Recent progress in the improvement of hydrothermal stability of zeolites.

Zeolites have been successfully employed in many catalytic reactions of industrial relevance. The severe conditions required in some processes, where high temperatures are frequently combined with the presence of steam, highlight the need of considering the evolution of the catalyst structure during the reaction. This review attempts to summarize the recently developed strategies to improve the hydrothermal framework stability of zeolites.

The impact of surface Cu of ZnO/(Cu Zn )O heterostructured nanowires on the adsorption and chemical transformation of carbonyl compounds.

The surface cation composition of nanoscale metal oxides critically determines the properties of various functional chemical processes including inhomogeneous catalysts and molecular sensors. Here we employ a gradual modulation of cation composition on a ZnO/(Cu Zn )O heterostructured nanowire surface to study the effect of surface cation composition (Cu/Zn) on the adsorption and chemical transformation behaviors of volatile carbonyl compounds (nonanal: biomarker). Controlling cation diffusion at the ZnO(core)/CuO(shell) nanowire interface allows us to continuously manipulate the surface Cu/Zn ratio of ZnO/(Cu Zn )O heterostructured nanowires, while keeping the nanowire morphology.

Reversible Pt-CH deuteration without methane loss: metal-ligand cooperation ligand-assisted Pt-protonation.

Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)Pt(CH), reacts with CDOD at 25 °C to undergo complete deuteration of Pt-CH fragments in ∼5 h without loss of methane to form (dpk)Pt(CD) in virtually quantitative yield. The deuteration can be reversed by dissolution in CHOH or CDOH. Kinetic analysis and isotope effects, together with support from density functional theory calculations indicate a metal-ligand cooperative mechanism wherein DPK enables Pt-CH deuteration by allowing non-rate-limiting protonation of Pt by CDOD.

A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals.

Organic radicals are an emerging class of luminophores possessing multiplet spin states and potentially showing spin-luminescence correlated properties. We investigated the mechanism of recently reported magnetic field sensitivity in the emission of a photostable luminescent radical, (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) doped into host -PyBTM molecular crystals. The magnetic field (0-14 T), temperature (4.

A protecting group strategy to access stable lacunary polyoxomolybdates for introducing multinuclear metal clusters.

Although metal-containing polyoxomolybdates (molybdenum oxide clusters) exhibit outstanding catalytic properties, their precise synthetic method has not yet been developed. This is mainly because the very low stability of the multivacant lacunary polyoxomolybdates limited their use as synthetic precursors. Here, we present a "protecting group strategy" in polyoxometalate synthesis and successfully develop an efficient method for synthesising multinuclear metal-containing polyoxomolybdates using pyridine as a protecting group for unstable trivacant lacunary Keggin-type polyoxomolybdate [PMoO].

Holmium(iii) molecular nanomagnets for optical thermometry exploring the luminescence re-absorption effect.

Coordination complexes of lanthanide(3+) ions can combine Single-Molecule Magnetism (SMM) with thermally modulated luminescence applicable in optical thermometry. We report an innovative approach towards high performance SMM-based optical thermometers which explores tunable anisotropy and the luminescence re-absorption effect of Ho complexes. Our concept is shown in dinuclear cyanido-bridged molecules, {[Ho(4-pyridone)(HO)][M(CN)]}·HO (M = Co, ; Rh, ; Ir, ) and their magnetically diluted analogues, {[Ho Y (4-pyridone)(HO)][M(CN)]}·HO (M = Co, = 0.

Dual Ag/Co cocatalyst synergism for the highly effective photocatalytic conversion of CO by HO over Al-SrTiO.

Loading Ag and Co dual cocatalysts on Al-doped SrTiO (AgCo/Al-SrTiO) led to a significantly improved CO-formation rate and extremely high selectivity toward CO evolution (99.8%) using HO as an electron donor when irradiated with light at wavelengths above 300 nm. Furthermore, the CO-formation rate over AgCo/Al-SrTiO (52.

Extremely low-frequency phonon material and its temperature- and photo-induced switching effects.

Atomic vibrations due to stretching or bending modes cause optical phonon modes in the solid phase. These optical phonon modes typically lie in the frequency range of 10 to 10 cm. How much can the frequency of optical phonon modes be lowered? Herein we show an extremely low-frequency optical phonon mode of 19 cm (0.

Stereo-controlled -hydromagnesiation of aryl alkynes by magnesium hydrides.

A concise protocol for -hydromagnesiation of aryl alkynes was established using 1 : 1 molar combination of sodium hydride (NaH) and magnesium iodide (MgI) without the aid of any transition metal catalysts. The resulting alkenylmagnesium intermediates could be trapped with a series of electrophiles, thus providing facile accesses to stereochemically well-defined functionalized alkenes. Mechanistic studies by experimental and theoretical approaches imply that polar hydride addition from magnesium hydride (MgH) is responsible for the process.

Ligand-protected gold/silver superatoms: current status and emerging trends.

Monolayer-protected gold/silver clusters have attracted much interest as nano-scale building units for novel functional materials owing to their nonbulk-like structures and size-specific properties. They can be viewed as ligand-protected superatoms because their magic stabilities and fundamental properties are well explained in the framework of the jellium model. In the last decade, the number of ligand-protected superatoms with atomically-defined structures has been increasing rapidly thanks to the well-established synthesis and structural determination by X-ray crystallography.

Carbonization of single polyacrylonitrile chains in coordination nanospaces.

It has been over half a century since polyacrylonitrile (PAN)-based carbon fibers were first developed. However, the mechanism of the carbonization reaction remains largely unknown. Structural evolution of PAN during the preoxidation reaction, a stabilization reaction, is one of the most complicated stages because many chemical reactions, including cyclization, dehydration, and cross-linking reactions, simultaneously take place.

"Eggs in egg cartons": co-crystallization to embed molecular cages into crystalline lattices.

Discrete (ML) cages assembled from a tripodal ligand (L) and metal ions (M: Cu(i) or Ag(i)) are embedded in networked coordination hosts formed by partial dissociation of the same discrete cages during the crystallization process. The resulting "eggs-in-an-egg-carton" structures provide unique examples of the co-crystallization of discrete and infinite coordination frameworks.

Key aurophilic motif for robust quantum-tunneling-based characterization of a nucleoside analogue marker.

A quantum sequencer offers a scalable electrical platform for single-molecule analysis of genomic events. A thymidine (dT) analog exhibiting uniquely high single-molecule conductance is a key element in capturing DNA synthesis dynamics by serving as a decodable marker for enzymatic labeling of nascent strands. However, the current design strategies of dT analogs that focus on their molecular orbital energy levels require bulky chemical modifications to extend the π-conjugation, which hinders polymerase recognition.

Multi-objective molecular design of organic structure-directing agents for zeolites using nature-inspired ant colony optimization.

Organic structure-directing agents (OSDAs) are often employed for synthesis of zeolites with desired frameworks. prediction of such OSDAs has mainly relied on the interaction energies between OSDAs and zeolite frameworks, without cost considerations. For practical purposes, the cost of OSDAs becomes a critical issue.

Self-activated Rh-Zr mixed oxide as a nonhazardous cocatalyst for photocatalytic hydrogen evolution.

Efficient, robust and environmentally friendly cocatalysts for photocatalysts are important for large-scale solar hydrogen production. Herein, we demonstrate that a Rh-Zr mixed oxide is an efficient cocatalyst for hydrogen evolution. Impregnation of Zr and Rh precursors (Zr/Rh = 5 wt/wt%) formed RhZrO cocatalyst particles on Al-doped SrTiO, which exhibited 31× higher photocatalytic water-splitting activity than a RhO cocatalyst.

Metal-metal cooperative bond activation by heterobimetallic alkyl, aryl, and acetylide Pt/Cu complexes.

We report the selective formation of heterobimetallic Pt/Cu complexes that demonstrate how facile bond activation processes can be achieved by altering the reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with the Pt center and with a Pt-bound alkyl group increases the stability of PtMe towards undesired rollover cyclometalation. The presence of the Cu center also enables facile transmetalation from an electron-deficient tetraarylborate [B(Ar)] anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center.

A cross-sectional cadaveric study of the correlation between genital organ measurements, serum testosterone, and serum prostate-specific antigen levels in Japanese male subjects.

Association of organ sizes in the genitalia have long been a topic of interest for the general public. However, factors such as selection bias, embarrassment, and invasive testing have hindered studies on living individuals. We obtained measurements of penile size, testicular weight, and prostate weight, and conducted related serum testing on 63 Japanese male adults who died of unexpected reasons and underwent autopsy from 2009 to 2013.

Construction of Pentacyclic Limonoid Skeletons via Radical Cascade Reactions.

Limonoids and share a 6/6/6/5-membered ABCD-ring system and a six-membered oxacycle and differ in their C9-stereochemistries. A new radical-based strategy was devised to construct the pentacyclic skeletons of and . An oxacycle-fused A-ring and enyne fragments were coupled to produce radical precursors - with different C7-oxygen functionalities.

Multiscale Structural Modulation of Anisotropic Graphene Framework for Polymer Composites Achieving Highly Efficient Thermal Energy Management.

Graphene is usually embedded into polymer matrices for the development of thermally conductive composites, preferably forming an interconnected and anisotropic framework. Currently, the directional self-assembly of exfoliated graphene sheets is demonstrated to be the most effective way to synthesize anisotropic graphene frameworks. However, achieving a thermal conductivity enhancement (TCE) over 1500% with per 1 vol% graphene content in polymer matrices remains challenging, due to the high junction thermal resistance between the adjacent graphene sheets within the self-assembled graphene framework.

Morphological Manipulation of DNA Gel Microbeads with Biomolecular Stimuli.

Hydrogels are essential in many fields ranging from tissue engineering and drug delivery to food sciences or cosmetics. Hydrogels that respond to specific biomolecular stimuli such as DNA, mRNA, miRNA and small molecules are highly desirable from the perspective of medical applications, however interfacing classical hydrogels with nucleic acids is still challenging. Here were demonstrate the generation of microbeads of DNA hydrogels with droplet microfluidic, and their morphological actuation with DNA strands.

Photoswitchable Nonlinear-Optical Crystal Based on a Dysprosium-Iron Nitrosyl Metal Assembly.

Nitrosyl metal complexes (M-NO), in which nitrosyl ligands are coordinated to transition-metal ions, have been studied from the viewpoints of physiological activity, catalytic activity, and photosensitivity. The structural flexibility and electric polarization of the nitrosyl ligand are attractive characteristics. Herein we show a photoswitchable nonlinear-optical (NLO) crystal based on a dysprosium-iron nitrosyl assembly.

Zn(ii)2,9-dimethyl-1,10-phenanthroline stimulates cultured bovine aortic endothelial cell proliferation.

Vascular endothelial cells cover the luminal surface of blood vessels in a monolayer. Proliferation of these cells is crucial for the repair of damaged endothelial monolayers. In the present study, we identified a zinc complex, Zn(ii)2,9-dimethyl-1,10-phenanthroline (Zn-12), that stimulates the proliferation of bovine aortic endothelial cells in a culture system.

Crystal growth control of rod-shaped ε-FeO nanocrystals.

Herein we report crystal growth control of rod-shaped ε-FeO nanocrystals by developing a synthesis based on the sol-gel technique using β-FeO(OH) as a seed in the presence of a barium cation. ε-FeO nanocrystals are obtained over a wide calcination temperature range between 800 °C and 1000 °C. A low calcination temperature (800 °C) provides an almost cubic rectangular-shaped ε-FeO nanocrystal with an aspect ratio of 1.