Sequential actions of cobalt nanoparticles and palladium(II) catalysts: three-step one-pot synthesis of fenestranes from an enyne and an alkyne diester

A three-step one-pot synthesis of fenestranes from a readily available enyne and an alkyne diester has been carried out with cobalt nanoparticles and palladium(II) as catalysts.     

Clinical significance of molecular genetic changes in sporadic invasive pituitary adenomas

Several molecular and genetic changes have been found in pituitary adenomas. We looked for correlations between these changes and the degree of invasiveness of the tumors. The invasiveness of 11 pituitary adenomas was graded by Hardy classification. We examined the retinoblastoma gene (RB1.20 on chromosome 13q) and the region around the MEN1 locus (chromosome 11q13.1-5) for loss of heterozygosity. Also examined are p53 mutations using single strain conformation polymorphism, p53 protein overexpression using immuno cytochemistry, homozygous deletions of p15 and p16 by polymerase chain reaction, and cellular proliferative activity using MIB-1 antibody. Six tumors (54.5%) had an LOH at either RB1.20 or the MEN1 locus. LOHs were found more frequently in Grade 4 and stage E tumors (72% and 67%) than in Grade 3 and stage D tumors (25% and 40%). However, no mutation or overexpression of p53 was found. No homozygous deletions of p15 or p16 were identified. The cell proliferative index ranged from 0 to 3%. LOH at 11q13 and 13q may be valuable in predicting the invasiveness of pituitary adenomas.     

Interfacial Characteristics and Fracture Toughness of Electrolytically Ni-Plated Carbon Fiber-Reinforced Phenolic Resin Matrix Composites

The electrolytic plating of metallic nickel on a carbon fiber surface has been carried out in order to improve the interfacial adhesion and the mechanical properties in carbon fiber/phenolic matrix composite systems. The surface and the mechanical interfacial properties of composites are characterized by X-ray photoelectron spectrometry (XPS), surface free energy, and the critical stress intensity factor (K(IC)). From the experimental results, it is clearly revealed that the oxygen functional groups and the metallic nickel on fibers largely affect the mechanical interfacial behavior of the composites, resulting in increased surface polarity, whereas the nitrogen functional groups have no effect. Also, a good correlation between surface oxygen functional groups and mechanical interfacial properties and between wettability and K(IC) is established and it is found that a 10 A m(-2) current density is the optimum condition for this system. Copyright 2001 Academic Press.     

Separation of 99Mo from a simulated fission product solution by precipitation with a-benzoinoxime

The formation property of Mo precipitate was investigated and improved the existing process was using H₂O₂ that acts as an interfering compound in a subsequent alumina adsorption process. The property of the Mo precipitate was investigated by using SEM, FTIR, TG-DTA, and XRD. The simulated solution consisted of 1M nitric acid containing seven elements (Mo, I, Ru, Zr, Ce, Nd, Sr) and their radioactive tracers. As a result, the precipitate was composed of the Mo precipitate and re-precipitated a-benzoinoxime which was added excessively for increasing the precipitation efficiency. It was confirmed that the Mo precipitate was formed by the reaction of two a-benzoinoxime molecules and one MoO₂ ²⁺. Molybdenum precipitate was dissolved in 0.4M NaOH solution within 5 minutes without H₂O₂. Hydrogen peroxide induced only the rapid dissolution of the a-benzoinoxime re-precipitate. Also, the dissolution method without H₂O₂ was favorable in the purification aspect because Zr and Ru were contained as a small fraction of 1.3% and 7.7%, respectively, in the dissolving solution.     

Improved expression by cytomegalovirus promoter/enhancer and behavior of vascular endothelial growth factor gene after myocardial injection of naked DNA

Direct injection of the vascular endothelial growth factor (VEGF) gene plasmid DNA into the myocardium was shown to induce development of new blood vessels to increase the circulation in the heart of patients with coronary artery diseases. However, such angiogenic gene therapy (via naked DNA) was limited by low level of gene expression. Furthermore, the temporal and spatial characteristics of VEGF gene transfer in the heart are not known. In this study, we demonstrated that a plasmid vector, containing the human cytomegalovirus immediate early (HCMV IE) promoter and enhancer, induces greater expression of gene in the rat heart monitored by gene fused to the chloramphenicol acetyl transferase (CAT) reporter, than four different viral and cellular promoters. Interestingly, expression of VEGF121 protein showed an earlier peak, a shorter duration, and a wider distribution than that of CAT only. Therefore, a plasmid vector with an HCMV IE promoter/enhancer provides clear advantages over other previously developed plasmids. Furthermore, expression profile of VEGF121 gene may provide useful information in the design of angiogenic gene therapy in the heart.     

Hydrodynamic microfabrication via"on the fly" photopolymerization of microscale fibers and tubes

A microfluidic apparatus capable of creating continuous microscale cylindrical polymeric structures has been developed. This system is able to produce microstructures (e.g. fibers, tubes) by employing 3D multiple stream laminar flow and "on the fly"in-situ photopolymerization. The details of the fabrication process and the characterization of the produced microfibers are described. The apparatus is constructed by merging pulled glass pipettes with PDMS molding technology and used to manufacture the fibers and tubes. By controlling the sample and sheath volume flow rates, the dimensions of the microstructures produced can be altered without re-tooling. The fiber properties including elasticity, stimuli responsiveness, and biosensing are characterized. Responsive woven fabric and biosensing fibers are demonstrated. The fabrication process is simple, cost effective and flexible in materials, geometries, and scales.     

Synthesis and structure of Li4Sr3Ge2N6: a new quaternary nitride containing Ge2N6 anions

A new Li-containing quaternary nitride, Li₄Sr₃Ge₂N₆, was obtained as single crystals from constituent elements in molten Na. It crystallizes in space group C2/m (No. 12) with a=6.1398(7) Å, b=10.021(1) Å, c=6.3130(7) Å, β=91.279(2)°, and Z=2. It contains the first example of isolated nitridogermanate anions of Ge₂N₆¹⁰⁻, which is also the first example of edge-sharing tetrahedral [GeN₄].     

Synthesis and Structures of Titanosiloxane Cage Compounds

Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl₃) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph₃CSiO(OH)]₃(Ph₃CSiO_3/2)(CpTiO_3/2)₄} (2) and cube type (Ph₃CSiO_3/2CpTiO_3/2)₄ (3). The 1:1 reaction of 1 and CpTiCl₃ in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl₃ under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of ¹H, ¹³C, ²⁹Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl₃ > hexane THF.     

All-solid-state carbonate-selective electrode based on a molecular tweezer-type neutral carrier with solvent-soluble conducting polymer solid contact

Carbonate-selective membranes were prepared by incorporating a molecular tweezer-type carbonate-selective neutral carrier [N,N-dioctyl-3alpha,12alpha-bis(4-trifluoroacetylbenzyloxy)-5beta-cholan-24-amide] into a room temperature vulcanizing-type silicone rubber (3140 RTV-SR) matrix, and deposited on the planar-type electrodes (Pt containing Ag/AgCl electrodes formed on a ceramic plate) with and without an intermediary conducting polymer layer. Two types of solvent-soluble conducting polymers [poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) or poly(3-octylthiophene-2,5-diyl)] have been examined as the solid contact material. Potentiometric properties of the resultant all-solid-state electrodes were evaluated in terms of their carbonate selectivity, response slope, potential stability and reproducibility. The sensitivity and carbonate selectivity of the SR membrane-based all-solid-state electrodes with conducting polymer solid contact were comparable to those of conventional electrodes. Experimental results also showed that the intermediary conducting polymer layer used in the all-solid-state electrodes greatly reduces the interference from dissolved oxygen.