Organofunctionalized catalyst surfaces highly active and selective for carbon–carbon bond-forming reactions

This article illustrates two types of organofunctionalized heterogeneous catalysts for variety of organic carbon–carbon bond-forming reactions, summarizing our previous reports and also presenting new data. Organic amines with an alkoxysilane moiety were immobilized on inorganic silica-alumina surfaces (SA-NR₂) by simple silane-coupling reactions between the silica-alumina surface (SA) and the alkoxysilane. This SA-NR₂ acted as acid–base bifunctional heterogeneous catalysts for carbon–carbon bond-forming reactions, such as cyano-ethoxycarbonylation, Michael reaction of nitriles, and nitro-aldol reaction. These reactions did not occur with either SA or homogeneous amine compounds. In addition, the mixture of SA and homogeneous amine showed low catalytic activity due to undesirable acid–base neutralization reaction. Achiral organic silane-coupling reagents with a variety of functional groups were also immobilized on a SiO₂ surface that had been immobilized with chiral bis(oxazoline) (BOX), to which Cu ions were coordinated to make chiral Cu–BOX complexes on the SiO₂ surface. The SiO₂-supported Cu–BOX complex catalyst functionalized with achiral 3-methacryloxypropyltrimethoxysilane dramatically increased enantioselectivity in the asymmetric Diels–Alder reaction of cyclopentadiene and 3-acryloyl-2-oxazolidinone. The organofunctionalized catalysts showed much better performances for the C–C bond-forming reactions compared to the corresponding homogeneous systems. The heterogeneous catalysts thus obtained were characterized by solid-state ¹³C and ²⁹Si MAS NMR, FT-IR, UV/vis, XAFS, ESR, XRF, and elemental analysis.     

Arrhythmogenic right ventricular cardiomyopathy underlies syndrome of right bundle branch block, ST-segment elevation, and sudden death

In all experimental mammals tested (rats, dogs, primates), intramuscular injections of the oil-soluble antimalarial artemisinin derivatives artemether and arteether have produced an unusual pattern of selective damage to brain stem centers predominantly involved in auditory processing and vestibular reflexes. Artesunate, the most widely used of these compounds, is a water soluble hemisuccinate derivative given parenterally either by intravenous or intramuscular injection. The neurotoxic potential of parenteral artesunate and artemether was compared in a murine model. Adult Swiss albino mice were assigned randomly to 28-day regimens of intramuscular artemether or artesunate in doses ranging from 30 to 100 mg/kg/day. At 30 mg/kg/day, no abnormalities were detected with either drug. At 50 mg/kg/day, abnormalities were observed in six of 12 artemether recipients and two of 12 artesunate recipients. These were reversible in all but one (artemether) mouse. At 100 mg/kg/day, eight of 36 artemether recipients, two of 36 artesunate recipients, and one of 18 control mice died. All but four surviving mice in the artemether group (86%) showed obvious and usually irreversible abnormalities of balance and equilibrium, whereas only four artesunate recipients (11%) exhibited abnormalities, and these were reversible in each case (P < 0.001). At this dose the relative risk (95% confidence interval) for death or disability was 5.3 (2.6-11.2) for artemether recipients. Intramuscular artemether is significantly more neurotoxic than intramuscular artesunate in this murine model.     

Digalactosyldiacylglycerol suppression of inhibition by sulfoquinovosyldiacylglycerol of alpha-glucosidase

Digalactosyldiacylglycerol (DGDG) suppressed the inhibition by sulfoquinovosyldiacylglycerol (SQDG) of an alpha-glucosidase reaction. Suppressing was considered to be an apparent decrease in inhibitory activity of SQDG ascribed to direct interaction between SQDG and DGDG. This suppression was presumed to be caused by less access of SQDG to the enzyme because SQDG and DGDG formed mixed micelles.     

The indirect hemagglutination test for onchocerciasis performed with blood collected on filter paper

In Guatemala, an indirect hemagglutination (IHA) test for onchocerciasis, performed with a crude saline extract of Onchocerca volvulus and blood samples taken on filter paper, showed a high level of sensitivity and specificity. IHA titers of blood samples from the ear lobe taken on filter paper and of sera obtained by venipuncture showed a high correlation.     

Immunohistochemical demonstration of 3,2''-dimethyl-4-aminobiphenyl DNA adduct formation in various organs of Syrian golden hamsters

We attempted to purify endogenous growth factors of chick embryonal retinal pigment epithelial cells from bovine neural retina. Ammonium sulfate precipitation, gel filtration, and anion exchange column chromatography were used. Though only partially purification, bovine retinal extract had two effects, growth and transformation, on chick embryonal pigment epithelial cells. We think that these purified factors may be novel from the estimation of their molecular weight by gel filtration.     

Serum concentrations of apolipoproteins in patients with thyroid dysfunction

We measured serum concentrations of apolipoproteins (apo A-I, A-II, B, C-II, C-III and E) in patients with thyroid disease (hyperthyroidism; n = 44, hypothyroidism; n = 15) and in normal subjects (n = 89). We found that apoA-II, B and C-III concentrations revealed significant difference among three groups of the normal (apoA-II; 31.4 +/- 4.9 mg/dl, apoB; 85.8 +/- 16.3 mg/dl, apoCIII; 7.45 +/- 2.99 mg/dl), hyperthyroidism (apoA-II; 29.8 +/- 5.4, apoB; 63.4 +/- 18.9, apoC-III; 6.28 +/- 2.45) and hypothyroidism (apoA-II; 27.5 +/- 5.3, apoB; 108.0 +/- 30.9, apoC-III; 9.43 +/- 2.74). Thyroid hormones showed clear negative correlation to apoB (r = 0.70, p < 0.001). Furthermore, apoC-III was also found to be negatively correlated with thyroid hormone concentrations (r = 0.47, p < 0.001).     

Reconstruction of lake-level and climate changes in Lake Qarun,Egypt, during the last 7000 years

Sediment cores from Lake Qarun provide a record of mid-late Holocene climatic changes in Northern and Eastern Africa as well as environmental changes due to the activities of ancient Egyptians. We used sedimentological, mineralogical, and geochemical analyses of the cores to investigate long-term variations in lake level due to changing hydrologic inputs. An age model based on three paired ¹⁴C and paleomagnetic measurements suggests that the base of the sediment cores is as old as ∼ 5000 B.C.E. Geochemical analyses indicated that lake sediments were derived from Nile floods with an admixture of Saharan sand. Laminated endogenic carbonate-rich clayey silt lithofacies with benthic diatoms are indicative of relatively low lake levels, saline waters and dry conditions; massive lithofacies with planktonic diatom species are indicative of relatively high lake levels, fresh waters and humid conditions. Faintly laminated clayey silt lithofacies suggest intermediate conditions. Variations in lithology as well as diatom composition suggest that the lake level has varied from relatively high levels in its early history to lower levels in later years although there have been numerous cycles in water level over the past 7000 years. A combination of climate changes in the source area of the Nile River as a result of monsoon dynamics; climatic changes in the setting area of the Lake Qarun; and human activities through the dynasties in Egypt produced these variations in lake level.     

Prospective method of lightning protection schemes in distribution system

Grounding wires and enclosed ZnO elements have been incorporated generally in 6.6‐kV distribution systems by TEPCO for the reduction of lightning overvoltages. At present, the reliability to lightning surges is tolerably good. However, the facility of grounding wires is not inexpensive and its maintenance is hard due to corrosion and disconnection in some areas. A typical model simulating TEPCO field adopting enclosed ZnO elements has been developed and we have evaluated relative failure risks systematically according to conditions with and without grounding wires against lightning overvoltages. Two kinds of failures discussed in the paper are the flashover of insulation and the overduty of ZnO elements, and two kinds of induced and direct lightning overvoltages are studied in flashover. The greatest problem with no grounding wire is the increase of ZnO elements' duty, but it was demonstrated that a short partial grounding wire around ZnO elements or the selection of heavier ZnO elements provides a solution. The main objectives of this study are to clarify the relative failure risks systematically according to realistic field conditions, the risk of small stroke currents having long duration to ZnO elements' duty, and countermeasures against ZnO elements' overduty. © 1999 Scripta Technica, Electr Eng Jpn, 127(1): 1–10, 1999