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.

The influence of HOPE VI public housing on public schools

In the United States, public school enrollment is typically organized by neighborhood boundaries. This dissertation examines whether the federally funded HOPE VI program influenced performance in neighborhood public schools. In effect since 1992, HOPE VI has sought to revitalize distressed public housing using the New Urbanism model of mixed income communities. There are 165 such HOPE VI projects nationwide. Despite nearly two decades of the program's implementation, the literature on its connection to public school performance is thin. My dissertation aims to narrow this research gap. There are three principal research questions: (1) Following HOPE VI, was there a change in socioeconomic status (SES) in the neighborhood public school? The hypothesis is that low SES (measured as the proportion of students qualifying for the Free and Reduced Lunch Program) would reduce. (2) Following HOPE VI, did the performance of neighborhood public schools change? The hypothesis is that the school performance, measured by the proportion of 5th grade students proficient in state wide math and reading tests, would increase. (3) What factors relate to the performance of public schools in HOPE VI communities? The focus is on non-school, neighborhood factors that influence the public school performance. For answering the first two questions, I used t-tests and regression models to test the hypotheses. The analysis shows that there is no statistically significant change in SES following HOPE VI. However, there are statistically significant increases in performance for reading and math proficiency. The results are interesting in indicating that HOPE VI neighborhood improvement may have some relationship with improving school performance. To answer the third question, I conducted a case study analysis of two HOPE VI neighborhood public schools, one which improved significantly (in Philadelphia) and one which declined the most (in Washington DC). The analysis revealed three insights into neighborhood factors for improved school performance: (i) a strong local community organization; (ii) local community's commitment (including the middle income families) to send children to the public school; and (iii) ties between housing and education officials to implement the federal housing program. In essence, the study reveals how housing policy is de facto education policy.

The investigation of photocatalysts and iron based materials in the oxidation and adsorption of toxic organic and chromium materials

The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.

Global data compilation of benthic data sets II

In this study we present a global distribution pattern and budget of the minimum flux of particulate organic carbon to the sea floor (J POC alpha). The estimations are based on regionally specific correlations between the diffusive oxygen flux across the sediment-water interface, the total organic carbon content in surface sediments, and the oxygen concentration in bottom waters. For this, we modified the principal equation of Cai and Reimers [1995] as a basic monod reaction rate, applied within 11 regions where in situ measurements of diffusive oxygen uptake exist. By application of the resulting transfer functions to other regions with similar sedimentary conditions and areal interpolation, we calculated a minimum global budget of particulate organic carbon that actually reaches the sea floor of ~0.5 GtC yr**-1 (>1000 m water depth (wd)), whereas approximately 0.002-0.12 GtC yr**-1 is buried in the sediments (0.01-0.4% of surface primary production). Despite the fact that our global budget is in good agreement with previous studies, we found conspicuous differences among the distribution patterns of primary production, calculations based on particle trap collections of the POC flux, and J POC alpha of this study. These deviations, especially located at the southeastern and southwestern Atlantic Ocean, the Greenland and Norwegian Sea and the entire equatorial Pacific Ocean, strongly indicate a considerable influence of lateral particle transport on the vertical link between surface waters and underlying sediments. This observation is supported by sediment trap data. Furthermore, local differences in the availability and quality of the organic matter as well as different transport mechanisms through the water column are discussed.

The role of impurities in the shape, structure and physical properties of semiconducting oxide nanostructures grown by thermal evaporation

A thermal evaporation method developed in the research group enables to grow and design several morphologies of semiconducting oxide nanostructures, such as Ga_2O_3, GeO_2 or Sb_2O_3, among others, and some ternary oxide compounds (ZnGa_2O_4, Zn_2GeO_4). In order to tailor physical properties, a successful doping of these nanostructures is required. However, for nanostructured materials, doping may affect not only their physical properties, but also their morphology during the thermal growth process. In this paper, we will show some examples of how the addition of impurities may result into the formation of complex structures, or changes in the structural phase of the material. In particular, we will consider the addition of Sn and Cr impurities into the precursors used to grow Ga_2O_3, Zn_2GeO_4 and Sb_2O_3 nanowires, nanorods or complex nanostructures, such as crossing wires or hierarchical structures. Structural and optical properties were assessed by electron microscopy (SEM and TEM), confocal microscopy, spatially resolved cathodoluminescence (CL), photoluminescence, and Raman spectroscopies. The growth mechanisms, the luminescence bands and the optical confinement in the obtained oxide nanostructures will be discussed. In particular, some of these nanostructures have been found to be of interest as optical microcavities. These nanomaterials may have applications in optical sensing and energy devices.

Nanostructured copper oxides and phosphates from a new solid-state route

Nanostructured copper containing materials of CuO, Cu3(PO4)3 and Cu2P2O7 have been prepared by solid-state pyrolysis of molecular CuCl2·NC5H4OH (I), CuCl2·CNCH2C6H4OH (II), oligomeric [Cu(PPh3)Cl]4 (III), N3P3[OC6H4CH2CN·CuCl]6[PF6] (IV), N3P3[OC6H5]5[OC5H4N·Cu][PF6] (V), polymeric chitosan·(CuCl2)n (VI) and polystyrene-co-4-vinylpyridine PS-b-4-PVP·(CuCl2) (VII) precursors. The products strongly depend on the precursor used. The pyrolytic products from phosphorus-containing precursors (III), (IV) and (V) are Cu phosphates or pyrophosphates, while non-phosphorous-containing precursors (VI) and (VII), result in mainly CuO. The use of chitosan as a solid-state template/stabilizer induces the formation of CuO and Cu2O nanoparticles. Copper pyrophosphate (Cu2P2O7) deposited on Si using (IV) as the precursor exhibits single-crystal dots of average diameter 100 nm and heights equivalent to twice the unit cell b-axis (1.5–1.7 nm) and an areal density of 5.1–7.7 Gigadots/in.2. Cu2P2O7 deposited from precursor (VI) exhibits unique labyrinthine high surface area deposits. The morphology of CuO deposited on Si from pyrolysis of (VI) depends on the polymer/Cu meta ratio. Magnetic measurements performed using SQUID on CuO nanoparticle networks suggest superparamagnetic behavior. The results give insights into compositional, shape and morphological control of the as-formed nanostructures through the structure of the precursors.

Nanotechnology in food industry II: risk assessment and legislation

Currently, there is increasing use of nanomaterials in the food industry thanks to the many advantages offered and make the products that contain them more competitive in the market. Their physicochemical properties often differ from those of bulk materials, which require specialized risk assessment. This should cover the risks to the health of workers and consumers as well as possible environmental risks. The risk assessment methods must go updating due to more widespread use of nanomaterials, especially now that are making their way down to consumer products. Today there is no specific legislation for nanomaterials, but there are several european dispositions and regulations that include them. This review gives an overview of the risk assessment and the existing current legislation regarding the use of nanotechnology in the food industry.

Fronteras en construcción: Diferenciación social y desterritorialización en el Sur ibérico (siglos IX-VI a.C.)

Durante las tres últimas décadas, numerosos/as arqueólogos/as han discutido extensamente sobre el ritual funerario original de las poblaciones del sur ibérico entre los siglos ix y vi a.c., esto es, cremación o inhumación. Este debate está además conectado con la existencia o no de complejidad social antes de la llegada fenicia, con la aparición de una élite “orientalizada” y con la adopción de nuevos objetos y prácticas por las poblaciones locales. En este artículo hago uso del concepto deleuziano de “desterritorialización” y lo asocio con el de “frontera” desarrollado por anzaldúa para interpretar la sociedad del sur ibérico. Para ello, analizo la evidencia funeraria indígena y cuestiono la división estricta entre cremación e inhumación en la región; así como examino la profundidad y significado de los cambios funerarios en las comunidades locales.

"Lancea", Lusitanian Word, and the "Lancienses" Ethnogenesis

Analysis of the word lancea, of Hispanic origin after Varro, and of place names, people´s names and personal names derived from it. It confirms that the spear was the most important weapon in the Bronze Age, belonging to the iuventus and used as heroic and divine symbol. This analysis confirms also the personality of the Lusitanians, a people related to the Celts but with more archaic archaeological, linguistic and cultural characteristics originated in the tradition of the Atlantic Bronze in the II millennium BC. It is also relevant to better know the organisation of Broze and Iron Age societies and the origin of Indo-Europeans peoples in Western Europe and of pre-Roman peoples of Iberia.

Cova dels Jurats at Calescoves (Alaior, Minorca). A Cave Shrine in the Talayotic context?

Excavations carried out in the Cova dels Jurats between 2010 and 2012 served to establish that, unlike the rest of the caves Calescoves, this one functioned as a sanctuary, with two different phases. The first one corresponds to the Final Talayotic Period, as the first cave shrine documented in the Talayotic culture. In Roman times, the place was still used as a sanctuary, but with a totally different ritual, linked to the inscriptions discovered at the entrance of the cave.

Evaluation of the Chemical Durability of Iowa Fly Ash Concretes, HR-327, Phase II Progress Report, 1992

The major objective of this research project is to investigate how fly ash influences the chemical durability of portland cement based materials. The testing program is evaluating how Iowa fly ashes influence the sulfate durability of portland cement-fly ash pastes, mortars, and concretes. Also, alkali-reactivity studies are being conducted on mortar bar specimens prepared in accordance with ASTM C 311. Prelimary sulfate test results, based only on mortar bar studies, indicate that only the very high-calcium fly ash (29 percent CaO, by weight) consistently reduced the durability of test specimens exposed to a solution containing 5 percent sodium sulfate. The remaining four fly ashes that were used in the study showed negligible to dramatic increases in sulfate resistance. Concrete specimens were only beginning to respond to the sulfate solutions after about one year of exposure; and hence, considerably more time will be needed to assess their performance. Preliminary results from the alkali-reactivity tests have indicated that the Oreopolis aggregate is not sensitive to alkali attack. However, some of the test results have indicated that the testing procedure may be prone to delayed expansion due to the presence of periclase (MgO) in the Class C fly ashes. Research is being planned to: (1) verify if the periclase is influencing test results; and (2) estimating the magnitude of the potential error.