Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Paganism, Traditionalism, Nationalism : Narratives of Russian Rodnoverie

The topic of this dissertation is Rodnoverie, a religion that revives pre-Christian Slavic spirituality. Rodnoverie has been noted to be one of the fastest growing new religions in Russia and the aim of the study is to analyse why and how the movement has attained its popularity. First, the analysis asks how Rodnovers themselves explain the revival of ancient Paganism at this particular historical moment. Secondly, these interpretations are reflected in the framework of sociological discussions about contemporary religiosity. The analysis discusses how the Rodnoverie movement corresponds to some tendencies that are considered to characterise late modern religiosity. The primary material of the research is Rodnoverie texts: books, newspapers and electronic articles. The published literature is supplemented by fieldwork material which includes interviews with some Rodnoverie leaders and the author s participant observation of rituals and gatherings. Methodologically, the study draws on a sociological narrative approach that is focused on examining how individuals and groups use narratives to construct their identities and to challenge mainstream discussions and interpretations. The analysis discerns three narratives. The first one of these portrays Rodnoverie as a revival of the native Russian or Slavic religion. The narrative provides a new version of the old Slavophile idea, according to which imitation of the West has misguided Russia and, therefore, Russians should turn to their own tradition. In the second narrative, Rodnoverie is presented as a nature religion that features tolerance and pluralistic values. According to these perceptions, the emergence of Rodnoverie marks the dead-end of the earlier hegemonic universalistic world-views, the mono-ideologies . While the nationalist narrative focuses on Russia s national heritage, the third narrative interprets the tradition in more universal terms as an alternative to modern values and way of life. The main argument of this narrative is that contemporary people have become alienated from nature, their roots and their community. The themes that are discussed in the theoretical literature on late modern religiosity often configure in Rodnovers interpretations either directly or when looked at through an analytical framework. Of the various themes that are addressed in a sociological study of religion the ones that have most relevance for Rodnoverie are the discussions on individualisation, globalisation and secularisation. Rodnoverie reflects such tendencies as the subjectivisation of religion and the modern crisis of authority. The movement also both exemplifies and actively promotes religious pluralisation in Russia.

Methods and tools for mass spectrometric lipidome analysis

The analysis of lipid compositions from biological samples has become increasingly important. Lipids have a role in cardiovascular disease, metabolic syndrome and diabetes. They also participate in cellular processes such as signalling, inflammatory response, aging and apoptosis. Also, the mechanisms of regulation of cell membrane lipid compositions are poorly understood, partially because a lack of good analytical methods. Mass spectrometry has opened up new possibilities for lipid analysis due to its high resolving power, sensitivity and the possibility to do structural identification by fragment analysis. The introduction of Electrospray ionization (ESI) and the advances in instrumentation revolutionized the analysis of lipid compositions. ESI is a soft ionization method, i.e. it avoids unwanted fragmentation the lipids. Mass spectrometric analysis of lipid compositions is complicated by incomplete separation of the signals, the differences in the instrument response of different lipids and the large amount of data generated by the measurements. These factors necessitate the use of computer software for the analysis of the data. The topic of the thesis is the development of methods for mass spectrometric analysis of lipids. The work includes both computational and experimental aspects of lipid analysis. The first article explores the practical aspects of quantitative mass spectrometric analysis of complex lipid samples and describes how the properties of phospholipids and their concentration affect the response of the mass spectrometer. The second article describes a new algorithm for computing the theoretical mass spectrometric peak distribution, given the elemental isotope composition and the molecular formula of a compound. The third article introduces programs aimed specifically for the analysis of complex lipid samples and discusses different computational methods for separating the overlapping mass spectrometric peaks of closely related lipids. The fourth article applies the methods developed by simultaneously measuring the progress curve of enzymatic hydrolysis for a large number of phospholipids, which are used to determine the substrate specificity of various A-type phospholipases. The data provides evidence that the substrate efflux from bilayer is the key determining factor for the rate of hydrolysis.

A role for calcium in gonadotrophin-releasing hormone (GnRH) stimulated secretion of chorionic gonadotrophin by first trimester human placental minces in vitro

In vitro studies using first-trimester human placental minces have shown that stimulation of human chorionic gonadotrophin (hCG) secretion by gonadotrophin-releasing hormone (GnRH) is dependent upon the presence of extracellular calcium. Addition of GnRH to first-trimester placental minces in vitro was found to stimulate 45Ca2+ uptake into placental minces, and the process was associated with an increase in immunoreactive hCG in the medium. Addition of GnRH to placental minces preloaded with 45Ca2+ stimulated the efflux of 45Ca2+ within one minute. The calmodulin inhibitors chlorpromazine andtrifluoperazine inhibited the basal uptake and efflux of 45Ca2+ suggesting the involvement of calmodulin in the mobilization of calcium in the placenta.

The prehistory of Suomussalmi, eastern Finland; the first billion years as revealed by isotopes and the composition of granitoid suites

The four papers summarized in this thesis deal with the Archean and earliest Paleoproterozoic granitoid suites observed in the Suomussalmi district, eastern Finland. Geologically, the area belongs to the Kianta Complex of the Western Karelian Terrane in the Karelian Province of the Fennoscandian shield. The inherited zircons up to 3440 Ma old together with Sm Nd and Pb Pb data confirm the existence of previously anticipated Paleoarchean protocrust in Suomussalmi. The general timeline of granitoid magmatism is similar to that of the surrounding areas. TTG magmatism occurred in three distinct phases: ca 2.95 Ga, 2.83 2.78 Ga and 2.76 2.74 Ga. In Suomussalmi the TTGs sensu stricto (K2O/Na2O less than 0.5) belong to the low-HREE type and are interpreted as partial melts of garnet amphibolites, which did not significantly interact with mantle peridotites. Transitional TTGs (K2O/Na2O more than 0.5), present in Suomussalmi and absent from surrounding areas, display higher LILE concentrations, but otherwise closely resemble the TTGs sensu stricto and indicate that recycling of felsic crust commenced in Suomussalmi 200 Ma earlier than in surrounding areas. The youngest TTG phase was coeval with the intrusion of the Likamännikkö quartz alkali feldspar syenite (2741 ± 2 Ma) complex. The complex contains angular fragments of ultrabasic rock, which display considerable compositional heterogeneity and are interpreted as cumulates containing clinopyroxene (generally altered to actinolite), apatite, allanite, epidote, and albite. The quartz alkali feldspar syenite cannot be regarded as alkaline sensu stricto, despite clear alkaline affinities. Within Likamännikkö there are also calcite carbonatite patches, which display mantle-like O- and C-isotope values, as well as trace element characteristics consistent with a magmatic origin, and could thus be among the oldest known carbonatites in the world. Sanukitoid (2.73 2.71 Ga) and quartz diorite suites (2.70 Ga) overlap within error margins and display compositional similarities, but can be differentiated from each other on the basis of higher Ba, K2O and LREE contents of the sanukitoids. The Likamännikkö complex, sanukitoids and quartz diorites are interpreted as originating from the metasomatized mantle and mark the diversification of the granitoid clan after 200 Ma of evolution dominated by the TTG suite. Widespread migmatization and the intrusion of anatectic leucogranitoids as dykes and intrusions of varying size took place at 2.70 2.69 Ga, following collisional thickening of the crust. The leucogranitoids and leucosomes of migmatized TTGs are compositionally alike and characterized by high silica contents and a leucocratic appearance. Due to compositional overlap, definitive discrimination between leucogranitoids and transitional TTGs requires isotope datings and/or knowledge of field relationships. Leucogranitoids represent partial melts of the local TTGs, both the sensu stricto and transitional types, mostly derived under water fluxed conditions, with possible fluid sources being late sanukitoids and quartz diorites as well as dehydrating lower crust. The Paleoproterozoic 2.44 2.39 Ga A-type granitoids of the Kianta Complex emplaced in an extensional environment are linked to the coeval and more widespread mafic intrusions and dykes observed over most of the Archean nucleus of the Fennoscandian shield. The A-type intrusions in the Suomussalmi area are interpreted as partial melts of the Archean lower crust and display differences in composition and magnetite content, which indicate differences in the composition and oxidation state of the source.

First total synthesis of a natural thapsane

A stereospecific first total synthesis of a natural thapsane 1, from the readily available cyclogeraniol 8, is described.

The Skill of ECMWF Medium-Range Forecasts during the Year of Tropical Convection 2008

This study uses the European Centre for Medium-Range Weather Forecasts (ECMWF) model-generated high-resolution 10-day-long predictions for the Year of Tropical Convection (YOTC) 2008. Precipitation forecast skills of the model over the tropics are evaluated against the Tropical Rainfall Measuring Mission (TRMM) estimates. It has been shown that the model was able to capture the monthly to seasonal mean features of tropical convection reasonably. Northward propagation of convective bands over the Bay of Bengal was also forecasted realistically up to 5 days in advance, including the onset phase of the monsoon during the first half of June 2008. However, large errors exist in the daily datasets especially for longer lead times over smaller domains. For shorter lead times (less than 4-5 days), forecast errors are much smaller over the oceans than over land. Moreover, the rate of increase of errors with lead time is rapid over the oceans and is confined to the regions where observed precipitation shows large day-to-day variability. It has been shown that this rapid growth of errors over the oceans is related to the spatial pattern of near-surface air temperature. This is probably due to the one-way air-sea interaction in the atmosphere-only model used for forecasting. While the prescribed surface temperature over the oceans remain realistic at shorter lead times, the pattern and hence the gradient of the surface temperature is not altered with change in atmospheric parameters at longer lead times. It has also been shown that the ECMWF model had considerable difficulties in forecasting very low and very heavy intensity of precipitation over South Asia. The model has too few grids with ``zero'' precipitation and heavy (>40 mm day(-1)) precipitation. On the other hand, drizzle-like precipitation is too frequent in the model compared to that in the TRMM datasets. Further analysis shows that a major source of error in the ECMWF precipitation forecasts is the diurnal cycle over the South Asian monsoon region. The peak intensity of precipitation in the model forecasts over land (ocean) appear about 6 (9) h earlier than that in the observations. Moreover, the amplitude of the diurnal cycle is much higher in the model forecasts compared to that in the TRMM estimates. It has been seen that the phase error of the diurnal cycle increases with forecast lead time. The error in monthly mean 3-hourly precipitation forecasts is about 2-4 times of the error in the daily mean datasets. Thus, effort should be given to improve the phase and amplitude forecast of the diurnal cycle of precipitation from the model.

Effects of Zr and Ti doping on the dielectric response of CeO2: A comparative first-principles study

Zr doping in ceria (CeO2) results in enhanced static dielectric response compared to pure ceria. On the other hand, Ti doping in ceria keeps its dielectric constant unchanged. We use first-principles density functional theory calculations based on pseudopotentials and a plane wave basis to determine electronic properties and dielectric response of Zr/Ti-doped and oxygen-vacancy-introduced ceria. Softening of phonon modes is responsible for the enhancement in dielectric response of Zr-doped ceria compared to that of pure ceria. The ceria-zirconia mixed oxides should have potential use as high-k materials in the semiconductor industry. (c) 2010 Elsevier Ltd. All rights reserved.

Embedded Storytelling and Gender Negotiations in Githa Hariharan's First Three Novels

This thesis treats Githa Hariharan s first three novels The Thousand Faces of Night (1992), The Ghosts of Vasu Master (1994) and When Dreams Travel (1999) as a trilogy, in which Hariharan studies the effects of storytelling from different perspectives. The thesis examines the relationship between embedded storytelling and the primary narrative level, the impact of character-bound storytelling on personal development and interpersonal relationships. Thus, I assume that an analysis of the instabilities between characters, and tensions between sets of values introduced through storytelling displays the development of the central characters in the novels. My focus is on the tensions between different sets of values and knowledge systems and their impact on the gender negotiations. The tensions are articulated through a resistance and/or adherence to a cultural narrative, that is, a formula, which underlies specific narratives. Conveyed or disputed by embedded storytelling, the cultural narrative circumscribes what it means to be gendered in Hariharan s novels. The analysis centres on how the narratee in The Thousand Faces of Night and the storyteller in The Ghosts of Vasu Master relate to and are affected by the storytelling, and how they perceive their gendered positions. The analysis of the third novel When Dreams Travel focuses on storytelling, and its relationship to power and representation. I argue that Hariharan's use of embedded storytelling is a way to renegotiate and even reconceptualise gender. Hariharan s primary concern in all three novels is the tensions between tradition or repetition, and change, and how they affect gender. Although the novels feature ancient mythical heroes, mice and flies, or are set in a fantasy world of jinnis and ghouls, they are, I argue, deeply concerned with contemporary issues. Whereas the first novel questions the demands set by family and society on the individual, the second strives to articulate an ethical relationship between the self and the other. The third novel examines the relationship between representation and power. These issues could not be more contemporary, and they loom large over both the regional and global arenas.

Signal subspace approach in localization of sound source in shallow water

A new algorithm based on signal subspace approach is proposed for localizing a sound source in shallow water. In the first instance we assumed an ideal channel with plane parallel boundaries and known reflection properties. The sound source is assumed to emit a broadband stationary stochastic signal. The algorithm takes into account the spatial distribution of all images and reflection characteristics of the sea bottom. It is shown that both range and depth of a source can be measured accurately with the help of a vertical array of sensors. For good results the number of sensors should be greater than the number of significant images; however, localization is possible even with a smaller array but at the cost of higher side lobes. Next, we allowed the channel to be stochastically perturbed; this resulted in random phase errors in the reflection coefficients. The most singular effect of the phase errors is to introduce into the spectral matrix an extra term which may be looked upon as a signal generated coloured noise. It is shown through computer simulations that the signal peak height is reduced considerably as a consequence of random phase errors.

Progression of diffuse gliomas - from the first diagnosis to recurrence

Gliomas are the most frequent primary brain tumours. The cardinal features of gliomas are infiltrative growth pattern and progression from low-grade tumours to a more malignant phenotype. These features of gliomas generally prevent their complete surgical excision and cause their inherent tendency to recur after initial treatment and lead to poor long-term prognosis. Increasing knowledge about the molecular biology of gliomas has produced new markers that supplement histopathological diagnostics. Molecular markers are also used to evaluate the prognosis and predict therapeutic response. The purpose of this thesis is to study molecular events involved in the malignant progression of gliomas. Gliomas are highly vascularised tumours. Contrast enhancement in magnetic resonance imaging (MRI) reflects a disrupted blood-brain barrier and is often seen in malignant gliomas. In this thesis, 62 astrocytomas, oligodendrogliomas and oligoastrocytomas were studied by MRI and immunohistochemistry. Contrast enhancement in preoperative MRI was associated with angiogenesis, tumour cell proliferation and histological grade of gliomas. Activation of oncogenes by gene amplification is a common genetic aberration in gliomas. EGFR amplification on chromosome 7p12 occurs in 30-40% of glioblastomas. PDGFRA, KIT and VEGFR2 are receptor tyrosine kinase genes located on chromosome 4q12. Amplification of these genes was studied using in situ hybridisation in the primary and recurrent astrocytomas, oligodendrogliomas and oligoastrocytomas of 87 patients. PDGFRA, KIT or VEGFR2 amplification was found in 22% of primary tumours and 36% of recurrent tumours including low-grade and malignant gliomas. The most frequent aberration was KIT amplification, which occurred in 10% of primary tumours and in 27% of recurrent tumours. The expression of ezrin, cyclooxygenase 2 (COX-2) and HuR was studied immunohistochemically in a series of primary and recurrent gliomas of 113 patients. Ezrin is a cell membrane-cytoskeleton linking-protein involved in the migration of glioma cells. The COX-2 enzyme is implicated in the carcinogenesis of epithelial neoplasms and is overexpressed in gliomas. HuR is an RNA-stabilising protein, which regulates the expression of several proteins including COX-2. Ezrin, COX-2 and HuR were associated with histological grade and the overall survival of glioma patients. However, in multivariate analysis they were not independent prognostic factors. In conclusion, these results suggest that contrast enhancement in MRI can be used as a surrogate marker for the proliferative and angiogenic potential of gliomas. Aberrations of PDGFRA, KIT and VEGFR2 genes, as well as the dysregulated expression of ezrin, COX-2 and HuR proteins, are linked to the progression of gliomas.

The first structurally characterized diruthenium(II,III) complex with four bridging arylcarboxylato ligands

The diruthenium(II,III) compound [Ru2Cl(O2CC6H4-p-OMe)4](H2O)0.25 (1) has been prepared and its crystal structure determined by X-ray studies. The crystals belong to the triclinic space group, PImage , and the asymmetric unit consists of one full dimer and two half dimers. The {Ru2(O2CC6H4-p-OMe)4+} units are bridged by chloride ions into an infinite zigzag chain, with an average Ru---Cl distance and Ru---Cl---Ru angle of 2.567(2) Å and 121.0(1)°, respectively. The average Ru---Ru distance of 2.286(1) Å in 1 is comparable with that in analogous tetra-alkylcarboxylates, Ru2Cl(O2CR)4 and tetra-amidates, Ru2Cl(ArCONH)4.

An Examination of How Entrepreneurs Can Improve Their Position in Relation to Investors

Previous research has been inconclusive regarding the impact of those who invest in entrepreneurs. Consider for a moment how potentially important they are to entrepreneurs. They for example decide who deserves funding, how much time they contribute to their portfolio firms, how they grant entrepreneurs access to their networks, and help entrepreneurs acquire additional funding. In sum, investors potentially have a great impact on the success of entrepreneurs. It is therefore important that we better understand the environment, relationships and context in which parties operate. This thesis contains five articles that explore investors’ and entrepreneurs’ relationships from various viewpoints, in theoretical frameworks, and use a variety of data and research methods. The first article is a literature review that summarises what we know of venture capital, business angel and corporate venture capital funding. The second article studies the entrepreneurs’ investor selection process, its consequences, and identifies key factors that influence the process. Earlier, the common approach has been to concentrate research on the investors’ selection policy, not the entrepreneurs’. The data and conclusions are based on multiple case studies. The article analyses how entrepreneurs can ensure that they get the best possible investor, when it is possible for an entrepreneur to select an investor, and what are the consequences of investor selection. The third article employs power constructs (dependency, power balance/imbalance, power sources) and analyses their applicability in the investor-entrepreneur relationship. Power constructs are extensively studied and utilised in the management and organisation literature. In entrepreneur investor relationships, power aspects are rarely analysed. However, having the ability to “get others to do things they would not otherwise do” is a very common factor in the investor-entrepreneur relationship. Therefore, employing and analysing the applicability of power constructs in this setting is well founded. The article is based on a single case study but suggests that power constructs could be applicable and consequently provide additional insights into the investor-entrepreneur relationship. The fourth article studies the role of advisors in the venture capital investment process and analyses implications for research and practice, particularly from the entrepreneurs’ perspective. The common entrepreneurial finance literature describes the entrepreneur-investor relationship as linear and bilateral. However, it was discovered that advisors may influence the relationship. In this article, the role of advisors, operating procedures and advisors’ impact on different parties is analysed. The fifth article concentrates on investors’ certification effect. The article measures and demonstrates that venture capital investment is likely to increase the credibility (in terms of media attention) of early stage firms, those that most often need additional credibility. Understanding investor certification can affect how entrepreneurs evaluate investment offers and how investors can make their offers appear more lucrative.