GPC analysis of polymer network formation

Size distribution of polymer clusters in pre-gel state has been measured by means of gel permeation chromatography (GPC) for crosslinking system between bifunctional prepolymer and trifunctional crosslinker. Experimental chromatograms have been obtained at various degree of conversion, and compared with theoretical chromatograms predicted by the Flory-Stockmayer model. Experimental size distribution at low conversion is well described by the theory. On the other hand, experimental chromatograms at higher conversions show a long tail in lower elution volume region which is unexpected by the theory. This result suggests that clusters with relatively linear structure which is not predicted by the theory are formed. The formation of the clusters with fairly linear structure is estimated to originate from unequality in reactivity of sites in crosslinker which is due to steric hindrance by the reacted sites. Received: 29 November 1996/Revised: 25 December 1996/Accepted: 27 December 1996     

Response of osteoblast-like MG63 cells to TiO2 layer prepared by micro-arc oxidation and electric polarization

Micro-arc oxidation (MAO) is one of the useful surface modifications of titanium implants to improve bioactivity. Also, electric polarization treatment enhances bioactivity of calcium phosphate. The aim of this study was to evaluate the effect of the combination of two surface modifications, micro-arc oxidation (MAO) with electric polarization, on the behavior of osteoblast-like osteosarcoma MG63 cells. MAO-treated materials had a surface geometry that was favored by MG63 cells as determined using scanning electron microscopy and X-ray diffraction; additionally, electric polarization induced surface electric fields, which were measured using thermally stimulated depolarization currents. The results of assays to study cell–material interactions suggest that these two approaches could regulate cell attachment, spreading, proliferation, and differentiation without the addition of other reagents. This new surface modification processes produce materials with a good surface geometry, generate surface electric fields and enhance the osteopromotive ability of osteoblasts.     

Epoxy Networks Modified by a New Class of Oligomeric Silsesquioxanes Bearing Multiple Intramolecular Rings Formed through Si?O?C Bonds

Summary: A new class of silsesquioxane (SSO), containing species with two to nine Si atoms bearing multiple intramolecular rings formed through Si? O? C bonds, was synthesized as a glassy powder. It was characterized by UV‐MALDI‐TOF MS, ²⁹Si NMR and FT IR. Solutions containing different amounts of SSO in the diglycidyl ether of bisphenol A (DGEBA), were homopolymerized in the presence of (4‐dimethylamino)pyridine (DMAP) as initiator, leading to SSO‐modified epoxy networks. SSO species were covalently bonded to the epoxy network without any evidence of phase separation. The SSO addition provoked an increase in the elastic modulus in the glassy state explained by an increase in the cohesive energy density. The SSO addition gave also place to an increase in the intensity of tan δ and a decrease in both the glass transition temperature and the elastic modulus in the rubbery state. This was explained by a decrease in crosslink density associated with the flexibility of SSO structures. DMAP was much more effective than other usual initiators (like benzyldimethylamine, BDMA), in increasing the crosslink density of the resulting epoxy network. This led to high values of the glass transition temperature and the elastic modulus in the rubbery state.

Schematic representation of the chemical structure of the most significant species containing three Si atoms, present in the silsesquioxane.     

Reinforcement Mechanism of Carbon Black (CB) in Natural Rubber Vulcanizates: Relationship Between CB Aggregate and Network Structure and Viscoelastic Properties

Carbon black (CB) aggregates in CB-filled natural rubber (NR) vulcanizate were joined together and formed CB aggregates in the CB region less than 20?phr. It was found that the viscoelastic behavior was related to the hydrodynamic interaction between CB aggregate and NR matrix. In the CB loading region more than 40?phr, CB aggregates formed CB network structure in it. Using the parallel mechanical model of the two phases of a rubber matrix and an immobilized CB/NR interfacial layer excluding a CB phase, it was possible to quantitatively explain the relationship between the viscoelastic behavior of CB network structure.     

Influence of the electron acceptor on nitrite reductase gene (nir) diversity in an activated sludge community

Analyses of the nitrite reductase gene diversities (nirK and nirS) in an activated sludge community fed with both nitrite and glucose were conducted. Results suggest that the topology of nirK and nirS gene fragment-based phylogenetic trees is influenced more by the available electron acceptor than by the carbon source. A denitrification reactor was operated for 53 days and a clone library constructed when the denitrifying communities in the SBR were supplied with both nitrite and glucose. Half of the nirK and nearly all the nirS gene fragments formed a cluster that was separate from a cluster containing nirK and nirS sequences derived from other communities in nitrate-fed reactors. On the other hand, nirK and nirS fragments obtained with glucose as the carbon source were similar to those detected in communities fed with other carbon sources.     

Tribochemical Reactions and Lubricating Effects of Fluorinated Methanes for Al2O3 Ceramic

It has been found that CF₃CH₂F (HFC-134a) gas is an effective lubricant for several ceramics because of the formation of fluorine-containing tribochemical products. To understand the influence of the molecular structure of fluorine-containing gases on the lubricating characteristics, the lubricating effects and tribochemical reactions of some fluorinated methanes for Al₂O₃ ceramic were studied. X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectroscopy (TOF-SIMS) were used to identify the chemical structure of tribochemical products. It was found that the friction and wear of Al₂O₃ ceramic were dependent on the molecular structure of the reacting fluorocarbon gases. The lowest friction was obtained in CH₂F₂. CHF₃ showed the best anti-wear effect. The results of surface analyses indicate that greater amounts of tribochemical products are produced when Al₂O₃ rubs in CH₂F₂ than in CF₄ and CHF₃ gases. C–C/C–H/carbon and AlF₃, which are mainly formed on the sliding surface in CH₂F₂, are responsible for the low friction. The mechanism of tribochemical reactions of the different environmental molecules on the nascent surface of Al₂O₃ was also discussed.     

High‐performance polymer‐stabilized blue‐phase LCD with low driving voltage

We have developed a polymer‐stabilized blue‐phase LCD in which the diffraction wavelength of blue‐phase liquid crystal is in the ultraviolet region and which is driven at a low voltage of V₁₀₀ = 27 V. Prototypes of 3.4‐in polymer‐stabilized blue‐phase LCDs were made, which include a highly reliable crystalline oxide semiconductor. We succeeded in fabricating not a test cell but a display having a contrast ratio higher than 1000 : 1 for the first time in the world.     

Production and characterization of a monoclonal antibody against recombinant thermolabile hemolysin and its application to screen for Vibrio parahaemolyticus contamination in raw seafood

Thermolabile hemolysin gene (tlh) is regarded as a species-specific marker for Vibrio parahaemolyticus. To assess the utility of the tlh gene product, thermolabile hemolysin (TLH), as a marker to screen for V. parahaemolyticus-contamination in raw seafood, we generated a monoclonal antibody (MAb) against recombinant TLH and established with an enzyme-linked immunosorbent assay using the MAb (TLH-ELISA). TLH-ELISA testing of broth cultures for 78 V. parahaemolyticus strains showed positive results all around. In contrast, most broth cultures of 53 non-V. parahaemolyticus species tested yielded negative results.We devised a screening method using TLH-ELISA to check for low-level contamination of V. parahaemolyticus in raw seafood within 24 h and evaluated its ability. In testing of V. parahaemolyticus-spiked raw seafood, results suggested that our screening method can detect 100 most-probable-number (MPN) of V. parahaemolyticus/g. Further, on testing 119 commercial raw seafood samples with our screening method, 117 samples were determined to contain less than 100 MPN of V. parahaemolyticus/g. All of the 117 samples were also estimated by the MPN method to contain less than 100 MPN of V. parahaemolyticus/g. Taken together, these results suggest that our screening method using TLH-ELISA is useful to check for low-level (<100 MPN/g) of V. parahaemolyticus in raw seafood.     

Removal of hazardous phenols by microalgae under photoautotrophic conditions

Various algae were screened for their ability to decrease the concentration of 2,4-dinitrophenol (DNP), as a model compound of hazardous phenols, under photoautotrophic conditions. Chlorella fusca var. vacuolata and Anabaena variabilis grew well and showed high DNP removal ability over the concentration range of 5 to 40 microM. Their abilities to remove various phenols were investigated. More than 90% of 40 microM o- and m-nitrophenol and DNP was removed during the cultivation period of 5 d. o-, p-Chlorophenol and 2,4-dichlorophenol could be removed, but not to a significant extent. C. fusca also removed 85% of bisphenol A, suspected to be an endocrine disrupter. It was found that microalgae would be applicable to the removal of hazardous phenols without the addition of any organic carbon sources.