Search

We determined the elemental and isotopic composition of Zn in sinking particles collected in the deep water of the northern South China Sea (NSCS) to investigate the relative contribution of various sources and assess their isotopic signatures. Using differentiable elemental ratios and δ66Zn of the potential sources, a mass balance approach estimates that anthropogenic aerosol Zn accounted for 64 ± 10% of the total Zn in sinking particles for more than 50% of the sampling period, indicating that anthropogenic aerosol Zn has become a dominant form of Zn source in the deep water. A relatively large discrepancy between the estimated and measured δ66Zn is observed during the high productivity season, which can be attributed to the elevated contribution of the biogenic hard parts or scavenging Zn on organic materials. Elevated δ66Zn values were observed at 3500 m during autumn which may be caused by the influence of authigenic particles during the lowest flux period. We found that the averaged measured output δ66Zn value, +0.35 ± 0.12‰, is significantly lighter than most of the output values proposed in previous studies. Due to recent findings highlighting the importance of anthropogenic aerosol Zn in the ocean, we have re-evaluated the solubility and fluxes of aerosol Zn in the ocean and found that the flux has been significantly underestimated in previous studies. The updated global aerosol Zn input to the ocean, ranging from 0.3 to 3.0 Gmol yr−1, is comparable to the output magnitude from hydrothermal and riverine sources. The updated Zn residence time would then be down to 1400 years on average. In addition to organic decomposition, the sinking particle data indicate that particle-associated removal and release processes play important roles in controlling Zn cycling in the water column. How anthropogenic aerosol deposition influences Zn fluxes and cycling in other oceanic regions deserves further investigation.

Ken Takata, Kentaro Uchida, Shotaro Takano, Manabu Mukai, Gen Inoue, Hiroyuki Sekiguchi, Jun Aikawa, Masayuki Miyagi, Dai Iwase, Masashi Takaso Department of Orthopedic Surgery, Kitasato University School of Medicine, Sagamihara City, Kanagawa, 252-0374, JapanCorrespondence: Kentaro UchidaDepartment of Orthopedic Surgery, Kitasato University School of Medicine, 1-15-1 Minami-Ku Kitasato, Sagamihara City, Kanagawa, 252-0374, JapanTel/Fax +81-042-778-9217Email kuchida@med.kitasato-u.ac.jpPurpose: Obesity is associated with the risk of developing knee osteoarthritis (KOA). Furthermore, synovial basic fibroblast growth factor (bFGF) is linked to the severity of KOA. We previously demonstrated that bFGF and mast cell (MC) marker expression were elevated in the synovial tissues (ST) of KOA patients with obesity. However, it remains unclear whether MCs contribute to bFGF expression and regulation.Patients and Methods: Radiographically diagnosed KOA patients (n=249) were assigned to groups based on the body mass index (BMI) classifications used by the World Health Organization: normal-weight (NW, BMI < 25 kg/m2, n=95), overweight (OW, BMI ≥ 25 and < 30, n=109) and obese (OB, ≥ 30 kg/m2, n=45). BFGF expression in the ST was examined using quantitative polymerase chain reaction and compared across the BMI groups. Additionally, BFGF and interleukin (IL) 13 expression were examined in freshly extracted MC-rich (THY-1-, CD3-, CD14-, and CD19-) and MC-poor (THY-1+, CD3+, CD14+, or CD19+) fractions from ST. Moreover, regulation of BFGF expression by IL-13 was studied in CD14-negative (fibroblast-rich) and CD14-positive (M&phis;-rich) and cells in culture.Results: BFGF expression was significantly higher in OB than in NW patients. Furthermore, although IL13 was significantly higher in the MC-rich than the MC-poor fraction, BFGF expression was comparable. Recombinant human IL-13 stimulated expression of BFGF in synovial fibroblast cells.Conclusion: BFGF expression is higher in the ST of KOA patients with obesity. Increased numbers of MCs may contribute to the elevated BFGF expression through IL-13 in KOA patients with obesity.Keywords: obesity, mast cell, osteoarthritis, BFGF, IL13, synovial tissues

Obesity is a risk factor for knee osteoarthritis (KOA). Neuromedin U (NMU) and NMU receptors (NMUR1 and NMUR2) are associated with obesity-related disorders and found in mast cells (MCs), which are elevated in osteoarthritis. However, NMU/NMUR expression was not examined in the synovial membrane (SM) or synovial MCs of obese osteoarthritis patients. We compared expression of NMU, NMUR1, NMUR2, and the mast cell (MC) marker, CPA3, in the SM of KOA patients categorized as normal weight (NW; BMI < 25 kg/m2, n = 79), overweight (OW; BMI ≥ 25 and

Purpose The mechanisms governing evidence that obesity is a risk factor for osteoarthritis (OA) are not well understood. We previously reported an increase in mast cell (MC) marker expression in the osteoarthritic synovial membrane (SM) of patients with obesity. We hypothesized that an enzyme produced by MC, β-tryptase, may be increased in the SM of obese patients with knee OA and contribute to synovial inflammation. This study investigated the expression of the β-tryptase encoding gene, TPSB2, in the SM of obese patients with knee OA and β-tryptase-mediated regulation of IL-1β in synovial cells. Patients and Methods A total of 216 patients radiographically diagnosed with knee OA were grouped according to the World Health Organization's body mass index classifications: normal weight (NW

Animal studies suggest that pain-related-molecule upregulation in degenerated intervertebral discs (IVDs) potentially leads to low back pain (LBP). We hypothesized that IVD mechanical stress and axial loading contribute to discogenic LBP’s pathomechanism. This study aimed to elucidate the relationships among the clinical findings, radiographical findings, and pain-related-molecule expression in human degenerated IVDs. We harvested degenerated-IVD samples from 35 patients during spinal interbody fusion surgery. Pain-related molecules including tumor necrosis factor alpha (TNF-alpha), interleukin (IL)-6, calcitonin gene-related peptide (CGRP), microsomal prostaglandin E synthase-1 (mPGES1), and nerve growth factor (NGF) were determined. We also recorded preoperative clinical findings including body mass index (BMI), Oswestry Disability Index (ODI), and radiographical findings including the vacuum phenomenon (VP) and spinal instability. Furthermore, we compared pain-related-molecule expression between the VP (−) and (+) groups. BMI was significantly correlated with the ODI, CGRP, and mPGES-1 levels. In the VP (+) group, mPGES-1 levels were significantly higher than in the VP (−) group. Additionally, CGRP and mPGES-1 were significantly correlated. Axial loading and mechanical stress correlated with CGRP and mPGES-1 expression and not with inflammatory cytokine or NGF expression. Therefore, axial loading and mechanical stress upregulate CGRP and mPGES-1 in human degenerated IVDs, potentially leading to chronic discogenic LBP.

Molybdenum (Mo) is a redox-sensitive element and its concentrations and stable isotope compositions are widely used as a redox proxy in paleoceanography. Tungsten (W) is an emerging new isotope proxy, which has potential as a tracer for hydrothermal and early diagenetic processes. We present a new method for the precise and accurate analysis of Mo and W concentrations and isotope compositions from one single sample aliquot, thus saving mass of a sample and making the results directly comparable without concerns related to analytical or natural sample heterogeneity. After acid digestion, Mo and W are separated from the sample matrix using chelating resin NOBIAS Chelate-PA1 and anion exchange resin AG1 X8. Matrix removal is highly efficient: the remaining percentage is 10−2 to 10−5% with respect to the initial weight. Subsequently, samples are measured for Mo and W concentrations and isotope compositions using multi-collector inductivity coupled plasma mass spectrometry (MC-ICP-MS). For mass bias correction and determination of concentrations, we use standard-sample bracketing and in addition an external correction method employing ruthenium (Ru) for Mo and rhenium (Re) for W. This double correction approach results in an external reproducibility of or below 0.10‰ (2SD) for δ98Mo and 0.05‰ for δ186W based on ICP standard solutions (NIST SRM 3134 lot No. 130418 for Mo and NIST SRM 3163 lot No. 080331 for W). We present data for Mo and W in 12 geological reference materials including igneous rocks, sedimentary rocks, marine sediments, and manganese nodules. For Mo our method reproduces published values for the geological standard materials within analytical error of published values. For W, although published data do not always agree for a given geological standard material, our data agree within error with more recent data. We interpret a cause of the deviations is due to unknown effects of a desolvating nebulizer for MC-ICP-MS.

Background. Previous studies suggest the presence of an association of vascular endothelial growth factor (VEGF) with osteoarthritis (OA) severity and pain in patients with knee OA. VEGF expression in human synovial fibroblasts (SFs) is induced by transforming growth factor-beta (TGFβ). However, the signaling pathway governing TGFβ-mediated regulation of VEGF in SFs has not been identified. Methods. OA patients who underwent total knee arthroplasty had their synovial tissue (SYT) extracted and the constituent SFs cultured. The cells were stimulated with culture medium (control), human recombinant TGFβ (hrTGFβ), hrTGFβ + ALK5 inhibitor SB505124, hrTGFβ + transforming growth factor activating kinase 1 (TAK1) inhibitor (5Z)-7-oxozeaenol, or hrTGFβ + p38 inhibitor SB203580 for 6 h. VEGF mRNA expression in SFs was examined using real-time polymerase chain reaction and VEGF protein production in the cell supernatant was examined using enzyme-linked immunosorbent assay. Additionally, phosphorylated levels of SMAD2 and p38 were examined using western blotting. Results. ALK5 (SB505124) and TAK1 (5Z-oxozeaenol) inhibitors completely suppressed TGFβ-induced VEGF mRNA expression and VEGF protein production. Both SB505124 and 5Z-oxozeaenol also suppressed SMAD2 and p38 phosphorylation. The p38 inhibitor (SB203580) partially inhibited TGFβ-mediated VEGF mRNA and VEGF protein production. Conclusion. TGFβ-mediated regulation of VEGF expression and VEGF protein production in the SYT of OA patients occurs through both the canonical and noncanonical pathway.

Aluminum (Al), manganese (Mn), cobalt (Co), and lead (Pb) are key trace elements in seawater and thus significant in chemical oceanography research. However, although all of these elements are highly scavenged in the ocean, only a few studies focus on the intercomparison of their distributions. Here, we report the basin-scale and full-depth sectional distributions of these elements observed during three GEOTRACES Japan cruises in the North Pacific. We confirmed that a surface maximum of the dissolved (d) species is not a common feature for the four elements and that the d species have the lowest concentrations in the Pacific Deep Water (PDW) as compared to other oceans. The elements showed different speciations and distributions. The fraction of labile particulate (lp) species was calculated as the difference between the total dissolvable (td) species and d species. The lpM/tdM ratio, where M refers to an element, is highest for Al, at 0.66 ± 0.31 (average ± sd, n = 489), and lowest for Pb, at 0.02 ± 0.08 (n = 575). Further, the distribution of each element is uniquely related to ocean circulation. The tdAl concentration is high in the Equatorial Under Current (EUC), the North Equatorial Current (NEC), and the Lower Circumpolar Deep Water (LCDW). Manganese is supplied from reductive sources such as sediments on the continental shelves around the northern boundary. Cobalt is concentrated in the North Pacific Intermediate Water (NPIW) and in the Equatorial Pacific Intermediate Water (EqPIW) owing to the combined effects of supply from the continental shelves, biogeochemical cycling, and scavenging. Lead shows a subsurface maximum centered at ∼35°N and ∼200 m depth, implying an association with the formation of the Subtropical Mode Water (SMW) and the Central Mode Water (CMW). Although the subsurface Pb maximum in the Atlantic has diminished over the last three decades owing to the ban on leaded gasoline use, it has been sustained in the North Pacific through the growth of other anthropogenic sources in Asia and Russia. We propose that the enrichment factor of dM, defined as EF(dM) = (dM/dAl)seawater/(M/Al)upper crust, where (M/Al)upper crust is the molar ratio in upper crustal abundance, can be a good parameter for the sources. The median is 1.3 × 102 (n = 436) for EF(dMn), 3.2 × 102 (n = 430) for EF(dCo), and 1.2 × 103 (n = 413) for EF(dPb). The EF(dPb) found in this study is on the same order of magnitude as the EF values for aerosols found in the literature, suggesting that the deposition of aerosols is a major source for dPb. Because EF(dMn) and EF(dCo) are ten to hundred times higher than the EF for aerosols, sources other than the aerosol deposition are more significant contributors to the concentrations of Mn and Co.

Several nerve conduits have been investigated for their potential as alternative sources of autografts for bridging neural gaps. However, autologous nerve transplants remain the most effective for nerve repair. We examined clinically approved nerve conduits containing collagen and polyglycolic acid (PGA-c) combined with collagen-binding basic fibroblast growth factor (bFGF) containing a polycystic kidney disease (PKD) domain and collagen binding domain (CBD) (bFGF-PKD-CBD) in a rat 15-mm sciatic nerve critical-size defect model. The treatment groups were: PGA-c immersed in phosphate-buffered saline (PBS) (PGA-c/PBS group), bFGF (PGA-c/bFGF group), or bFGF-PKD-CBD (PGA-c/bFGF-PKD-CBD group), and no treatment (Defect group). Gait and histological analyses were performed. Four weeks after treatment, the recovery rate of the paw print area was significantly greater in the PGA-c/bFGFPKD-CBD group than the PGA-c/PBS and PGA-c/bFGF groups. Mean intensity of paw prints was significantly greater in the PGA-c/bFGF-PKD-CBD group than the PGA-c/PBS and Defect groups. Swing time was significantly greater in the PGA-c/PBS, PGA-c/bFGF, and PGA-c/bFGF-PKD-CBD groups than the Defect group. At 8 weeks, all three parameters were significantly greater in the PGA-c/PBS, PGA-c/bFGF, and PGA-c/bFGF-PKD-CBD groups than the Defect group. Regenerated myelinated fibers were observed in 7/8 (87.5%) rats in the PGA-c/bFGF-PKD-CBD group after 8 weeks, and in 1/8 (12.5%) and 3/8 (37.5%) rats in the PGA-c/PBS and PGA-c/bFGF groups, respectively. PGA-c/bFGF-PKD-CBD composites may be promising biomaterials for promoting functional recovery of long-distance peripheral nerve defects in clinical practice.

Cadmium stable isotope ratios (δ114Cd) have become a useful tool for oceanographers investigating the biogeochemical and physical processes that affect the nutrient-like distribution of the bioactive trace metal cadmium (Cd) throughout the oceans. Here, we present a meridional transect of dissolved Cd and δ114Cd from Japanese GEOTRACES section GP19 along 170°W from 64°S in the Southern Ocean to the equatorial Pacific. Along the GP19 section, the deep ocean (>1500 m) shows small variability in dissolved Cd (0.75–0.9 nmol kg−1) and a homogeneous δ114Cd signature (+0.26 ± 0.06‰, 2SD, n = 60; relative to NIST SRM-3108). Adding these data to previously published work allows us to calculate a deep Pacific and Southern Ocean (>1500 m) mean δ114Cd of +0.26 ± 0.10‰ (2SD, n = 436). Higher in the water column, depth profiles of Cd along the GP19 section exhibit a strong vertical gradient from a maximum (up to 0.9 nmol kg−1) at 1500–2000 m up to depleted surface waters ( Overall, the distribution of Cd and δ114Cd along the GP19 section is remarkably well explained by large scale mixing of water mass endmembers with defined δ114Cd signatures, emphasizing the importance of surface Southern Ocean processes for the distribution of trace metals such as Cd in the subsurface Southwest Pacific. At the regional scale, however, two other processes may overprint this mixing relationship. First, by comparison with the nearby Southeast Pacific GP16 section, we find that the δ114Cd signature of equatorial intermediate water masses shows little zonal variation across the equatorial Pacific, despite becoming enriched in dissolved Cd due to remineralization. We propose that this uniformity is explained by complete utilization of Cd in the surface tropical Pacific and remineralization of Cd with an isotopic signature similar to intermediate waters, therefore conserving the southern-sourced isotopic signature. Similarly, the observed increase of about 30% in deep ocean Cd concentrations from the South to the North Pacific is associated with a near-constant δ114Cd signal. These observations enable us to constrain the net δ114Cd of Cd added by remineralization to the deep ocean, with the caveat that such a signal is integrated over the entire Pacific, and that remineralization under different oceanic regimes such as HNLC areas may add Cd with different isotopic compositions to deep waters. Second, at GP19 stations close to the equator, subtle Cd depletion (relative to phosphate) is observed associated with low-oxygen subsurface waters, consistent with other studies from the North Pacific. Discerning the effects of such processes on Cd isotopic distributions is an important step to a more detailed understanding of the biogeochemical cycling of Cd in the modern ocean, and the application of δ114Cd as a tracer of past deep water circulation. This article is part of a special issue entitled: “Cycles of trace elements and isotopes in the ocean – GEOTRACES and beyond” - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. Gonzalez.

Purpose: While research suggests that obesity is a risk factor for knee osteoarthritis (KOA), the mechanisms are not fully understood. Mast cell (MC) numbers are increased in the osteoarthritic synovium and in the adipose tissue of obese individuals. We hypothesized that MC numbers are increased in the synovium of obese KOA patients. This study investigated MC marker and MC-generated cytokine/growth factor expression in the synovium of obese KOA patients. Patients and methods: Patients radiographically diagnosed with KOA (male: 38, female: 132) were allocated to three groups based on their body mass index (BMI): normal (

Upregulation of inflammatory cytokines and various growth factors is a significant contributor to discogenic low back pain. The aim of this study was to investigate possible regulation of pain-related molecules by macrophages and the role of macrophage-derived molecules in injured intervertebral disc (IVD)s. C57BL/6J mice were used in this study. We characterized the expression profiles of genes for tumor necrosis factor (TNF)-alpha, interleukin (IL)-1beta, nerve growth factor (NGF), and vascular endothelial growth factor (VEGF) in both intact and injured IVDs. We examined whether macrophage depletion, induced by systemic injection of clodronate-laden liposomes, affected the expression of these molecules in injured IVDs. The effect of TNF-alpha on cultured F4/80-CD11b-cells in injured IVDs was investigated. Expression of TNF-alpha and IL-1beta was significantly increased in injured IVDs, but decreased by macrophage depletion. Expression of NGF and VEGF was also significantly increased, but by contrast was not decreased by macrophage depletion. TNF-alpha treatment of F4/80-cells from injured IVDs upregulated NGF, VEGF, cyclooxygenase (COX)-2, and microsomal prostaglandin E synthase-1 (mPGES1). IVD injury upregulated inflammatory cytokines and various growth factors. Macrophages in the injured IVDs produced inflammatory cytokines, but not growth factors. Macrophage-derived inflammatory cytokines regulate growth factors and pain-related molecules. These findings demonstrate further complexity in the pathogenesis of discogenic pain. © 2018 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res.

Introduction Studies have identified the presence of M1 and M2 macrophages (Mϕ) in injured intervertebral discs (IVDs). However, the origin and polarization-regulatory factor of M2 Mϕ are not fully understood. TGF-β is a regulatory factor for M2 polarization in several tissues. Here, we investigated the source of M2 Mϕ and the role of TGF-β on M2 polarization using a mice disc-puncture injury model. Methods To investigate the origin of M2 macrophages, 30 GFP chimeric mice were created by bone marrow transplantation. IVDs were obtained from both groups on pre-puncture (control) and post-puncture days 1, 3, 7, and 14 and CD86 (M1 marker)- and CD206 (M2 marker)-positive cells evaluated by flow cytometry ( n = 5 at each time point). To investigate the role of TGF-β on M2 polarization, TGF-β inhibitor (SB431542) was also injected on post-puncture days (PPD) 5 and 6 and CD206 expression was evaluated on day 7 by flow cytometry ( n = 5) and real time PCR ( n = 10). Results The proportion of CD86+ Mϕ within the GFP+ population was significantly increased at PPD 1, 3, 7, and 14 compared to control. CD206-positive cells in GFP-populations were significantly increased on PPD 7 and 14. In addition, the percentage of CD206-positive cells was significantly higher in GFP-populations than in GFP+ populations. TGF-β inhibitor reduced CD206-positive cells and Cd206 expression at 7 days after puncture. Conclusion Our findings suggest that M2 Mϕ following IVD injury may originate from resident Mϕ. TGF-β is a key factor for M2 polarization of macrophages following IVD injury.

A novel (PNO)Rh/CuBr (PNO: phosphine-quinolinolate) tandem catalyst system was developed for facile synthesis of α-monosubstituted propargylamines from aliphatic terminal alkynes and secondary amines. Various terminal alkynes and amines were applicable to this reaction and the corresponding propargylamines were obtained in good yields.

Stable isotope ratios of nickel, copper, and zinc are powerful tools for elucidating the biogeochemical cycling of trace metals in the ocean. However, analytical difficulties have impeded isotopic studies of these metals. We present a simple and rapid method for simultaneous analysis of Ni, Cu, and Zn isotope ratios in seawater using NOBIAS Chelate-PA1 resin and anion exchange resin. A NOBIAS Chelate-PA1 resin column was used to quantitatively collect Ni, Cu, and Zn from seawater and thoroughly remove the seawater matrix. Subsequent anion exchange purified and separated the Ni, Cu, and Zn from each other. The blanks used in this method (0.22 ng for Ni, 0.29 ng for Cu, and 0.53 ng for Zn) were sufficiently low to determine the isotope ratios of Ni, Cu, and Zn in surface seawater. Using this method, we analyzed GEOTRACES reference seawater samples (i.e., SAFe D1 and SAFe D2), National Research Council Canada certified materials (i.e., CASS-5 and NASS-6), and seawater samples collected from different depths in the subarctic South Pacific. The results were consistent with previously reported values. This method is expected to accelerate isotopic research and contribute to our understanding of biogeochemical cycling in the ocean.

A central theme of the ongoing GEOTRACES program is to improve the understanding of processes occurring at ocean interfaces with continents, sediments, and ocean crust. In this context, we studied the distributions of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb around the Juan de Fuca Ridge (JdFR) in total dissolvable (td), dissolved (d), and labile particulate (lp) fractions, which represent a fraction in unfiltered samples, filtered samples through an AcroPak capsule filter, and the difference between td and d, respectively. Al and Fe were dominated by lp-species, while Ni, Zn, and Cd were dominated by d-species with undetectable amounts of lp-species. Major findings in this study are as follows: (1) The continental margin (CM) provided large sources of Al, Mn, Fe, and Co from the surface to ~2000 m in depth. The supply from CM caused high surface concentrations of dMn and dCo, a subsurface (100–300 m depth) maximum of dCo, and intermediate (500–2000 m depth) maxima of lpAl and lpFe. The supply of dFe from CM was ~10 times that from the high-temperature hydrothermal activity at station BD21, which is located at ~3 km from the Middle Valley venting site and ~ 200 km from Vancouver Island. (2) DPb was maximum at the top layer of North Pacific Intermediate Water, probably owing to isopycnal transport of anthropogenic Pb via advection of subducted surface waters. Although dCo and dPb had different sources in the upper water, they showed a strong linearity below 300 m (r 2 = 0.95, n = 38), indicating concurrent scavenging. (3) A high-temperature hydrothermal plume occurred at a depth of 2300 m at BD21, accounting for maxima of dAl, dMn, dFe, lpCu, and lpPb and a minimum of dCu. (4) Strong bottom maxima of lpAl, lpMn, lpFe, lpCo, and lpPb occurred above the abyssal plain at the western foot of the JdFR, indicating resuspension of sediments. However, bottom maxima of d-species were apparent only for dAl and dCu.

Cell-based regenerative therapy has the potential to repair bone injuries or large defects that are recalcitrant to conventional treatment methods, including drugs and surgery. Here, we developed a multilayered cell-based bone formation system using cells coated with fibronectin-gelatin (FN-G) nanofilms. The multilayered mesenchymal cells (MLMCs) were formed after two days of culture and were shown to express higher levels of BMP-2 and VEGF compared to monolayer cultures of MCs. The MLMCs were used as a graft material in combination with a fusion protein consisting of basic fibroblast growth factor (bFGF), polycystic kidney disease (PKD) domain, and the collagen-binding domain (CBD) of Clostridium histolyticum collagenase. In femur sites grafted with the MLMCs, significantly higher levels of callus volume and bone mineral content were observed compared to the sham controls. The callus volume and bone mineral content were further increased in femur sites grafted with bFGF-PKD-CBD/MLMCs. Taken together, these results suggest that bFGF-PKD-CBD/MLMCs, which can be simply and rapidly generated in vitro, have the potential to promote bone repair when grafted into large defect sites.

We report here on the syntheses of rhodium(I) complexes bearing a phosphine-quinolinolate ligand and the isolation of two classes of important intermediates in the anti-Markovnikov hydroamination of terminal alkynes with secondary amines: vinylidene-bridged dirhodium complexes and (amino)carbene complexes. We first prepared various rhodium(I) complexes bearing a phosphine-quinolinolate ligand and found that some of these complexes had catalytic activity for the anti-Markovnikov hydroamination of terminal alkynes with secondary amines. The reaction of stoichiometric amounts of a (PNO)Rh complex with terminal alkynes provided vinylidene-bridged dirhodium complexes. When the resulting vinylidene complexes were reacted with secondary amines, (amino)carbene complexes were generated, which gave the hydroamination product upon heating with an additive. These results suggest that this anti-Markovnikov hydroamination catalyzed by (PNO)Rh complexes proceeds via vinylidene and (amino)carbene complexes.

This paper describes the experimental study on the liquid droplet impingement erosion of metal materials to understand the influence of material hardness on the erosion rate. The experiment is carried out using a water spray jet apparatus with a condition of relatively thin liquid film thickness. The metal materials tested are pure aluminum, aluminum alloy, brass, mild steel, carbon steel and stainless steel. The liquid droplets considered are 30 ± 5 μm in volume average diameter of water, which is the same order of droplet diameter in the actual pipeline in nuclear/fossil power plants. In order to understand the influence of material hardness on the liquid droplet impingement erosion, the scanning electron microscope (SEM) observation on the eroded surface and the measurement of erosion rate are carried out in the terminal stage of erosion. The experimental results indicate that the erosion rates are expressed by the droplet velocity, volume flux, Vickers hardness and the liquid film thickness, which are fundamentals of the liquid droplet impingement erosion. The empirical formula shows that the power index for droplet velocity dependency is found to be 7 with a scattering from 5 to 9 depending on the materials, while the power index for Vickers hardness dependency is found as −4.5.

A novel automated off-line preconcentration system for trace metals (Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in seawater was developed by improving a commercially available solid-phase extraction system SPE-100 (Hiranuma Sangyo). The utilized chelating resin was NOBIAS Chelate-PA1 (Hitachi High-Technologies) with ethylenediaminetriacetic acid and iminodiacetic acid functional groups. Parts of the 8-way valve made of alumina and zirconia in the original SPE-100 system were replaced with parts made of polychlorotrifluoroethylene in order to reduce contamination of trace metals. The eluent pass was altered for the back flush elution of trace metals. We optimized the cleaning procedures for the chelating resin column and flow lines of the preconcentration system, and developed a preconcentration procedure, which required less labor and led to a superior performance compared to manual preconcentration (Sohrin et al. [5] ). The nine trace metals were simultaneously and quantitatively preconcentrated from ∼120 g of seawater, eluted with ∼15 g of 1 M HNO3, and determined by HR-ICP-MS using the calibration curve method. The single-step preconcentration removed more than 99.998% of Na, K, Mg, Ca, and Sr from seawater. The procedural blanks and detection limits were lower than the lowest concentrations in seawater for Mn, Ni, Cu, and Pb, while they were as low as the lowest concentrations in seawater for Al, Fe, Co, Zn, and Cd. The accuracy and precision of this method were confirmed by the analysis of reference seawater samples (CASS-5, NASS-5, GEOTRACES GS, and GD) and seawater samples for vertical distribution in the western North Pacific Ocean.

In order to increase the critical current density of high temperature superconductors, it is commonly employed to disperse nonsuperconducting particles as flux pinning centers into the superconductive matrix. For Y-Ba-Cu-O bulk superconductors Y2BaCuO5 (Y211) phase particles are known to be effective pinning centers. It has been proposed that magnetic particles are more efficient pinning centers, since they will have a stronger positive interaction with quantized fluxoids. A combined addition of Y211 and magnetic metal fine powders has been reported to be effective in improving flux pinning performances. Therefore, in this study we aimed at improving the pinning forces of Y-Ba-Cu-O bulk superconductors by introducing the Fe-Al-Si-based alloys that are ferromagnetic. We also studied the effect of the addition of γ-hematite, which is non-magnetic, in order to compare the contribution to the flux pinning enhancement. For comparative study, we measured the trapped field in single-domain bulk superconductors and found that a small addition of Fe-Al-Si based ferromagnetic powders and γ-hematite improved field trapping ability.

Recent studies have revealed that an addition of binder such as acrylic is effective in reducing cracking during the preparation processes of the precursors and thus in promoting the grain growth of good quality bulk superconductors. However, when the distribution of binder is not uniform, some defects are introduced in the precursors and thereby the grain growth is inhibited. At present, the optimum conditions for mixing binders and precursor superconducting raw materials are not yet established. In this work, we have studied the effects of the liquid binder addition on the superconducting properties and the grain growth behavior of bulk Y-Ba-Cu-O superconductors about 40 mm in diameter produced with the top-seed melt-growth process. We have found that optimized binder additions contribute to the consolidation of the bulk precursor and further to the grain growth of single-grain bulk superconductors.

Background Calcitonin gene-related peptide (CGRP) is a 37-amino-acid vasodilatory neuropeptide that binds to receptor activity-modifying protein 1 (RAMP1) and the calcitonin receptor-like receptor (CLR). Clinical and preclinical evidence suggests that CGRP is associated with hip and knee joint pain; however, the regulation mechanisms of CGRP/CGRP receptor signaling in synovial tissue are not fully understood. Methods Synovial tissues were harvested from 43 participants with radiographic knee osteoarthritis (OA; unilateral Kellgren/Lawrence (K/L) grades 3–4) during total knee arthroplasty. Correlationships between the mRNA expression levels of CGRP and those of tumor necrosis factor-α (TNF-α), interleukin (IL)-1β, IL-6, and cycloxygenase-2 (COX-2) were evaluated using real-time PCR analysis of total RNA extracted from the collected synovial tissues. To investigate the factors controlling the regulation of CGRP and CGRP receptor expression, cultured synovial cells were stimulated with TNF-α, IL-1β, IL-6, and prostaglandin E2 (PGE2) and were also treated with PGE2 receptor (EP) agonist. Results CGRP and COX-2 localized in the synovial lining layer. Expression of COX-2 positively correlated with CGRP mRNA expression in the synovial tissue of OA patients. The gene expression of CGRP and RAMP1 increased significantly in synovial cells exogenously treated with PGE2 compared to untreated control cells. In cultured synovial cells, CGRP gene expression increased significantly following EP4 agonist treatment, whereas RAMP1 gene expression increased significantly in the presence of exogenously added EP1 and EP2 agonists. Conclusions PGE2 appears to regulate CGRP/CGRP receptor signaling through the EP receptor in the synovium of knee OA patients.