Predicted radiolysis yield in a Fricke solution irradiated with various heavy ions

Experimental data on the spatial distribution of the energy deposited around an energetic heavy ion, from 1 MeV proton to 5.9 MeV/n uranium ion, which have been reported in the literature were documented to obtain a scaled radial dose distribution; (β/Z*)² D(Z*, β,t)=200 (for t=0–1), 200/t² (for t=1t_c), and 200 t_c/t³ (for t>t_c) where Z* and β are the effective charge and velocity relative to c, the velocity of light, of the incident ion, respectively, D the dose in unit of Gy, t the radial distance in unit of nm, t_c the critical distance empirically determined.

Then, if we know the yield of any chemical reaction as a function of dose from the results of experiments using γ-radiations or fast electrons or theoretical calculations, we can calculate the probability for the yield of the chemical reaction in the system bombarded with a heavy ion of the effective charge Z* and velocity β. The results of the present calculation of the LET-values and of G(Fe³⁺) in the ferrous sulfate acidic solution are presented and compared with reported experimental results.     

New asymmetric vanadium catalyst for highly selective oxidative coupling polymerization

Novel oxovanadium(IV)–bisoxazoline catalysts, such as vanadyl sulfate (VOSO₄)–(R)‐2,2′‐isopropylidenebis(4‐phenyl‐2‐oxazoline) [(R)Phbox], for the asymmetric oxidative coupling polymerization (AOCP) of 2,3‐dihydroxynaphthalene were developed. For example, the AOCP with VOSO₄–(R)Phbox in CH₂Cl₂–MeOH [7/1 (v/v)] at room temperature for 24 h under an O₂ atmosphere, followed by acetylation of the hydroxyl groups, afforded a polymer in a 58% yield with a specific rotation of [α]_D = ?147. The enantioselectivity during the polymerization was estimated to be 80% enantiomeric excess (S), a value much higher than that observed for the polymerizations with the copper(I)‐based catalyst systems and the typical oxovanadium(IV) catalysts reported for the asymmetric oxidative coupling producing the 1,1′‐bi‐2‐naphthol derivatives. © 2005 Wiley Periodicals, Inc., Inc. J Polym Sci Part A: Polym Chem 43: 5872–5878, 2005     

Aggregation structure and mechanical properties of functionally graded polyurethane elastomers

Functionally graded polyurethane elastomers (FGPUEs) were prepared with two molds fixed at different temperatures (30 and 150 °C). The effects of the molar ratio of the curing agent (60/40, 75/25, or 97/3 1,4‐butane diol/1,1,1‐trimethylol propane) and the molecular weight of the polymer glycol (number‐average molecular weight = 2000 or 3000) on the molecular aggregation state and mechanical properties of the FGPUEs were investigated with differential scanning calorimetry, polarized optical microscopy, dynamic viscoelastic measurements, and tensile tests. The aggregation state of the FGPUEs was changed continuously from the one side (lower temperature side) to the other side (higher temperature side); for example, the glass‐transition temperature gradually increased in this direction. Also, the number of spherulites formed in the FGPUEs increased in the same manner. In the mechanical tests, the tensile strength and elongation at break of the lower temperature side were higher than those of the higher temperature side. This was correlated with the strong phase separation of the lower temperature side. The poly(oxytetramethylene glycol)‐based FGPUE with a chain extender of 75 wt % showed the largest degree of the temperature gradient. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2355–2363, 2003     

Crosstalk Suppression in Header Recognition Unit Using Time-Space Conversion

We demonstrate a suppression effect of a crosstalk among a target and similar header signals using the header recognition filter designed by a design technique of the multiple-object discriminant filter.     

Phase transition of layer structure of poly(p-benzenedithiol-co-p-diethynylbenzene) by heat or photon mode

Phase transition of the layer structure of poly(p-benzenedithiol-co-p-diethylbenzene) obtained in solid state polymerization was studied by a thermal treatment or UV irradiation under a nitrogen atmosphere. The peak intensities in the X-ray diffraction diagram of polymers gradually decreased with the thermal treatment time above 55°C. Below 50°C the layer structure of polymers hardly changed. The apparent activation energy for the phase transition was about 15 Kcal/mol [63 KJ/mol] at the initial stage and gradually decreased to a few Kcal/mol [ca. 2 KJ/mol]. UV light from a high-pressure mercury lamp also gradually induced the phase transition from the layer structure to an amorphous one. The pristine polymer possesses phase transition points at 75, 95 and 130°C. The exothermic transition at 75°C can be understood as the thermal destruction of the semistable layer structure. The exothermic transition at 95°C may be correspond to the cis → trans thermal isomerization of the C?°C bond in the polymer main chain. The diffuse reflectance spectrum of the pristine polymer differed from that of the amorphous polymer obtained by the thermal treatment of the pristine polymer. SEM photographs of the pristine polymer showed a particular surface structure, i.e. entangled fibrous material. TEM photographs of the pristine polymer exhibited a bright valley-and-hill structure, whereas that of the amorphous polymer obtained by thermal treatment exhibited a plain surface.     

Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl₂(PPh₃)₃ as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003     

Analog vision chip for motion detection of an approaching object against a moving background based on the insect visual system

A network for motion detection of an approaching object without influence of the moving background was proposed based on the insect visual system. The two-dimensional array of the analog complementary metal oxide semiconductor (CMOS) circuits for extracting the edge signals of the approaching object without outputting those of the moving background was inserted at the first stage of the network. At the next stage, analog CMOS circuits for detection of approaching velocity and direction, which accept the extracted edge signals, were inserted based on the locust vision system. A chip of the proposed network was fabricated with the 1.2 mm CMOS process. It was clarified from the measured results and the simulation results with the simulation program with integrated circuit emphasis (SPICE) that the two-dimensional circuits of the first stage can only generate the signals of target edges. The measured results showed that the chip can detect the approaching velocity and direction of the target in the image which contains the moving background.     

An analysis of SEM techniques used to profile chemical etching on the semiconductor Hg1-xCdxTe

Various methods have been used to obtain accurate cross-sectional profiles of Hg_1-xCd_xTe devices after etching. Preliminary measurements from different etching techniques are also presented. Techniques used were scanning electron microscopy with stereo pairs and cleaved cross-sections, topography SEM (multiple detector SEM) and atomic force microscopy.     

Ruthenium-catalyzed cycloaddition of 1,6-diynes with isothiocyanates and carbon disulfide: first transition-metal catalyzed [2 + 2 + 2] cocyclotrimerization involving C=S double bond.

In the presence of 10 mol % Cp*Ru(cod)Cl, 1,6-diynes with a tertiary center at 4-position reacted with various isothiocyanates at their C=S double bond to afford bicyclic (2H)-thiopyranimines in 35-88% yields. The (2H)-thiopyran structure was unequivocally determined by X-ray analysis. The cycloaddition of carbon disulfide with a diyne similarly gave the expected bicyclic dithiopyrone in 50% yield.     

Reconstitution of Biosynthetic Machinery for the Synthesis of the Highly Elaborated Indole Diterpene Penitrem

Penitrem A is one of the most elaborated members of the fungal indole diterpenes. Two separate penitrem gene clusters were identified using genomic and RNA sequencing data, and 13 out of 17 transformations in the penitrem biosynthesis were elucidated by heterologous reconstitution of the relevant genes. These reactions involve 1) a prenylation‐initiated cationic cyclization to install the bicyclo[3.2.0]heptane skeleton (PtmE), 2) a two‐step P450‐catalyzed oxidative processes forming the unique tricyclic penitrem skeleton (PtmK and PtmU), and 3) five sequential oxidative transformations (PtmKULNJ). Importantly, without conventional gene disruption, reconstitution of the biosynthetic machinery provided sufficient data to determine the pathway. It was thus demonstrated that the Aspergillus oryzae reconstitution system is a powerful method for studying the biosynthesis of complex natural products.