On-line sample preconcentration and separation technique based on transient trapping in microchip micellar electrokinetic chromatography

This paper describes a novel on-line sample preconcentration and separation technique named transient trapping (tr-trapping), which improves the efficiencies of separation and concentration by using a partially injected short micellar plug in microchip electrophoresis. Although a longer separation length often provides a better resolution of complexed or closely migrating analytes, our proposed theoretical model indicated that a trap-and-release mechanism enables a short micellar zone, which was partially injected into the separation channel, to work as an effective concentration and separation field. Application of the tr-trapping technique to microchip micellar electrokinetic chromatography (MCMEKC) was performed on a newly fabricated 5-way-cross microchip by using sodium dodecyl sulfate and rhodamine dyes as test micelle and analytes, respectively. When the injection times of micelle (t(inj),M) and sample solution (t(inj),S) were 1.0 and 2.0 s, respectively, both the preconcentration and separation of the dyes were completely finished within only 3.0 s. At t(inj),S of 8.0 s, a 393-fold improvement of the detectability was achieved in comparison with conventional MCMEKC. The resolution obtained with tr-trapping-MCMEKC was also better than that with conventional MCMEKC in spite of the 160-fold shorter length of the injected micellar zone at t(inj),M of 1.0 s. These results clearly demonstrated that the tr-trapping technique in MCMEKC provides a rapid, high-resolution and detectability analysis even in the short separation channel on the microchips.     

HYDRATION AND PHASE SEPARATION OF TEMPERATURE-SENSITIVE WATER-SOLUBLE POLYMERS

Collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating and phase diagrams of aqueous PNIPAM solutions with very fiat LCST phase separation line are theoretically studied on the basis of cooperative dehydration (simultaneous dissociation of bound water molecules in a group of correlated sequence), and compared with the experimental observation of temperature-induced coil-globule transition by light scattering methods. The transition becomes methanol is also studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer-methanol.The downward shift of the cloud-point curves (LCST cononsolvency) with the mole fraction of methanol due to the competition is calculated and compared with the experimental data. Aqueous solutions of hydophobically-modified PNIPAM carrying short alkyl chains at both chain ends (telechelic PNIPAM) are theoretically and experimentally studied. The LCST of these solutions is found to shift downward along the sol-gel transition curve as a result of end-chain association (association-induced phase separation), and separate from the coil-globule transition line. Associated structures in the solution, such as flower micelles, mesoglobules and higher fractal assembly, are studied by USANS with theoretical modeling of the scattering function.     

Suppression of higher harmonics resonance in a distribution system

There are many PWM control devices, which are higher harmonics current sources, in distribution systems, and higher harmonics cause overcurrents by parallel resonance. To avoid overcurrents, it is necessary to suppress resonance. In this paper, a new suppression method, which uses the effect of source connected points in resonance circuits, is proposed. First it shows that the optimal point, which gives a minimum current amplification degree, is orthogonal to the static condenser voltage. Then, using the eigenvector of the state equation, the participation factor is defined. When the participation factor is zero, the orthogonality condition is introduced. Therefore, the optimal point is obtained with the participation factor. Finally, numerical investigation shows that multiple optimal points usually exist. Therefore, we can choose the most advantageous point as a source‐connected node. © 2012 Wiley Periodicals, Inc. Electr Eng Jpn, 182(1): 18–29, 2013; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.22307     

Ex Vivo Expanded and Activated Natural Killer Cells Prolong the Overall Survival of Mice with Glioblastoma-like Cell-Derived Tumors

Glioblastoma (GBM) is the leading malignant intracranial tumor and is associated with a poor prognosis. Highly purified, activated natural killer (NK) cells, designated as genuine induced NK cells (GiNKs), represent a promising immunotherapy for GBM. We evaluated the anti-tumor effect of GiNKs in association with the programmed death 1(PD-1)/PD-ligand 1 (PD-L1) immune checkpoint pathway. We determined the level of PD-1 expression, a receptor known to down-regulate the immune response against malignancy, on GiNKs. PD-L1 expression on glioma cell lines (GBM-like cell line U87MG, and GBM cell line T98G) was also determined. To evaluate the anti-tumor activity of GiNKs in vivo, we used a xenograft model of subcutaneously implanted U87MG cells in immunocompromised NOG mice. The GiNKs expressed very low levels of PD-1. Although PD-L1 was expressed on U87MG and T98G cells, the expression levels were highly variable. Our xenograft model revealed that the retro-orbital administration of GiNKs and interleukin-2 (IL-2) prolonged the survival of NOG mice bearing subcutaneous U87MG-derived tumors. PD-1 blocking antibodies did not have an additive effect with GiNKs for prolonging survival. GiNKs may represent a promising cell-based immunotherapy for patients with GBM and are minimally affected by the PD-1/PD-L1 immune evasion axis in GBM.     

Three‐site mechanism and molecular weight: Time dependency in liquid propylene batch polymerization using a MgCl2‐supported Ziegler‐Natta catalyst

This article demonstrates that the molecular weight of propylene homopolymer decreases with time, and that the molecular weight distribution (MWD) narrows when a highly active MgCl₂‐supported catalyst is used in a liquid pool polymerization at constant H₂ concentration and temperature. To track the change in molecular weight and its distribution during polymerization, small portions of homo polymer samples were taken during the reaction. These samples were analyzed by Cross Fractionation Chromatograph (CFC), and the resulting data were treated with a three‐site model. These analyses clearly showed that the high molecular weight fraction of the distribution decreases as a function of time. At the same time, the MWD narrows because the weight‐average molecular weight decreases faster than the number‐average molecular weight. A probable mechanism based on the reaction of an external donor with AlEt₃ is proposed to explain these phenomena. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1035–1047, 2001     

Relocations are determined by firms' relationships with financing institutions: A paper based on network data for Japanese firms

Both theoretical and empirical research studies the factors influencing firms' location choices. This paper presents a new viewpoint by considering relationship continuity to explain small-scale relocations and relocations of small and medium-sized enterprises (SMEs), which represent the majority of firms. The influences of firms' relationships with financing institutions are studied using a two-stage nested logit model. Consequently, the positive effect of relationships on location choices is revealed and the factors preventing firms from moving are described. The model is valid for estimating relocations to medium-sized cities, and the influences on shrinking firms as opposed to expanding firms are especially strong.     

On criteria for craze initiation in glassy polymers

The previous published data on biaxial critical stresses for craze initiation on the surface of cylindrical specimen of glassy polymers have been reexamined. A new interpretation is presented for the trend of crazing stress near pure shear state in the second quadrant of principal stress space which was observed in air at elevated temperatures. That is, an increase in the tensile stress for crazing with an increase in the magnitude of the compressive stress is interpreted not to be followed by a decrease in the dilatational stress but by development of shear yielding. On the basis of this interpretation, a new empirical criterion for craze initiation is proposed by considering the stress concentration due to surface scratch. The theoretical crazing locus accorded with the previous experimental results, except for the data near the shear yield locus in the second quadrant, which were considered to be affected by shear yielding. It was also indicated in the calculation that the shape and direction of surface scratch exert a considerable influence on the trend of biaxial crazing stress.     

Acid hydrolysis behaviour of microbial cellulose II

A mutant strain of Acetobacter xylinum produces cellulose of anomalous band-like form (‘native band’), and this material has been found to be cellulose II, presumably having a folded-chain structure (according to recent work by Kuga et al.). In addition to the previous results of electron diffraction, X-ray analysis showed that this band material was composed of virtually pure cellulose II. We have studied the acid hydrolysis behaviour of this material to obtain additional evidence for the proposed structure. When hydrolysed with 1 N hydrochloric acid at 100°C, the degree of polymerization (DP) of the material decreased rapidly from 322 ( ) to 18.3 ( ). The latter value (levelling-off DP) corresponds to the observed width (10 nm) of strand-like constituents of the band material. The sample dissolved in and regenerated from 8.75% aqueous sodium hydroxide lost its original characteristic morphology and became irregular-shaped agglomerates. The leveling-off DP of this regenerated sample was 55.2 ( ), a typical value for common regenerated celluloses. These findings as a whole strongly suggest that the cellulose molecules in the native band are selectively cleaved at sharply folded parts by acid, producing fragments of the length of folding periodicity.     

Glycosylphosphatidylinositol-anchor-deficient mice: implications for clonal dominance of mutant cells in paroxysmal nocturnal hemoglobinuria

Paroxysmal nocturnal hemoglobinuria (PNH) is an acquired hematopoietic stem cell disorder characterized by complement-mediated hemolysis. Abnormal hematopoietic cells from patients with PNH are deficient in glycosylphosphatidylinositol (GPI)-anchored proteins and clonally dominate various hematopoietic lineages in the bone marrow and the peripheral blood. Analysis of many patients with PNH has showed that somatic mutation in the X-linked gene PIG-A is responsible for the GPI-anchor deficiency in PNH. The PIG-A mutation must also be relevant to the clonal dominance of GPI-anchor deficient (GPI-) blood cells because two or more PIG-A mutant clones become dominant in many patients. However, whether the PIG-A mutation alone is sufficient for clonal dominance is not known. To address this question, we generated chimeric mice using Pig-a (the murine homologue of PIG-A) disrupted embryonic stem (ES) cells, in which the animals are chimeric with respect to the surface expression of GPI-anchored proteins. The chimerism of hematopoietic and nonhematopoietic tissues in such mice was always low, suggesting that the higher contribution of Pig-a disrupted GPI- cells had a lethal effect on the chimera. GPI- cells appeared in the peripheral blood of some of the chimeric mice. However, the percentage of GPI- erythrocytes did not increase for 10 months after birth, implying that the Pig-a mutation alone does not immediately cause the clonal dominance of GPI- blood cells; another pathologic or physiologic change(s) in the hematopoietic environments or in the clone itself may be necessary.