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Dissolved palladium (Pd), platinum (Pt), and gold (Au) form inert chloride complexes at low concentrations of pmol/kg in environmental water, thus rendering difficulty in the development of a precise analytical method for these metals. Herein, we report the preconcentration of Pd, Pt, and Au with a chelating fiber Vonnel-en and a chelating resin TYP-en with ethylenediamine (en) groups. Batch adsorption experiments reveal the adsorption capacity of Vonnel-en for Pd(II), Pt(IV), and Au(III) in 0.10 M HCl as 0.53, 0.22, and 0.27 mmol/g, respectively. The adsorption capacity of TYP-en for Pd(II), Pt(IV), and Au(III) in 0.10 M HCl is 0.31, 0.17, and 0.52 mmol/g, respectively. In column extraction experiments using small-volume samples containing Pd(II), Pt(II), Pt(IV), Au(I), or Au(III) at concentrations of μmol/kg, TYP-en is able to quantitatively recover Pd, Pt, and Au from 0.01 to 0.2 M HCl irrespective of their oxidation states. In contrast, Vonnel-en is unable to quantitatively recover Au(I). In column extraction experiments using large-volume samples containing Pd(II), Pt(IV), and Au(III) at concentrations of pmol/kg, the recovery of Pd(II), Pt(IV), and Au(III) by TYP-en from 0.07 M HCl is 100–105%. However, the recovery of Pd(II), Pt(IV), and Au(III) by Vonnel-en from 0.03 to 0.3 M HCl is 102–110, 7–15, and 20–52%, respectively. Thus, the chelating resin TYP-en has a high potential for the multielemental determination of Pd, Pt, and Au in environmental water. Graphical abstract

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.

Titanium dioxide (TiO2) in mineral dust is considered as one of the driving forces of photocatalytic reaction at the aerosol surface in the atmosphere. As a precursor of mineral dust, soil contains ilmenite (FeTiO3) and titanite (CaSiTiO5), which have lower photochemical reactivities than TiO2. However, Ti species other than TiO2 in aerosol particles are not well recognized due to the lack of observation in ambient samples. In this study, Ti species in size-fractionated aerosol samples collected in the Noto Peninsula, Japan, were determined by macroscopic and semi-microscopic X-ray absorption fine structure spectroscopy. Regardless of aerosol particle size, Ti species were primarily composed of rutile, anatase, ilmenite, and titanite. Semi-microscopic Ti speciation showed that Ti-poor spots associated with mineral dust were composed of a mixture of rutile, anatase, ilmenite, and titanite, and Ti-rich spots were primarily composed of TiO2 (rutile or anatase) derived from authigenic minerals or anthropogenic materials. Thus, the Ti species in aerosol particles, especially mineral dust, were not composed solely of TiO2 polymorphs. Therefore, the photochemical reactivities of Ti in aerosol particles may be overestimated when laboratory experiments or model studies employ TiO2 as the representative Ti species.

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

In this study, we have investigated the evolution of concentrations and isotope ratios of dissolved nickel (Ni), copper (Cu), and zinc (Zn) from the North Equatorial Current in the western North Pacific to the Kuroshio in the East China Sea, where the inputs of anthropogenic and lithogenic materials through riverine and aeolian pathways are relatively high. The concentrations and isotope ratios for Ni, Cu, and Zn in the deep water of the East China Sea are similar to those of the western North Pacific. The concentrations of Ni, Cu, and Zn in the Changjiang diluted water (

Nickel (Ni), copper (Cu), and zinc (Zn) are commonly used in human activities and pollute aquatic environments including rivers and oceans. Recently, Ni, Cu, and Zn isotope ratios have been measured to identify their sources and cycles in environments. We precisely determined the Ni, Cu, and Zn isotope ratios in rain, snow, and rime collected from Uji City and Mt. Kajigamori in Japan, and investigated the potential of isotopic ratios as tracers of anthropogenic materials. The isotope and elemental ratios suggested that road dust is the main source of Cu in most rain, snow, and rime samples and that some of the Cu may originate from fossil fuel combustion. Zinc in the rain, snow, and rime samples may be partially attributed to Zn in road dust. Zinc isotope ratios in the Uji rain samples are lower than those in the road dust, which would be emitted via high temperature processes. Nickel isotope ratios are correlated with V/Ni ratios in the rain, snow, and rime samples, suggesting that their main source is heavy oil combustion. Furthermore, we analyzed water samples from the Uji and Tawara Rivers and the Kakita River spring in Japan. Nickel and Cu isotope ratios in the river water samples were significantly heavier than those in rain, snow, and rime samples, while Zn isotope ratios were similar. This is attributed to isotopic fractionation of Cu and Ni between particulate-dissolved phases in river water or soil.

Background Muscle weakness is associated with osteoarthritis pathology. A recent study demonstrated that measuring muscle volume using computed tomography (CT)-based analysis and comparing bilateral muscles in the same patient allowed for accurate evaluation of muscle volume in unilateral hip osteoarthritis (OA) patients. Here, we evaluated muscle volume using CT-based analysis and compared bilateral muscles in knee OA (KOA) patients. Methods CT images were obtained from 35 female radiographic KOA patients the day prior to total knee replacement surgery. Muscle volume (MV) was semi-automatically analyzed. Knee extension muscle strength (MS) was determined using a hand-held dynamometer. The severity of KOA patients’ clinical symptoms was examined using four domains of the Japanese Orthopedic Association (JOA) score. We compared the difference in MS (ΔMS) and MV (ΔMV) between the operated side (OS), which exhibited severe radiographic OA or severe pain, and the contralateral side (CS). Results JOA score was significantly lower in the OS than CS. MV and MS were also significantly lower in the OS than CS. There was no correlation between MV and MS or between MV and MS as a percentage of body weight on either side. However, ΔMV was positively correlated with ΔMS and pain on walking in the JOA. Conclusions We evaluated MV and MS using bilateral CT images of the legs of KOA patients. A reduction in MV was observed on the OS, and was correlated with a reduction in MS and pain on walking. Bilateral CT image analysis may be useful for evaluating the relationship between OA pathology and muscle atrophy.

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

Both molybdenum (Mo) and tungsten (W) form soluble oxyanions in oxic seawater, whereas Mo forms insoluble thiomolybdate and W forms soluble thiotungstate in sulfidic seawater. Thus, concentrations and stable isotope ratios of Mo and W in sediments may fluctuate due to changes in redox conditions and can be used to estimate paleoenvironmental changes. The modern Japan Sea is oxic from the surface to the bottom, whereas deep water became anoxic several times from the late Pleistocene to the Holocene. Detailed information on redox conditions is still lacking. In this study, we analyzed a sediment core that was collected from offshore Iwanai, Hokkaido (43°22ʹ36ʺ N, 140°04ʹ10ʺ E, water depth 900 m). To the best of our knowledge, our study is the first to report stable isotope data of Mo and W in sediments of the Japan Sea. We observed maxima in the Mo concentration of up to 29 ppm in the sediment layers of 11–10 ka, 17–14 ka (the last glacial maximum), 31 ka, and 45 ka in accordance with the maxima of total sulfur, thereby indicating the deposition of thiomolybdate MoOxS₄₋x²⁻ (0 ≤ x ≤ 3). δ⁹⁸Mo, however, was between –0.19 and 0.69‰ at these ages, suggesting that the H₂S concentration in bottom water never exceeded 11 μmol kg⁻¹. The concentration and isotopic ratio of W were relatively constant throughout the core; W = 1.2 ± 0.2 ppm and δ¹⁸⁶W = 0.03 ± 0.03‰ (ave ± sd). The authigenic Mo and W ratio, Moauth/Wauth (mol/mol), was 10.5 ± 7.3 except for the above four ages, supporting the control of Mn and Fe (oxyhydr)oxides on Moauth and Wauth under oxic conditions.

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 Female patients with osteoarthritis report more severe knee pain compared to men. However, the mechanism underlying sex differences in pain remains unclear. We previously found that calcitonin gene-related peptide (CGRP) was expressed in synovial tissue and that this localization may play a role in pain associated with knee osteoarthritis (KOA). Several animal studies have shown that the expression of CGRP and its receptor (receptor activity modifying protein 1, RAMP1) differs by sex. Here, we investigated synovial CGRP and RAMP1 expression in male and female patients with KOA. Methods Synovial tissue (ST) was harvested from male and female subjects (n=30 each) with radiographically confirmed unilateral Kellgren/Lawrence grade 3-4 KOA during total knee arthroplasty. Patients’ subjective pain severity was scored on a 0 to 10 cm visual analog scale (VAS). We compared the expression of CGRP and RAMP1 in ST from men and women and examined the correlation between mRNA levels of CGRP and RAMP1 and pain severity. Results Synovial expression of CGRP and RAMP1 was significantly elevated in women compared to men (CGRP, P=0.017; RAMP1, P=0.028). While CGRP expression was positively correlated with pain severity in females (ρ=0.443, P=0.014), no correlation was observed in men (ρ=-0.021, P=0.913). RAMP1 expression was not correlated with pain severity in either men or women (male, ρ=-0.114, P=0.939; female, ρ=-0.047, P=0.807). Conclusion CGRP and RAMP1 expression levels differ between men and women. Differential CGRP levels may suggest the presence of different pain mechanisms in men and women with KOA.

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.

Zirconium, niobium, hafnium, and tantalum are dissolved in seawater as hydroxide complexes at a concentration as low as 0.01 - 370 pmol kg-1 and are expected to be potential tracers for water masses in the ocean. Herein, we report a new analytical method for the multielemental determination of the four elements on the basis of column extraction, using a NOBIAS Chelate-PA 1 resin that contains ethylenediaminetriacetic acid groups. The elements were collected on the resin from seawater that had been added with 3.8 mM HF at pH 6.0, and were eluted with 5 M HF. After the evaporation of 5 M HF, the elements were dissolved in 0.5 M HNO3-6 mM H2SO4-1 mM HF and were determined by a high resolution ICP-MS, using a calibration curve method. We optimized the procedure to achieve quantitative recoveries and low backgrounds for the elements, although the complex formation between the metal ions and NOBIAS Chelate-PA 1 was decelerated by the seawater matrix. The method was tested by investigating the seawater samples of reference material and those collected from the depths at a station in the western North Pacific Ocean.

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 (

Both 2:1 and 1:1 couplings of alkylacetylenes with secondary amines were achieved using 8-quinolinolato rhodium catalysts and CsF. The 2:1/1:1 selectivity was switched by choosing the reaction solvent. In DMA, an unprecedented 2:1 coupling reaction of alkylacetylenes with amines proceeded to give 2-aminodiene products. One-pot 2:1 coupling/reduction provided rapid access to various allylamines, while one-pot coupling/hydrolysis gave enones as products. In toluene, anti-Markovnikov hydroamination occurred under relatively mild conditions to give 1:1 coupling products.

The stable isotope ratio of W is a new tracer in oceanographic studies and a new proxy in paleoceanographic studies; however, precise data for modern seawater have not been reported to date. Because the concentration of W in seawater is as low as 49 pmol kg−1, an ~3000-fold preconcentration is necessary prior to measurement by multicollector inductivity coupled plasma mass spectrometry (MC-ICP-MS). For the preconcentration, we investigated solid-phase extraction using chelating resins, namely, NOBIAS Chelate-PA1 with ethylenediaminetriacetic acid groups and TSK-8HQ with 8-hydroxyquinolie groups. We report that TSK-8HQ is useful because the effects of the seawater matrix are minor thermodynamically and kinetically. We present a novel method for analysis of the concentrations and isotope ratios of W and Mo in seawater, consisting of solid phase extraction, chromatographic separation using anion exchange resin AG1 X8, and measurement by MC-ICP-MS. Both W and Mo are quantitatively recovered by this method, which was applied to seawater samples collected from the North Pacific Ocean. The measured concentration of W and the concentration and isotope ratio of Mo are consistent with those in the literature. The isotope ratio of W is found to be uniform throughout the water column in the western North Pacific Ocean; δ186/184W is 0.55 ± 0.12‰ (ave ± 2sd, n = 7) using NIST SRM 3163 as a reference for W. On the basis of this data, we determined that the isotopic difference in δ186/184W is ~0.49‰ between seawater and oxic sediments in the modern ocean. This value accords with the reported experimental data for the isotope fractionation of W during adsorption on manganese and iron (oxyhydr)oxides, suggesting the validity of our data.

Multiple human and animal studies suggest that the upregulation of inflammatory cytokines and other pain-related molecules in degenerated or injured intervertebral discs (IVDs) may cause discogenic low back pain (LBP). We previously reported that macrophages in injured IVD in mice produced inflammatory cytokines, but not other pain-related molecules. CD14 is a monocyte marker expressed mainly by macrophages. The aim of the current study was to evaluate the role of CD14-positive cells in inflammatory cytokine and pain-related molecule expression in human degenerated IVD. IVD samples were harvested from 14 patients, including 10 with lumbar spinal stenosis, four with adult spinal deformity, and one with lumbar disc herniation during spinal interbody fusion surgery. Harvested IVD-derived mononuclear cells were obtained and CD14-positive (+) and CD14-negative (-) cells were separated using CD14 antibody and streptavidin-labeled magnetic beads. Inflammatory cytokines messenger RNA (mRNA) in the CD14(+) and CD14(-) cells, including tumor necrosis factor ɑ (TNFA), in, terleukin-1β (IL1B) and IL6, were determined using quantitative polymerase chain reaction (qPCR) and their expression levels were compared. To evaluate factors controlling the regulation of pain-related molecules mRNA expression, cultured CD14(-) and CD14(+) cells from IVDs were stimulated with recombinant human TNF-ɑ and IL-1β and levels of pain-related molecules, including calcitonin gene-related peptide (CGRP) and nerve growth factor (NGF) were determined using qPCR. Levels of TNFA, IL1B, IL6, and NGF in CD14(+) cells were significantly increased compared with those in CD14(-) cells (TNFA, p = 0.006; IL1B, p = .017; IL6, p = .010; NGF, p = .027). Following TNFA stimulation, NGF levels were significantly increased in CD14(-) and CD14(+) cells (CD14(-), p = .003; CD14(+), p < .001) and CGRP was significantly increased in CD14(-) IVD cells (p = .040). Following IL1B stimulation, NGF levels were significantly increased in CD14(-) cells (p = .004). CD14(+) cells had higher TNFA, IL1B, IL6, and NGF expressions than CD14(-) cells in human degenerated IVDs. Additionally, TNFA stimulation promoted the upregulation of NGF and CGRP in CD14(-) cells. These findings suggested that CD14(+) cells directly and indirectly contributed to inflammatory cytokine and pain-related molecule expression in human degenerated IVD. CD14(+) cells might be important in the pathological mechanism of chronic discogenic LBP in humans.

The North Pacific Ocean is the largest basin and is located at the end point of the thermohaline circulation of deep water. Few concurrent data of Cd, Ni, Zn, and Cu in seawater have been reported ...

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.

8-Quinolinolate is a monoanionic, hard, strongly σ-donating ligand that can form strong chelates with various metals. However, studies of the catalytic activities of soft transition metal complexes such as greater than second row, low-valent, late-transition metals having 8-quinolinolate ligands had not been well explored until recently. In recent years, several research groups including our own have studied and developed various reactions of terminal alkynes using rhodium(I) catalysts containing an 8-quinolinolate ligand. In this Perspective, we surveyed the transformations of terminal alkynes using 8-quinolinolato rhodium(I) catalyst such as additions of alcohols, amines, and thiols as well as polymerization, trimerization, dimerization, and alkyne/alkene [2 + 2] cycloaddition. Mechanistic studies based on theoretical calculations of hydroalkoxylation of alkynes and alkyne/alkene [2 + 2] cycloaddition reactions have also been described.