Photodegradation of polyethylene in the presence of ferric salt: Influence of ferric acetylacetonate on model compounds

The influence of ferric acetylacetonate [Fe(acac)₃] on the photodegradation of model compounds of polyethylene (PE) was examined. By studying electron-spin-resonance (ESR) spectra of photoirradiated compounds such as 1-octene and 1,7-octadiene, which contain carbon double bonds, Fe(acac)₃ was found to accelerate the formation of allyl radical by contact with them. On the other hand, Fe(acac)₃ suppressed the radical formation based on Norrish type I reaction in a carbonyl group of compounds such as 2-octanone and 3-octanone. Based on the study of ultraviolet (UV) spectra as well as ESR spectra on photoirradiated samples, the influence of Fe(acac)₃ on the photodecomposition of model compounds of PE was discussed. Finally, the discussion turned to the mechanism of photodecomposition of PE in the presence of ferric salt.     

Comments on the primary and scatter dose-spread kernels used for convolution methods

The basic primary and scatter dose-spread kernels used for convolution methods are usually produced by Monte Carlo simulations with the interaction point forced to the center of a large water phantom. However, it is still not clear whether such Monte Carlo based kernels allow accurate dose calculations with a wide range of field sizes and depths, especially in thorax phantoms. Using the differential primary and scatter concept, this paper proposes another type of basic kernel, with which perfectly accurate primary and scatter absorbed dose calculations can be performed under conditions that the beam is parallel, the incident beam intensity is uniform within and zero outside the field, and the primary beam attenuation coefficient along raylines is not a function of depth and off-axis distance.     

Synthesis, structure, and physical properties of 1,11-o-benzeno[2]orthocyclo[2](1,2)tropyliophane

The title compound (2) has been synthesized, the structure and the physical properties of which are investigated by X-ray, spectroscopic analyses, and MO calculations. There exists charge transfer (CT) interaction between the tropylium ion and the facing phenyl ring. From the pK_R⁺ value of 2, it can be clear that the cation 2 is stabilized by the CT interaction. In spite of the presence of bond weakening σ-π orbital mixing, the cation 2 withstands retro[4+4]type bond cleavage, which is quite interesting when compared to a facile cleavage for the congener with anthracene photodimer type structure.     

Polymerization of tetraallyl ammonium chloride

The radical polymerization of tetraallyl ammonium chloride (TAAC) was carried out in water using azo-initiator as compared to that of diallyl dimethyl ammonium chloride (DADMAC); the rate of polymerization was quite low for TAAC, around one-third of DADMAC. Kinetic discussion revealed the importance of degradative chain transfer in the polymerization of TAAC. The cyclopolymerizability of TAAC was estimated kinetically as the ability of 5-membered monocyclic radical to form a bicyclic ring, giving the cyclization constant of 21 mol/L at [M] = 2 mol/L. Gelation occurred at around 20% conversion.     

Selective separation of Am(III) from lanthanides(III) by solvent extraction with hydrophobic field of "superweak" anion

The weakly coordinating hydrophobic anion TFPB-, whose surface is covered with a hydrophobic field, gives rise to a selective separation of Am(III) from lanthanides(III) in their solvent extraction even with a hard-donor extractant that shows no selectivity for Am(III) in traditional solvent extraction.     

Thermody namic functions of 1,2-alkanediols in dilute aqueous solutions

The heat capacities of binary aqueous solutions of 1,2-ethanediol, 1,2-propanediol and 1,2-butanediol were measured at temperatures ranging from 283.15 to 338.15 K by differential scanning calorimetry. The partial molar heat capacities at the infinite dilution were then calculated for the respective alkanediols. For 1,2-ethanediol or 1,2-propanediol, the partial molar heat capacities at the infinite dilution of increased with increasing temperature. In contrast, the partial molar heat capacities of 1,2-butanediol at the infinite dilution decreased with increasing temperature. Heat capacity changes by dissolution of the alkanediols were also determined. Heat capacity changes caused by the dissolution of 1,2-ethanediol or 1,2-propanediol were increase with increasing temperature. On the other hand, heat capacity changes caused by the dissolution of 1,2-butanediol are decrease with increasing temperature. Thus our results indicated that the structural changes of water caused by the dissolution of 1,2-butanediol differed from that of the two other alkanediols. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies of the polymerization of diallyl compounds. XXVII. Copolymerization of diallyl tartrate with several vinyl monomers

The radical copolymerization of diallyl tartrate (DATa) (M₁) with diallyl succinate (DASu), diallyl phthalate (DAP), allyl benzoate (ABz), vinyl acetate (VAc), or styrene (St) was investigated in order to disclose in more detail the characteristic hydroxyl group's effect observed in the homopolymerization of DATa. In the copolymerization with DASu or DAP as a typical diallyldicarboxylate, the dependence of the rate of copolymerization on monomer composition was different for different copolymerization systems and unusual values larger than unity for the product of monomer reactivity ratios, r₁r₂, were obtained. In the copolymerization with ABz or VAc (M₂), the r₁ and r₂ values were estimated to be 1.50 and 0.64 for the DATa/ABz system and 0.76 and 2.34 for the DATa/VAc system, respectively; the product r₁r₂ for the latter copolymerization system was found again to be larger than unity. In the copolymerization with St, the largest effect due to DATa monomer of high polarity was observed. Solvent effects were tentatively examined to improve the copolymerizability of DATa. These results are discussed in terms of hydrogen-bonding ability of DATa.     

Hair analysis of nicotine and cotinine for evaluating tobacco smoke exposure by liquid chromatography-mass spectrometry

A simple liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for the determination of nicotine and cotinine in human hair was established. In the procedure, a hair sample (10 mg) was washed with dichloromethane and digested in 2.5 M sodium hydroxide. The digest was extracted with dichloromethane and then 25 mM hydrochloric acid in methanol was added to the extract, to prevent loss of analytes. The solution was evaporated and redissolved in the mobile phase, methanol/10 mM ammonium acetate (30/70, v/v). A 20 microL aliquot of redissolved solution was subjected to analysis. Nicotine and cotinine in human hair were quantified by using deuterated analytes as internal standards. The quantification limits were 8 microg/L for nicotine and 0.9 microg/L for cotinine. The proposed method was applied to measure the concentrations of nicotine and cotinine in hair of smokers and non-smokers to evaluate their self-reported smoking and exposure to environmental tobacco smoke. In both cases, the method provided good selectivity, accuracy and precision.     

Application of samarium diiodide (SmI2)-induced reduction of gamma-acetoxy-alpha,beta-enoates with alpha-specific kinetic electrophilic trapping for the synthesis of amino acid derivatives

Gamma-acetoxy-alpha,beta-enoates were easily reduced by samarium diiodide (SmI2) in THF to generate samarium dienolates which were kinetically trapped with ease at their alpha-positions by electrophiles (proton, aldehydes or ketones) to yield (E)-alkene dipeptide isosteres or gamma-amino acid derivatives in high chemical yields.     

Direct observation of the multistep helix formation of poly-L-glutamic acids

The helix formation dynamics of poly-L-glutamic acids (PGAs) were observed by the microsecond-resolved Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopies. The helix formation of 34-residue PGA from random coil at pH (or pD for FTIR) 8.0 was initiated by a pH jump to 4.9 using the rapid solution mixer whose mixing dead time is 50 micros. The amide I' line in the time-resolved FTIR spectra exhibited the fast (<100 micros) increase of the total helical content. The time-resolved CD spectra of the same process also showed the fast (<150 micros) formation of short helical segments (5 +/- 1 residues), which was followed by the slower (<1 ms) elongation of the short helices to longer helices (>10 residues). Similar dynamics were observed for the same pH jump of approximately 190-residue PGA, although there were additional steps that made the helix formation of approximately 190-residue PGA more complex. The observed multistep helix formation is likely caused by the strong hydrogen-bonding interactions between the protonated side chains of PGAs.