Influence of the nigrosine dye on the thermal behavior of polyamide 66

To reveal the effect of the nigrosine dye, that the addition of the dye lowers the crystallization point (T_c) of molten polyamide resins with substantially no shift in the melting point (T_m), thus suppressing the crystallization enhancement of the crystalline nucleation agents, the characteristics of polyamide 66 (PA‐66) containing nigrosine dye EX (N‐EX) were investigated. Differential scanning calorimetry (DSC) analysis showed that the addition of N‐EX reduced the crystallization rate and T_c of molten PA‐66 with substantially no shift in T_m, and the crystallization enthalpy per unit of weight of PA‐66 was substantially constant. T_c of molten PA‐66 was lowered with an increase in the amount of N‐EX and reached its maximum at 13 wt % N‐EX. Dynamic mechanical analysis showed that the glass‐transition temperature and the secondary glass‐transition temperature increased with an increasing amount of the dye. On the other hand, the DSC and X‐ray diffraction results indicated that no dye molecule was present in the crystal structure of PA‐66. This effect of the nigrosine dye on PA‐66 is in contrast to those of crystalline nucleation agents, plasticizers, and antiplasticizers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3270–3274, 2006     

On-chip fabrication of magnetic alginate hydrogel microfibers by multilayered pneumatic microvalves

Alginate hydrogel has widespread applications in tissue engineering, cancer therapy, wound management and drug/cell/growth factor delivery due to its biocompatibility, hydrated environment and desirable viscoelastic properties. However, the lack of controllability is still an obstacle for utilizing it in the fabrication of 3D tissue constructs and accurate targeting in mass delivery. Here, we proposed a new method for achieving magnetic alginate hydrogel microfibers by dispersing magnetic nanoparticles in alginate solution and solidifying the magnetic alginate into hydrogel fiber inside microfluidic devices. The microfluidic devices have multilayered pneumatic microvalves with hemicylindrical channels to fully stop the fluids. In the experiments, the magnetic nanoparticles and the alginate solution were mixed and formed a uniform suspension. No aggregation of magnetic nanoparticles was found, which is crucial for flow control inside microfluidic devices. By regulating the flow rates of different solutions with the microvalves inside the microfluidic device, magnetic hydrogel fibers and nonmagnetic hydrogel fibers were fabricated with controlled sizes. The proposed method for fabricating magnetic hydrogel fiber holds great potential for engineering 3D tissue constructs with complex architectures and active drug release.     

Guinea pig bone marrow cells treated with platelet-activating factor generate factor(s) which affects their DNA synthesis and microbicidal activity

We have previously reported that platelet-activating factor (PAF) induces proliferation and microbicidal activity of guinea pig bone marrow cells. In the present study, we have found that the conditioned medium of PAF- or nonmetabolizable PAF agonist-treated guinea pig bone marrow cells augmented DNA synthesis and induced microbicial activity of bone marrow cells. A PAF specific antagonist, CV-6209, inhibited generation of the active conditioned medium by PAF. Addition of the PAF antagonist only partially suppressed the augmentative effect of the active conditioned medium on DNA synthesis; this is consistent with the fact that, because of the rapid breakdown, no appreciable amount of PAF remained in the conditioned medium of PAF-treated cells. Although mouse bone marrow cells did not respond to PAF unlike guinea pig cells, their DNA synthesis was significantly enhanced by the conditioned medium of PAF-treated guinea pig bone marrow cells. Thus, some newly generated factor(s) distinct from the originally inoculated PAF seemed to modulate the bioactions of PAF on bone marrow cells. An appreciable amount of PAF was produced by calcium ionophore-treated guinea pig bone marrow cells. These findings indicate that PAF synthesized in guinea pig bone marrow cells induces generation in the cells of some factor(s) which affects proliferation or microbicidal activity. Presented at The Third International Conference on Platelet-Activating Factor and Structurally Related Ether Lipids, Tokyo, Japan, May 1989.     

Synthesis, characterization and photocatalytic reactivity of Ti-containing micro- and mesoporous materials

Ti-oxides incorporated within the framework of microporous zeolites and mesoporous molecular sieves were found to exhibit high and unique photocatalytic activity for the decomposition of NO into N₂ and O₂ as well as the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH. Spectroscopic investigations of these catalytic systems using photoluminescence, UV-vis, XAFS (XANES and FT-EXAFS) and IR analyses revealed that the charge transfer excited state of the isolated tetra-coordinated Ti-oxides plays a vital role in these photocatalytic reactions. The reactivity of such Ti-oxides was found to depend strongly on their local structures which were controlled by the unique framework structures of the micro- and mesoporous material supports.     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Free energy perturbation study on a Trp-binding mutant (Ser88 ->Cys) of the trp-repressor

The Ser⁸⁸Cys mutant of the trp-repressor showed a lower affinityfor the corepressor than the wild-type repressor [G = 1.7 ±0.3 kcal/mol, Chou and Matthews (1989) J. Biol. Chem., 264,18314–18319].A molecular dynamics/free energy cycle perturbation study wasperformed to understand the origin of the decreased affinity.A value (G = 1.58 ± 0.28 kcal/mol) comparable with theexperimental value was obtained by the simulation. Free energycomponent analysis revealed that destabilization of the vander Waals interaction between Ser⁸⁸ and Trp¹⁰⁹ (corepressor)mainly contributed to the decreased affinity of the mutant.The rotational transition of the hydroxyl (sulfhydryl) groupof Ser⁸⁸ (Cys⁸⁸) during the simulations affected the contributionsof Arg⁸⁴ and water to the free energy change in the aporepressorand those of Arg⁸⁴ and Trp ¹⁰⁹ to that in the holorepressor.However, the contributions from different residues compensatedeach other, and the total free energy changes were almost invariablein the various simulations.     

Shear-rate dependence of first normal stress difference of poly(isoprene-b-styrene) in solution near the order-disorder transition temperature

Viscoelastic properties of poly(isoprene-b-styrene) in dioctylphthalate under steady shear flow were measured near the order—disorder transition temperature. In ordered states, first normal stress difference N₁ is proportional to shear rate at low region, but becomes proportional to at the high region, similar to the N₁ behaviour of polymer blends undergoing shear-induced homogenization. Because the existence of microdomains was confirmed at the high region by the flow birefringence method, it is concluded that the above N₁ behaviour is not caused by shear-induced homogenization, but is probably caused by the shear-induced alignment of the microdomain structure.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.     

Phase evolution and <110>-orientation mechanism in RTGG-processed BaTiO3 ceramics with electrical properties

The <110>-oriented BaTiO₃ ceramics were fabricated using BaCO₃ matrix and H_1.08Ti_1.73O₄.nH₂O (HTO) template particles, and the mechanism of BaTiO₃ phase formation was investigated. The dielectric, ferroelectric, and piezoelectric properties were also investigated. The transformation of the HTO phase into the TiO₂ bronze or TiO₂ (B) phase was observed at 600°C, where the BaTiO₃ nucleation was accompanied by the formation of a Ba₂TiO₄ phase. The TiO₂ phase reacted with the Ba₂TiO₄ phase at 800°C to give a BaTiO₃ phase, whereas its reaction with the BaTiO₃ resulted in the formation of BaTi₂O₅ phase that got decomposed into BaTiO₃ and Ba₆Ti₁₇O₄₀ phase at sintering temperature ≥1300°C. Sintering with samples’ embedding in BaTiO₃ powders prevented the formation of the Ba₆Ti₁₇O₄₀ secondary phase. The crystallographic orientation along the <110> direction (F₁₁₀) was developed by the epitaxial grain growth mechanism. In addition to the contribution of the grain-size increment for enhancing the F₁₁₀, the preservation of the platelike structure was also found to have a significant impact. The ceramics prepared by the embedded sintering (grain size ≈12.4 µm and F₁₁₀ = 83%) exhibited the room-temperature dielectric constant of 1708 and piezoelectric strain constant of 445 pm/V, which are higher than those of the BaTiO₃ ceramics with randomly oriented grains.     

Applying MHD technology to the continuous casting of steel slab

The application of magnetohydrodynamics (MHD) in the continuous casting process started with the electromagnetic stirring of the stand pool with a traveling magnetic field. It has now advanced to the electromagnetic stirring of molten steel in the mold and the control of molten steel flow by an in-mold direct current magnetic field brake. These applied MHD techniques are designed to further improve the continuous casting process capability. They improve the surface quality of cast steel by homogenizing the meniscus temperature, stabilizing initial solidification, and cleaning the surface layer. They also improve the internal quality of cast steel by preventing inclusions from penetrating deep into the pool and promoting the flotation of argon bubbles. Applied MHD technology is still advancing in scope and methods in addition to the improvement of conventional continuously cast slab qualities. The continuous casting of bimetallic slab by suppressing mixing in the pool is one example of this progress.