New hybrid materials based on the grafting of Pd(II)-amino complexes on the graphitic surface of AC: preparation, structures and catalytic properties

A novel procedure for the preparation of solid Pd(II)-based catalysts consisting of the anchorage of designed Pd(II)-complexes on an activated carbon (AC) surface is reported. Two molecules of the Ar–S–F type (where Ar is a plane-pyrimidine moiety, F a Pd(II)-ligand and S an aliphatic linker) differing in F, were grafted on AC by π–π stacking of the Ar moiety and the graphene planes of the AC, thus favouring the retaining of the metal-complexing ability of F. Adsorption of Pd(II) by the AC/Ar–S–F hybrids occurs via Pd(II)-complexation by F. After deep characterization, the catalytic activities of the AC/Ar–S–F/Pd(II) hybrids on the hydrogenation of 1-octene in methanol as a catalytic test were evaluated. 100% conversion to n-octane at T = 323.1 K and P = 15 bar, was obtained with both catalysts and most of Pd(II) was reduced to Pd(0) nanoparticles, which remained on the AC surface. Reusing the catalysts in three additional cycles reveals that the catalyst bearing the F ligand with a larger Pd-complexing ability showed no loss of activity (100% conversion to n-octane) which is assigned to its larger structural stability. The catalyst with the weaker F ligand underwent a progressive loss of activity (from 100% to 79% in four cycles), due to the constant aggregation of the Pd(0) nanoparticles. Milder conditions, T = 303.1 K and P = 1.5 bar, prevent the aggregation of the Pd(0) nanoparticles in this catalyst allowing the retention of the high catalytic efficiency (100% conversion) in four reaction cycles.

Oxygen, pH and calcium dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH and across a range of irradiances

Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4' diisothiocyanatostilbene-2,2'-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA.

Oxygen content and paleoproductivity from surface sediment samples Y69-86 to PLDS-004G

Quantitative estimation of surface ocean productivity and bottom water oxygen concentration with benthic foraminifera was attempted using 70 samples from equatorial and North Pacific surface sediments. These samples come from a well defined depth range in the ocean, between 2200 and 3200 m, so that depth related factors do not interfere with the estimation. Samples were selected so that foraminifera were well preserved in the sediments and temperature and salinity were nearly uniform (T = 1.5° C; S = 34.6 per mil). The sample set was also assembled so as to minimize the correlation often seen between surface ocean productivity and bottom water oxygen values (r**2 = 0.23 for prediction purposes in this case). This procedure reduced the chances of spurious results due to correlations between the environmental variables. The samples encompass a range of productivities from about 25 to >300 gC m**-2 yr**-1, and a bottom water oxygen range from 1.8 to 3.5 ml/L. Benthic foraminiferal assemblages were quantified using the >62 µm fraction of the sediments and 46 taxon categories. MANOVA multivariate regression was used to project the faunal matrix onto the two environmental dimensions using published values for productivity and bottom water oxygen to calibrate this operation. The success of this regression was measured with the multivariate r? which was 0.98 for the productivity dimension and 0.96 for the oxygen dimension. These high coefficients indicate that both environmental variables are strongly imbedded in the faunal data matrix. Analysis of the beta regression coefficients shows that the environmental signals are carried by groups of taxa which are consistent with previous work characterizing benthic foraminiferal responses to productivity and bottom water oxygen. The results of this study suggest that benthic foraminiferal assemblages can be used for quantitative reconstruction of surface ocean productivity and bottom water oxygen concentrations if suitable surface sediment calibration data sets are developed and appropriate means for detecting no-analog samples are found.

(Table 1) Planktonic foraminifera counts and stable oxygen isotope ratios of Pacific Ocean surface sediments

Core-top samples from the eastern tropical Pacific (10°N to 20°S) were used to test whether the ratio between Globorotalia menardii cultrata and Neogloboquadrina dutertrei abundance (Rc/d) and the oxygen isotope composition (?18O) of planktonic foraminifera can be used as proxies for the latitudinal position of the Equatorial Front. Specifically, this study compares the ?18O values of eight species of planktonic foraminifera (Globigerinoides ruber sensu stricto (ss) and sensu lato (sl), Globigerinoides sacculifer, Globigerinoides triloba, Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, Globorotalia menardii menardii, Globorotalia menardii cultrata and Globorotalia tumida) with the seasonal hydrography of the region, and evaluates the application of each species or combination of species for paleoceanographic reconstructions. The results are consistent with sea surface temperature and water column stratification patterns. We found that in samples north of 1°N, the Rc/d values tend to be higher and d18O values of G. ruber, G. sacculifer, G. triloba, P. obliquiloculata, N. dutertrei, and G. menardii cultrata tend to be lower than those from samples located south of 1°N. We suggest that the combined use of Rc/d and the d18O difference between G. ruber and G. tumida or between P. obliquiloculata and G. tumida are the most suitable tools for reconstructing changes in the latitudinal position of the Equatorial Front and changes in the thermal stratification of the upper water column in the eastern tropical Pacific.

High-Resolution In Situ Oxygen-Argon Studies of Surface Biological and Physical Processes in the Polar Oceans

The Arctic Ocean and Western Antarctic Peninsula (WAP) are the fastest warming regions on the planet and are undergoing rapid climate and ecosystem changes. Until we can fully resolve the coupling between biological and physical processes we cannot predict how warming will influence carbon cycling and ecosystem function and structure in these sensitive and climactically important regions. My dissertation centers on the use of high-resolution measurements of surface dissolved gases, primarily O2 and Ar, as tracers or physical and biological functioning that we measure underway using an optode and Equilibrator Inlet Mass Spectrometry (EIMS). Total O2 measurements are common throughout the historical and autonomous record but are influenced by biological (net metabolic balance) and physical (temperature, salinity, pressure changes, ice melt/freeze, mixing, bubbles and diffusive gas exchange) processes. We use Ar, an inert gas with similar solubility properties to O2, to devolve distinct records of biological (O2/Ar) and physical (Ar) oxygen. These high-resolution measurements that expose intersystem coupling and submesoscale variability were central to studies in the Arctic Ocean, WAP and open Southern Ocean that make up this dissertation.

Key findings of this work include the documentation of under ice and ice-edge blooms and basin scale net sea ice freeze/melt processes in the Arctic Ocean. In the WAP O2 and pCO2 are both biologically driven and net community production (NCP) variability is controlled by Fe and light availability tied to glacial and sea ice meltwater input. Further, we present a feasibility study that shows the ability to use modeled Ar to derive NCP from total O2 records. This approach has the potential to unlock critical carbon flux estimates from historical and autonomous O2 measurements in the global oceans.

Stable oxygen isotope data of Thoracosphaera heimii in surface sediment samples of the equatorial Atlantic and South Atlantic

To investigate the potential use of the stable isotope composition of the vegetative cysts of the photosynthetic dinoflagellate Thoracosphaera heimii for quantitative palaeotemperature reconstructions a method has been developed to purify T. heimii cysts from sediment samples. Stable oxygen and carbon isotopes have been measured on T. heimii cysts from 21 surface sediment samples from the equatorial Atlantic and South Atlantic Oceans. Calculated temperatures based on the palaeotemperature equation for inorganic calcite precipitation generally reflect mean annual temperatures of the upper water column, notably of thermocline depths. Although the present results suggest that the isotopic composition of T. heimii shells might be formed in equilibrium with the seawater in which the shells are being formed, future investigations are required to determine possible effects of metabolic and kinetic processes on the fractionation process. This pilot study therefore forms the basis for future investigations on the development of this tool and the determination of a species-specific palaeotemperature equation. The wide geographic and stratigraphic distribution of T. heimii cysts in sediments, the stable position of T. heimii within the water column and the high resistance of its cysts against calcite dissolution underline its potential for a wide usability in palaeotemperature reconstructions.

(Table 3) Oxygen and carbon isotopic record of living (Rose Bengal Stained) benthic foraminifera of North Atlantic surface sediments

Variation of the d13C of living (Rose Bengal stained) deep-sea benthic foraminifera is documented from two deep-water sites (~2430 and ~3010 m) from a northwest Atlantic Ocean study area 275 km south of Nantucket Island. The carbon isotopic data of Hoeglundina elegans and Uvigerina peregrina from five sets of Multicorer and Soutar Box Core samples taken over a 10-month interval (March, May, July, and October 1996 and January 1997) are compared with an 11.5 month time series of organic carbon flux to assess the effect of organic carbon flux on the carbon isotopic composition of dominant taxa. Carbon isotopic data of Hoeglundina elegans at 3010 m show 0.3 per mil lower mean values following an organic carbon flux maximum resulting from a spring phytoplankton bloom. This d13C change following the spring bloom is suggested to be due to the presence of a phytodetritus layer on the seafloor and the subsequent depletion of d13C in the pore waters within the phytodetritus and overlying the sediment surface. Carbon isotopic data of H. elegans from the 2430 m site show an opposite pattern to that found at 3010 m with a d13C enrichment following the spring bloom. This different pattern may be due to spatial variation in phytodetritus deposition and resuspension or to a limited number of specimens recovered from the March 1996 cruise. The d13C of Uvigerina peregrina at 2430 m shows variation over the 10 month interval, but an analysis of variance shows that the variability is more consistent with core and subcore variability than with seasonal changes. The isotopic analyses are grouped into 100 µm size classes on the basis of length measurements of individual specimens to evaluate d13C ontogenetic changes of each species. The data show no consistent patterns between size classes in the d13C of either H. elegans or U. peregrina. These results suggest that variation in organic carbon flux does not preferentially affect particular size classes, nor do d13C ontogenetic changes exist within the >250 to >750 µm size range for these species at this locality. On the basis of the lack of ontogenetic changes a range of sizes of specimens from a sample can be used to reconstruct d13C in paleoceanographic studies. The prediction standard deviation, which is composed of cruise, core, subcore, and residual (replicate) variability, provides an estimate of the magnitude of variability in fossil d13C data; it is 0.27 per mil for H. elegans at 3010 m and 0.4 per mil for U. peregrina at the 2430 m site. Since these standard deviations are based on living specimens, they should be regarded as minimum estimates of variability for fossil data based on single specimen analyses. Most paleoceanographic reconstructions are based on the analysis of multiple specimens, and as a result, the standard error would be expected to be reduced for any particular sample. The reduced standard error resulting from the analysis of multiple specimens would result in the seasonal and spatial variability observed in this study having little impact on carbon isotopic records.

Sample locations, stratigraphic information and listing of carbon and oxygen isotope data of the measured planktonic foraminifera of surface sediments in the western South Atlantic Ocean (Table 1)

We explored the potential to use the stable isotopic compositions of planktonic foraminifera as a proxy for the position of the Brazil-Malvinas Confluence (BMC) in the Argentine Basin. For this purpose, we measured the oxygen and carbon isotopic compositions of Globigerinoides ruber (pink and white varieties measured separately), Globigerinoides trilobus, Globigerina bulloides, Globorotalia inflata and Globorotalia truncatulinoides (left- and right-coiling forms measured separately) from a latitudinal transect of 56 surface sediment samples from the continental slope off Brazil, Uruguay and Argentina between 20 and 48°S. Lowest oxygen isotopes values were found in G. ruber (pink), followed by G. ruber (white) and G. trilobus reflecting the highly stratified near surface water conditions north of the BMC. Globigerina bulloides was present mainly south of the BMC and records subsurface conditions supporting earlier plankton tow studies. Globorotalia inflata and G. truncatulinoides (left and right) were both available over the whole transect and calcify in the depth level with the steepest temperature change across the BMC. Accordingly, the delta18O of these species depict a sharp gradient of 2? at the confluence with remarkably stable values north and south of the BMC. Our data show that the oxygen isotopic composition of G. inflata and G. truncatulinoides (left and right) are the most reliable indicators for the present position of the BMC and can therefore be used to define the past migration of the front if appropriate cores are available.

Controlled surface nanotopography and oxygen plasma treatment of PEEK to improve cellular response

Poly(aryl-ether-ether-ketone) (PEEK) is a semi crystalline polymer which exhibits properties that make it an attractive choice for use as an implant material. It displays natural radiolucency, and MRI compatibility, as well as good chemical and sterilization resistance, both of which make it of particular interest in orthopaedic implants. However, PEEK has demonstrated poor cellular adhesion both in vitro and in vivo. This is problematic as implant surfaces that do not develop a layer of adhesive cells are at risk of undergoing fibrous encapsulation, which in turn leads to lack of a strong interface between the implant device and the patient tissue, which can in turn lead to failure of the implant and revision surgery . As incorporating nanotopography into a polymer surface has been demonstrated to be able to direct the differentiation behaviour of stem cells, a possible solution to PEEKs underlying issues with poor cellular response would be to incorporate specific nanoscale topography into the material surface through injection moulding, and then analysing if this is a viable method for addressing PEEKs issues with cellular response. In addition to nanoscale topography, the experimental PEEK surfaces were treated with oxygen plasma to address the underlying cytophobicity of the material. As this type of treatment has been documented to be capable of etching the PEEK surface, experiments were carried out to quantify the effect of this treatment, both on the ability of cells to adhere to the PEEK surface, as well as the effect it has upon the nanotopography present at the PEEK surface. The results demonstrated that there were a range of plasma treatments which would significantly improve the ability of cells to adhere to the PEEK surface without causing unacceptable damage to the nanotopography. Three different types of cells with osteogenic capacity were tested with the PEEK surfaces to gauge the ability of the topography to alter their behaviour: SAOS-2, osteoprogenitors and 271+ MSCs. Due to PEEKs material properties (it is non transparent, exhibits birefringence and is strongly autofluorescent) a number of histological techniques were used to investigate a number of different stages that take place in osteogenesis. The different cell types did display slightly different responses to the topographies. The SAOS-2 cells cultured on surfaces that had been plasma treated for 2 minutes at 200W had statistically significantly higher levels of von Kossa staining on the NSQ surface compared to the planar surface, and the same experiment employing alizarin red staining, showed a statistically significantly lower level of staining on the SQ surface compared to the planar surface. Using primary osteoprogenitor cells designed to look into if whether or not the presence of nanotopography effected the osteogenic response of these cells, we saw a lack of statistically significant difference produced by the surfaces investigated. By utilising HRP based immunostaining, we were able to investigate, in a quantitative fashion, the production of the two osteogenic markers osteopontin and osteocalcin by cells. When stained for osteocalcin, the SQ nanotopography had total percentage of the surface with stained material, average area and average perimeter all statistically significantly lower than the planar surface. For the cells that were stained for osteopontin, the SQ nanotopgraphy had a total percentage of the surface with stained material, average area and average perimeter all highly statistically significantly lower than those of the planar surface. Additionally, for this marker the NSQ nanotopography had average areas and average perimeters that were highly significantly higher than those of the planar surface. There were no significant differences for any of the values investigated for the 271+ MSC’s When plasma treatment was varied, the SAOS-2 cells demonstrated an overall trend i.e. increasing the energy of plasma treatment in turn leads to an increase in the overall percentage of staining. A similar experiment employing stem cells isolated from human bone marrow instead of SAOS-2 cells showed that for polycarbonate surfaces , used as a control, mineralization is statistically significantly higher on the NSQ nanopattern compared to the planar surface, whereas on the PEEK surfaces we observe the opposite trend i.e. the NSQ nanotopography having a statistically significantly lower amount of mineralization compared to the planar surface at the 200W 2min and 30W 1min plasma treatments. The standout trend from the PEEK results in this experiment was that the statistically significant differences on the PEEK substrates were clustered around the lower energy plasma treatments, which could suggest that the plasma treatment disrupted a function of the nanotopograhy which is why, as the energy increases, there are less statistically significant differences between the NSQ nanotopography and the Planar surface This thesis documents the response of a number of different types of cells to specific nanoscale topographies incorporated into the PEEK surface which had been treated with oxygen plasma. It outlines the development of a number of histological methods which measure different aspects of osteogenesis, and were selected to both work with PEEK, and produce quantitative results through the use of Cell Profiler. The methods that have been employed in this body of work would be of interest to other researchers working with this material, as well as those working with similarly autofluorescent materials.