Reaction between rare earth elements and HFNO2 solution

Rare earth elements react with HFNO₂ solution to produce nitrosylium fluorometallates (NO)_xLnF_x+3. The value of x is 1.0 or 1.5 for light rare earth elements and 0.5 or 1.0 for heavy rare earths. Nitrosylium fluorometallates of rare earth elements can be decomposed into the simple fluoride and nitrosyl fluoride at low temperatures (46–68°C).     

Efficient photocleavage of DNA utilising water-soluble lipid membrane-incorporated [60]fullerenes prepared using a [60]fullerene exchange method

Various types of lipid membrane-incorporated C60 with high C60 concentrations can be prepared easily in several hours using the C60 exchange method and the photocleaving activity of cationic lipid membrane-incorporated C60 was appreciably higher than that of the C60.gamma-CDx complex.     

Scattering theory for threadlike micellar solutions

Association-dissociation equilibria and the static scattering function were formulated using precise thermodynamic functions for nonionic surfactant solutions including long, stiff, threadlike micelles. The present theory is applicable for micellar solutions with the surfactant concentration much higher than the critical micelle concentration and containing highly growing threadlike micelles. The scattering function formulated was compared with experimental light scattering data for aqueous solutions of a nonionic surfactant, penta(oxyethylene glycol) n-decyl ether (C12E5), at different surfactant concentrations and also temperatures.     

Leakage of immobilized IgG from therapeutic immunoadsorbents

In developing therapeutic immunoadsorbents (IAs), antibodies (IgG molecules) covalently immobilized on porous carriers, a leak of IgG was determined both in the storage test with buffers at 25 and 4 degrees C and in contact with plasma at room temperature (RT). The amount of antibody released from therapeutic IAs must be minimized to avoid side effects during treatment. The amount of IgG released was a. Dependent on the amount of IgG immobilized b. Much greater with CNBr-activated Sepharose 4B, or Formyl-Cellulofine as a support material than with aminopropyl CPG (controlled pore glass) c. Found to yield again during another storage in buffers after the IAs were washed and their buffers replaced with fresh ones and d. Decreased after the IAs were treated with glutaraldehyde (GA) solutions. Whereas treating the IAs with GA solutions significantly reduced the amount of IgG released, it caused some deterioration of the adsorption characteristics of the IAs. An irradiation dose of 2.5 Mrad as a crosslinking procedure also reduced the amount of IgG released; its effect was comparable to that of 0.025% GA, the lowest concentration used.     

The study of sensitivity and resolution of microautoradiography using Auger electrons

By using low energy beta emitter to microautoradiography, it is expected that high resolution microautoradiogram can be made. In this report, the authors pay attention to the use of monochromatic and low energy electron on the metallic samples, and used⁵¹Cr that emits Auger electrons with the energy of 4.5keV and⁶⁵Zn that emits Auger electrons with energy of 7keV in the study of the resolution of Auger electron microautoradiograph. From the results of the study, it was clearly confirmed that the resolution of the microautoradiograph using⁵¹Cr was better than 0.5 m and the resolution using⁶⁵Zn was better than 1 m.In order to make high resolution microautoradiograph, it is essentially important to know the sensitivity of the nuclear emulsion to the low energy electrons in advance, for securing the reasonable exposure to the nuclear emulsion. In this regard, the investigation on the sensitivities of those emulsions to the Auger electrons with the energy of 5.4keV from⁵⁵Fe and 7keV from⁶⁵Zn was made using Ilford and Fuji nuclear emulsions.     

Crystal field calculation of g values and zero-field splitting for high spin ferric complexes of rhombic character

For high spin ferric ions in rhombic symmetry, we have used a crystal field model to relate term splittings of the ⁴ T ₁, ² T ₂ and ⁴ T ₂ excited states to zerofield split energies and g values of the ⁶ A ₁ term. In this model five crystal field parameters were used, namely, one cubic parameter, two tetragonal parameters and second and fourth order rhombic parameters. In tetragonal symmetry with only three crystal field parameters, a simpler model including only the ⁴ T ₁ and ² T ₂ excited states is adequate to relate term energies to g values and zero-field split energies. However, we have demonstrated the importance of the ⁴ T ₂ state in rhombic crystalline fields. No higher lying terms other than ⁴ T ₂ can influence the ⁴ T ₁ term directly through the tetragonal or rhombic crystal field, Furthermore, we show that the fourth order rhombic crystal field parameter is a key parameter because the rhombic splitting of the dominant low lying ⁴ T ₁ term of high spin ferric complexes depends to first order on the fourth order crystal field potential. We have performed a computer diagonalization of the spin-orbit, electrostatic and crystal field perturbation matrix, and calculated g values and zero-field splittings in seventeen high spin ferric mixed crystalline species of varying rhombicities and for metmyoglobin and cytochrome P-450. The high spin and spin-mixed regions are developed completely to yield the crystal field term energies, zero-field splittings and basis functions together with g values.     

Vinyl polymerization initiated by the (dimethylaniline-n-oxide)/(phenacyl bromide) system

Binary systems consisting of dimethylaniline-N-oxide (DMOA) and some α-halo-carbonyl compounds, such as phenacyl halide and α-halo-acetic acid ester, were found to induce radical polymerization of vinyl monomers. Bromo-derivatives showed higher initiating activities than chloroderivatives. The polymerization of methyl methacrylate (MMA) with DMAO and phenacyl bromide (PBr) was investigated kinetically. The polymerization rate (R_p) was expressed as follows; $\text{R}{}_{\mathrm{<mtext>p</mtext>}}\text{=}\text{k[DMAO]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{[}\text{PBr}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{[}\text{MMA}\text{]}$.The overall activation energy of the polymerization was calculated to be 42.7 kJ mol^?1. No noticeable chain-transfer from the polymer radical to DMAO or PBr was observed. The benzoyl radical was trapped by 2-nitroso-2-methylpropane, a spin trapping reagent, in the reaction of DMAO and PBr. The u.v. spectrum of poly (MMA) obtained suggests that the polymer contains end-groups similar to acetophenone and DMA. From the results, an initiation mechanism for the polymerization has been proposed and discussed.     

An allyltitanium derived from acrolein 1,2-dicyclohexylethylene acetal and (eta(2)-propene)Ti(O-i-Pr)(2) as a chiral propionaldehyde homoenolate equivalent that reacts with imines with excellent stereoselectivity. An efficient and practical access to optically active gamma-amino carbonyl compounds

A chiral allyltitanium compound 2, prepared in situ by the reaction of optically active acrolein 1,2-dicyclohexylethylene acetal (3) with (eta(2)-propene)Ti(O-i-Pr)(2) (1), reacts with a variety of acyclic and cyclic imines 4 in a regiospecific way to afford alpha-addition products 5 as a mixture of the E- and Z-isomers in good combined yield, where the former is predominant in a ratio of 92:8 to >95:5. The mixture of (E)- and (Z)-5 and pure (E)-5 which could be isolated in several cases were respectively converted to the corresponding beta-amino ester 6 to confirm the absolute configuration and enantiomeric purity. The ee of the newly formed asymmetric center of 5 is more than 78% for the mixture of (E)- and (Z)-5 and more than 96% for pure (E)-5. By taking advantage of the versatility of the vinyl ether moiety in 5, optically active gamma-amino aldehydes 8, gamma-amino aldehyde acetals 7 and 10, gamma-amino acids 9, beta-amino esters 6, and pyrrolidinoisoquinolines 12 were readily prepared. In the reaction of 2 with optically active alpha-silyloxyimine 4n, remarkable double stereodifferentiation was observed; thus, the reaction of 2 derived from (S,S)- or (R,R)-3 provided syn- and anti-5n in a ratio of 55:45 or 0:100, respectively. Meanwhile, the stereochemistry of the product in the reaction of 2 with beta-silyloxyimine 4o was controlled mainly by 2. Thus, the reaction of beta-silyloxyimine 14 with 2 derived from 1 and (R,R)-3 afforded gamma-silyloxyimine 15 with 92% diastereoselectivity, from which 4-amino-6-hydroxypentadecanal dimethyl acetal (13), a key intermediate for the synthesis of batzelladine D, was synthesized.     

Sterilization of health care products by 5 MeV bremsstrahlung (X ray)

Radiation sensitivities of . pumilus and spores were examined to bremsstrahlung of 5 MeV EB and Cobalt -60 γ rays in order to confirm the effects of radiation and dose rate. Biological indicators (SPORTROL, NAmSA, USA) were irradiated with the X ray in the dose rate range of 4.7–47kGy/h. D-value of spores was 1.4–1.5 kGy, and that of was 1.1–1.3 kGy. The D-values of and have very small dose rate dependences to X ray, and the D-values are similar to those of γ ray. Dose distribution by X-ray and γ irradiation was measured for cartons containing 32 unit dialyzers. The D_max./D_min. of the X-ray irradiation (1.2) was smaller than that of γ ray (1.3).