Studies on thermally induced structural changes in silicon based polymers by positron annihilation

Temperature dependence of positron annihilation lifetime spectra of polysilanes such as, poly(methyl-n-propylsilane) (PMPrS) and poly(di-n-hexylsilane) (PDHS) has been investigated. The τ₃ in PMPrS is seen to increase monotonically around the solid–liquid transition temperature. The transition temperature and free volume are observed to depend on the molecular weight and/or packing of the backbones. For PDHS, a sharp change in τ₃ and I₃ is seen at the solid–solid transition temperature. Free volume radius probability density functions, above and below the transition temperature, are presented in PMPrS and PDHS. Positron studies are complimented by conventional thermal analysis studies.     

Synthesis of 5,10-dideazaminopterin

The synthesis of 5,10-dideazaaminopterin by two independent routes is described. Condensation of the piperidine enamine of 4-p-carbomethoxyphenylbutyraldehyde ( 4 ) with ethoxymethylenemalononitrile followed by treatment of the resultant arylethylenaminomalononitrile ( 5 ) with methanolic ammonia produced 2-amino-3-cyano-5-p-carbomethoxyphenethylpyridine ( 6 ). Cyclization of the aminocyanopyridine with guanidine afforded 4-amino-4-deoxy-5,10-dideazapteroic acid ( 8 ). Coupling of the pteroate intermediate with glutamate yielded the target 5,10-dideazaaminopterin ( 10 ). Alternatively, reduction of 2,4-diamino-6-formyl-5-deazapteridine ( 11 ) with sodium borohydride gave the 6-hydroxymethyl compound 12 . Conversion to the bromide was followed by alkylation of dimethyl homoterephthalate to afford methyl 4-amino-4-deoxy-10-carbomethoxy-5,10-dideazapteroate ( 14 ). Decarboxylation with ester cleavage (sodium cyanide in dimethyl sulfoxide at 180°) also gave the diaminopteroic acid ( 8 ). 5,10-dideazaaminopterin ( 10 ) was an effective growth inhibitorof folate dependent bacteria, S. faecium and L. casei.     

Effects of low-LET radiations on CR-39 track detector

The effects of Co-60 gamma-rays and about 25-MeV pulsed electrons have been investigated on CR-39 plastic nuclear track detector. The bulk etch rate was measured as a function of the absorbed dose under three different irradiation conditions; gamma-ray exposure in air at the dose rate of 6 kGy/h, that in vacuum and electron shower in air at 126 kGy/h on average. It was found that the bulk etch rate (V) increased nearly exponentially with the dose (D); V=V₀exp(kD), and the characteristic parameter (k) was 35, 9 and 12 MGy⁻¹, respectively. It is considered that a lack of oxygen in damage formation processes could occur momentarily during a short electron pulse, just similarly to the vacuum effect of reduction in track etch rates in outgassed CR-39 plastic.     

Free vibration of non-circular cylindrical shells with variable circumferential profile

An analysis is presented of the free vibration of non-circular cylindrical shells with a variable circumferential profile expressed as an arbitrary function. The applicability of thin-shell theory is assumed and the governing equations of vibration of a non-circular cylindrical shell are written in a matrix differential equation by using the transfer matrix of the shell. Once the transfer matrix has been determined by numerical integration of the matrix equation, the natural frequencies and mode shapes of vibration are calculated numerically in terms of the matrix elements. The method is applied to cylindrical shells of three or four-lobed cross-section, and the effects of the length of the shell and the radius at the lobed corners on the vibration are studied.     

Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp² structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp³-rich region remained at the topmost DLC surface. The formation of an sp³-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.     

Amphiphilic molecular design as a rational strategy for tailoring bicontinuous electron donor and acceptor arrays: photoconductive liquid crystalline oligothiophene--C60 dyads

For tailoring solution-processable optoelectronic thin films, a rational strategy with amphiphilic molecular design is proposed. A donor-acceptor dyad consisting of an oligothiophene and C60, when modified with a hydrophilic wedge on one side and a paraffinic wedge on the other (1Amphi), forms over a wide temperature range a photoconducting smectic A liquid crystal having bicontinuous arrays of densely packed donor and acceptor units. In contrast, when modified with only paraffinic wedges (1Lipo), the dyad forms a smectic A liquid crystalline mesophase, which however is poorly conductive. As indicated by an absorption spectral feature along with a synchrotron radiation small-angle X-ray scattering profile, 1Lipo in the lamellar structure does not adopt a uniform head/tail orientation. Such defective donor and acceptor arrays likely contain a large number of trapping sites, leading to short-lived charge carriers, as observed by a flash photolysis time-resolved microwave conductivity study.     

Prominent electron transport property observed for triply fused metalloporphyrin dimer: directed columnar liquid crystalline assembly by amphiphilic molecular design

A triply fused copper porphyrin dimer, when site-specifically modified on its periphery with hydrophobic and hydrophilic wedges (1C12/TEG), self-assembles into a columnar liquid crystalline (LC) mesophase over a wide-temperature range from -17 to 99 degrees C but gives rise to an amorphous solid when modified with only hydrophobic (1C12/C12) or hydrophilic wedges (1TEG/TEG). A LC film of 1C12/TEG displays at 16 degrees C a top-class one-dimensional electron mobility (0.27 cm2/V x s), as evaluated from its maximum flash-photolysis time-resolved microwave conductivity.     

Atmospheric deposition of35S

Extraction of actinides like neptunium, plutonium and americium have been performed using polyphosphine polyoxides. Phosphorus compounds with (O)PCP(O) linkage exhibit very high liquid-liquid extraction properties. They demonstrate also quantitative and selective transport properties of some actinides by supported liquid membrane (SLM) technology.     

The effect of oxygen vacancy on the oxide ion mobility in LaAlO3-based oxides

The electrical property of (La_1−xSr_x)_1−z(Al_1−yMg_y)O_3−δ (LSAM; x≤0.3, y≤0.15 and z≤0.1) was measured using the DC four-probe method as a function of temperature (500–1000°C) and oxygen partial pressure (1–10⁻²² atm). Among LSAMs, (La_0.9Sr_0.1)AlO_3−δ showed the highest ionic conductivity, σ_i=1.3×10⁻² S cm⁻¹ at 900°C. A simultaneous substitution at A and B sites or A site deficiency is expected to create larger oxygen vacancy and higher ionic conductivity. However, it showed a negative effect. The effect of the vacancy increase did not effect monotonously the ionic conductivity. It was found that the concentration of oxygen vacancy, [V_O], influences not only the oxide ion conductivity, σ_i, but also the mobility, μ_v, of [V_O]. These properties exhibit a maximum at around [V_O]=0.05. With the increase in [V_O], the activation energy, E_a, of the ionic conduction dropped from 1.8 to ca. 1.0 eV at [V_O]=0.05 and became almost constant at [V_O]>0.05. The dependency of the pre-exponential term, μ⁰_v, and E_a on [V_O] was analyzed and their effect on μ_v and σ_i was discussed with respect to crystal structure and defect association. It was estimated that the crystal structure mainly governs these properties. The effect of defect association could not be ignored but is considered to be a complicated correlation.     

Experimental probe for hyperconjugative resonance contribution in stabilizing the singlet state of 2,2-dialkoxy-1,3-diyls: Regioselective 1,2-oxygen migration

A detailed study of the regioselectivity of 1,2-oxygen migration was conducted using the unsymmetrically substituted singlet 2,2-dialkoxy-1,3-diarylcyclopentane-1,3-diyls 5. The alkoxy group selectively migrates to the electron-donating p-methoxyphenyl-substituted carbon. The regioselective migration of oxygen clearly indicates a hyperconjugative resonance structure, that is, zwitterionic characteristics, in singlet 2,2-dialkoxy-1,3-diyls. This represents the first attempt to experimentally probe the contribution of hyperconjugation to stabilizing the singlet state.