Formation of Metal Selenide and Metal-Selenium Nanoparticles using Distinct Reactivity between Selenium and Noble Metals.

Small Se nanoparticles with a diameter of ≈20 nm were generated by the reduction of selenium chloride with NaBH4 at -10 °C. The reaction with Ag at 60 °C yielded stable Ag2 Se nanoparticles, which subsequently were transformed into M-Se nanoparticles (M=Cd, Zn, Pb) through cation exchange reactions with corresponding ions. The reaction with Pt formed Pt layers that were evenly coated on the surface of the Se nanoparticles, and the dissolution of the Se cores with hydrazine generated uniform Pt hollow nanoparticles. The reaction with Au generated tiny Au clusters on the Se surface, and eventually formed acorn-shaped Au-Se nanoparticles through heat treatment. These results indicate that small Se nanoparticles with diameters of ≈20 nm can be used as a versatile platform for the synthesis of metal selenide and metal-selenium hybrid nanoparticles with complex structures.

Fate mapping of ptf1a-expressing cells during pancreatic organogenesis and regeneration in zebrafish.

BACKGROUND: Pancreas development in zebrafish shares many features with mammals, including the participation of epithelial progenitor cells expressing pancreas transcription factor 1a (ptf1a). However, to date it has remained unclear whether, as in mammals, ptf1a-expressing zebrafish pancreatic progenitors are able to contribute to multiple exocrine and endocrine lineages. To delineate the lineage potential of ptf1a-expressing cells, we generated ptf1a:creER(T2) transgenic fish and performed genetic-inducible lineage tracing in developmental, regenerating, and ptf1a-deficient zebrafish pancreas. RESULTS: In addition to their contribution to the acinar cell lineage, ptf1a-expressing cells give rise to both pancreatic Notch-responsive-cells (PNCs) as well as small numbers of endocrine cells during pancreatic development. In fish with ptf1a haploinsufficiency, a higher proportion of ptf1a lineage-labeled cells are traced into the PNC and endocrine compartments. Further reduction of ptf1a gene dosage converts pancreatic progenitor cells to gall bladder and other non-pancreatic cell fates. CONCLUSIONS: Our results confirm the presence of multipotent ptf1a-expressing progenitor cells in developing zebrafish pancreas, with reduced ptf1a dosage promoting greater contributions towards non-acinar lineages. As in mammals, loss of ptf1a results in conversion of nascent pancreatic progenitor cells to non-pancreatic cell fates, underscoring the central role of ptf1a in foregut tissue specification.

Chemical approach to a new crystal structure: phase control of manganese oxide on a carbon sphere template.

The stabilization and growth of a non-native structure, hexagonal wurtzite MnO (h-MnO), is explored via kinetic control of manganese precursor on a carbon sphere template. MnO is most stable in the cubic rock-salt structure (c-MnO), and a number of studies have focused on the synthesis and properties of this rock-salt phase. However, h-MnO has not been fully characterized before our work. Prolonged heating at a relatively low temperature yields c-MnO, whereas rapid heating of the reaction mixture at reflux produces h-MnO in the presence of carbon spheres. The effect of benzyl amine concentration on the formation of two different oxidation states (c-MnO and t-Mn3O4) was examined as well. Moreover, the structural stability of the manganese oxides and phase transition of MnO in terms of the wurtzite to rock-salt structural transformation have been investigated.

Designed synthesis of well-defined Pd@Pt core-shell nanoparticles with controlled shell thickness as efficient oxygen reduction electrocatalysts.

Improving the electrocatalytic activity and durability of Pt-based catalysts with low Pt content toward the oxygen reduction reaction (ORR) is one of the main challenges in advancing the performance of polymer electrolyte membrane fuel cells (PEMFCs). Herein, a designed synthesis of well-defined Pd@Pt core-shell nanoparticles (NPs) with a controlled Pt shell thickness of 0.4-1.2 nm by a facile wet chemical method and their electrocatalytic performances for ORR as a function of shell thickness are reported. Pd@Pt NPs with predetermined structural parameters were prepared by in situ heteroepitaxial growth of Pt on as-synthesized 6 nm Pd NPs without any sacrificial layers and intermediate workup processes, and thus the synthetic procedure for the production of Pd@Pt NPs with well-defined sizes and shell thicknesses is greatly simplified. The Pt shell thickness could be precisely controlled by adjusting the molar ratio of Pt to Pd. The ORR performance of the Pd@Pt NPs strongly depended on the thickness of their Pt shells. The Pd@Pt NPs with 0.94 nm Pt shells exhibited enhanced specific activity and higher durability compared to other Pd@Pt NPs and commercial Pt/C catalysts. Testing Pd@Pt NPs with 0.94 nm Pt shells in a membrane electrode assembly revealed a single-cell performance comparable with that of the Pt/C catalyst despite their lower Pt content, that is the present NP catalysts can facilitate low-cost and high-efficient applications of PEMFCs.

Nitrogen-Doped Pt/C Electrocatalysts with Enhanced Activity and Stability toward the Oxygen Reduction Reaction.

Recently, nitrogen-doped carbon materials have proved to be effective catalytic platforms for the oxygen reduction reaction (ORR). Despite the recent synthetic advances for the preparation of nitrogen-incorporated carbon materials, the low-temperature and water-based synthesis of nitrogen-doped carbon materials has rarely been explored due to the difficulties in nitrogen-doping under such mild conditions. Here, nitrogen-doped Pt/C (Pt/NC) catalysts are prepared using a facile, low-temperature, aqueous-phase method. Hydrazine treatment of a Pt/C catalyst successfully yields Pt/NC with controlled nitrogen content. The as-prepared Pt/NC catalysts exhibit enhanced electrocatalytic activity and stability toward ORR in comparison to nitrogen-free Pt/C, and their ORR activities are highly dependent on the level of nitrogen-doping. The Pt/NC catalyst containing 2.0 at % nitrogen results in the largest improvement of ORR activity.

Composition-controlled PtCo alloy nanocubes with tuned electrocatalytic activity for oxygen reduction.

Modification of the electronic structure and lattice contraction of Pt alloy nanocatalysts through control over their morphology and composition has been a crucial issue for improving their electrocatalytic oxygen reduction reaction (ORR) activity. In the present work, we synthesized PtCo alloy nanocubes with controlled compositions (Pt(x)Co NCs, x = 2, 3, 5, 7, and 9) by regulating the ratio of surfactants and the amount of Co precursor to elucidate the effect of the composition of nanocatalysts on their ORR activity. Pt(x)Co NCs had a Pt-skin structure after electrochemical treatment. The electrocatalysis experiments revealed a strong correlation between ORR activity and Co composition. Pt3Co NCs exhibited the best ORR performance among the various Pt(x)Co NCs. From density functional theory calculations, a typical volcano-type relationship was established between ORR activity and oxygen binding energy (E(OB)) on NC surfaces, which showed that Pt3Co NCs had the optimal E(OB) to achieve the maximum ORR activity. X-ray photoelectron spectroscopy and X-ray diffraction measurements demonstrated that the electronic structure and lattice contraction of the Pt(x)Co NCs could be tuned by controlling the composition of NCs, which are highly correlated with the trends of E(OB) change.

Hollow Sn-SnO(2) nanocrystal/graphite composites and their lithium storage properties.

Hollow spheres have been constructed by applying the Kirkendall effect to Sn nanocrystals. This not only accommodates the detrimental volume expansion but also reduces the Li(+) transport distance enabling homogeneous Li-Sn alloying. Hollow Sn-SnO2 nanocrystals show a significantly enhanced cyclic performance compared to Sn nanocrystal alone due to its typical structure with hollow core. Sn-SnO2/graphite nanocomposites obtained by the chemical reduction and oxidation of Sn nanocrystals onto graphite displayed very stable cyclic performance thanks to the role of graphite as an aggregation preventer as well as an electronic conductor.

New crystal structure: synthesis and characterization of hexagonal wurtzite MnO.

Most transition metal oxides have a cubic rocksalt crystal structure, but ZnO and CoO are the only stable transition metal oxides known to possess a hexagonal structure. Unprecedented hexagonal wurtzite MnO has been prepared by thermal decomposition of Mn(acac)(2) on a carbon template. Structural characterization has been carried out by TEM, SAED, and a Rietveld analysis using XRD. The experimental and theoretical magnetic results indicate magnetic ordering of the hexagonal wurtzite MnO. Density functional calculations have been performed in order to understand the electronic and piezoelectric properties of the newly synthesized hexagonal wurtzite MnO.

Tetraglyme-mediated synthesis of Pd nanoparticles for dehydrogenation of ammonia borane.

Palladium nanoparticles (PdNPs) were conveniently prepared in tetraglyme (TG) solution using a variety of palladium precursors. At 140 °C, TG promoted Pd(3)(OAc)(6) to produce irregular shaped PdNPs with an average size of 4 nm. When these PdNPs were re-dispersed in TG and used for the dehydrogenation of ammonia borane (AB) at 85 °C, remarkably enhanced catalytic performance was achieved to release 2.3 equiv. of H(2) in 1 h.

[100] Directed Cu-doped h-CoO nanorods: elucidation of the growth mechanism and application to lithium-ion batteries.

Thermal decomposition of Co(acac)(3) and Cu(acac)(2) in benzylamine leads to the formation of [100] directed Cu-doped h-CoO nanorods, which are very stable in an aqueous solution. The formation mechanism of the [100] directed Cu-doped h-CoO nanorods is fully elucidated by using first-principles calculations, demonstrating that Cu-doping not only changes the growth direction but also enhances the stability of the nanorods significantly. Evaluation of the electrochemical performance of Cu-doped h-CoO nanorods shows high initial Coulombic efficiency and ultrahigh capacity with excellent cycling performance, indicating their suitability as an anode material for next generation lithium-ion batteries.

Phosphidation of Li4Ti5O12 nanoparticles and their electrochemical and biocompatible superiority for lithium rechargeable batteries.

Phosphidated-Li(4)Ti(5)O(12) shows high capacity with a significantly enhanced kinetics opening new possibilities for ultra-fast charge/discharge of lithium rechargeable batteries. The in vitro cytotoxicity test proves its fabulous cell viability, indicating that the toxicity problem of nanoparticles can be also solved by phosphidation.

Assembly of individual TiO2-C60/porphyrin hybrid nanoparticles for enhancement of photoconversion efficiency.

Rational organization of porphyrin and C60 on the electrode surface in photovoltaic structures is essential to yield high quantum efficiency. In the present work, individual TiO2 nanoparticles were modified by introducing C60 and porphyrin units on the surface, and then electrophoretically deposited on an ITO/SnO2 electrode. The morphology of the photoactive layer on the electrode was significantly different from that of the layer produced as a result of separate deposition of C60 and porphyrin. The maximum incident photon to current efficiency of the resulting electrode approached 88% at 410 nm, which is the highest value among molecule-based photovoltaic cells reported to date. This indicates that molecular assembly of the C60 and porphyrin units on the individual nanoparticles through strong chemical attachment is a key factor in improving effective electron transfer between the photoactive units and the electrodes.

The role of water for the phase-selective preparation of hexagonal and cubic cobalt oxide nanoparticles.

A selective preparation and the formation mechanism of hexagonal and cubic CoO nanoparticles from the reaction of [Co(acac)(2)] (acac=acetylacetonate) and amine have been investigated. CoO nanoparticles with a hexagonal pyramidal shape were yielded under decomposition conditions with amine. Importantly, the addition of water altered the final phase to cubic and comprehensively changed the reaction mechanism. The average sizes of the hexagonal and cubic CoO nanoparticles could be controlled either by changing the amine concentration or by using different reaction temperatures. Detailed formation mechanisms are proposed on the basis of gas chromatography-mass spectrometry data and color changes of the reaction mixture. The hexagonal CoO phase is obtained through two distinct pathways: solvolysis with C-C bond cleavage and direct condensation by amine. On the other hand, the cubic CoO nanoparticles were synthesized by strong nucleophilic attack of hydroxide ions from water and subsequent C-C bond breaking. The resulting caboxylate ligand can stabilize a cobalt hydroxide intermediate, leading to the generation of a thermodynamically stable CoO phase.

Synthesis and characterization of Pt(9)Co nanocubes with high activity for oxygen reduction.

Monodisperse, crystalline Pt(9)Co nanocubes were prepared by a one-pot colloidal method. The prepared Pt(9)Co nanocubes showed significantly enhanced electrocatalytic activity toward oxygen reduction.

Remarkably efficient photocurrent generation based on a [60]fullerene-triosmium cluster/Zn-porphyrin/boron-dipyrrin triad SAM.

A new artificial photosynthetic triad array, a [60]fullerene-triosmium cluster/zinc-porphyrin/boron-dipyrrin complex (1, Os(3)C(60)/ZnP/Bodipy), has been prepared by decarbonylation of Os(3)(CO)(8)(CN(CH(2))(3)Si(OEt)(3))(mu(3)-eta(2):eta(2):eta(2)-C(60)) (6) with Me(3)NO/MeCN and subsequent reaction with the isocyanide ligand CNZnP/Bodipy (5) containing zinc porphyrin (ZnP) and boron dipyrrin (Bodipy) moieties. Triad 1 has been characterized by various spectroscopic methods (MS, NMR, IR, UV/Vis, photoluminescence, and transient absorption spectroscopy). The electrochemical properties of 1 in chlorobenzene (CB) have been examined by cyclic voltammetry; the general feature of the cyclic voltammogram of 1 is nine reversible one-electron redox couples, that is, the sum of those of 5 and 6. DFT has been applied to study the molecular and electronic structures of 1. On the basis of fluorescence-lifetime measurements and transient absorption spectroscopic data, 1 undergoes an efficient energy transfer from Bodipy to ZnP and a fast electron transfer from ZnP to C(60); the detailed kinetics involved in both events have been elucidated. The SAM of triad 1 (1/ITO; ITO=indium-tin oxide) has been prepared by immersion of an ITO electrode in a CB solution of 1 and diazabicyclo-octane (2:1 equiv), and characterized by UV/Vis absorption spectroscopy, water contact angle, X-ray photoelectron spectroscopy, and cyclic voltammetry. The photoelectrochemical properties of 1/ITO have been investigated by a standard three-electrode system in the presence of an ascorbic acid sacrificial electron donor. The quantum yield of the photoelectrochemical cell has been estimated to be 29 % based on the number of photons absorbed by the chromophores. Our triad 1 is unique when compared to previously reported photoinduced electron-transfer arrays, in that C(60) is linked by pi bonding with little perturbation of the C(60) electron delocalization.

Monodisperse Pt and PtRu/C(60) hybrid nanoparticles for fuel cell anode catalysts.

Monodisperse Pt and PtRu/C(60) hybrid nanoparticles with controlled diameters were synthesized by the reduction of metal precursors in the presence of C(60); the resulting metal/C(60) hybrid nanocatalyst exhibited a remarkable enhancement of methanol oxidation activity over commercial E-TEK catalysts.

Identification of Pbx1, a potential oncogene, as a Notch3 target gene in ovarian cancer.

Notch3 gene amplification has recently been identified in ovarian cancer but the Notch3 effectors that are involved in the development of ovarian cancer remain elusive. In this study, we have identified Pbx1, a proto-oncogene in hematopoietic malignancy, as a Notch3 target gene. Pbx1 expression is transcriptionally regulated by Notch3 activation, and Notch3/CSL protein complex directly binds to the Pbx1 promoter segment harboring the CSL-binding sequence. The growth-inhibitory effect of gamma-secretase inhibitor could be partially reversed by ectopic Pbx1 expression. Furthermore, functional studies by Pbx1 short hairpin RNA knockdown show that Pbx1 is essential for cell proliferation and tumorigenicity. Taken together, the above findings indicate that Pbx1 is a direct Notch3-regulated gene that mediates the survival signal of Notch3 in ovarian cancer.

Jagged-1 and Notch3 juxtacrine loop regulates ovarian tumor growth and adhesion.

Notch3 gene amplification and pathway activation have been reported in ovarian serous carcinoma. However, the primary Notch3 ligand that initiates signal transduction in ovarian cancer remains unclear. In this report, we identify Jagged-1 as the highest expressed Notch ligand in ovarian tumor cells as well as in peritoneal mesothelial cells that are in direct contact with disseminated ovarian cancer cells. Cell-cell adhesion and cellular proliferation were reduced in Notch3-expressing ovarian cancer cells that were cocultured with Jagged-1 knockdown mesothelial and tumor feeder cells. Interaction of Notch3-expressing ovarian cancer cells with Jagged-1-expressing feeder cells activated the promoter activity of candidate Notch3 target genes, and this activity was attenuated by Notch3 siRNA. Constitutive expression of the Notch3 intracellular domain significantly suppressed the Jagged-1 shRNA-mediated growth inhibitory effect. In Notch3-expressing ovarian cancer cells, Jagged-1-stimulating peptides enhanced cellular proliferation, which was suppressed by gamma-secretase inhibitor and Notch3 siRNA. Taken together, our results show that Jagged-1 is the primary Notch3 ligand in ovarian carcinoma and Jagged-1/Notch3 interaction constitutes a juxtacrine loop promoting proliferation and dissemination of ovarian cancer cells within the intraperitoneal cavity.