The amount of available redox reaction sites in the film has Purmorphamine strong influence on the electrocatalytic activity for redox electrolyte as well as on the efficiency of the devices. Therefore, the specific capacitance and the available redox reaction sites of the above mentioned two CuxS films were investigated using cyclic voltammetry. Fig. 3 shows the cyclic voltammogram of the chemically deposited CuxS thin film in an already reported aqueous electrolyte containing 1 MH2SO4and 0.1 M CuSO4.However, the cyclic voltammogram of the both compact and porous CuxS films did not show the distinctive peaks during oxidation and reduction cycles (Fig. 3). Oxidation of the CuxS is not a simple, but is made up of a series of consecutive reactions. Different researchers have argued different series of assumptions about the mechanism of electrochemical oxidation of CuxS , , , ,  and . However, the most acceptable mechanism presumes that the metal ions from the mineral crystal lattice are transferred into the solution, leaving a surface region with the higher content of sulfur. That sulfur can be treated as adsorbed species giving rise to the pseudo-capacitance exhibited by CuxS.
It is well-known that there is an electron counting rule in Nowotny chimney ladder phases. The stability of these phases is strongly correlated with the total number of valence electrons per transition metal atom. For example, in Ru2Sn3 which was considered the prototype of the new phase, each Ru immunoglobulin light chain contributes 8 electrons, and each Sn atom contributes 4 electrons resulting the total number of electrons in each formula unit to be 28. Considering that in each formula there are two Ru atoms, therefore there are 14 electrons for each Ru atom. This rule is called 14 electron rule, which is an experimental rule, and such a unique crystal structure feature and the 14 electron rule should be related to the electronic structure of the compounds, such as the energy gap at Fermi level to decrease the total electronic energy as found in Peierls distortion . To date, the nature of such a rule is still not revealed, but the rule has been well followed by many Nowotny alloys , , , ,  and . In addition, by substitution of elements with different valence electrons, crystal structure change can be predicted according to this rule as demonstrated in previous work  and . Here, if each Fe atom also contributes 8 electrons, and each Ge atom contributes 4 electrons, then Fe2Ge3 should be a stable structure. But according to our result, the structure of the new phase is different from the Ru2Sn3 type, and the composition is slightly deviated from the Fe/Ge ratio of 2/3. There are many phases in Fe-Ge system, for the convenience of reference, this new phase is named as σ phase in the Fe-Ge binary system. A slight revision was made to the prior suggested phase diagram  which is shown in Fig. 6.
As shown in Fig. 2, the crystalline structure exhibits Eu3+ concentration-dependence for samples 2 and 3. Since the synthesis in situ should be considered as IDH-C35 of Eu3 + and Zn2 + in the bond formation coordination with BDC ligand, at a quite low concentrations of Eu3+ (compared to Zn2 +) structure would mainly be formed via the privileged coordination of Zn2+ with BDC ligand, meanwhile Eu3+ ions, playing a role of the dopant, could somewhat distort the basic structure. With increasing concentration of Eu3+, different structures can be formed due to more coordination bonds of Eu3+ with BDC ligand, competing with those of Zn2+ with BDC ligand. Normally, for relatively low input doping levels of rare earth (∼10–15% as in this study), in order to further investigate and corroborate the findings, the single-crystal X-ray structural analysis combining crystal parameter calculation and refinement is required and afterwards the influence of experimental conditions on the XRD patterns could have clarified in details. However, this investigation is quite complicated and possibly is beyond the initial scope of this paper, we cannot take upon ourselves here to solve root cap now but in the upcoming study.
Full-size image (52 K)
1H NMR spectra of PC-PEG-b-PLA(a) and PMPC-g-PLA(b) (in deuterate chloroform), and PMPC-g-(PEG-b-PLA) (c) (in deuterate chloroform and methanol, 90:10 v/v).
3.2. Surface properties of film
PLA film was coated with MPC copolymers by a solvent YM 155 technique. The surfaces of the films were analyzed and measured using XPS and WCA.
Fig. 2 shows the XPS spectra of C1s, N1s, and P2p on the surface of the PC-PEG-b-PLA, PMPC-b-PLA, and PMPC-g-(PEG-b-PLA) with the PLA substrate. In the case of PMPC-g-PLA, a strong carbon peak attributed to backbone methyl or methylene carbons (285 eV) of MPC was presented in the C1s spectrum. For PEG-containing copolymers, peaks at the 286.8 eV attributed to ether carbon (–O–C–) were enhanced dramatically. This suggested that the flexible PEG chain stretched-out towards the surface that had been pretreated with water. Both the phosphorous peak at 133 eV and the nitrogen peak at 402 eV were easily observed on the surface of the PMPC-g-PLA and PMPC-g-(PEG-b-PLA), while only a weak P2p peak was found on the surface of the PC-PEG-b-PLA owing to a low content of PC groups in the polymer. All these results indicated that the surface of the PLA film was covered with a polar component of a copolymer and that the outer surfaces of polymer films were dominated by PC groups.
Distribution of dissolved methane (nmol L− 1) along a) NL, b) ML and c) NLSE/NLSW lines with the junction indicated by Pifithrin vertical line. Note the differing colour scale on c) to enhance details.
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Distributions of a) temperature (°C), b) salinity (psu), and c) dissolved oxygen (mL/L) along the NL, ML and NLSE and NLSW lines.
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The distribution of dissolved methane for the entire study area shown as a function of potential temperature and salinity where the black circle diameter is Laurentia proportional to CH4 saturation in the range 6 to 1057%. Coloured ellipses represent the temperature and salinity range of water masses where WGSW: Western Greenland Shelf Water, AW: Arctic Water, BBDW: Baffin Bay Deep Water, BBIW: Baffin Bay Intermediate Water, LSW: Labrador Sea Water and DSOW: Denmark Strait Overflow Water, after Curry et al. (2011), Tang et al. (2004) and Azetsu-Scott et al. (2005).
3.2. Phenol identification and quantification
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Catechin and sinapic AMN-107 chemical structure.
Catechin is a flavonoid type compound with a catechol group in the B-ring, a resorcinol group in the A-ring and a hydroxyl group at position 3 in the C-ring (Fig. 2). The reduction of Fe(III) to Fe(II) in the presence of catechin (initial Fe(III):catechin ratio, 1:5) in 0.7 M NaCl-2 mM NaHCO3 was followed by adding FZ to the Fe(III)-catechin solution at three different pH values 8.0, 7.5 and 6.0. The presence of the Fe(II) chelator FZ in the media acted as a sink for the released Fe(II), thereby preventing any back reactions and allowing the determination of the direct reduction process. Fig. 3 shows that Fe(II) was efficiently formed and this process was pH dependent. The reduction of Fe(III) followed a pseudo-first order kinetic with the rate constant (k′ in s− 1) increasing as pH decreases from log k′ = − 5.35 ± 0.07 at pH = 8.00 to log k′ = − 3.68 ± 0.13 at pH 6.0 ( Table 2).
Type II photosensitized oxidation of the 2-Methoxyestradiol phytyl side-chain leads to the production of 3-methylidene-7,11,15-trimethylhexadecan-1,2-diol (phytyldiol) (Rontani et al., 1994). Phytyldiol is ubiquitous in the environment and constitutes a stable and specific tracer for photodegradation of chlorophyll phytyl side-chain (Rontani et al., 1996 and Cuny and Rontani, 1999). The molar ratio phytyldiol:phytol (Chlorophyll Phytyl side-chain Photodegradation Index, CPPI) was proposed to estimate the extent of chlorophyll photodegraded in natural marine samples (Cuny et al., 2002). The very high value (CPPI = 71) measured in senescent P. sativum leaves attests to a complete photodegradation of chlorophyll tetrapyrrolic structure, while other very reactive lipid components of chloroplasts (e.g. oleic acid) are only very weakly affected. These results suggest that during the senescence of temperate terrestrial higher plants, the very quick photodegradation of chlorophyll should considerably limit its photosensitizing properties relative to the other cell components and notably to sitosterol.
In autumn, at all stations along the Browns Bank Line, surface DIC was reduced relative to spring conditions discussed above (compare Fig. 3c and g). This DIC decrease was most pronounced at the nearshore station BBL1 and the offshore station BBL7 (Fig. 3g). Autumn surface concentrations ranged from 1945 μmol kg−1 (BBL1) to 1998 μmol kg−1 (BBL5). In the subsurface (from 50 to 100 m) there was ly900009 increase in DIC in autumn relative to spring, particularly evident at stations BBL1, BBL3, BBL4 and BBL7, on the order of 30 to 50 μmol DIC kg−1. Increases in surface pH, from values of roughly 7.9 at all stations along the Browns Bank Line, to values of up to 8.0 at stations BBL5 and BBL7 were observed between spring and autumn (Fig. 7a). The pH profiles shown are not at in-situ temperature, but normalised to 25 °C to remove the effects of changing temperature. This pH increase can thus be attributed in part to the biological uptake of carbon, decreasing the surface pCO2 and enhancing the aragonite saturation state (Ω, Fig. 8a) in autumn. Surface values of Ω along the Browns Bank Line increased from roughly 2.0 in spring to values greater than 2.0 and approaching 3.0 at the offshore station BBL7.
0810 725 745 0811 265 270 0812 960 990 0813 835 860 a Flux = BaAdd × 137.327 × 100/(10 × 530 × 2.5). Table options Full-size image (24 K) Fig. 6. The Ba concentration–salinity relation for samples having salinity ≤ 34.6. The red, green and blue symbols represent samples from the depth horizons of ≤ 5, 5–50 and 50–100 m. High Ba in surface waters of the station 0816 (enclosed by green circle) falls far outside the linear trend set by other data and hence DSIP excluded from the regression analysis. Figure options Full-size image (110 K) Fig. 7. Ba concentration–salinity–potential temperature plots for samples below a depth horizon of 500 m in the BoB. The symbols are same as given in Fig. 2. The Ba concentrations in these samples show a very significant and strong inverse correlation (R2 > 0.95; P < 0.0001) with the salinity. The linear potential temperature–salinity plots argue in favor of a dominant control of water mixing in determining the Ba concentrations and confirm its conservative behavior in BoB deep waters. However, the Ba concentrations in some of the bottom waters seem to be higher than that set by the linear trend from the stations 0807 and 0811 (enclosed by the green circles). The trend of Ba distribution with salinity obtained for station 0807 is similar to that of the nearby GEOSECS-445 (shown by pink squares in the plot for 0807). These higher values are attributed to possible benthic fluxes.
Increases in UV S and SR have been shown to correlate with decreases in average CDOM molecular weight for terrestrial waters ( Helms et al., 2008). For our unextracted samples, S and SR decreased with depth at the North Pacific ALOHA site ( Fig. 7.) In the same region the fraction of high molecular weight DOC recoverable by 1000 Dalton cutoff ultrafiltration membranes decreases with depth ( Benner, 2002). Thus the molecular weight information obtained from optical parameters must be confined to the CDOM pool and not extrapolated to the bulk DOC pool, since the distribution and cycling of the two pools in the open ocean are largely decoupled ( Swan et al., 2009 and Stedmon and Alvarez-Salgado, 2011). It is also possible that Pracinostat the relationship between S and molecular weight observed elsewhere is dominated by the relative abundance of terrestrial DOM and therefore has limited relevance to the open ocean. Other studies have revealed CDOM optical properties to be strongly correlated with CDOM aromaticity ( Weishaar et al., 2003), dissolved lignin ( Spencer et al., 2009 and Fichot and Benner, 2012), and dissolved black carbon ( Stubbins et al., 2012). Condensed aromatics (dissolved black carbon) in the oceans are a significant fraction of the DOM pool and have similar distributions to those for CDOM, i.e., with highest concentrations in terrestrially influenced surface waters, moderate values in the deep oceans, and lowest values in the photobleached subtropical gyres ( Dittmar and Paeng, 2009 and Nelson and Siegel, 2013). Trends in dissolved black carbon match those for CDOM as both have a strong photochemical sink ( Stubbins et al., 2012). Further work is required to determine which pools of aromatic carbon, lignin, dissolved black carbon or others play quantitatively significant roles in determining the optical properties of deep ocean waters.