Preparation of amphiphilic organoiron(1+) complexes having two long-chain alkyl groups and their molecular assemblage characteristics

[o-, m- and p-Bis(alkylamino or alkyloxy)benzene] (cyclopentadienyl)iron(1+) hexafluorophosphates {2 and 4; [(C_nH_2n+1X)₂C₆H₄](C₅H₅)Fe⁺PF₆^?, X?NH or O} were prepared by aromatic nucleophilic substitution of the (dichlorobenzene)iron cationic complexes (1). Critical micelle concentrations of the complex chlorides (3), prepared from 2 (n=8, X?NH) by anion exchange and soluble in water, gave much smaller values than those of bis(long-chain alkyl)dimethylammonium surfactants. Furthermore, the substitution positions scarcely affected their surface activites. However, the surface pressure-molecular area isotherm of the hexafluorophosphates (2 and 4, n=18, X?NH; insoluble in water) were severely transformed by change in the substitution position of the long-chain alkyl groups on the benzene ligand in the iron cationic complexes: the o-substituted complex gave a molecularly assembled film by the Langmuir-Blodgett (LB) method, but the P-substituted one did not.     

Ultrasonic attenuation measurements in ErRh4B4 near 1 K

Ultrasonic attenuation measurements on a polycrystalline specimen of ErRh₄B₄ near 1° K and in magnetic fields up to 14 kOe are reported. A broad peak in zero-field attenuation is observed near T_c2, the temperature at which ferromagnetic order appears. At large magnetic fields ( > H_c2) a larger attenuation is observed when the propagation vector of the sound wave is perpendicular to the field direction than when it is parallel. The interpretation of these results is discussed.     

High-Spin Nitrene Fine-Structure ESR Spectroscopy in Frozen Rigid Glasses: Exact Analytical Expressions for the Canonical Peaks and A D-Tensor Gradient Method for Line Broadening

In high-spin chemistry, random-orientation fine-structure electron paramagnetic resonance (FS ESR) spectroscopy holds the advantages of the most facile and convenient method to identify high-spin systems. The FS ESR spectroscopy for high spins in frozen rigid glasses has seemingly been well established since the first spin-quintet m-dicarbene and m-dinitrene appeared in 1967. The FS ESR spectra of organic quintet entities generated by photolysis in the 2-methyltetrahydrofuran (2-MTHF) glass, however, have never been fully analyzed due to a peculiar line broadening appearing at many canonical peaks. The line broadening has been a notorious obstacle that masks key FS transitions of many cases in organic glasses or argon matrices. We examine the origin of the line broadening, illustrating the comprehensive spectral analysis for m-dinitrenes and other types of typical quintet-state dinitrenes observed in the 2-MTHF glass. Our new approach to the line broadening analysis invokes both exact analytical solutions for the resonance fields of canonical peaks and a magnetic-parameter gradient method. We have derived the exact analytical expressions for FS canonical peaks for high-spin states, for the first time. A microscopic origin of the line broadening observed for high-spin nitrenes generated by photolysis in rigid glasses is proposed on the basis of quantum chemical calculations of the D-tensor.     

Supramolecular gelation of alcohol and water by synthetic amphiphilic gallic acid derivatives

The supramolecular organogelation of alcohols was observed in relatively hydrophobic amphiphiles with a short oligo(ethylene glycol) unit and three long alkyl chains at room temperature, while the hydrogelation occurred in more hydrophilic gelators with a longer poly(ethylene glycol) unit and two long alkyl chains at various temperatures. When a hot aqueous solution of some of the synthetic hydrogelators was cooled down, the supramolecular hydrogel was formed at room temperature. In some other amphiphiles with less intermolecular interactivity in water at room temperature, a reverse phase transition of sol to gel was observed by elevating the temperature of their aqueous systems, especially below a physiological temperature, 37 °C. The supramolecular hydrogelation at a low or high temperature was dependent on a slight molecular modification of the synthetic amphiphiles.     

Synthesis and properties of 2-(2-pyridyl)-1-azaazulene

The title azaazulene 3 was synthesized either by reaction of tropone with N-{(2-pyridyl)acetyl}pyridinium iodide in the presence of ammonium acetate or by palladium-catalyzed cross-coupling between 2-halo-1-azaazulene and 2-substituted pyridine. The compound shows relatively stronger basicity compared with 2,2′-bipyridyl. While 3 showed no emission from the S₁ state but from the S₂ state like azulene does, the protonated species of 3 exhibited emission from the S₁ state. Cationic metal-dependent absorption and emission relating to complexation were also studied.     

Catalytic fluorination of 1,3-dicarbonyl compounds using iodoarene catalysts

Catalytic fluorination of 1,3-dicarbonyl compounds with aqueous hydrofluoric acid proceeded efficiently with the aid of iodoarene catalysts in the presence of m-CPBA as a terminal oxidant. o-Iodotoluene, o-iodoanisole, and o-ethyliodobenzene showed a high catalytic efficiency to give 2-fluoro-1,3-dicarbonyl compounds in good yields.     

Efficient Synthesis of β‐Primeverosides as Aroma Precursors by Transglycosylation of β‐Diglycosidase from Penicillium multicolor

The enzyme activity transferring a β‐primeverosyl unit was found from culture filtrates of Penicillium multicolor IAM7153 and was useful for synthesizing a series of β‐primeverosides via a β‐primeverosyl transfer reaction in an aqueous‐organic biphasic system. With the acceptors benzyl alcohol, 2‐phenylethanol, and (Z)‐3‐hexenol, the enzyme induced the transfer products benzyl, 2‐phenylethyl, and (Z)‐3‐hexyl β‐primeverosides in high yields of 51% to 70% based on the donor added. When geraniol and eugenol were used as acceptors, the corresponding geranyl and eugenyl β‐primeverosides were obtained in lower yields of 8% to 12%. The enzyme was an excellent tool for producing naturally occurring β‐primeverosides on a mmol scale.     

A purification system for 64Cu produced by a biomedical cyclotron for antibody PET imaging

Ion exchange is a simple and efficient method for separating no-carrier-added ⁶⁴Cu from an irradiated Ni target. We developed a semi-automated two-round ⁶⁴Cu separation system equipped with a strong-base anion exchange resin column. We first verified the efficiency of the system using a non-radioactive substitute consisting of 25 mg of Ni and 127 ng of Cu, and confirmed that Cu was completely eluted at the second round of the separation step. After the bombardment, separation of ⁶⁴Cu from the Ni target was achieved with high radiochemical purity. ⁶⁴Cu produced and separated in this study had an extremely low level of Ni impurity. It could be used for labeling monoclonal antibodies for antibody positron emission tomography imaging and synthesizing radiopharmaceuticals.     

STRUCTURES OF PHOSPHAETHYLENES AND A 1-PHOSPHAALLENE CONTAINING PHOSPHORUS IN LOWER COORDINATION STATE

Abstract

The X-ray analyses of sterically protected Z-2-t-butyldimethylsilyloxy-2-phenylphosphaethylene (Z-2) and 3,3-diphenyl-1-phosphaallene (3) were carried out and the structures of the parent compounds, HP[dbnd]CH₂ and HP[dbnd]C[dbnd]CH₂, were optimized by ab initio methods.     

Chemistry of Sterically Protected Bis(Phosphinidene)-Cyclobutenes

Abstract:

Sterically protected low-coordinated phosphorus-containing cyclobutenes were prepared and characterized as well as [4]radialenes. The reactions were studied involving E/Z isomerization, transition-metal complex formation, and coupling reactions catalyzed by some palladium complex ligated with diphosphacyclobutenes.