Rodlike bimetallic ruthenium and osmium complexes bridged by phenylene spacers. Synthesis, electrochemistry, and photophysics

In the search for light-addressable nanosized compounds we have synthesized 10 dinuclear homometallic trisbipyridyl complexes of linear structure with the general formula [M(bpy)3-BL-M(bpy)3]4+ [M = Ru(II) or Os(II); BL = polyphenylenes (2, 3, 4, or 5 units) or indenofluorene; bpy = 2,2′-bipyridine]. By using a "chemistry on the complex" approach, different sizes of rodlike systems have been obtained with a length of 19.8 and 32.5 Å for the shortest and longest complex, respectively. For one of the ruthenium precursors, [RUbpy-ph2-Si(CH3) 3][PF6]2, single crystals were obtained by recrystallization from methanol. Their photophysical and electrochemical properties are reported. All the compounds are luminescent both at room and low temperature with long excited-state lifetimes due to an extended delocalization. Nanosecond transient absorption showed that the lowest excited state involves the chelating unit attached to the bridging ligand. Electrochemical data indicated that the first reduction is at a slightly more positive potential than for the reference complexes [M(bpy)3]2+ (M = Ru, Os). This result confirms that the best acceptor is the bipyridine moiety connected to the conjugated spacers. The role of the tilt angle between the phenylene units, in the two series of complexes, for the ground and excited states is discussed.

Silylation of layered double hydroxides via a calcination−rehydration route

Silylated layered double hydroxides (LDHs) were synthesized through a surfactant-free method involving an in situ condensation of silane with the surface hydroxyl group of LDHs during its reconstruction in carbonate solution. X-ray diffraction (XRD) patterns showed the silylation reaction occurred on the external surfaces of LDHs layers. The successful silylation was evidenced by 29Si cross-polarization magic-angle spinning nuclear magnetic resonance (29Si CP/MAS NMR) spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and infrared emission spectroscopy (IES). The ribbon shaped crystallites with a “rodlike” aggregation were observed through transmission electron microscopy (TEM) images. The aggregation was explained by the T2 and T3 types of linkage between adjacent silane molecules as indicated in the 29Si NMR spectrum. In addition, the silylated products show high thermal stability by maintained Si related bands even when the temperature was increased to 1000 °C as observed in IES spectra.

Detection of dsRNA from Cleistothecia and Conidia of the Grape Powdery Mildew Pathogen, Uncinula Necator

Double-stranded RNA species ranging in molecular weight from 0.95 to 6.3 × 106 were detected in grapevines in New York. We recently showed that two of the species (Mr = 5.3 and 4.4 × 106) are associated with rupestris stem pitting disease. In this report, we show that the other eight detectable dsRNA species are associated with the powdery mildew fungus, Uncinula necator. These dsRNAs associated with the powdery mildew fungus were previously detected in leaves and epidermal stem tissue of grapevines infected with powdery mildew. The same dsRNA species were also detected from extracts of isolated cleistothecia and conidia of U. necator devoid of plant tissue. Isometric and rigid rodlike particles were observed in single cleistothecia preparations when examined under transmission electron microscopy.

Amine-sssisted route to fabricate LiNbO3 particles with a tunable shape

An ethylenediamine-assisted route has been designed for one-step synthesis of lithium niobate particles with a novel rodlike structure in an aqueous solution system. The morphological evolution for these lithium niobate rods was monitored via SEM: The raw materials form large lozenges first. These lozenges are a metastable intermediate of this reaction, and they subsequently crack into small rods after sufficiently long time. These small rods recrystallize and finally grow into individual lithium niobate rods. Interestingly, shape-controlled fabrication of lithium niobate powders was achieved through using different amine ligands. For instance, the ethylenediamine or ethanolamine ligan can induce the formation of rods, while n-butylamine prefers to construct hollow spheres. These as-obtained lithium niobate rods and hollow spheres may exhibit enhanced performance in an optical application field due to their distinctive structures. This effective ligand-tuned-morphology route can provide a new strategy to facilely achieve the shape-controlled synthesis of other niobates.

Formation of one-dimensional capped ZnO nanoparticle assemblies at the air/water interface

The self-assembling behavior and microscopic structure of zinc oxide nanoparticle Langmuir-Blodgett monolayer films were investigated for the case of zinc oxide nanoparticles coated with a hydrophobic layer of dodecanethiol. Evolution of nanoparticle film structure as a function of surface pressure (π) at the air-water interface was monitored in situ using Brewster’s angle microscopy, where it was determined that π=16 mN/m produced near-defect-free monolayer films. Transmission electron micrographs of drop-cast and Langmuir-Schaefer deposited films of the dodecanethiol-coated zinc oxide nanoparticles revealed that the nanoparticle preparation method yielded a microscopic structure that consisted of one-dimensional rodlike assemblies of nanoparticles with typical dimensions of 25 x 400 nm, encased in the organic dodecanethiol layer. These nanoparticle-containing rodlike micelles were aligned into ordered arrangements of parallel rods using the Langmuir-Blodgett technique.