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Background and aims Immunoglobulin 4 (IgG4)-related disease (IgG4-RD) is a lymphoproliferative disorder characterized by elevated serum IgG4 levels and tissue infiltration of IgG4-positive plasma cells. We analyzed the serum proteins, whose levels varied based on the disease state and treatment. Materials and methods Serum proteins from patients with IgG4-related disease and healthy subjects were resolved using two-dimensional electrophoresis, silver-stained, and scanned. Alternatively, the proteins were labeled with Cy2, Cy3, and Cy5 before electrophoresis. The proteins, whose expression differed significantly between patients and healthy individuals, and between before and after steroid treatment, were identified and validated using enzyme-linked immunosorbent assays. Results Pre-treatment sera from patients with IgG4-related disease was characterized by increased levels of immunoglobulins such as IgG1, IgG4; inflammatory factors such as α-1 antitrypsin (A1AT); and proteins associated with immune system regulation such as clusterin and leucine-rich α-2-glycoprotein (LRG-1). The serum levels of A1AT, LRG-1 and clusterin, during treatment with prednisolone for up to 12 months revealed that LRG-1 levels were halved after 1 month of treatment, comparable to those in healthy subjects; LRG-1 levels remained normal until the end of treatment. Conclusion LRG-1 could serve as a novel biomarker of IgG4-related diseases.

The carbonyl reductase from the methylotrophic yeast Ogataea minuta can catalyze the regio- and enantio-selective reduction of prochiral ketones to chiral alcohols, and is available for industrial manufacturing of statin drugs. We previously conducted a directed evolution experiment of the enzyme, and obtained a mutant (OCR_V166A) with improved tolerance to organic solvents. This expanded the applicability of the enzyme to the bioconversion of water-insoluble compounds (Honda et al., J. Biosci. Bioeng., 123, 673-678, 2017). In the present study, we expressed OCR_V166A in Rhodococcus opacus cells, which have a highly lipophilic surface structure and are dispersible in anhydrous organic solvents, and developed a whole-cell biocatalyst which can function in an organic-solvent-based reaction medium. The secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus (TeADH) was employed as an NADPH-regenerating enzyme and co-expressed with OCR_V166A in R. opacus. The whole-cell bioconversion of 2,2,2-trifluoroacetophenone to α-(trifluoromethyl)benzyl alcohol was performed in organic solvents, including isopropanol, isobutanol, and cyclohexanol, which served both as reaction media and as substrates for TeADH. The type of organic solvents markedly affected not only the product titer but also the enantio-purity of the product. When isobutanol was used as the reaction medium, the whole-cell biocatalyst showed higher stability than the isolated enzyme. Consequently, a high concentration (1 M) of the substrate was converted to the product with an overall conversion yield of 81% (mol/mol) in 24 h.

The diagnosis of myelodysplastic syndromes (MDS) is based on morphology and cytogenetics. However, limited information is currently available on the interobserver concordance of the assessment of dysplastic lineages (10% or ≥10% in bone marrow (BM)). The revised International Prognostic Scoring System (IPSS-R) described a new threshold (2%) for BM blasts. However, the interobserver concordance of the categories (0-≤2% and2-5%) has limited data. The purpose of the present study was to investigate the assessment of dysplastic lineages and IPSS-R reproducibility. Our study was divided into two Steps. In each Step, the microscopic examinations were performed separately by two morphologists. Regarding the category of BM blasts ≤2% and2-5%, interobserver agreement was more than 'moderate' in all pairs (kappa test: 0.43-0.90). Regarding dysgranulopoiesis (dysG) and dyserythropoiesis (dysE) in BM, interobserver agreement was more than 'moderate' in all pairs (kappa test, dysG: 0.45-0.96, dysE: 0.45-0.81). Regarding the category of dysmegakaryopoiesis (dysMgk) in BM, interobserver agreement was more than moderate in 4 out of 5 pairs (kappa test: 0.58-1.00), and was fair for one pair (kappa test: 0.37). We consider that high interobserver concordance may be possible for the BM blast cell count (≤2% or2-5%) and dysplasia (10% or ≥10%) of each lineage.

We investigated the Sr–Nd–Hf–Pb isotope compositions of clinopyroxene separates and strongly leached bulk rock powders from the basalt lavas on Raivavae Island in the South Pacific. These data allowed us to explore the magma chamber processes of the two basalt groups: the high-μ-type (μ = 238 U/204Pb, HIMU) Rairua basalts erupted at ~ 9 Ma, and the depleted mantle (DM)-type Anatonu basalts erupted at ~ 6 Ma. We assessed different analytical techniques for clinopyroxene sample treatment, including leaching, sample digestion, chemical separation, and determination of parent/daughter ratios for use in age corrections. The age-corrected initial Sr–Nd–Hf isotope compositions of clinopyroxene samples solely overlap on the bulk rock compositions of each basalt type. The initial Pb isotope compositions show significant differences between the clinopyroxenes and bulk rock samples in both the Rairua and Anatonu basalts. The clinopyroxenes have less radiogenic Pb than their hosts, reflecting the magma chamber processes. The overall variations in the bulk rock Pb isotopes are explained by mixing of melts from the HIMU- and DM-type sources in the plume. In detail, early stage Rairua magma was more influenced by DM melts from which Rairua clinopyroxene was crystallized. Subsequent supply of dominant HIMU melts drove the bulk rock magma chemistry more HIMU-like. The Anatonu DM magma was largely from depleted mantle that differs from the Pacific MORB source. Subordinate contribution of a Pacific alkali-basalt-like component is suggested from the clinopyroxene chemistry of Anatonu perhaps from impregnated pyroxenite in the lithospheric mantle.

Magnesium isotopic fractionation during basalt differentiation is commonly thought to be negligible at current levels of analytical precision. However, Mg isotopic variation of ∼ 0.4 ‰ ( δ 26 Mg) can be observed in some highly evolved volcanic rocks with MgO contents of δ 26 Mg range (−0.23‰ to −0.32‰), while the evolved rocks saturated with Fe–Ti oxides (MgO δ 26 Mg vary to higher ( − 0.14 ‰ ) or lower ( − 0.36 ‰ ) values relative to mantle value ( δ 26 Mg = − 0.25 ± 0.04 ‰ ). For most of the Fe–Ti oxide saturated samples, their δ 26 Mg values are positively correlated with TiO2 contents and Ti/Ti* ratios and negatively correlated with total-alkali contents. This indicates that detectable Mg isotopic fractionation occurred in MgO-poor samples, probably through fractional crystallization of Mg-bearing Fe–Ti oxides. Further Mg isotopic analysis of Fe–Ti oxide phenocrysts (titanomagnetite) in the evolved samples reveals that titanomagnetite has remarkably higher δ 26 Mg value (+0.15‰ to +0.52‰) than the corresponding bulk sample and silicate minerals. Fractional crystallization of such isotopically heavy titanomagnetite is thus expected to drive the residual magma progressively enriched in light Mg isotopes. In order to reproduce the observed Mg isotopic variation in St. Helena evolved samples, quantitative modeling requires a titanomagnetite-melt Mg isotopic fractionation factor ( Δ 26 MgTi-Mgt−melt) of ∼0.6 ‰, which is among our measured δ 26 Mg difference value (0.41–0.73‰) between titanomagnetite and bulk samples. When combining our results with published data for alkaline lavas from the Antipodes volcano (New Zealand), contrasting patterns of Mg isotope fractionation emerge during late-stage basalt differentiation. Quantitative modeling shows that the positive and negative δ 26 Mg–MgO correlations shown by evolved lavas could be related to segregation of isotopically heavy titanomagnetite and isotopically light ilmenite, respectively, depending on redox state of the magma system. Therefore, this study highlights that basalt differentiation involving separation of Fe–Ti oxides may induce resolvable Mg isotopic fractionation, and the δ 26 Mg values of compositionally evolved rocks should be used with caution in studies of petrogenesis.

We studied a 107 Ma vogesite (a kind of lamprophyre with alkali-feldspar > plagioclase, and hornblende ± clinopyroxene ± biotite) dike in the Kinki district of the Tamba Belt, Kyoto Prefecture, SW Japan, using petrography, mineralogy, K–Ar ages, and geochemistry to evaluate its petrogenesis and tectonic implications. The dike has the very specific geochemical characteristics of a primitive high-Mg basalt, with 48–50 wt.% SiO2 (anhydrous basis), high values of Mg# (67.3–72.4), and high Cr (~ 431 ppm), Ni (~ 371 ppm), and Co (~ 52 ppm) contents. The vogesite is alkaline and ne-normative with high concentrations of large ion lithophile elements (LILEs: Sr = 1270–2200 ppm, Ba = 3910–26,900 ppm), light rare earth elements (LREEs) [(La/Yb)n = 58–62), and high field strength elements (HFSEs: TiO2 = 1.5–1.8 wt.%, Nb = 24–33 ppm, Zr = 171–251 ppm), and the vogesite can be classified as a high-Nb basalt (HNB). The vogesite was formed by the lowest degree of melting of metasomatized mantle in the garnet stability field, and it may also have been formed at higher melting pressures than other Kyoto lamprophyres. The low degree of melting is the primary reason for the high-Nb content of the vogesite, not mantle metasomatism, and a higher degree of melting would have changed the primary magma composition from a HNB to a Nb-enriched basalt (NEB). The vogesite magma was contaminated at an early stage of its development by melts derived from sediments drawn down a subduction zone, as indicated by some geochemical indices and the initial Nd isotope ratios. The vogesite exhibits positive correlations between eSr(107 Ma) values (5.4–50.9) and its high Ba and Sr concentrations, and it has a limited range of eNd(107 Ma) values (+ 0.97 to + 2.4). The fact that the vogesite contains centimeter-sized xenoliths of chert, which are composed of polycrystalline quartz, calcite, barite, pyrite, and magnetite, indicates that the barium contamination took place during the ascent of the lamprophyric magma through the upper crust. The episode of magmatism at c. 107 Ma extended regionally from the Kinki district, through the Chugoku district and North Kyushu in SW Japan, to Korea as a result of slab roll-back at the eastern margin of Asia.

The Outer Zone of the SW Japan and northernmost Ryukyu arcs was affected by intense igneous activity during the Miocene, characterized by MORB-like basalts, alkaline basalts, and S-type (with subordinate I-type) felsic to intermediate volcano-plutonic complexes. These igneous rocks are inferred to be the products of near-trench magmatism. Early Miocene (∼18 Ma) alkaline basalt dikes from the Shingu–Otoyo area in central northern Shikoku, and an alkaline lamprophyre dike from Tanegashima, one of the northernmost Ryukyu Islands, pre-date the Middle Miocene felsic to intermediate igneous rocks. The basalts and lamprophyre have compositions of basanite, basalt, trachybasalt and phonotephrite. They are characterized by elevated large-ion lithophile elements (LILEs; e.g., Sr, Ba, and Th) and high concentrations of high-field strength elements (HFSEs; e.g., TiO 2 , Nb, and Zr). The geochemical signatures of the basalts and lamprophyre suggest an ocean island basalt-type (OIB-type) mantle source. The occurrence of alkaline basalts and lamprophyre with OIB-type, intraplate geochemical signatures in a near-trench setting is unusual with regard to plate tectonic processes. We propose that trench-ward motion of the overriding plate during the period around the Early Miocene resulted in a shallowly dipping slab, and interplate coupling between the subducting Philippine Sea Plate (PSP) and the overlying crust beneath most of the Outer Zone in the western part of SW Japan and the northernmost Ryukyu Islands. The OIB-type magmatism in the near-trench environment is most plausibly explained by the upwelling of asthenospheric material from beneath the subducting slab, which migrated through fractures and/or tears in the slab. We envisage two possible scenarios for the formation of these fractures or tears: (1) the shallowing dip angle of the subducted PSP resulted in concave-upwards flexure of the slab, generating fractures in the flexed region; and (2) differential motion within the subducting slab induced slab tearing and segmentation.

Chemical compositions of Fe-Mg biotite have been used to understand the petrogenesis of metamorphic and igneous rocks. However, biotite is affected by sub-solidus hydrothermal alteration, metamorphism, and chemical exchange with other common coexisting phases such as garnet and muscovite. Therefore, the interpretation of igneous and metamorphic processes using biotite compositions is not always straightforward. Here we compare biotite compositions in igneous rocks, meta-igneous rocks, and meta-sedimentary rocks from localities in northeast (Dehnow, Khalaj, Khajeh Morad) and central (Jandaq and Airekan) Iran, with similar rock types in the global GEOROC database and from other localities, in order to constrain associated petrogenetic classification schemes. We find important compositional contrasts in biotite associated with muscovite and/or garnet (in both igneous and metamorphic rocks), suggesting careful use of common discrimination schemes. For example, magmatic biotite associated with garnet and/or muscovite (i.e., Bt + Ms, Bt + Ms + Grt, Bt + Grt) is often enriched in Al and depleted in Fe, Mg, and Ti, likely due to crystallization prior to muscovite but synchronous with or following garnet crystallization. Metamorphic biotites in garnet- and/or muscovite-bearing rocks tend to be enriched in Ti, Fe, and Mg and depleted in Al. The contrasting compositional behavior of magmatic and metamorphic biotites also poses problems for garnet-biotite, biotite-muscovite, and Ti-in-biotite thermometers. Our analysis indicates that biotite rare earth and trace element concentrations are strongly influenced by co-existing garnet and muscovite. When magmatic biotite crystallization occurs with muscovite and garnet, HREE concentrations respectively decrease and increase.

Virus-associated hemorrhagic cystitis (VAHC) is a formidable complication after allogeneic hematopoietic stem cell transplantation (allo-HSCT). The standard management of severe VAHC after allo-HSCT has not been established. Intravenous administration of cidofovir (CDV), an acyclic nucleoside analogue with broad-spectrum activity against DNA viruses, has been reported to be effective for VAHC, but it can cause severe renal toxicity. Here we report four cases who achieved clinical responses with intravesical instillation of CDV for severe VAHC after allo-HSCT. Median age was 57 years (40-63), and all were male. The underlying diseases were hematological malignancies. Three had received bone marrow transplantation, and one received cord blood transplantation twice. Conditioning regimen was myeloablative for one, and reduced-intensity for three. The viral types were BK virus and/or adenovirus. Two patients had received CDV intravenously prior to the intravesical therapy. A dose of intravesical CDV was 2-5 mg/kg. In all cases, symptoms of cystitis improved dramatically within a few days without showing any systemic adverse effects. The virological response was observed in two cases. This local therapy was effective even in the cases refractory to the intravenous CDV and a case with severe renal failure. Along with the review of literature, we propose that the intravesical instillation of CDV can be a therapeutic option for severe VAHC after allo-HSCT.

Electronic structures and formation mechanism of hydrogen functionalized carbon nanotube (CNT) have been investigated by means of density functional theory (DFT) method. The mechanism of hydrogen addition reaction to the CNT surface was also investigated. Pure and boron-nitrogen (BN) substituted CNT (denoted by CNT and BN-CNT, respectively) were examined as the carbon nanotubes. It was found that the additions of hydrogen atom to B (boron atom) and C (carbon atom) sites of BN-CNT proceed without activation barrier, whereas the hydrogenation of N (nitrogen atom) site needs the activation energy. The electronic states of hydrogen functionalized CNT and BN-CNT were discussed on the basis of theoretical results.

During the Integrated Ocean Drilling Program (IODP), a total of 41.54 m of basement rock, consolidated volcaniclastic sediment, was recovered beneath a thin sediment cover. The drilled site is at the eastern end of the crestal area of Bowers Ridge, a north and westward sweeping offshoot of the Aleutian Arc into the Bering Sea. The volcanic sequence recovered from Holes U1342A and U1342D was divided into six major lithologic units. We used the single grain 40 Ar– 39 Ar dating method performed by step-wise heated laser fusion technique to date andesites of Unit 1. Thereby two ages of Oligocene volcanism (34–32 Ma, 28–26 Ma) were distinguished each other according to our 40 Ar– 39 Ar data. These ages refute a hypothesized Cretaceous origin in the North Pacific as an exotic arc massif or sector of the Hawaiian-Emperor chain and indicate that the Bowers Ridge is a Bering-Sea formed arc or remnant arc that ceased forming in the latest Oligocene to the earliest Miocene time.

The electronic states and band gaps of carbon materials such as graphene, fullerene, and carbon nanotubes are strongly affected by radical addition. In the present study, the reactions of graphene nanoflakes with fluorine (F) atoms were investigated by density functional theory (DFT) in order to elucidate the nature of the bonding between the F atoms and the graphene nanoflakes. Graphene nanoflakes composed of 4–37 benzene rings were used as graphene models. The present calculations reveal that F atoms react with graphene surfaces and bind directly to carbon atoms to form strong C–F bonds. The binding sites are locally Cδ+-Fδ– polarized and have large dipole moments. The binding energy of F to graphene was calculated to be 30 kcal/mol, which is 1.5 times larger than that for the addition of hydrogen. Fluorine atoms also add to these surfaces without activation barriers, which is very different to hydrogen-addition reactions that have barriers of 5–6 kcal/mol. The electronic states of the fluorinated graphenes are discussed on the basis of the theoretical results.

Structures and electronic states of organic–inorganic compound of 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) with alkali metals, Mn(NTCDA) (M Li and Na, n = 0–2), have been investigated by means of hybrid density functional theory (DFT) calculations. From the DFT calculations, it was found that the electronic state of the complex at the ground state is characterized by a charge-transfer state expressed by (M)+(NTCDA)−. The alkali metals were bound equivalently to the carbonyl oxygen and ether oxygen atoms of NTCDA. The C O double bond character of NTCDA was changed to a C–O single bond like character by the strong interaction of M to the C O and O sites. This change was the origin of the red-shift of the IR spectrum. The UV–vis absorption spectra of Mn(NTCDA) were theoretically predicted on the basis of theoretical results.

HIMU (high- μ ; 238 U/ 204 Pb) is a mantle reservoir that has been thought to form by subduction and subsequent storage of ancient oceanic crust and lithosphere in the mantle. In order to constrain the processes that acted on subducted materials over several billion years, we present precise Pb–Sr–Nd–Hf–He isotopic data together with 40 Ar/ 39 Ar and K/Ar ages of HIMU lavas from St. Helena in the Atlantic. Clinopyroxene separates were analyzed together with whole-rock samples to better describe the geochemical characteristics of the HIMU component. Although isotopic variations are small in the St. Helena lavas (20.6–21.0 for 206 Pb/ 204 Pb) between 12 and 8 Ma, the younger lavas have more HIMU-like isotopic compositions than the older lavas. The mixing arrays defined by these lavas are remarkably similar to those observed in HIMU lavas from Austral Islands in the Pacific, suggesting that the two HIMU reservoirs located in different mantle domains are characterized by similar isotopic compositions with radiogenic 206 Pb/ 204 Pb and 208 Pb/ 204 Pb, enriched Nd and Hf isotopes, depleted Sr isotopes, and radiogenic 3 He/ 4 He. However, there is a significant difference between the St. Helena and Austral Islands lavas in 207 Pb/ 204 Pb. The St. Helena lavas show systematically higher 207 Pb/ 204 Pb for a given 206 Pb/ 204 Pb. Lead isotope evolution models suggest that both HIMU reservoirs formed around 2 Ga; however, the HIMU reservoir for St. Helena is about 0.3 Ga older than that for Austral Islands. The relation between 206 Pb/ 204 Pb and 208 Pb/ 204 Pb could reflect the time-integrated κ ( 232 Th/ 238 U) in the components. The HIMU components for St. Helena and Austral Islands have κ values between 3.3 and 3.7, which are intermediate between the present-day fresh mid-ocean ridge basalts (MORB; 2.6–3.2) and the chondritic silicate Earth (∼4). This is consistent with the model that the HIMU precursor is subducted oceanic crust created around 2 Ga from depleted upper mantle, in which κ monotonously decreased from the chondritic to the present-day values since late Archean or early Proterozoic, because of enhanced U recycling from the Earth’s surface back to the mantle in response to the increasing oxygen levels in the hydrosphere. Moreover, the fact that the HIMU components have much higher κ than the present-day hydrothermally altered MORB (0.2–2) suggests that either the HIMU precursor was an unaltered ancient oceanic crust, or more likely, an altered oceanic crust with minimal U enrichment by hydrothermal fluids in the less oxic marine environment of the late Archean or early Proterozoic. The unradiogenic 87 Sr/ 86 Sr of the HIMU components also suggests formation of ancient oceanic crust altered with hydrothermal fluids having much lower 87 Sr/ 86 Sr in that eon than at present, followed by removal of Rb from it by subduction dehydration.

Through-space electron transfer between the benzene rings of [3 n ]cyclophanes, n = 2 – 5, was investigated using density functional theory calculations, CAM-B3LYP/6-311++G**. An external point charge, q , was placed on the axis perpendicular to a benzene ring of the cyclophane molecule. The dependence of the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap and bond overlap population (BOP) of cyclophanes on the values of q and n are discussed. The HOMO–LUMO gap generally decreases as q decreases and n increases. It is found from the BOP analysis that electron transfer occurs mainly through LUMO + 2 for n = 2, LUMO for n = 3 and n = 4, and LUMO + 4 for n = 5. The result that the values of the BOP for n = 2 and 5 increase as q decreases means that the through-space electron transfer is enhanced by the negative charge on the neighboring molecule in the solid.

The effects of hydrogenation on the band gap of graphene have been investigated by means of density functional theory method. It is generally considered that the band gap increases with increasing coverage of hydrogen atom on the graphene. However, the present study shows that the band gap decreases first with increasing hydrogen coverage and reaches the lowest value at finite coverage (γ = 0.3). Next, the band gap increases to that of insulator with coverage from 0.3 to 1.0. This specific feature of the band gap is reasonably explained by broken symmetry model and the decrease of pi-conjugation. The electronic states of hydrogenated graphene are discussed.

Energy gap, Mulliken population, and bond-overlap population analyses were carried out to investigate the intermolecular interaction modulation in pentacene clusters by neighboring artificially charged pentacene molecules, which model a charge-carrier injection into a crystal. Two common pentacene clusters, type-1 and type-2, obtained from the crystal structure of pentacene, were examined. A larger decrease in the band gap was observed for the type-2 orientation, whereas a positive intermolecular interaction was observed for the type-1 cluster. Both closing of the energy gap and the positive intermolecular interaction (bonding nature) were found only in the extreme n-type state.

The feasibility of oceanic igneous crust melting in stagnant slabs has previously been proposed from experimental petrological research. However, geochemical evidence for such melting has not yet been found from igneous rocks. We present evidence to suggest that melts from the igneous layer in the stagnant Pacific slab contributed to the source composition of basalts erupted in eastern China. Fe-rich (> 13 wt.%), Si-poor (

Hydrogen transfer reactions at the ground and excited states of tert-butyl radical to form iso-butyl radical have been investigated by means of ab initio calculation and electron spin resonance (ESR) spectroscopy. It was found that tert-butyl radical irradiated with 254 nm ultraviolet light converts quite efficiently to iso-butyl radical. Also, it was suggested that this conversion occurs as an intramolecular hydrogen transfer from a methyl group of tert-butyl radical to a radical site (central carbon atom). The theoretical calculations showed that barrier height of hydrogen transfer at the excited state is significantly lower than that of ground state. The mechanism of internal hydrogen atom conversion from tert-butyl to iso-butyl radicals was discussed.

Electron trapping behavior at the interface between N , N ′-ditridecyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C13) film and thermal SiO 2 was investigated by utilizing ultrathin poly(methyl methacrylate) (PMMA) gate passivation layers. From the capacitance–voltage analysis for the PTCDI-C13/PMMA/SiO 2 interface, it is found that the electron tunneling appeared with PMMA thinner than 0.8 nm, and that the thickness of the gate passivation layer should be at least 1 nm for preventing injection-type hysteresis in the capacitance–voltage curve. The effective electron mobility of organic thin-film transistors (OTFTs) based on PTCDI-C13 with SiO 2 gate insulator was increased by suppressing shallow-level interface traps on SiO 2 with the PMMA layer, which can be partially accounted for by the multiple trap and release model. In this work, the thickness and the density of the PMMA layers were precisely controlled with a simple spin-coating process. Even 1.3-nm thick PMMA layer caused the improvements of the electron mobility and the air stability of the n -channel conduction.

N -channel operation of pentacene thin-film transistors with ultrathin poly(methyl methacrylate) (PMMA) gate buffer layer and gold source–drain electrode was observed. We prepared pentacene thin-film transistors with an 8-nm thick PMMA buffer layer on SiO 2 gate insulators and obtained electron and hole field-effect mobilities of 5.3 × 10 −2 cm 2 /(V s) and 0.21 cm 2 /(V s), respectively, in a vacuum of 0.1 Pa. In spite of using gold electrodes with a high work function, the electron mobility was considerably improved in comparison with previous studies, because the ultrathin PMMA film could decrease electron traps on SiO 2 surfaces, and enhance the electron accumulation by applied gate voltages.

Hybrid density functional theory (DFT) calculations have been carried out for oligomer species of a fused porphyrin, denoted by P(n), where n represents the number of porphyrin rings in the oligomer, to elucidate the electronic structures at ground and excited states. A polymer of fused porphyrin (p-Por) was also investigated using one-dimensional periodic boundary conditions (PBC) for comparison. It was found that the lowest energy band is located below 0.6 eV in the case of oligomers larger than n = 8, which corresponds to a band gap of p-Por. Carrier transport pathways in p-Por were discussed on the basis of theoretical results.

The structures and electronic states of sodium ion (Na + ) trapped on the graphene have been investigated by means of density functional theory (DFT) calculation to elucidate the nature of interaction between Na + and the graphenes. In addition, direct molecular orbital-molecular dynamics (MO-MD) calculation [Tachikawa, J. Phys. Chem. C, 112 (2008) 10193] was applied to diffusion processes of the Na + ion on graphene. The graphene composed of 37 benzene rings was used as a model of graphene. The B3LYP/LANL2MB calculation showed that the sodium ion is stabilized in hexagonal site and is located at ca. 2.230 A from the graphene surfaces. The direct MO-MD calculation showed that the Na + ion diffuses freely on the graphene surface, but the ion did not approach the edge region due to the fact that a high potential barrier exists near the edge region. The nature of interaction between Na + and graphene was discussed on the basis of theoretical results.

The usefulness of the difluoromethylene fullerenes C 60 (CF 2 ) n ( n = 1, 2) materials for the organic devices is theoretically discussed, comparing with C 60 , about the following three points: electron transport in the material, electron injection from the electrode into the material, and thin-film formation of the material. Concerning the thin-film formation, dipole moments are calculated. Frontier orbital energies and adiabatic electron affinities are discussed in connection with the electron injection from the electrode into the material. Additionally, the inter-molecular electron transport is discussed from the viewpoint of the reorganization energy based on the Marcus theory. These results indicate the usage of some C 60 (CF 2 ) n isomers as the useful electron-transport materials.

The association of iron overload with complications of allogeneic hematopoietic stem cell transplantation (HSCT) has been suggested in previous studies. Because hepcidin plays a central role in the regulation of iron homeostasis, we analyzed the association between pretransplant serum hepcidin-25 levels and early infectious complications after allogeneic HSCT. We studied 55 consecutive adult patients with a median age of 47 years (range: 20–64 years) who underwent allogeneic HSCT for hematologic malignancies at our institution. Thirty-two patients had myelogenous malignancies; the remaining 23 had lymphogenous malignancies. The median pretransplant serum hepcidin level of patients in the study was 21.6 ng/mL (range: 1.4–371 ng/mL), which was comparable to that of healthy volunteers (median: 19.1 ng/mL [range: 2.3–37 ng/mL]; n=17). When cumulative incidences of documented bacterial and cytomegalovirus (CMV) infections at day 100 were compared according to pretransplant hepcidin-25 levels, the incidence of bacterial, but not CMV, infection, was significantly higher in the high-hepcidin group (≥50 ng/mL; n=17) than in the low-hepcidin group (

DNA repair reactions of the thymine dimer (T) 2 following the hole capture have been investigated by means of direct ab initio molecular dynamics (MD) method in order to elucidate the mechanism of repair processes of thymine dimer interacting with a photo-enzyme. The thymine dimer has two C–C single bonds between thymine rings at neutral state expressed by (T T). After the hole capture of (T T), one of the C–C bonds was preferentially broken, while the structure of (T T) + was spontaneously changed to an intermediate having a C–C single bond expressed by (T–T) + . Time scale of the C–C bond breaking and formation of the intermediate was estimated to be 60–180 fs. The mechanism of repair reactions of the thymine dimer was discussed on the basis of theoretical results.

Hybrid density functional theory calculations have been carried out for the organic–inorganic hybrid complex of 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) with an indium atom (In) to elucidate the degradation mechanism of thin films of molecular organic semiconductors by water molecules. This compound has been used as an organic semiconductor. The band gap of NTCDA was calculated to be as high as 3.39 eV as a single molecule, whereas a new band of NTCDA was formed as low-lying excited state (1.64 eV) after the interaction with the In atom. The water molecule attacked preferentially the In atom of In-NTCDA, and the solvation structure was formed around the In atom (solvation). Further addition of a water molecule to the system, the In atom is stripped off from NTCDA by water molecules, and solvation shell around the In atom is formed (separated solvation). The hydrogen-bond network was broken by the formation of solvation shell. The mechanism of degradation of the electron conductivity has been discussed on the basis of theoretical results.

The electronic states of sodium ion (Na+) trapped on the model surfaces of amorphous carbon have been investigated by means of hybrid density functional theory (DFT) calculations to elucidate the nature of interaction between Na+/Na and the amorphous carbon surfaces. Also, direct molecular orbital–molecular dynamics (MO–MD) calculation [Tachikawa and Shimizu, J. Phys. Chem. B, 110 (2006) 20445] was applied to diffusion processes of the Na+ ion on the model surface of amorphous carbon. Seven models of graphene sheets (n = 7, 14, 19, 29, 37, 44 and 52, where n means numbers of rings in each carbon cluster) were considered in the present study. The B3LYP/LANL2MB calculations showed that the sodium ion is located at 2.24–2.26 A from the graphene surfaces. The direct MO–MD calculations showed that the Na+ ion diffuses freely on the surface above 300 K. At higher temperature (1100 K), the Na+ ion moved from the center to edge region of the model surface. The nature of the interaction between Na+ and the amorphous carbon surfaces was discussed on the basis of theoretical results.

Hybrid density functional theory (DFT) calculations have been carried out for neutral and radical cation of fused furan oligomer, denoted by F(n) where n means number of furan rings in the oligomer, to elucidate the electronic structures at ground and low-lying excited states. A polymer of fused furan was also investigated using one-dimensional periodic boundary condition (PBC) for comparison. It was found that the reorganization energy of radical cation of F(n) from vertical hole trapping point to its relaxed structure is significantly small. Also, the reorganization energy decreased gradually with increasing n, indicating that F(n) has an effective hole transport property. It was found that the cation radical of F(n) has a low energy band at near IR region, which is strongly correlated to hole conductivity. The relation between the electronic states and hole conductivity was discussed on the basis of theoretical calculations.

Structures and electronic states of paramagnetic species in co-deposit film composed of 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) and aluminum (Al) have been investigated by means of hybrid density functional theory (DFT) calculations to determine the species in detail. Al–NTCDA 1:1 complex, 1:3 Al 3 –NTCDA complex and an Al metal bridged dimer Al–(NTCDA) 2 were examined as paramagnetic species of Al–NTCDA complexes. The simulated electron paramagnetic resonance (EPR) spectra of the 1:3 complex and the dimer were in reasonable agreement with experiment reported previously by Tachikawa et al. [Tachikawa et al., J. Phys. Chem. B 109 (2005) 3139]. It was found that the contribution from the 1:1 complex to the EPR spectra was very small. From the comparison with theoretical and experimental UV and EPR spectra, it was found that several paramagnetic and diamagnetic species exist in the co-deposit film of Al/NTCDA. The structures and electronic states were discussed on the basis of theoretical results.

The electronic states of radical cations of oligo[methyl(phenyl)silane] (OMPSi+) with all trans form (n = 2–8, where n is number of monomer unit of OMPSi) have been investigated by means of density functional theory (DFT) calculation to shed light on the mechanism of hole-transport in oligosilanes with phenyl group in the side chain. For the shorter oligomers (n

Hybrid density functional theory (DFT) calculations have been carried out for neutral, radical cation and dication of permethyl-oligosilane, Si n (CH 3 ) 2 n +2 ( n = 4–30), to elucidate the electronic structures at ground and low-lying excited states. It was found that a hole is distributed in both the Si–Si skeleton (main chain) and methyl group (side chain) in the case of shorter chain-lengths below n = 6, whereas the spin density (hole) in the methyl group becomes significantly smaller in longer chain-lengths ( n > 7). The IR-band of radical cation were assigned on the basis of theoretical calculations.

The structures and electronic states of phenyl-capped terthiophene (denoted by P3T) and the ionic species of P3T have been investigated by means of density functional theory (DFT) and direct MO dynamics calculations. P3T is one of the high-performance molecular devices, which has been utilized as a semi-conductor. The calculations indicated that the neutral P3T has a non-planar structure whose the phenyl rings in both ends of thiophene chain are largely deviated from the molecular plane. The cation and anion radicals, dication and dianion were considered as its ionic states. The structure for cation radical of P3T is close to more planar than that of neutral P3T. The structures for anion radical, dication and dianion take a pure planar structure. The first excitation energy of neutral P3T is calculated to be 2.90 eV at the TD-B3LYP/6-31G(d)//B3LYP/6-311+G(d) level, while the P3T cation and anion radicals have lower excitation energies (1.22 and 1.10 eV, respectively). The direct MO dynamics calculation showed that neutral, cation and anion hold near planar structure at 300 K. On the other hand, oligothiophene (n = 5) and its ionic species are strongly deformed from the planar structure, and thiophene rings in both ends of chain rotate rapidly by thermal activation. The mechanism of the electron conductivity in P3T was discussed on the basis of theoretical results.

Hybrid density functional theory (DFT) calculations have been carried out for the nitric oxide NO molecule on the Cu model cluster in order to shed light on the diffusion mechanism of the NO molecule on the Cu(100) cluster model surface. The metal surface was represented approximately by a finite metal cluster Cu 9 . Three binding sites, ‘two-fold site’, ‘four-fold site’, and ‘on-top site’, were considered in the present study. In two-fold site, NO binds to two Cu atoms in the shorter Cu–Cu bond of the surface, whereas NO in four-fold site was bound in the longer Cu–Cu bond and interacts with four Cu atoms. The binding energies of NO were larger in the order, on-top

Calc-alkaline intermediate rocks are spatially and temporally associated with high-Mg andesites (HMAs, Mg#>60) in Middle Miocene Setouchi volcanic belt. The calc-alkaline rocks are characterized by higher Mg# (strongly calc-alkaline trend) than ordinary calc-alkaline rocks at equivalent silica contents. Phenocrysts in the intermediate rocks have petrographical features such as: (1) coexisting reversely and normally zoned orthopyroxene phenocrysts in single rock; (2) sieve type plagioclase in which cores are mantled by higher An%, melt inclusion-rich zone; and (3) reversely zoned amphibole phenocrysts with opacite cores. In addition, mingling textures and magmatic inclusions were observed in some rocks. These petrographic features and the mineral chemistry indicate that magma mixing was the most important process in producing the strongly calc-alkaline rocks. The core composition of normally zoned orthopyroxene phenocrysts and the mantle composition of reversely zoned orthopyroxene phenocrysts have relatively high Mg# (85–90) in maximum. Although basaltic and high-Mg andesitic magmas are candidate as possible mafic end-member magmas, basaltic magma is excluded in terms of phenocryst assemblage and bulk composition. HMA magmas are suitable mafic end-member magmas that precipitated high Mg# (∼90) orthopyroxene, whereas andesitic to dacitic magma are suitable felsic end-members. In contrast, it is difficult to produce the strongly calc-alkaline trend through fractional crystallization from a HMA magma, because it would require removal of plagioclase together with mafic minerals from the early stage of crystallization, whereas the precipitation of plagiolase is suppressed due to the high water content of HMA magmas. These results imply that Archean Mg#-rich TTGs (>45–55), which are an analog of the strongly calc-alkaline rocks in terms of chemistry and magma genesis, can be derived from magma mixing in which a HMA magma is the mafic end-member magma, rather than by fractional crystallization from a HMA magma.

It was found that lanthanum metal caused the dehalogenation of o -dihalogen substituted arenes and α,α′-dihalogen substituted o -xylenes to generate the corresponding benzynes and o -quinodimethanes. When o -dihalogen substituted arenes were allowed to react with lanthanum metal in the presence of dienes, the Diels–Alder products between benzyne and dienes were formed in moderate to good yields. Similarly, the Diels–Alder adducts of o -quinodimethane with dienophiles were obtained, in the reaction of α,α′-dibromo- o -xylenes with lanthanum metal in the presence of dienophiles.

The structures and electronic states of acetone–metal complexes (Ac–M, where M=Ga, Al, and B) have been calculated by means of ab-initio DFT and configuration interaction (CI) calculations in order to shed light on the mechanism of the electron conductivity and doping effects. It was found that the electronic states of Ac–Ga and Ac–Al at the ground state are composed of ion-pair state expressed approximately by (Ac δ− )(M δ+ ): the electron is transferred from metal to the carbonyl group, suggesting that the carbonyl compound interacting with Ga and Al behaves as an n-type semiconductor. In the case of the Ac–B complex, on the other hand, the electron on Ac is significantly transferred to the boron atom, expecting that hole is transferred in the boron-doped carbonyl compound (p-type semiconductor). In these complexes, the first electronic transition is a charge-transfer band between metal and carbonyl group. The mechanism of the electronic conductivity was discussed on the basis of theoretical results.

In most cells, transferrin receptor (TfR1)-mediated endocytosis is a major pathway for cellular iron uptake. We recently cloned the human transferrin receptor 2 (TfR2) gene, which encodes a second receptor for transferrin (Kawabata, H., Yang, R., Hirama, T., Vuong, P. T., Kawano, S., Gombart, A. F., and Koeffler, H. P. (1999) J. Biol. Chem. 274, 20826-20832). In the present study, the regulation of TfR2 expression and function was investigated. A select Chinese hamster ovary (CHO)-TRVb cell line that does not express either TfR1 or TfR2 was stably transfected with either TfR1 or TfR2-alpha cDNA. TfR2-alpha-expressing cells had considerably lower affinity for holotransferrin when compared with TfR1-expressing CHO cells. Interestingly, in contrast to TfR1, expression of TfR2 mRNA in K562 cells was not up-regulated by desferrioxamine (DFO), a cell membrane-permeable iron chelator. In MG63 cells, expression of TfR2 mRNA was regulated in the cell cycle with the highest expression in late G(1) phase and no expression in G(0)/G(1). DFO reduced cell proliferation and DNA synthesis of CHO-TRVb control cells, whereas it had little effect on TfR2-alpha-expressing CHO cells when measured by clonogenic and cell cycle analysis. In addition, CHO cells that express TfR2-alpha developed into tumors in nude mice whereas CHO control cells did not. In conclusion, TfR2 expression may be regulated by the cell cycle rather than cellular iron status and may support cell growth both in vitro and in vivo.

The interaction of magnesium (Mg) with a graphene surface has been investigated by means of density functional theory (DFT) method. Also, the direct molecular orbital–molecular dynamics (MO-MD) calculation [Tachikawa, J. Phys. Chem. C, 112 (2008) 10193] have been applied to the dynamics of Mg on the graphene surface. The B3LYP/LANL2MB calculations showed that the Mg atom is bound to a hexagonal site and is located in 2.02 A from the graphene surface. The direct MO-MD calculations showed that the Mg atom vibrates in the hexagonal site and diffusion does not occur even at 1000 K. The nature of the interaction between the Mg atom and the graphene sheet was discussed on the basis of theoretical results.

Excimer fluorescence of 1,3-bis-(1-pyrenyl)propane (Py-Py) doped in a PMMA polymer film with a peak at ∼470 nm is quenched by an external electric field extremely well. It is suggested that a field-assisted charge separation of Py-Py followed by efficient charge transports occurs only in the excimer with a sandwich-type configuration. The electroluminescence spectrum which is similar to the excimer fluorescence is generated at high fields without photoirradiation, probably by a radiative recombination of the hole–electron pair through a short methylene chain. A good correlation is found between the efficient fatigue of the excimer fluorescence and the generation of the electroluminescence.

Transferrin receptor (TfR) plays a major role in cellular iron uptake through binding and internalizing a carrier protein transferrin (Tf). We have cloned, sequenced, and mapped a human gene homologous to TfR, termed TfR2. Two transcripts were expressed from this gene: α (∼2.9 kilobase pairs), and β (∼2.5 kilobase pairs). The predicted amino acid sequence revealed that the TfR2-α protein was a type II membrane protein and shared a 45% identity and 66% similarity in its extracellular domain with TfR. The TfR2-β protein lacked the amino-terminal portion of the TfR2-α protein including the putative transmembrane domain. Northern blot analysis showed that the α transcript was predominantly expressed in the liver. In addition, high expression occurred in K562, an erythromegakaryocytic cell line. To analyze the function of TfR2, Chinese hamster ovary TfR-deficient cells (CHO-TRVb cells) were stably transfected with FLAG-tagged TfR2-α. These cells showed an increase in biotinylated Tf binding to the cell surface, which was competed by nonlabeled Tf, but not by lactoferrin. Also, these cells had a marked increase in Tf-bound 55Fe uptake. Taken together, TfR2-α may be a second transferrin receptor that can mediate cellular iron transport.

An NADPH-dependent aldehyde reductase was purified to homogeneity from Candida magnoliae AKU4643 through four steps, including Blue-Sepharose affinity chromatography. The relative molecular mass of the enzyme was estimated to be 33,000 on high performance gel-permeation chromatography and 35,000 on sodium dodecyl sulfate polyacrylamide gel electrophoresis. The substrate specificity of the enzyme was broad and resembled those of other aldo–keto reductases. The partial amino acid sequences of the enzyme showed that it belongs to the aldo–keto reductase superfamily. The enzyme catalyzed the stereoselective reduction of ethyl 4-chloro-3-oxobutanoate to the corresponding ( R )-alcohol, with a 100% enantiomeric excess. The enzyme was inhibited by 1 mM quercetin, CuSO 4 , ZnSO 4 and HgCl 2 . The thermostability of the enzyme was inferior to that of the ( S )-CHBE-producing enzyme from the same strain.

Multiple ethyl 4-chloro-3-oxobutanoate (COBE)-reducing enzymes were isolated from a cell-free extract of Candida magnoliae. A NADPH-dependent COBE-reducing enzyme, distinct from the carbonyl reductase and aldehyde reductase previously reported, was purified to homogeneity using five steps, including polyethylene glycol treatment. The relative molecular mass of the enzyme was estimated to be 86,000 on high performance gel-permeation chromatography and 29,000 on sodium dodecyl sulfate polyacrylamide gel electrophoresis. The enzyme catalyzed the reduction of COBE to the corresponding (S)-alcohol with a 51% enantiomeric excess. The substrate specificity of the enzyme was different from those of the other COBE-reducing enzymes of the same strain. The partial amino acid sequences of the enzyme showed that it belongs to the short chain alcohol dehydrogenase/reductase (SDR) family. This is the first report of multiple COBE-reducing enzymes with various stereoselectivities occurring in the same strain but belonging to different (super)families.

Endonucleases capable of producing internucleosomal DNA cleavage are one of the key enzymes in apoptosis. We examined endonuclease activities contained in nuclei of CD34 + and erythroid cells in the bone marrow (BM) from 12 patients with the myelodysplastic syndromes. The levels of Mg 2+ -dependent and acidic endonucleases showed little changes as compared with those from normal BM. By contrast, the level of Ca 2+ Mg 2+ -dependent endonuclease was appreciably higher in MDS erythroid cells than normal counterparts, although the activity varied markedly in CD34 + and erythroid cells. Our results suggested that Ca 2+ Mg 2+ -dependent endonuclease is related to ineffective erythropoiesis in MDS.

A new method for the reductive debromination of 1,2-bis(bromomethyl)arenes has been developed. The treatment of 1,2-bis(bromomethyl)benzene with tetrakis(dimethylamino)ethylene (TDAE) ( 1 ) in the presence of olefins gave 1,2,3,4-tetrahydronaphthalenes in moderate to good yields.

A new generation method of benzyne has been developed. When 1,2-dihalogen substituted arenes were allowed to react with lanthanum metal in the presence of dienes, Diels–Alder products between benzyne and dienes were formed in moderate to good yields.

Electric field effects on fluorescence of pyrene deposited in a mixed LB film with a definite direction are very different from those of pyrene doped randomly in a polymer film. In polymer films, both the sharp structured monomer fluorescence emitted from the locally excited state and the sandwich-type excimer fluorescence with a peak at ∼470 nm are quenched by an electric field, whereas another excimer fluorescence with a peak at ∼415 nm is enhanced by an electric field. In LB films, the latter excimer fluorescence is not affected by an electric field.