Surface magnetism of β-FeO(OH) by Mössbauer spectroscopy

Fine particles of -FeO(OH) were prepared using the⁵⁶Fe isotope and the surfaces of the particles were coated with extremely thin⁵⁷Fe(III) layers. Mössbauer results show that the Fe(III) ions in the top surface layer are involved in the magnetic order and occupy two kinds of surface sites. Both of the two exchange field at surface sites, estimated from the temperature dependences of the hyperfine fields, are smaller than the bulk value. The decrease of exchange fields at the surface sites corresponds to the reduced number of neighboring magnetic ions at each site.     

Conversion electron Mössbauer spectroscopy using a CAMAC data acquisition system (KODAQ)

For simple depth selective conversion electron Mössbauer spectroscopy (CEMS) by using a He+CH₄ proportional counter, a flexible and versatile CAMAC data acquisition system (KODAQ) which works on a popular Japanese personal computer PC9801VX (NEC) was applied. It is demonstrated that CEM spectra of the oxidized Fe thin film which is composed of Fe₃O₄, Fe_1–xO and -Fe metal are successfully obtained.     

o-Phenylene halocarbenonitrenes and o-phenylene chlorocarbenocarbene: a combined experimental and computational approach

[reaction: see text] Computations find that o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, have quinoidal singlet biradical ground states such as the parent o-phenylenecarbenonitrene (2-HN). Compared to the parent 2-HN, halogen substitution stabilizes the A' states relative to the A' ones. Halogen substitution also affects the barrier and exothermicity of the ring-opening reaction (to form unsaturated nitriles 4-XN, X = F, Cl, Br), but it has a smaller effect on the ring-closing reaction (to form benzo(aza)cyclobutadiene 3-XN, X = F, Cl, Br). Attempts to generate and observe the o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, using matrix isolation spectroscopy under conditions similar to those of the successful observation of 2-HN failed. Instead, the observed photoproducts were a mixture of 3-XN and 4-XN. In each case, the major product of the mixture appears to be the thermodynamically more stable one. In the case of X = Br, the observed mixture contains an additional component that is postulated to be Z-6-BrN. o-Phenylenechlorocarbenocarbene is also computed to have a quinoidal singlet biradical ground state and relatively stabilized A' excited states. Attempts to generate the biscarbene under matrix isolation conditions led to the detection of benzochlorocyclobutadiene (3-ClC), small amounts of the ring-open product (dienediyne 4-ClC), and cycloalkyne 5-ClC. Computations suggest that the formation of 5-ClC implies the generation of Z-6-ClC, which is analogous to the formation of Z-6-BrN from 2-BrN.     

Aminyl radical cyclization by means of anodic oxidation. Stereoselective synthesis of cis-1-methyl-2,5-disubstituted pyrrolidines

Neutral aminyl radicals generated by anodic oxidation of lithium alkenylamides 2 undergo a stereoselective cyclization to give $\text{cis}$-1-methyl-2,5-disubstituted pyrrolidines 4. Their $\text{cis}$ stereochemistry was confirmed by a comparison with $\text{trans}$-1,2-dimethyl-5-phenylpyrrolidine, the structure of which was established by X-ray crystallographic analysis of its quarternary ammonium bromide 6.     

Transformation of thioacetals to cyclopropanes

Cyclopropanes were obtained by the titanocene(II)-promoted reaction of thioacetals with vinyl pivalate. It was also found that vinycyclopropanes were produced by a similar treatment of thioacetals with the titanocene(II) species in the presence of 1,3-dienes.     

Phase-transfer reactions catalyzed by polymer-supported crown ethers

Polymer-supported crown ethers were prepared from chloromethylated or ω-bromoalkylated polystyrene resins and hydroxymethylbenzo-18-crown-6 and 15- or 18-membered monoazacrown ethers. Effects of the cavity size of crown ethers, the degree of crosslinking, the degree of ring substitution, particle size, spacer chains, and solvents on the activity of the polymer-supported crown ethers in the reaction of 1-chloro- or 1-bromo-octane with aqueous NaI or KI were investigated and mechanisms of the reaction were discussed in terms of mass transfer, intraparticle diffusion, and intrinsic reactivity.     

Thermal degradation of poly[(tetramethyl-p-silphenylene) siloxane]

For the purpose of studying the mechanism of thermal degradation of poly[(tetramethyl-p-silphenylene) Siloxane] (poly TMPS) a series of polymers with silphenylene and siloxane bonds in the main chain were prepared and subjected to thermogravimetry (TG) and pyrolysis study. Analyses of products from poly TMPS degradation (in vacuum at a constant temperature) by gas chromatography (GC), infrared (IR), nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry (GC–MS) revealed that degradation occurs at the silphenylene bonds. The TG curves obtained in He for heating rates of 1,2,2.5,7.5, and 10°C/min were analyzed by the Ozawa method; activation energies of 39 ± 1 and 45 ± 2 kcal/mol were obtained respectively for the initial cleavage of the methyl side group and the later-stage scission of the main-chain silphenylene bond which leads to a major weight loss. The results agree with those obtained for other structurally similar polymers.     

High resolution capillary gas chromatographic hydrocarbon-type analysis of naphtha and gasoline

A slightly modified, commercially available high resolution capillary gas chromatograph and a PC-based data processing system running proprietary software (“PONA”) have been employed in the development of a system for petroleum type analysis which would be equivalent or superior to the FIA (fluorescent indicator adsorption) method in terms of ease of use and the speed, variety, and accuracy of the analytical data produced. The system is capable of performing identification and quantitation of most of the individual components in a complex gasoline sample consisting of more than 230 components and can report weight percentage and/or volume percentage for each component as well as types by carbon number (e.g., isoparaffins, normal paraffins, olefins, naphthenes, aromatic compounds) within a ca. 70 minute analysis cycle. Precolumn sulfonation to trap olefins and aromatic compounds has been used as an complementary technique to the basic mass spectrometric identification of components of interest. The estimation of correction factors for weight percentage (or volume percentage) calculation are also discussed. Comparisons are made between this system and others, and the results indicate that the proposed method supersedes the conventional method employing FIA.     

Solvent effect on protein binding by polymer brush grafted onto porous membranes

An epoxy-group-containing polymer chain was grafted onto the hollow-fiber form of a porous polyethylene membrane by the immersion of the electron beam-irradiated trunk polymer in glycidyl methacrylate diluted with methanol and 1-butanol. The epoxy group density ranged from 8.5 to 13.4 mol per kg of the trunk polymer. Subsequently, the epoxy groups produced were converted into sulfonic acid and diethylamino groups. The density of -SOH and -N(C2H5), groups was 0.40 and 2.2 mol per kg of the product. respectively. The polymer brush, defined as a polymer chain extending from the surface of a pore toward the interior of the pore, was evaluated from the determination of an equilibrium binding capacity of hen egg lysozyme (HEL) and bovine serum albumin (BSA). The polymer brush prepared in 1-butanol was found to be longer than that prepared in methanol from the determinations of liquid permeability and protein adsorptivity. The proteins were bound to the polymer brush prepared in 1-butanol, followed by the functionalization, at higher degrees of multilayer binding: about 30 for HEL and 6 for BSA.     

Hydrogenation of benzaldehyde and cinnamaldehyde in compressed CO2 medium with a Pt/C catalyst: a study on molecular interactions and pressure effects

The hydrogenation of benzaldehyde and cinnamaldehyde has been studied with a 5% Pt/C catalyst in compressed CO(2). The effect of CO(2) pressure on the total conversion was found to be different between the two aldehydes. The total conversion of benzaldehyde merely decreases with increasing CO(2) pressure, while that of cinnamaldehyde shows a maximum at a certain pressure. High-pressure FTIR measurements indicate the existence of interactions of CO(2) with the aldehydes. The absorption of nu(C=O) red-shifts at increasing CO(2) pressure, and this red-shift is more significant for cinnamaldehyde than for benzaldehyde, indicating that the C=O bond of the former becomes more reactive than the latter. The difference in the mode of interactions of CO(2) with these aldehydes has also been indicated by changes of nu(C=O) of CO(2). Thus, the conversion of benzaldehyde will decrease with increasing CO(2) pressure because of a simple dilution by introducing a larger quantity of CO(2). For cinnamaldehyde, the conversion will increase at low pressures because of increasing interactions with CO(2) molecules (increasing the reactivity of the C=O bond) but decrease at high pressures because of the simple dilution effect, similar to the case of benzaldehyde. The dense CO(2) molecules are not likely to change the catalytic activity of supported Pt particles, which was previously suggested from optical absorption of supported fine metal (Au) particles in a compressed CO(2) medium.