Preparation of zinc oxide nanorods using pulsed laser ablation in water media at high temperature

ZnO columnar single crystals were formed by pulsed laser ablation in deionized water and surfactant aqueous solutions of lauryl dimethylaminoacetic acid (LDA) and cetyltrimethylammonium bromide (CTAB) at 80 degrees C. ZnO particles produced by laser ablation were dissolved at a higher temperature than 60 degrees C, and then crystalline growth to columnar structure proceeded. While large ZnO columnar crystals were obtained in deionized water, the crystals prepared in surfactant solution were smaller than those in deionized water due to inhibition of crystalline growth by surfactant adsorption on ZnO surfaces. The size of ZnO nanorods depended on how surfactant molecules adsorb on ZnO surface.     

Boron‐Ketoiminate‐Based Polymers: Fine‐Tuning of the Emission Color and Expression of Strong Emission Both in the Solution and Film States

In this research, the synthesis of boron‐ketoiminate‐containing polymers is reported with large molecular weights ( = 20 000) and their optical properties are examined by UV–vis absorption and photoluminescence spectrometries. It is shown that the polymers exhibit strong emission both in the solution and solid states (Φ _PL,THF = 0.46–0.80, Φ _PL,film = 0.13–0.38). These optical properties can be explained by a donor–acceptor interaction between the boron ketoiminate and the electron‐donating comonomer such as fluorene or bithiophene. Furthermore, in the solid states, their emission colors can be successfully tuned from blue to orange by the substituents on the nitrogen atom with the difference of the steric hindrance (λ _PL,THF = 464–546 nm, λ _PL,film = 486–604 nm).

     

Control of the Transition between Ni‐C and Ni‐SIa States by the Redox State of the Proximal Fe?S Cluster in the Catalytic Cycle of [NiFe] Hydrogenase

[NiFe] hydrogenase catalyzes the reversible cleavage of H₂. The electrons produced by the H₂ cleavage pass through three Fe–S clusters in [NiFe] hydrogenase to its redox partner. It has been reported that the Ni‐SI_a, Ni‐C, and Ni‐R states of [NiFe] hydrogenase are involved in the catalytic cycle, although the mechanism and regulation of the transition between the Ni‐C and Ni‐SI_a states remain unrevealed. In this study, the FT‐IR spectra under light irradiation at 138–198 K show that the Ni‐L state of [NiFe] hydrogenase is an intermediate between the transition of the Ni‐C and Ni‐SI_a states. The transition of the Ni‐C state to the Ni‐SI_a state occurred when the proximal [Fe₄S₄]_p^2+/+ cluster was oxidized, but not when it was reduced. These results show that the catalytic cycle of [NiFe] hydrogenase is controlled by the redox state of its [Fe₄S₄]_p^2+/+ cluster, which may function as a gate for the electron flow from the NiFe active site to the redox partner.     

Selective Ion Exchange in Supramolecular Channels in the Crystalline State

Artificial ion channels are of increasing interest because of potential applications in biomimetics, for example, for realizing selective ion permeability through the transport and/or exchange of selected ions. However, selective ion transport and/or exchange in the crystalline state is rare, and to the best of our knowledge, such a process has not been successfully combined with changes in the physical properties of a material. Herein, by soaking single crystals of Li₂([18]crown‐6)₃[Ni(dmit)₂]₂(H₂O)₄ ( 1 ) in an aqueous solution containing K⁺, we succeeded in complete ion exchange of the Li⁺ ions in 1 with K⁺ ions in the solution, while maintaining the crystalline state of the material. This ion exchange with K⁺ was selectively conducted even in mixed solutions containing K⁺ as well as Na⁺/Li⁺. Furthermore, remarkable changes in the physical properties of 1 resulted from the ion exchange. Our finding enables not only the realization of selective ion permeability but also the development of highly sensitive biosensors and futuristic ion exchange agents, for example.     

The Role of Hydrogen Bond and Crystal Solvent in the Solid-state (β-α) Photoisomerization of Novel 2-(N-phenylcarbamoyl)ethyl Cobaloxime Complexes [1]

Abstract

The 2-(phenylcarbamoyl)ethyl group bonded to the cobalt atom in cobaloxime complexes was isomerized on exposure to visible light in the solid-state. The three complexes with different amines as axial base ligands were prepared and their crystal structures were determined by X-ray analysis. The reaction rates in the solid-state were mainly affected by the hydrogen bonds of the reactive group with the neighboring molecules and the occupation of crystal solvent molecules around the reactive group.     

Self‐assembly of Functionalized Gold Nanoparticles with Rigid and Flexible Multifunctional Linkers

The interparticle spacing of carboxyl functionalized gold nanoparticles (Au‐COOH) were mediated by rigid crosslinkers, octa(3‐aminopropyl)octasilsesquioxane (POSS‐NH₃ ⁺) and poly(amidoamine) dendrimer terminated with hydroxyl groups (PAMAM‐OH), and a flexible polymeric linker, poly(hexanul viologen) (6‐VP). Regular interparticle spacing was achieved by utilizing POSS‐NH₃ ⁺ and PAMAM‐OH dendrimer as cross linkers, whereas size growth of Au‐COOH was observed featuring no interparticle spacing by utilizing 6‐VP as the crosslinker.     

Simultaneous determination of tungsten and molybdenum in sea water by catalytic current polarography after preconcentration on a resin column

The simultaneous determination of tungsten and molybdenum in sea water is based on preconcentration by column extraction with 7-(1-vinyl-3,3,5,5-tetramethylhexyl)-8-quinolinol (Kelex- 100) resin, and measurement of the polarographic catalytic currents obtained in a solution of chlorate, benzilic acid and 2-methyl-8-quinolinol. When the concentration factor is 50, the detection limits are 2.4 pM for tungsten and 17 pM for molybdenum (for a signal-to-noise ratio of 3). The precision of the determination is ca. 10% for 67 pM tungsten and ca. 5% for 106 nM molybdenum in sea water (n=4). Results for sea water and other natural waters are presented.     

Planar‐Chiral Through‐Space Conjugated Oligomers: Synthesis and Characterization of Chiroptical Properties

Optically active through‐space conjugated oligomers, namely, a dimer, trimer, tetramer, and cyclic trimer, consisting of a planar‐chiral [2.2]paracyclophane skeleton were synthesized. In the ground state, observed similarities in the chiroptical properties of the oligomers were attributed to the equivalent orientations of two adjacent chromophores. In the excited state, the oligomers were folded into a form analogous to a one‐handed helix by photoexcitation. All the compounds in dispersed solution exhibited intense circularly polarized luminescence with relatively large anisotropy factors on the order of 10^?3.     

Efficient generation and trapping of acylbenzynes from hypervalent iodine compounds

[5-Acyl-2-(trimethylsilyl)phenyl]iodonium triflates were prepared for the generation of benzynes bearing ketone function. Treatment of the iodonium triflates with Bu₄NF in CH₂Cl₂ in the presence of furan at room temperature gave 6-acyl-1,4-epoxy-1,4-dihydronaphthalenes in high yields. The mild conditions and the tolerance of the ketone function on benzyne generation are attributable to the advantage of hypervalent iodine compounds.