Structural studies of high dispersion H3PW12O40/SiO2 solid acid catalysts

Highly dispersed H3PW12O40/SiO2 catalysts with loadings between 3.6 and 62.5 wt% have been synthesised and characterised. The formation of a chemically distinct interfacial HPW species is identified by XPS, attributed to pertubation of W atoms within the Keggin cage in direct contact with the SiO2 surface. EXAFS confirms the Keggin unit remains intact for all loadings, while NH3 adsorption calorimetery reveals the acid strength >0.14 monolayers of HPW is loading invariant with initial ΔHads = −164 kJ mol−1. Lower loading catalysts exhibit weaker acidity which is attributed to an inability of highly dispersed clusters to form crystalline water. For reactions involving non-polar hydrocarbons the interfacial species where the accessible tungstate is highest confer the greatest reactivity, while polar chemistry is favoured by higher loadings which can take advantage of the H3PW12O40 pseudo-liquid phase available within supported multilayers. © the Owner Societies 2006.

Labeled EF-Tus for rapid kinetic studies of pretranslocation complex formation

The universally conserved translation elongation factor EF-Tu delivers aminoacyl(aa)-tRNA in the form of an aa-tRNA·EF-Tu·GTP ternary complex (TC) to the ribosome where it binds to the cognate mRNA codon within the ribosomal A-site, leading to formation of a pretranslocation (PRE) complex. Here we describe preparation of QSY9 and Cy5 derivatives of the variant E348C-EF-Tu that are functional in translation elongation. Together with fluorophore derivatives of aa-tRNA and of ribosomal protein L11, located within the GTPase associated center (GAC), these labeled EF-Tus allow development of two new FRET assays that permit the dynamics of distance changes between EF-Tu and both L11 (Tu-L11 assay) and aa-tRNA (Tu-tRNA assay) to be determined during the decoding process. We use these assays to examine: (i) the relative rates of EF-Tu movement away from the GAC and from aa-tRNA during decoding, (ii) the effects of the misreading-inducing antibiotics streptomycin and paromomycin on tRNA selection at the A-site, and (iii) how strengthening the binding of aa-tRNA to EF-Tu affects the rate of EF-Tu movement away from L11 on the ribosome. These FRET assays have the potential to be adapted for high throughput screening of ribosomal antibiotics.

High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Site specific growth of metal catalyzed silica nanowires for biological and chemical sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050°C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1μg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.

Screening of pharmaceuticals and other pollutants of concern by a combination of chemical and biological methods

This study examined the occurrence of pharmaceuticals and personal care products (PPCP's) in surface waters of Florida and their potential to be use as indicators of wastewater contamination. Previous studies have shown that elimination of pharmaceuticals in municipal sewage treatment plants is often incomplete. Aquatic ecosystems are under increased stress from human activities, particularly in heavily populated areas. The purpose of this study was to find an ideal indicator for wastewater. The applied methods, GC/MS and LC/MS, were suitable for the determination of pharmaceuticals and personal care products in aqueous environmental samples to the lower parts-per-trillion (ng/L) level. As a result of this study a snapshot view of the occurrence of pharmaceuticals and personal care products in south Florida was produced. PPCP's were commonly detected in coastal environments of South Florida at relatively low concentrations. In general, PPCP's were higher inside the canals and contained bodies of water than in open water systems. Caffeine was successfully used to describe impacted versus pristine locations. However, no particular correlation was observed among caffeine and other traditional water quality parameters.

Oceanographic investiations from the Sea of Ochotsk

The Sea of Okhotsk is a marginal sea of the Pacific Ocean, which is characterized by strong variations in the productivity and sediment supply due to sea ice transport and river input. Furthermore the variations in the hydrological cycle determine the formation of the SOIW (Sea of Okhotsk Intermediate Water) which plays an important role in the ventilation processes in the intermediate water of the N-Pacific. Isotope data measured on planktonic and benthic foraminifera, sedimentological and geochemical studies of sediment cores and surface samples from the Sea of Okhotsk are used to reconstruct the paleoceanography during the past 350.000 years. The dating and correlation of the sediments are based on oxygen isotope stratigraphy, absolute ages, magnetic susceptibility as well as a detailled tephrachronology of the entire basin. The sedimentation rates are characterized by temporal and spatial variations. The maximum sedimentation rate takes place at the continental slope off Sakhalin due to the input of the Amur River, the sea ice drift and the high productivity. The sedimentation rate in the eastern part of the Sea of Okhotsk is generelly high because of the influence of the nutrient-rich Kamchatka Current. In the central and northern parts of the Sea of Okhotsk, areas with low productivity and reduced terrestrial supply, the sedimentation rate is the lowest. The analyses of the surface sediment samples make it possible to characterize the (sub)- recent sediment supply and transportation processes. The bulk sediment measurements, isotope data and the accumulation rate of ice-rafted debris (IRD) show a dominant sea ice cover and a region with a high productivity as well as a high Amur River input in the western part of the sea. The eastern part of the Sea of Okhotsk, however, is marked by the predominance of warm and nutrient-rich water masses coming from the Kamchatka Current which restricts the sea ice cover. This is reflected in low content of ice-rafted debris and high productivity proxies as well as in isotope data. The deposits of the Sea of Okhotsk are characterized by terrestrial, biogenic and volcanogenic sediment input which varies temporally and spatially. Here, the sedimentation pattern is dominated by the terrestrial input. Bulk sediment measurements and sample analyses of the > 63 micron particle input make it possible to distinguish glacial and interglacial fluctuations. The sedimentation processes during glacial times are determined by a high content of ice-rafted debris, whereas the primary production is higher during interglacial periods. During the last glacial/interglacial cycle the IRD-distribution pattern indicates a strong sea ice transport in the western part and in large areas of the open sea in the eastern part of the Sea of Okhotsk with a relatively constant ice-drift system. The IRD flux in sediments of the oxygen isotope Stage 6 reflects a new sedimentation pattern in the eastern part of the sea. This high IRD accumulation rate indicates ice advances beyond the shelf margin and an iceberg transport from NE-E direction into the Sea of Okhotsk. The several large, brief, negative anomalies in d13C values of Neogloboquadrina pachyderma (s) show releases of methane from basin sediments which correspond to periods of relative sea level falls. The high sedimentation rates on the Sakhalin slope allow insights into the climatic history in Holocene and indicate shorter-scale variations oscillation in Stage 3, which correlate with the global climatic changes. These variations are described as Dansgaard-Oeschger cycles in Greenland ice cores and as Heinrich-Events in several marine sediment cores from the N-Atlantic.

Chemical composition of bottom sediments from the Kara Sea and estuaries of the Ob and Enisey Rivers

Data obtained during Cruse 49 of R/V Dmitry Mendeleev and of post-cruise studies.

Grain size and chemical composition of the surface sediment layer from the Pacific Ocean

The book is devoted to results of studies of Pacific sediment composition, regularities of their distribution and processes of sedimentation in the Pacific Ocean. Materials obtained by Soviet expeditions are the main part of the book.

(Table, page 351-359) Chemical composition of manganese nodules and crusts from the Pacific and Indian Ocean

Chemical and mineralogical analyses of manganese nodules from a large number of widely spaced localities in the Pacific and Indian Oceans have shown that their mineralogy and chemical composition varies both areally and with depth of formation. This is considered to result from a number of factors, important among which are: (a) their proximity to continental or volcanic sources of elements; (b) the chemical environment of deposition, including the degree of oxygenation; and (c) local factors such as the upward migration of reduced manganese in sediments from certain areas. Sub-surface nodules appear to share the chemical characteristics of their surface counterparts, especially those from volcanic areas where sub-surface sources of elements are probably important.

(Table 1) Chemical composition of phillipsites from pelagic bottom sediments of the Transpacific profile

Results of petrographic, chemical and X-ray studies of zeolites in sediments in the Transpacific lithological profile from the coast of Japan to the coast of Mexico are reported. For ocean phillipsites constancy of Si/Al ratio (2.44-2.87) and unstable cation composition in quantitative predominance of potassium over sodium are characteristic. Two groups of ocean phillipsites are distinguished: of deep-water basins and of submarine rises. The first spread over broad areas of the pelagic zone, and are formed by diagenetic transformation of fine dispersed pyroclastic material in minimum sedimentation rates, the latter occur locally - in areas of basaltic volcanism manifestations.

Chemical composition of a manganese nodule from the Tiki Basin, Touamotou Archipelago, Pacific Ocean

The text studies the deep-sea red clays in the East-Central Pacific ocean (Tahiti-Touamotou Archipelago), their authigenic formation, transport and diagenetic character in particular through their composition in REE.