Reduction of dislocation density and improvement of optical quality in ZnO layers by MgO-buffer annealing

Optical properties of ZnO thin films with/without MgO-buffer annealing were investigated by low and room temperature photoluminescence measurements. The ZnO films were grown on c-sapphire substrates by plasma-assisted molecular-beam epitaxy employing a thin MgO-buffer layer. Dislocation density of ZnO layer was reduced from 5.3 × 10⁹ to 1.9 × 10⁹ cm⁻² by annealing MgO-buffer prior to the growth of ZnO. The intensity of free exciton emission from the sample with MgO-buffer annealing was almost twice of that from the sample without annealing, while the deep level emission from the sample with MgO-buffer annealing was about 1/3 of that without annealing. The MgO-buffer annealing improves optical quality of overgrown ZnO films.     

High pressure and high temperature investigations in the system MgOSiO2H2O

The system MgOSiO₂H₂O was investigated at pressures between 40 and 95 kbar and at temperatures between 500 and 1400°C. The reaction products were examined by X-ray, optical and thermal analysis techniques and the density of phase A discovered by Ringwood and Major was also measured. It was found that phase A was hydrated and its chemical formula was H₆Mg₇Si₂O₁₄. When the $\text{Mg}\text{Si}$ ratio of the system is 2, phase A + clinoenstatite, and forsterite are stable at temperatures lower and higher than a boundary curve T (°C) = 10P (kbar), respectively. When the $\text{Mg}\text{Si}$ ratio of the system is 3, phase A + phase D (which is completely different from the phases, A, B and C discovered by Ringwood and Major, and any other known phases of magnesium silicate) and phase D + brucite are stable at temperatures lower and higher than a boundary curve T(°C) = 10P (kbar) + 200. Phase A has approximately an hexagonal symmetry and the space group and the lattice parameters are determined as P6₃ or $\text{P6}{}_3\text{m}$ and a = 7.866(2) Å and c = 9.600(3) Å, respectively. The measured density is 2.96 ± 0.02 g/cm³. The optical observations show that phase A is biaxial positive crystal with refractive indices α = 1.638 ± 0.001, β = 1.640 ± 0.002, and γ = 1.649 ± 0.001. Some interpretation is given on the inconsistency between the symmetry determined by the X-ray diffraction and the optical observation. The new phase D belongs to the space group $\text{P2}{}_1\text{c}$ with lattice parameters a = 7.914(2)Å, b = 4.752(1) Å, c = 10.350(2) Å and β = 108.71(5)° and is a biaxial crystal with refractive indices α = 1.630 ± 0.002, β = 1.642 ± 0.002 and γ = 1.658 ± 0.001.     

Non-glutamate type pyrrolo[2,3-d]pyrimidine antifolates. III. Synthesis and biological properties of N(omega)-masked ornithine analogs

The glutamic acid moiety of N-[4-[3-(2,4-diamino-7H-pyrrolo[2,3-d]pyrimidin-5-yl)propyl]benzoyl]-L-g lutamic acid (1b, TNP-351) and the related compound (1a), was replaced with various N(omega)-acyl-, sulfonyl-, carbamoyl- and aryl-2,omega-diaminoalkanoic acids, and the inhibitory effects of the resulting products (9, 11, 14, 18, 21, 23, 25, 30, 36) on dihydrofolate reductase (DHFR), the growth of murine fibrosarcoma Meth A cells, and methotrexate-resistant human CCRF-CEM cells, were examined. Compounds (9a-f) acylated with a hemiphthaloyl group were efficiently synthesized by coupling pyrrolo[2,3-d]pyrimidine carboxylic acids (7a,b) and N(omega)-phthaloyl 2,omega-diaminoalkanoic acid methyl esters (6a-c) and subsequent hydrolysis. The other N(omega)-acyl- and sulfonyl-ornithine analogs (21, 23, 25) were synthesized by acylation of free amino intermediates (19a,b) derived from tert-butoxycarbonyl-ornithine analogs (17a,b). A free ornithine analog (18) did not strongly inhibit Meth A cell growth, whereas all N(omega)-acyl-, sulfonyl-, carbamoyl- and aryl-ornithine analogs (9, 11, 21, 23, 25, 30, 36) exhibited much more potent inhibitory activities against both DHFR and Meth A cell growth. In particular, compounds 9c, 21k and 36a also showed remarkable growth-inhibitory activities against methotrexate-resistant CCRF-CEM cells. These results demonstrate that the potent inhibitory activities of N(omega)-masked ornithine analogs against the growth of Meth A cells and methotrexate-resistant CCRF-CEM cells, results from effective uptake via reduced folate carrier and their potent DHFR inhibition.     

Electrochemical control of CO/NO ligand exchange in a triruthenium cluster monolayer assembled on a gold electrode surface

A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices.     

Determination of alkylphenols and alkylphenol polyethoxylates by reversed-phase high-performance liquid chromatography and solid-phase extraction

A simple, accurate and reproducible reversed-phase high-performance liquid chromatography (HPLC) method was developed for the separation and characterisation of alkylphenols (APs) and alkylphenol polyethoxylates (APEOs), using a C18 octadecyl silica (ODS) column. APs and each APEO oligomer were separated successfully within a reasonable time without gradient elution. An excellent resolution was obtained, even for mixtures of APs and low EO number APEOs, which are otherwise difficult to separate using conventional normal-phase HPLC methods. This method, combined with solid-phase extraction, was highly applicable for the simultaneous determination of alkylphenols and alkylphenol ethoxylates in real samples.     

Polymerization of vinyl chloride and copolymerization with propylene by a ternary catalyst system

Polymerization of vinyl chloride by the ternary catalyst system of VOCl₃–AIR_nCl_3–n complexing agent was investigated. It was suggested that the formation of a polar complex (or charge-transfer complex) between AlR_nCl_3–n and the complexing agent participated in the polymerization of vinyl chloride. In the copolymerization of vinyl chloride with propylene with the present catalyst system, it was more difficult to incorporate the propylene unit in the copolymer than with a typical radical catalyst.