Geminate charge recombination in liquid alkane with concentrated CCl4: effects of CCl4 radical anion and narrowing of initial distribution of Cl-

Dynamics of radical cations and electrons in an admixture of a linear saturated hydrocarbon (n-dodecane) and halocarbon (carbon tetrachloride, CCl(4)) were investigated by picosecond electron beam pulse radiolysis. The decay of thermalized electrons (e(th)(-)) observed in infrared transient photoabsorption were simply accelerated by the addition of CCl(4), giving a high rate constant of 2.3 × 10(11) mol(-1) dm(3) s(-1). The decrease of the initial yield of e(th)(-) was quantified by C(37) (50 mmol), which is linked to the reaction of epithermal electrons (e(-)) with CCl(4). In contrast, the n-dodecane radical cation (RH(2)(?+)) monitored in the near-infrared indicated a convex-type dependence of the decay rate on CCl(4) concentration, although the initial yield of RH(2)(?+) remained almost constant up to a much higher CCl(4) concentration. The decay of RH(2)(?+) was analyzed by Monte Carlo simulations of geminate ion recombination with e(th)(-), chlorine anion (Cl(-)) formed via dissociative electron attachment, and CCl(4) radical anion. The results showed a good agreement with the experiments by considering two assumptions: (1) CCl(4) radical anion formed via e(th)(-) attachment and (2) narrowing of the initial distribution of Cl(-). The decrease in the initial yield of RH(2)(?+) at high CCl(4) concentration was well explained by immediate decomposition of CCl(4)(?+) to CCl(3)(+) and hole transfer from CCl(4)(?+) to adjacent RH(2) without diffusive motion of the reactants. Time-dependent density functional theory supported the spectroscopic assignment of intermediate species in the n-dodecane/CCl(4) system. The present results would be of help in understanding the electron capture reaction in multicomponent systems such as a chemically amplified resist in lithography.     

Millimeter-sized flat crystalline sheet architectures of fullerene assemblies with anisotropic photoconductivity

The coassembly of C(60) derivatives through arene-perfluoroarene interactions has been used for the first time to develop millimeter-sized flat crystalline sheets. Time-resolved microwave conductivity (TRMC) measurements exhibited anisotropic features with over double the charge carrier mobility in the direction parallel to the plane of the crystal than perpendicular to the plane. This study demonstrates a strategy to obtain large-sized 2-dimensional architectures of C(60) with anisotropic optoelectronic functions.     

Synthesis of porous vinylnaphthalene/divinylnaphthalene copolymers and their sorptive properties towards phenol and its derivatives

Four porous vinylnaphthalene/divinylnaphthalene (VN/DVN) polymers having three different nominal crosslinking degrees (60, 80 and 100 wt.%) have been synthesized using the suspension polymerization method in the presence of toluene and decane.The use of various crosslinking levels and inert diluents was aimed at changing the extent of polymeric network-diluent interactions. The resultant polymers have specific surface area in the range 450-700 m²/g depending on the DVN content. Two sets of pores were detected in all resins: one with the diameter of ≈2 nm and the second one in the range of 30-40 nm. Their sorptive properties have been studied using dilute (0.5 mmol/l) solutions of phenol and its derivatives (o-chlorophenol, 2-methylphenol, o-nitrophenol, m-nitrophenol and p-nitrophenol). It has been found that sorption, at low equilibrium concentration, follows the order: o-nitrophenol > o-chlorophenol > m-nitrophenol > o-methylphenol > p-nitrophenol > phenol. Full characteristics of the porous structure of resultant polymers was obtained by nitrogen adsorption at 77 K and their surface properties analyzed using Inverse Gas Chromatography.     

Application of 4-(4-nitrophenyl)-1,2,4-triazoline-3,5-dione to analysis of 25-hydroxyvitamin D3 in human plasma by liquid chromatography/electron capture atmospheric pressure chemical ionization-mass spectrometry.

The utility of 4-(4-nitrophenyl)-1,2,4-triazoline-3,5-dione (NPTAD) as a derivatization reagent in the analysis of 25-hydroxyvitamin D3 [25(OH)D3] using liquid chromatography/electron capture atmospheric pressure chemical ionization-mass spectrometry (LC/ECAPCI-MS) was examined. The derivatives of 25(OH)D3 with NPTAD underwent electron capture in the APCI source in the negative-ion mode and provided 30-fold higher sensitivity compared to an intact compound. This derivatization-LC/ECAPCI-MS method was applied to a plasma 25-hydroxyvitamin D3 assay, and gave satisfactory results in sensitivity, specificity, measurable range and throughput of the analysis.     

Studies on the charge transfer complex and polymerization. XVI. Spontaneous copolymerization of cyclopentene and sulfur dioxide

The alternating copolymerization of cyclopentene and sulfur dioxide was studied. It takes place spontaneously at ?15°C. The rate of copolymerization in toluene was found to be proportional to [CPT]³ and [SO₂]² with the overall activation energy of 16.5 kcal/mole. Terpolymerizations with eight different third monomers were carried out to examine the character and behavior of the copolymerization system of CPT and SO₂. However, the polymerizations with styrene and methyl methacrylate as the third monomers were found to be extraordinary, in that all the three components are not incorporated into the polymer chain.     

Angle-resolved photoemission study of CoSi2 nanofilms grown on Si(111) substrates

We have carried out an angle-resolved photoemission study for CoSi₂ nanofilms grown on the Si(111)-7×7 substrates. The surface of CoSi₂(111) nanofilm changes from the bulk-truncated surface to the surface with additional Si-bilayer by annealing at higher temperature above 825 K. The angle-resolved photoemission spectra of the CoSi₂ nanofilm annealed at 853 K show the spectral features originated from the surface resonance state on the CoSi₂ surface terminated by Si-bilayer. From the detailed photoemission study, we discuss the surface electronic structure in CoSi₂(111) nanofilms grown on Si(111) substrates.