Effects of cation substitutions on the physical properties of M2M1T2O6 pyroxenes

In this PhD study, the effects of the cation substitutions on the physical properties of pyroxenes have been discussed. The results of this work extend the knowledge on pyroxenes with different chemical compositions. These properties might be used in the development of ceramic pigments, advanced materials and for the mineralogical phase identification. First of all, the crystallographic differences between Ge and Si pyroxenes have been examined. The structure of C2/c Ca rich Ge clinopyroxenes is very close to the low pressure C2/c structural configuration found in Ca-rich Si-pyroxenes. The shear of the unit cell is very similar, and the difference between a Ge end member and the corresponding Si-rich one is less than 1°. Instead, a remarkable difference exists between Ca-poor Si and Ge clinopyroxenes. First, Ca-poor Ge pyroxenes do not display a P21/c symmetry, but retain the C2/c symmetry; second, the observed C2/c structure shows, at room pressure, the configuration with highly kinked tetrahedral chains characteristic of the high pressure C2/c symmetry of Si Ca-poor pyroxenes. In orthopyroxenes, with Pbca symmetry, Ge-pyroxenes have volume larger than Si-pyroxenes. Samples along the system CaCoGe2O6 - CoCoGe2O6 have been synthesized at three different temperatures: 1050 °C, 1200 °C and 1250 °C. The aim of these solid state syntheses was to obtain a solid solution at ambient pressure, since the analogues Si-system needs high pressure. Unfortunately, very limited solution occurs because the structure forms of the two end member (high temperature for CaCoGe2O6 and high pressure CoCoGe2O6) are incompatible. The phase diagram of this system has been sketched and compared to that of Si. The cobalt end member (CoCoGe2O6) is stable at ambient pressure in two symmetries: at 1050 °C C2/c and 1200 °C Pbca. The impurity phase formed during these experiments is cobalt spinel. Raman spectroscopy has been used to investigate the vibrational properties of Ca-pyroxenes CaCoGe2O6, CaMgGe2O6, CaMgSi2O6 and CaCoSi2O6. A comparison between silicate and germanate pyroxenes shows significant changes in peak positions of the corresponding modes caused mainly by the difference of the Ge-Si atomic weight along with the distortion and compression of the coordination polyhedra. Red shift in Raman spectra of germanates has been calculated by a rough scale factor calculated by a simple harmonic oscillator model, considering the different bond lengths for 4-coordinated Si ~ 1.60- 1.65 Å vs Ge–O distance ~1.70 - 1.80 Å. The Raman spectra of CaMgGe2O6 and CaCoGe2O6 have been classified, in analogy with silicate (Wang et al., 2001) counterparts, in different ranges: - R1 (880-640 cm-1): strong T-O stretching modes of Ge and non-bridging O1 and O2 atoms within the GeO4 tetrahedron; - R2 (640-480 cm-1): stretching/bending modes of Ge-Obr-Ge bonds (chain stretching and chain bending); - R4 (480-360 cm-1): O-Ge-O vibrations; - R3 (360-240 cm-1): motions of the cations in M2 and M1 sites correlated with tetrahedral chain motion and tilting tetrahedra; - R5 (below 240 cm-1): lattice modes. The largest shift with respect to CaMgSi2O6 - CaCoSi2O6 is shown by the T-O stretching and chain modes. High-pressure Raman spectroscopy (up to about 8 GPa) on the same samples of Ca-pyroxenes using an ETH-type diamond anvil cell shows no phase transition within the P-ranges investigated, as all the peak positions vary linearly as a function of pressure. Our data confirm previous experimental findings on Si-diopside (Chopelas and Serghiou, 2000). In the investigated samples, all the Raman peaks shift upon compression, but the major changes in wavenumber with pressure are attributed to the chain bending (Ge-Obr-Ge bonds) and tetrahedra stretching modes (Ge-Onbr). Upon compression, the kinking angle, the bond lengths and T-T distances between tetrahedra decrease and consequently the wavenumber of the bending chain mode and tetrahedra stretching mode increases. Ge-pyroxenes show the higher P-induced peak-position shifts, being more compressible than corresponding silicates. The vibrational properties of CaM2+Ge2O6 (M2+ =Mg, Mn, Fe, Co, Ni, Zn) are reported for the first time. The wavenumber of Ge-Obr-Ge bending modes decreases linearly with increasing ionic radius of the M1 cation. No simple correlation has been found with M1 atomic mass or size or crystallographic parameters for the peak at ~850 cm-1 and in the low wavenumber regions. The magnetic properties of the system CaCoSi2O6 - CoCoSi2O6 have been investigated by magnetometry. The join is always characterized by 1 a.p.f.u. of cobalt in M1 site and this causes a pure collinear antiferromagnetic behaviour of the intra-chain superexchange interaction involving Co ions detected in all the measurements, while the magnetic order developed by the cobalt ions in M2 site (intra-chain) is affected by weak ferromagnetism, due to the non-collinearity of their antiferromagnetic interaction. In magnetically ordered systems, this non-collinearity effect promotes a spin canting of anti-parallel aligned magnetic moments and thus is a source of weak ferromagnetic behaviour in an antiferromagnetic. The weak ferromagnetism can be observed only for the samples with Co content higher than 0.5 a.p.f.u. in M2, when the concentration is sufficiently high to create a long range order along the M2 chain which is magnetically independent of M1 chain. The ferromagnetism was detected both in the M(T) at 10 Oe and M(H).

Geochemical and Sr, Nd, Pb isotope investigation of the New Caledonia ophiolite

The New Caledonia ophiolite hosts one of the largest obducted mantle section in the world, hence providing a unique insight for the study of upper mantle processes. These mantle rocks belong to an “atypical” ophiolitic sequence, which is dominated by refractory harzburgites but it also includes minor spinel and plagioclase lherzolites. Upper crust is notably absent in the ophiolite, with the exception of some mafic-ultramafic cumulates cropping out in the southern part of the island. Although the New Caledonia ophiolite has been under investigation for decades, its ultra-depleted nature has made its characterization an analytical challenge, so that few trace element data are available, while isotopic data are completely missing. In this thesis a comprehensive geochemical study (major, trace element and Sr-Nd-Pb isotopes) of the peridotites and the associated intrusive mafic rocks from the New Caledonia ophiolite has been carried out. The peridotites are low-strain tectonites showing porphyroclastic textures. Spinel lherzolites are undepleted lithotypes, as attested by the presence of 7-8 vol% of Na2O and Al2O3-rich clinopyroxene (up to 0.5 wt% Na2O; 6.5 wt% Al2O3), Fo content of olivine (88.5-90.0 mol%) and low Cr# of spinel (13-17). Conversely, harzburgites display a refractory nature, proven by the remarkable absence of primary clinopyroxene, very high Fo content in olivine (90.9-92.9 mol%), high Mg# in orthopyroxene (89.8-94.2) and Cr# in spinel (39-71). REE contents show abyssal-type patterns for spinel lherzolites, while harzburgites display U-shaped patterns, typical of fore-arc settings. Spinel lherzolites REE compositions are consistent with relatively low degree (8-9%) of fractional melting of a DMM source, starting in the garnet stability field. Conversely, REE models for harzburgites indicate high melting degrees (20-25%) of a DMM mantle source under spinel faies conditions, consistent with hydrous melting in forearc setting. Plagioclase lherzolites exhibit melt impregnation microtextures, Cr- and TiO2-enriched spinels and REE, Ti, Y, Zr progressive increase with respect to spinel lherzolites. Impregnation models indicate that plagioclase lherzolites may derive from spinel lherzolites by entrapment of highly depleted MORB melts in the shallow oceanic lithosphere. Mafic intrusives are olivine gabbronorites with a very refractory composition, as attested by high Fo content of olivine (87.3-88.9 mol.%), very high Mg# of clinopyroxene (87.7-92.2) and extreme anorthitic content of plagioclase (An = 90-96 mol%). The high Mg#, low TiO2 concentrations in pyroxenes and the anorthitic composition of plagioclase point out an origin from ultra-depleted primitive magmas in a convergent setting. Geochemical trace element models show that the parental melts of gabbronorites are primitive magmas with striking depleted compositions, bearing only in part similarities with the primitive boninitic melts of Bonin Islands. The first Sr, Nd and Pb isotope data obtained for the New Caledonia ophiolite highlight the presence of DM mantle source variably modified by different processes. Nd-Sr-Pb isotopic ratios for the lherzolites (+6.98≤epsilon Ndi≤+10.97) indicate a DM source that suffered low-temperature hydrothermal reactions. Harzburgites are characterized by a wide variation of Sr, Nd and Pb isotopic values, extending from DM-type to EM2 compositions (-0.82≤ epsilon Ndi≤+17.55), suggesting that harzburgite source was strongly affected by subduction-related processes. Conversely, combined trace element and Sr-Nd-Pb isotopic data for gabbronorites indicate a derivation from a source with composition similar to Indian-type mantle, but affected by fluid input in subduction environment. These geochemical features point out an evolution in a pre-Eocenic marginal basin setting, possibly in the proximity of a transform fault, for the lherzolites. Conversely, the harzburgites acquired their main geochemical and isotopic fingerprint in subduction zone setting.

The other on display: translation in the Ethnographic Museum

The ethnographic museum in the West has a long and troubling history. The display of 'exotic peoples' in travelling exhibitions began as early as the sixteenth century, but it was the mid and late nineteenth century that saw the great expansion of museums as sites to show artefacts collected - under anything but reputable circumstances - from what were considered the 'primitive', 'natural', or 'tribal' peoples of the world. Today the ethnographic museum is still a feature of large European cities, though faced with newly formulated dilemmas in the postcolonial world. For how can the material culture of a non-western people be collected and displayed in the West without its makers being translated into wordless and powerless objects of visual consumption? In national museums the processes of choosing, contextualizing and commentating exhibits help form national identity; in the ethnographic museum, similarly, they shape perceptions of the apparently distant Other. Like written ethnography, the museum is a 'translation of culture', with many of the associated problems traced by Talal Asad (1986). Like the written form, it has to represent the dialogic realities of cultural encounters in a fixed and intelligible form, to propose categories that define and order the material it has gathered. As the public face of academic ethnography, the museum interprets other cultures for the benefit of the general reader, and in that task museum practice, like all ethnography, operates within very specific historical and political parameters. How are museums in western Europe responding to the issues raised by critical ethnographers like James Clifford (1988), with their focus on the politics of representation? Is globalisation increasing the degree of accountability imposed on the ethnographic museum, or merely reinforcing older patterns? What opportunities and problems are raised by the use of more words - more 'translation' in the narrower sense - in ethnographic museums, and how do museums gain from introducing a reflexive and contextualizing concept of "thick translation" (Appiah 1993) into their work of interpretation?

Skin delivery potency and antitumor activities of temozolomide ester prodrugs

Clinical trials have shown temozolomide to be an effective agent for treatment of malignant melanoma. In order to investigate its suitability for delivery via the skin, a series of temozolomide esters was synthesized as prodrugs. In vitro assays demonstrated temozolomide, temozolomide acid and the hexyl ester equi-effective against selected cancer cell lines. The susceptibility of the esters to enzyme hydrolysis and their effectiveness for application to the skin were investigated. The esters effectively diffuse through rat skin and the hexyl ester demonstrated profound potency for penetrating through skin. Topical application of 5% (w/v) hexyl ester in DMSO solution on a mouse model demonstrated a significant inhibition of tumor growth. These results suggest that temozolomide esters could be an effective alternative to temozolomide in the treatment of skin cancer. © 2005 Elsevier Ireland Ltd. All rights reserved.

A cationic vaccine adjuvant based on a saturated quaternary ammonium lipid have different in vivo distribution kinetics and display a distinct CD4 T cell-inducing capacity compared to its unsaturated analog

Adjuvants are often composed of different constituents that can be divided into two groups based on their primary activity: the delivery system which carries and presents the vaccine antigen to antigen-presenting cells, and the immunostimulator that activates and modulates the ensuing immune response. Herein, we have investigated the importance of the delivery system and in particular its physical characteristics by comparing the delivery properties of two lipids which differ only in the degree of saturation of the acyl chains, rendering the liposomes either rigid (DDA, dimethyldioctadecylammonium) or highly fluid (DODA, dimethyldioleoylammonium) at physiological temperature. We show that these delivery systems are remarkably different in their ability to prime a Th1-directed immune response with the rigid DDA-based liposomes inducing a response more than 100 times higher compared to that obtained with the fluid DODA-based liposomes. Upon injection with a vaccine antigen, DDA-based liposomes form a vaccine depot that results in a continuous attraction of antigen-presenting cells that engulf a high amount of adjuvant and are subsequently efficiently activated as measured by an elevated expression of the co-stimulatory molecules CD40 and CD86. In contrast, the fluid DODA-based liposomes are more rapidly removed from the site of injection resulting in a lower up-regulation of co-stimulatory CD40 and CD86 molecules on adjuvant-positive antigen-presenting cells. Additionally, the vaccine antigen is readily dissociated from the DODA-based liposomes leading to a population of antigen-presenting cells that are antigen-positive but adjuvant-negative and consequently are not activated. These studies demonstrate the importance of studying in vivo characteristics of the vaccine components and furthermore show that physicochemical properties of the delivery system have a major impact on the vaccine-induced immune response. © 2012 Elsevier B.V. All rights reserved.

Discovery of active proteins directly from combinatorial randomized protein libraries without display, purification or sequencing:identification of novel zinc finger proteins.

We have successfully linked protein library screening directly with the identification of active proteins, without the need for individual purification, display technologies or physical linkage between the protein and its encoding sequence. By using 'MAX' randomization we have rapidly constructed 60 overlapping gene libraries that encode zinc finger proteins, randomized variously at the three principal DNA-contacting residues. Expression and screening of the libraries against five possible target DNA sequences generated data points covering a potential 40,000 individual interactions. Comparative analysis of the resulting data enabled direct identification of active proteins. Accuracy of this library analysis methodology was confirmed by both in vitro and in vivo analyses of identified proteins to yield novel zinc finger proteins that bind to their target sequences with high affinity, as indicated by low nanomolar apparent dissociation constants.