Configurationally Nonselective Aquation of a Mononuclear Ru(II) Chloro Complex to Aquo Complex Isomers with Distinctive Aspects in Photoisomerization, Redox, and Catalytic Water Oxidation.

-[Ru(EtOtpy)(pynp)Cl] (-) (EtOtpy = 4'-ethoxy-2,2':6',2″-terpyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine), and /-[Ru(EtOtpy)(pynp)OH] (/-) complexes were newly synthesized to investigate the synergistic influence of the geometric configuration coupled with substituent introduction of an ethoxy (EtO) group on the physicochemical properties and reactions of the Ru(II) complexes. Configurationally nonselective aquation of - was uniquely observed to form /- isomers in water, in contrast to configurationally selective aquation of -[Ru(tpy)(pynp)Cl] (-, tpy = 2,2':6',2″-terpyridine) without the EtO group [Yamazaki, H. .

Temperature-Controlled Transformation of WO Nanowires into Active Facets-Exposed Hexagonal Prisms toward Efficient Visible-Light-Driven Water Oxidation.

A unique transformation of WO nanowires (NW-WO) into hexagonal prisms (HP-WO) was demonstrated by tuning the temperature of the (NH)WO precursor suspension prepared from tungstic acid and hydrazine as a structure-directing agent. The precursor preparation at 20 °C followed by calcination at 550 °C produced NW-WO nanocrystals ( <100 nm width, 3-5 μm length) with anisotropic growth of monoclinic WO crystals to (002) and (200) planes and a polycrystalline character with randomly oriented crystallites in the lateral face of nanowires. The precursor preparation at 45 °C followed by calcination at 550 °C produced HP-WO nanocrystals ( 500-1000 nm diameter) with preferentially exposed (002) and (020) facets on the top-flat and side-rectangle surfaces, respectively, of hexagonal prismatic WO nanocrystals with a single-crystalline character.

N-Rich, Polyphenolic Porous Organic Polymer and Its In Vitro Anticancer Activity on Colorectal Cancer.

N-rich organic materials bearing polyphenolic moieties in their building networks and nanoscale porosities are very demanding in the context of designing efficient biomaterials or drug carriers for the cancer treatment. Here, we report the synthesis of a new triazine-based secondary-amine- and imine-linked polyphenolic porous organic polymer material TrzTFPPOP and explored its potential for in vitro anticancer activity on the human colorectal carcinoma (HCT 116) cell line. This functionalized (-OH, -NH-, -C=N-) organic material displayed an exceptionally high BET surface area of 2140 m g along with hierarchical porosity (micropores and mesopores), and it induced apoptotic changes leading to high efficiency in colon cancer cell destruction via p53-regulated DNA damage pathway.

Distinctive Aspects in Aquation, Proton-Coupled Redox, and Photoisomerization Reactions between Geometric Isomers of Mononuclear Ruthenium Complexes with a Large-π-Conjugated Tetradentate Ligand.

Geometric isomers of mononuclear ruthenium(II) complexes, /-[Ru(tpy)(dpda)Cl] (/-, tpy = 2,2':6',2″-terpyridine, dpda = 2,7-bis(2-pyridyl)-1,8-diazaanthracene), were newly synthesized to comprehensively investigate the geometric and electronic structures and distinctive aspects in various reactions between isomers. The ultraviolet (UV)-visible absorption spectra of /- isomers show intense bands for metal-to-ligand charge transfer (MLCT) at close wavelengths of 576 and 573 nm, respectively. However, time-dependent density functional theory (TD-DFT) calculations suggest that the MLCT transition of - involves mainly single transitions to the π* orbital of the dpda ligand in contrast to mixing of the π* orbitals of the dpda and tpy ligands for -.

Synergistic Effects of Earth-Abundant Metal-Metal Oxide Enable Reductive Amination of Carbonyls at 50 °C.

Reductive amination of carbonyls to primary amines is of importance to the synthesis of fine chemicals; however, this reaction with heterogeneous catalysts containing earth-abundant metals under mild conditions remains scarce. Here, we show that the nickel catalyst with mixed oxidation states enables such synthesis of primary amines under low temperature (50 °C) and H pressure (0.9 MPa).

Electronic Effect in a Ruthenium Catalyst Designed in Nanoporous N-Functionalized Carbon for Efficient Hydrogenation of Heteroarenes.

Active metal catalysts are the key in chemical industry for sustainable production of multitude of chemical resources. Here, we report a new ruthenium (Ru) composite with a synergistically controlled nanostructure and electronic properties as a highly efficient hydrogenation catalyst which comprises stable small Ru nanoparticles (mean particle size, 0.9 nm) in situ generated into a nanoporous N-functionalized carbon with high surface area ( 650 m g) and has strong electron-donating power of Ru sites of nanoparticles.

Folic acid-conjugated magnetic mesoporous silica nanoparticles loaded with quercetin: a theranostic approach for cancer management.

The development of drug carriers based on nanomaterials that can selectively carry chemotherapeutic agents to cancer cells has become a major focus in biomedical research. A novel pH-sensitive multifunctional envelope-type mesoporous silica nanoparticle (SBA-15) was fabricated for targeted drug delivery to human colorectal carcinoma cells (HCT-116). SBA-15 was functionalized with folic acid (FA), and the material was loaded with the water-insoluble flavonoid, quercetin (QN).

Ag nanoparticle-decorated, ordered mesoporous silica as an efficient electrocatalyst for alkaline water oxidation reaction.

In recent years, several novel strategies for speeding up the slow kinetics of the water oxidation reaction have attracted considerable attention for generation of O2. This is particularly important from the environmental perspective. Here we report a SBA-15 type, 2D-hexagonal functionalized mesoporous organosilica material as support for small Ag nanoparticles (NPs) by grafting the silica surface with 3-aminopropyltriethoxysilane, followed by chemical impregnation of Ag NPs at its surface, to obtain a AgNPs@SBA-NH2 material.

A high performance catalyst of shape-specific ruthenium nanoparticles for production of primary amines by reductive amination of carbonyl compounds.

The creation of metal catalysts with highly active surfaces is pivotal to meeting the strong economic demand of the chemical industry. Specific flat-shaped pristine fcc ruthenium nanoparticles having a large fraction of atomically active {111} facets exposed on their flat surfaces have been developed that act as a highly selective and reusable heterogeneous catalyst for the production of various primary amines at exceedingly high reaction rates by the low temperature reductive amination of carbonyl compounds. The high performance of the catalyst is attributed to the large fraction of metallic Ru serving as active sites with weak electron donating ability that prevail on the surface exposed {111} facets of flat-shaped fcc Ru nanoparticles.

Visible Light-Driven Water Oxidation on an In Situ N -Intercalated WO Nanorod Photoanode Synthesized by a Dual-Functional Structure-Directing Agent.

With a view to developing a photoanode for visible light-driven water oxidation in solar water splitting cells, pure-monoclinic WO nanorod crystals with N intercalated into the lattice were synthesized by using hydrazine with a dual functional role-as an N atom source for the in situ N intercalation and as a structure-directing agent for the nanorod architecture-to gain higher incident photon-to-current conversion efficiency at 420 nm than with most previously reported WO electrodes.

Dual-Functional Surfactant-Templated Strategy for Synthesis of an In Situ N -Intercalated Mesoporous WO Photoanode for Efficient Visible-Light-Driven Water Oxidation.

N -Intercalated crystalline mesoporous tungsten trioxide (WO ) was synthesized by a thermal decomposition technique with dodecylamine (DDA) as a surfactant template with a dual role as an N-atom source for N intercalation, alongside its conventional structure-directing role (by micelle formation) to induce a mesoporous structure. N physisorption analysis showed that the specific surface area (57.3 m  g ) of WO templated with DDA (WO -DDA) is 2.

Carbonate Ions Induce Highly Efficient Electrocatalytic Water Oxidation by Cobalt Oxyhydroxide Nanoparticles.

Synthetic models of oxygen evolving complex (OEC) are used not only to gain better understanding of the mechanism and the roles of cofactors for water oxidation in photosynthesis, but also as water oxidation catalysts to realize artificial photosynthesis, which is anticipated as a promising solar fuel production system. However, although much attention has been paid to the composition and structure of active sites for development of heterogeneous OEC models, the cofactors, which are essential for water oxidation by the photosynthetic OEC, remain little studied. The high activity of CoO(OH) nanoparticles for electrocatalytic water oxidation is shown to be induced by a CO cofactor.

Characterization of Interfacial Charge-Transfer Photoexcitation of Polychromium-Oxo-Electrodeposited TiO as an Earth-Abundant Photoanode for Water Oxidation Driven by Visible Light.

Polychromium-oxo-deposited TiO (Cr O /TiO ) electrodes were fabricated by a simple electrochemical technique by using different TiO basal electrodes (anatase, rutile, and mixed polymorphic phases P25) as earth-abundant photoanodes for visible-light-driven water oxidation. The high-resolution transmission electron microscopy (HR-TEM) observation illustrated that an Cr O layer with approximately 2-3 nm thickness was formed on the surface of the crystalline TiO particles. Upon visible-light irradiation of the electrodes, the photoanodic current based on water oxidation was generated at the Cr O /TiO electrodes.

Open pore architecture of an ordered mesoporous IrO2 thin film for highly efficient electrocatalytic water oxidation.

We report the first accessible channel-like open pore architecture of ordered 2D hexagonal mesoporous IrO2 films and its utilization as an efficient anode for electrocatalytic water oxidation. A well-ordered mesostructure of circa 7 nm pores were obtained by a facile one-pot soft-templating strategy, employing a [Ir(OH)6](2-) precursor stabilized by a triblock copolymer "Pluronic F127" as a pore-directing template. A mesoporous IrO2 film calcined at 400 °C (∼70 nm thick) affords a high surface area of 512 m(2)  cm(-3) and 2 times higher O2 evolution during the electrocatalytic water oxidation relative to an untemplated IrO2 coating film.

Unique and facile solvothermal synthesis of mesoporous WO3 using a solid precursor and a surfactant template as a photoanode for visible-light-driven water oxidation.

Mesoporous tungsten trioxide (WO3) was prepared from tungstic acid (H2WO4) as a tungsten precursor with dodecylamine (DDA) as a template to guide porosity of the nanostructure by a solvothermal technique. The WO3 sample (denoted as WO3-DDA) prepared with DDA was moulded on an electrode to yield efficient performance for visible-light-driven photoelectrochemical (PEC) water oxidation. Powder X-ray diffraction (XRD) data of the WO3-DDA sample calcined at 400°C indicate a crystalline framework of the mesoporous structure with disordered arrangement of pores.

Connectivity of PS-b-PEO templated spherical pores in titanium oxide films.

Titania films having relatively uniform spherical pores were successfully fabricated using polystyrene-block-poly(ethylene oxide) (PS(n)-b-PEO(m)) diblock copolymers. Depending on the molecular weight of PS(n)-b-PEO(m), the spherical pores were varied from large mesopores (n = 40,000, m = 53,000; ∼40 nm) to macropores (n = 58,600, m = 71,000; ∼60 nm, n = 100,000, m = 150,000; ∼100 nm) in diameter. It was confirmed that the porous structures were thermally stable with crystallization of the titania frameworks.

Template directed synthesis of mesoporous ZnO having high porosity and enhanced optoelectronic properties.

A simple route for the synthesis of a novel mesoporous zinc oxide material having wurtzite like nanocrystalline pore walls by using Schiff-base amine as template is reported, which shows very high BET surface area (456 m(2) g(-1)) and remarkably enhanced photoconductivity and photoluminescence at room temperature under visible light irradiation vis-à-vis bulk ZnO material.