Preparation and properties of biodegradable network poly(ester-carbonate) elastomers

Biodegradable elastomeric network poly(ester-carbonate)s were prepared from multifunctional aliphatic carboxylic acids such as tricarballylic acid (Y_t) or trimesic acid (Y) and polycarbonate diols (PCD) with molecular weights of 1000 and 2000 g/mol. Prepolymers prepared by a melt polycondensation were cast from dimethylformamide solution and postpolymerized at 270 °C for 40-80 min to form a network. The resultant films were transparent, flexible and insoluble in organic solvents. WAXS exhibited the crystalline peaks due to polycarbonate segments for the network films from PCD₂₀₀₀, while those from PCD₁₀₀₀ were amorphous. The tensile properties were determined for these network films at the temperatures 22, 30, 40 and 50 °C. These films showed elastomeric properties at all temperatures measured. The elongation at break was much higher for the films from PCD₂₀₀₀ (208-434%) than those from PCD₁₀₀₀ (40-120%), and decreased with increasing temperatures. The weight losses of the network films degraded in the buffer solution of Rhizopus delemar lipase at 37 °C increased with time, suggesting that these network films are biodegradable. The degradation rate of the network films from Y_t is faster than that from Y. The GPC curves showed that the lipase hydrolyzed both the ester linkages between Y or Y_t and PCD as well as polycarbonate moiety in the network polymer.     

Formation of deagglomerated PLGA particles and PLGA-coated ultra fine powders by rapid expansion of supercritical solution with ethanol cosolvent

Rapid expansion of supercritical solution (RESS) was used for preparing polymer particles and polymer coating of ultra fine powders. The polymer of pharmaceutical interest was Poly(lactic-co-glycolic acid) (PLGA with PLA: PGA ratio of 85: 15 and MW of 50,000–75,000) and the simulated core particles were 1.4-μm SiO₂ and 70-nm TiO₂ particles. The supercritical solution was prepared by dissolving PLGA in supercritical carbon dioxide with ethanol as a cosolvent. Supercritical solution of CO₂-PLGA was sprayed through capillary nozzles to ambient conditions, resulting in formation of submicron PLGA particles. Similarly, rapid expansion of supercritical solution of CO₂-PLGA suspended with the core particles could provide solvent evaporation and deposition of submicron PLGA particles on the surface of the core particles, resulting in the formation of coating films on dispersed particles of SiO₂ and agglomerates of TiO₂. The influences of the core particle size, spray nozzle diameter as well as powder-to-polymer weight ratio were also investigated and discussed with respect to the coating performance.     

In vivo visual reporter system for detection of estrogen-like substances by transgenic medaka

Detection of endocrine disrupting chemicals, in particular, environmental estrogens with living organisms, has many advantages if compared to chemical analysis. The screening of novel pollutants with meaningful endpoints, the integration of uptake, bioconcentration, and excretion as well as the evaluation of endocrine disrupting effects with respect to toxicity require in vivo biotests for estrogen-like substances (ELSs). Critical disadvantages of whole organism biotests are their low sensitivity and the need for laborious and time-consuming work. To overcome these problems, we have developed a transgenic medaka strain harboring the green fluorescence protein (GFP) gene driven by choriogenin H gene regulatory elements. Choriogenin H is an egg envelope protein induced by estrogens in the liver. With yolk sac larvae of this strain, GFP induction in liver was observed 24 h after onset of aqueous exposure to 0.63 nM 17beta-estradiol (E2), 0.34 nM ethynylestradiol, or 14.8 nM estrone. Furthermore, concentrated sewage treatment effluent induced GFP expression. Comparison of E2 equivalents estimated by GFP-induction in transgenic medaka, a YES assay, and GC/MS showed detection limits in the same order of magnitude. These results indicated that the sensitivity of the transgenic medaka strain was sufficient for application as an alternative model in monitoring environmental water samples for ELSs.     

Dioxin concentrations in the edible parts of Japanese common squid and saury

We examined the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in muscle and gut tissues from Japanese common squid and saury. These body parts are often eaten in Japan, so it is important to measure their dioxin concentrations and evaluate the risks to consumers. The toxic equivalent (TEQ) concentrations in the squid gut samples (1.0 to 14 pg-TEQ/g fresh weight, n=3) were 50-fold larger than those in the muscle tissues (0.020 to 0.22 pg-TEQ/g fresh weight, n = 3) taken from the same samples. By contrast, the TEQ concentrations in the saury gut samples (0.35 to 0.63 pg-TEQ/g fresh weight, n=3) were only 1.1- to 1.7-fold greater than those in the muscle tissues (0.33 to 0.37 pg-TEQ/g fresh weight, n= 3) from the same samples. The TEQ contents in the squid gut tissues ranged from 60 to 990 pg-TEQ/squid, accounting for about 95% of the total dioxin content of the edible parts of the samples. By contrast, the TEQ contents in the saury gut tissues ranged from 4.4 to 12 pg-TEQ/saury, accounting for less than 25% of the total dioxin content of the edible parts of the samples. These tissues showed comparable PCDD/PCDF-congener and dioxin-like PCB-isomer profiles in both species. The results indicate that squid gut tissues occasionally contain high levels of dioxins, and consumption of this foodstuff could potentially significantly increase the dietary intake of dioxins.     

Effect of surface properties of silica nanoparticles on their cytotoxicity and cellular distribution in murine macrophages

In this study, complexes composed of poly-l-tyrosine (pLT) and single-walled carbon nanotubes (SWCNTs) were produced and the dispersibility of the pLT/SWCNT complexes in water by measuring the ζ potential of the complexes and the turbidity of the solution were investigated. It is found that the absolute value of the ζ potential of the pLT/SWCNT complexes is as high as that of SWCNTs modified with double-stranded DNA (dsDNA) and that the complexes remain stably dispersed in the water at least for two weeks. Thermogravimetry analysis (TGA) and visualization of the surface structures of pLT/SWCNT complexes using an atomic force microscope (AFM) were also carried out.     

Reaction of Syringylglycerol-β-Syringyl Ether Type of Lignin Model Compounds in Alkaline Medium

Reactions of three kind of syringylglycerol- β-syringyl ether type model compounds under alkaline medium were investigated. Sinapyl alcohol and β-hydroxypropiosyringone were formed as phenyl propanoid moieties from syringylglycerol- β-(methyl-syringyl) ether 1 by the β-aryl ether cleavage under soda treatment, while only sinapyl alcohol was formed from syringylglycerol- β-syringyl ether 2. The formation of both two degradation products are quite interesting because there is no nucleophilic additives in soda liquor. A possible reaction mechanisms for the β-aryl cleavage of syringylglycerol-β-syringyl ether type is homolytical cleavage via quinone methide.     

Viewpoints to characterize precision evaluation methods in binary measurements

Precision evaluation in quantitative measurements is a thoroughly discussed topic and the established methods are in use. Many methods are proposed for qualitative data including binary data, but their effectiveness and statistical properties are not so clear.     

The dependence of hydrofluoric acid concentration during anodization on photoluminescence of porous silicon

The mixture of hydrofluoric (HF) acid and ethanol is used as an electrolyte during anodization of silicon. We investigated the effect of the ratio of HF acid to ethanol on photoluminescence. It is concluded that porous silicon anodized with the electrolyte containing 35 or 40% HF acid provides strong photoluminescence. The fact implies the existence of a chemical reaction including ethanol during anodization other than electrochemical reaction.     

High‐pressure short time behavior of traction fluids

The squeeze film formation ability of traction fluids is studied under impact load by dropping a steel ball‐bearing against a flat anvil made of mild steel. The effect of the pressure–viscosity coefficient and of the viscosity is investigated for plastic impact. The depth difference between the lubricated surface dent and the dry dent increases linearly with the product αη of the pressure–viscosity coefficient α and the viscosity η. The importance of the lubricant parameter αη is observed under the squeeze film formation ability from contact voltage or elastohydrodynamic lubrication central film thickness measurement at rolling condition. The intensity of each impact collision is measured by means of an acoustic emission (AE) sensor. The high‐pressure short‐time solidification of traction fluids was confirmed by dent analysis after the impact tests and AE analysis under impact loads. Copyright © 2006 John Wiley & Sons, Ltd.