array on silicon surface by a simple self-assembly method combined with an AFM nanolithography technique. Current-voltage measurements of the Au@SiO2 composite nanoparticles (shell thickness of 6 nm) show a well-pronounced Coulomb staircase with a period of 300 mV at room temperature, demonstrating single electron transistor behavior. The step width of the Coulomb staircase can be tuned by controlling the thickness of SiO2 shell. The tunable single electron tunneling properties make the 2D array of Au@SiO2 composite nanoparticles an ideal candidate for planar single electron transistor devices.

Reduction mechanism for Eu ions in Al2O3-containing glasses by heat treatment in H2 gas.

Superior functional glasses doped with rare-earth ions have been prepared by controlling the valence states of rare-earth ions. However, recent work has revealed unresolved questions about the controlling mechanism of rare-earth ions' valence states. To address these questions, oxide glasses with and without Al2O3 and doped with Eu(3+) ions were prepared by a melting process; then, the valence states of Eu(3+) ions were investigated during heating under a hydrogen environment. The Eu(3+) ions were reduced to Eu(2+) only in the glass containing Al(3+) ions; the reduction occurred in the center of the glass over a short heating period. It was discovered that the reduction of Eu(3+) ions concurrently occurred with the formation of OH bonds which were bound with Al(3+) ions. Considering this and the data for the H2 gas diffusion through the glass, we conclude that diffusing H2 gas molecules react with Al-O(-) bonds surrounding Eu(3+) ions to form AlOH bonds and reduce Eu(3+) ions to Eu(2+) via the extracted electrons. When H2 reacts with a glass structure, that hydrogen has transformed into -OH bonds and the hydrogen concentration in the glass decreases. In order to make up the lost hydrogen, more hydrogen molecules can enter into the glass, resulting in the fast reduction of Eu(3+) ions in the center of the glass.

Large-scale template-free synthesis of ordered mesoporous platinum nanocubes and their electrocatalytic properties.

Here we report a facile, one-pot and template-free approach to synthesize mesoporous monocrystalline Pt nanocubes with uniform shapes and sizes, in which small Pt particles with a size of ∼5 nm are three-dimensionally and periodically built up into cubes with a size of ∼50 nm. The forming process is illustrated through a novel meso-crystal self-assembly mechanism. Very interestingly, the mesoporous structures are ordered, which are thought to be beneficial to increase their catalytic activity. Compared with nonporous Pt nanoparticles and porous Pt nanoparticles without order, the ordered mesoporous Pt nanocubes exhibit a highly improved electrocatalytic ability for methanol and formic acid oxidation, and are potentially applicable as electrocatalysts for direct methanol and formic acid fuel cells. Furthermore, this approach can be used to synthesize other Pt-series metallic mesoporous nanoparticles, such as Pd.

Bioactive calcium phosphate invert glass-ceramic coating on beta-type Ti-29Nb-13Ta-4.6Zr alloy.

A fine, strong coating consisting of a bioactive calcium phosphate invert glass-ceramic can be prepared easily by reaction of the glassy phase with an oxide layer formed on a new beta-type titanium alloy, Ti-29Nb-13Ta-4.6Zr, when the metal, on which the mother glass powders with a composition of 60CaO-30P(2)O(5)-7Na(2)O-3TiO(2) in mol% are placed, is heated at 800 degrees C in air. A compositionally gradient layer is developed on the titanium alloy during the heating. Tensile bonding strength of the coating to the metal is significantly higher than those of the coatings to conventional metals such as Ti-6Al-4V alloy or pure titanium. The oxidized layer on Ti-29Nb-13Ta-4.6Zr alloy is relatively thinner than that on Ti-6Al-4V alloy even with heat treatment in air; large tensile stresses are not generated in the layer.

Preparation of poly(lactic acid) composites containing calcium carbonate (vaterite).

A new type of ceramic-polymer biomaterial having excellent apatite-forming ability in simulated body fluid was prepared by hot-pressing a mixture of poly(-L-lactic acid) (PLA) and calcium carbonate (vaterite). After PLA dissolved in methylene chloride was mixed with calcium carbonate consisting of vaterite, the mixture was dried completely and subsequently hot-pressed uniaxially under a pressure of 40 MPa at 180 degrees C. When 30 wt% vaterite was introduced, the modulus of elasticity was effectively improved by 3.5-6 GPa, which was about twice higher than the modulus of PLA. The composite showed no brittle fracture behavior and a comparably high bending strength of approximately 50 MPa. The composite containing 30 wt% vaterite formed a 5-15-microm-thick bonelike apatite layer on its surface after soaking in SBF at 37 degrees C even for 1-3d.

Ordered mesoporous phosphosilicate glass electrolyte film with low area specific resistivity.

Ordered mesoporous phosphosilicate glass electrolyte film exhibiting low area specific resistivity (ASR) compared with those of Nafion has been synthesized using non-ionic surfactant as the structure-directing agent.