Permeation of Zidovudine and Probenecid from Oily Bases Containing Alcohols Through Rat Skin

Permeation of zidovudine (3'-azido-3'-deoxythymidine, AZT) and probenecid from oily bases containing an alcohol through rat skin was examined. Isopropyl myristate (IPM), as an oily vehicle, showed a penetration enhancing effect for AZT and probenecid. Ethanol, n-propanol, and n-butanol were used as additives in IPM and were examined for their own permeation and the enhancing effect on the permeation of AZT and probenecid. The skin permeation of AZT and probenecid from IPM was enhanced by addition of the alcohol in IPM. The degree of the enhancement was decreased with increasing lipophilicity of the alcohol used. me permeation rate of the drug from those systems was shown to be governed by penetration-enhancing effects of the oily base and alcohol, and the penetration of the alcohol itself through the skin.     

Transdermal Absorption of Zidovudine from Ethanol-Isopropyl Myristate Mixed System and Influence of Probenecid on It in Rats

Transdermal absorption of zidovudine (AZT) from an ethanol-isopropyl myristate (IPM) mixed system was examined in rats. For comparison of bioavailability (BA) after topical applications, 0.25 ml of the ethanol/IPM system containing 40% ethanol and 60 mM AZT was applied as a standard formulation. Values of the area under the plasma concentration-time curves of AZT for 8 hr (AUC_0-8), as indices of BA, following application of various formulations were compared with that of the standard formulation. Then the influence of content of the drug and ethanol, and application volume of the system was evaluated. BA was effectively improved only when the total amount of ethanol applied on the skin was increased. On the other hand, simultaneous transdermal application of AZT and probenecid increased the AU_0-8, of AZT without necessitating the increase in ethanol content in the formulation. In addition, coadministered probenecid improved cerebrospinal fluid/plasma concentration ratio of AZT.     

Synthesis of boron nitride from triammoniadecaborane and hydrazine under pressure

Boron nitride (BN) of low crystallinity was synthesized from triammoniadecaborane (TAD) and hydrazine at 125 MPa below 650° C. TAD itself was pyrolysed at 600° C and 125 MPa to form a mixture of amorphous boron and boron nitride containing BH and NH bonds. The infrared spectrum of the pyrolysed product of TAD itself at 600° C and 125 MPa showed the BNB absorption at 800cm^–1 due to the formation of B₃N₃ structures. The X-ray diffraction (XRD) of the reaction product from TAD and hydrazine at 600° C had broad diffractions centred at 2=25.5° and 43.0° (CuK). The BH absorption at 2500cm^–1 decreased in intensity on increasing the N/B ratio from 0.3 to 0.85, and disappeared finally at a ratio of N/B=1.3. The reaction product at 125 MPa had a porous structure. The electron diffraction of the specimen changed from faint rings to spots on circular rings after heat treatment at 800° C for 10 h. The heat-treated specimen, however, did not give sharp reflections corresponding to hexagonal BN in the XRD profile. BN of low crystallinity was transferred to cubic BN at 1200° C and 6.5 GPa in a 90% yield, which was higher than that of well-crystallized BN in the presence of AIN.     

Preparation of multiple oxide BaTiO3 fibres by the sol-gel method

Multiple oxide BaTiO₃ gel fibres were prepared by the sol-gel method from Ba(OC₂H₅)₂-Ti(O-isoC₃H₇)₄-H₂O-C₂H₅OH-CH₃COOH and Ba(CH₃COO)₂-Ti(O-isoC₃H₇)₄-H₂O-CH₃COOH solutions. Relatively long gel fibres of 10cm length were obtained from both solutions in the limited composition region. The latter solution in particular showed a spinnability even when it contained no water. Therefore, the occurrence of spinnability of the solution was considered to be due to the formation of linear polymers composed of bridging acetate groups such as TiO-C(CH₃)-O-Ti rather than metalloxane bonding as Ti-O-Ti. Addition of water to the solutions seems to break the bridging acetate bonds and replace some of them by bridging oxygen bonds. The as-drawn gel fibres which were X-ray amorphous crystallized into BaTiO₃ ceramic fibres of 5mm average length upon heating above 600 ° C. However, the gel fibres drawn from the sols without water became powdery on heating because of the lack of Ti-O-Ti metalloxane bonds. The crystallization behaviour of the BaTiO₃ gel fibres is discussed based on the infrared spectroscopy, X-ray diffraction analysis and thermogravimetric-differential thermal analysis.     

Living cationic polymerization of p-methoxystyrene by hydrogen iodide/zinc iodide at room temperature

Summary Cationic polymerization of p-methoxystyrene initiated by HI/ZnI₂ in toluene afforded living polymers not only at low temperature (–15°C) but at room temperature (+25°C) as well. The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit hydrogen iodide. On addition of a fresh feed of monomer at the end of the first-stage polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage; the polymer molecular weight further increased in direct proportion to monomer conversion and was close to the calculated value for living polymer. Throughout these reactions, the molecular weight distribution of the polymers stayed very narrow (¯M_w/¯M_n<1.1). This is the first example of living cationic polymerizations of styrene derivatives that proceed even at room temperature.     

Living cationic polymerization of vinyl monomers by organoaluminum halides

Summary Well-defined living polymers of isobutyl vinyl ether were obtained in the polymerization initiated with ethylaluminum dichloride (EtAlCl₂) in conjunction with a stoichiometric excess of dioxane (5–10 vol%) in n-hexane at 0°C. Under these conditions, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, while the molecular weight distribution stayed narrow (M_w/M_n = 1.1–1.25). In sharp contrast, the EtAlCl₂-initiated polymerization in the absence of dioxane led to non-living polymers with a broad molecular weight distribution. It was concluded that the propagating carbocation is stabilized not by the counteranion but by an externally added basic compound (dioxane) that strongly interacts with the active end.     

Living cationic polymerization of isobutyl vinyl ether by the diphenyl phosphate/zinc iodide initiating system

Summary The first example of the living cationic polymerization of isobutyl vinyl ether via the phosphate counteranion has been achieved in toluene below 0°C with a new initiating system that consists of diphenyl phosphate and zinc iodide, (C₆H₅0)₂P(0)0H/ZnI₂. The number-average molecular weight of the polymers increased in direct proportion to monomer conversion, and was in excellent agreement with the calculated value assuming that one polymer chain forms per unit diphenyl phosphate. On addition of a fresh feed of monomer at the end of the polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage, and the polymer molecular weight further increased in direct proportion to monomer conversion. Throughout the reaction, the molecular weight distribution of the polymers stayed very narrow (¯M/¯M_n 1.1). At room temperature (+25 °C), however, the molecular weight distribution of the polymers slightly broadened (¯M_w/¯M_n 1.2) at high conversions where the polymer molecular weight became smaller than the calculated value. Evidently, the (C₆H₅0)₂-P(0)0H/ZnI₂ system indeed generates a propagating species of a long life-time at room temperature, but the perfectly living polymerization by this system operates below 0°C.Living cationic polymerization of vinyl ethers by electrophile     

Copper ⇌ Alkali Ion Exchange of Alkali Aluminosillcate Glasses in Copper-Containing Molten Salt: I, Monovalent Copper Salt, CuCl

Cu⁺⇌ R⁺ (R = Li, Na, and K) ion exchange experiments were conducted for 20R₂O·10Al₂O₃·70SiO₂ glasses in molten CuCl at 550°C in air and nitrogen atmospheres. The depth profiles of the copper incorporated into glasses were determined with an electron microprobe X-ray analyzer. The total amount of diffusing copper, M _t, strongly depended on the type of alkali ion in the glass and the ion-exchange atmosphere; i.e., M _t increased with increasing cationic size in the order Li < Na < K and M _t was greater in air than in nitrogen. The Cu ⇌ R⁺ ion exchange kinetics are discussed in detail.     

Conformational studies of poly(N-methyl-l-alanine) by n.m.r. spectroscopy

Nuclear magnetic resonance (n.m.r.) and circular dichroism of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ in methylene $\text{chloride}\text{-d}{}_2\text{dichloroacetic acid}$ were investigated. In methylene chloride-d₂$\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was found to consist of nearly all-trans amide bonds and assume a stable secondary structure. Trace amounts of cis amide bonds were also present. The addition of dichloroacetic acid destroyed the secondary structure and induced a drastic change of the n.m.r. spectrum, which was similar to that observed with the monomeric amide, $\text{N-}\text{acetyl}\text{-N-}\text{methyl-}\text{l}\text{-alanine}$ dimethylamide. In comparison of the polymer with the monomeric amide, it was concluded that the transition of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was caused by the isomerization of amide bonds. The complex n.m.r. spectrum was interpreted in terms of the distribution along the polymer chain of various non-planar amide links as well as planar cis and trans amide links. The difference of the mechanism of conformational transition between poly(amino acid) and poly(imino acid) is also discussed.     

Accelerator-driven system for transmutation of high-level waste

The accelerator-driven transmutation system has been studied at the Japan Atomic Energy Research Institute. This system is a hydrid system which consists of a high intensity accelerator, a spallation target and a subcritical core region. In the conceptual design study, two types of system concepts, sodium cooled and lead-bismuth cooled system, are being studied. In this study, we fucus on our lead-bismuth cooled accelerator-driven transmutation system to investigate basic characteristics. The fuel compositions were optimized for efficient transmutation of minor actinide. The transmutation of long-lived fission products was also considered.