Cyclopalladation compounds of the 2-pyridylhydrazone derivatives of p-substituted acetophenones and acetylthiophenes

Cyclopalladation occurs for 2-pyridylhydrazones(HL) of p-methyl-, p-methoxy-, p-chloro-, and p-nitro-acetophenone, and 3-acetyl- and 2-acetyl-thiophene with lithium tetrahalopalladate to give the complexes [PdXL] (X = Cl and Br) and some iodo complexes are prepared by metathesis of the chloro complexes with lithium iodide. These complexes are characterized spectroscopically. The hydrazones are coordinated to palladium through benzene or thiophene ortho-carbon, hydrazone-nitrogen, and pyridine ring-nitrogen atoms forming fused five-membered chelate rings.     

Orbital magnetism and spin-orbit effects in the electronic structure of BaIrO3

The electronic structure and magnetism of Ir 5d5 states in nonmetallic, weakly ferromagnetic BaIrO3 are probed with x-ray absorption techniques. Contrary to expectation, the Ir 5d orbital moment is found to be ~1.5 times larger than the spin moment. This unusual, atomiclike nature of the 5d moment is driven by a strong spin-orbit interaction in heavy Ir ions, as confirmed by the nonstatistical large branching ratio at Ir L(2,3) absorption edges. As a consequence, orbital interactions cannot be neglected when addressing the nature of magnetic ordering in BaIrO3. The local moment behavior persists even as the metallic-paramagnetic phase boundary is approached with Sr doping or applied pressure.     

Two-dimensional crystal growth and stacking of bis(phthalocyaninato) rare earth sandwich complexes at the 1-phenyloctane/graphite interface

Initial stages of two-dimensional crystal growth of the double-decker sandwich complex Lu(Pc*)2 [Pc* = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] have been studied by scanning tunneling microscopy at the liquid/solid interface between 1-phenyloctane and highly oriented pyrolytic graphite. High-resolution images strongly suggest alignment of the double-decker molecules into monolayers with the phthalocyanine rings parallel to the surface. Domains were observed with either hexagonal or quadrate packing motifs, and the growing interface of the layer was imaged. Molecular resolution was achieved, and the face of the phthalocyanine rings appeared as somewhat diffuse circular features. The alkyl chains are proposed to be interdigitating to maintain planar side-by-side packing.     

Development of high resolution resonance ionization mass spectrometry for trace analysis of 93mNb

⁹³Nb(n, n′)^93mNb reaction allows retrospective estimation of integrated fast neutron dose in nuclear reactor. We proposed isomer-selective trace analysis of ^93mNb by Resonance Ionization Mass Spectrometry (RIMS) combined with a gas-jet atomic source and an injection locked Ti:Sapphire laser system operated at several kHz. Resonant ionization spectroscopy of Nb in gas-jet using Ti:Sapphire laser was demonstrated.     

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Treatment of a meso‐diarylporphyrin with PhI(OAc)₂ in the presence of BF₃ ? OEt₂ and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso‐meso β–β doubly‐fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO‐LUMO gap owing to expanded and low‐symmetry π‐planes.     

Control of chain ends of polyesters in polycondensation of AA and BB monomers by use of solid‐phase reagent

For selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol ( 1a ) and sebacoyl chloride ( 2a ) and between 1,12‐dodecanediol ( 1b ) and isophthaloyl chloride ( 2b ) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and ¹H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end ( poly 1 ), but also polyester with anilides at both ends ( poly 2 ). The product ratio of poly 1 to poly 2 ( poly 1 / poly 2 ) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1 / poly 2 ratio of 81/21 and moderate molecular weight (M_n = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1379–1386     

DNA Origami Scaffolds as Templates for Functional Tetrameric Kir3 K+ Channels

In native systems, scaffolding proteins play important roles in assembling proteins into complexes to transduce signals. This concept is yet to be applied to the assembly of functional transmembrane protein complexes in artificial systems. To address this issue, DNA origami has the potential to serve as scaffolds that arrange proteins at specific positions in complexes. Herein, we report that Kir3 K⁺ channel proteins are assembled through zinc‐finger protein (ZFP)‐adaptors at specific locations on DNA origami scaffolds. Specific binding of the ZFP‐fused Kir3 channels and ZFP‐based adaptors on DNA origami were confirmed by atomic force microscopy and gel electrophoresis. Furthermore, the DNA origami with ZFP binding sites nearly tripled the K⁺ channel current activity elicited by heterotetrameric Kir3 channels in HEK293T cells. Thus, our method provides a useful template to control the oligomerization states of membrane protein complexes in vitro and in living cells.     

Gold-bead scanning near-field optical microscope with laser-force position control

We have developed a scanning near-field optical microscope with an optically trapped metallic particle that has a small diameter compared to the wavelength of visible light. In this microscope we employed spot illumination to enhance the intensity of light scattered from a probe particle so we could reduce the diameter of the probe particle to 40nm. We detected slight irregularities of the surface of the cover glass near 10-nm depth. Also, we observed gold colloidal particles on the surface of the cover glass.