Spectroscopic, microscopic and first rheological investigations in charge-transfer interaction induced organogels

This article describes two-component charge-transfer interaction mediated organogels (CT-gels) derived from anthracene carboxamides obtained from 2-amino 2-hydroxymethyl-1,3-propanediol (TRIS), and 2,3-dialkoxyanthracenes as donors, with 2,4,7-trinitrofluorenone (TNF) as the common acceptor. We demonstrate the versatility of TNF as an electron acceptor in the formation of these gels. The effect of subtle changes in the donor structure on the gelation ability has been investigated by varying the alkyl chain length in the dialkoxyanthracene donors, and by varying the position of the TRIS substituent in the anthracene carboxamide donors. Distinct differences have been observed in the nature of the CT-gels based on these two kinds of anthracene donors. It has been reported in the literature that 2,3-dialkoxyanthracenes form gels on their own in various aliphatic hydrocarbons and alcohols for linear alkyl chains bearing at least 6mcarbon atoms (C-6). In the present study, it is shown that themCT-complex of these molecules with TNF is able to gel many alcoholic and a few hydrocarbon solvents. Also, in the presence of TNF, the 2,3-dialkoxyanthracenes (C-4-C-5) which were non-gelators on their own at ambient temperatures, form CT-gels in a number of alcohols. The other series of gelators discussed, the anthracene carboxamides, require the mandatory presence of TNF to form gels. This donor-acceptor complex forms gels in various aliphatic alcohols. Interestingly, the formation of these CT-gels requires rapid cooling in most of the cases. Thermal stability studies with both types of CT-gels indicate an optimum stoichiometry of 1 : 1 between the donor and the acceptor. Dynamic rheological experiments reveal these gels as viscoelastic soft materials, with the mechanical strength of these gels depending on the amount of TNF present. This provides a means to tune the strength of the gel by varying the doping concentration of the acceptor.

Vanhurskautta, oikeutta vai uskollisuutta? : ṣdq -sanue vuoden 1992 Kirkkoraamatun Psalmien kirjassa

Righteousness, justice or faithfulness? The Hebrew Root ṣdq in the Psalter of the Finnish Church Bible of 1992 This study attempts to answer three questions. Firstly, what do the derivates of the root ṣdq mean in the Hebrew Psalter? Secondly, with which equivalents are these Hebrew words translated in the Psalter of the Finnish Church Bible of 1992 and why? And thirdly, how is the translation of the root ṣdq in the Psalter placed in comparison with the translations of the root ṣdq in certain ancient and modern Bible translations? The root ṣdq has a very wide semantic field in Biblical Hebrew. The basic meaning of the root ṣdq is ‘right’ or ‘to be in the right’. The traditional English equivalent of the root ṣdq is righteousness. In many European languages the equivalent of the root ṣdq has some connection with the word ‘right’, but this is not the case in Finnish. The Finnish word vanhurskaus has been present since the first Finnish Bible translation by Mikael Agricola in 1548. However, this word has nothing to do with the Finnish word for ‘right’. The word vanhurskaus has become a very specific religious and theological word in Finnish, and it can be a word that is not obvious or at all understandable even to a native Finnish speaker. In the Psalter of the earlier Finnish Church Bible of 1938 almost every derivate of the root ṣdq (132/139) was translated as vanhurskaus. In the Psalter of the Finnish Church Bible of 1992 less than half of these derivates (67/139) are translated as that. Translators have used 20 different equivalents of the Hebrew derivates of the root ṣdq. But this type of translation also has its own problems. The most disputed is the fact that in it the Bible reader finds no connections between many Bible verses that have obvious connections with each other in the Hebrew Bible. For example, in verse Ps. 118, 15 one finds a Finnish word for ‘saved’ and in verse Ps. 142, 8 one finds another Finnish word for ‘friends’, while in the Hebrew Bible the same word is used in both verses, ṣaddîqīm. My study will prove that it is very challenging to compare or fit together the semantics of these two quite different languages. The theoretical framework for the study consists of biblical semantic theories and Bible translation theories. Keywords: religious language, Bible translations, Book of Psalms.

First-principles analysis of electron correlation, spin ordering and phonons in the normal state of FeSe1-x

We present first-principles density-functional-theory-based calculations to determine the effects of the strength of on-site electron correlation, magnetic ordering, pressure and Se vacancies on phonon frequencies and electronic structure of FeSe1-x. The theoretical equilibrium structure (lattice parameters) of FeSe depends sensitively on the value of the Hubbard parameter U of on-site correlation and magnetic ordering. Our results suggest that there is a competition between different antiferromagnetic states due to comparable magnetic exchange couplings between first- and second-neighbor Fe sites. As a result, a short range order of stripe antiferromagnetic type is shown to be relevant to the normal state of FeSe at low temperature. We show that there is a strong spin-phonon coupling in FeSe (comparable to its superconducting transition temperature) as reflected in large changes in the frequencies of certain phonons with different magnetic ordering, which is used to explain the observed hardening of a Raman-active phonon at temperatures (similar to 100 K) where magnetic ordering sets in. The symmetry of the stripe antiferromagnetic phase permits an induced stress with orthorhombic symmetry, leading to orthorhombic strain as a secondary order parameter at the temperature of magnetic ordering. The presence of Se vacancies in FeSe gives rise to a large peak in the density of states near the Fermi energy, which could enhance the superconducting transition temperature within the BCS-like picture.

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.

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.

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.

The Church and Its Boundaries : A Study of the Special Commission on Orthodox Participation in the WCC

The relationship between the Orthodox Churches and the World Council of Churches (WCC) became a crisis just before the 8th Assembly of the WCC in Harare, Zimbabwe in 1998. The Special Commission on Orthodox Participation in the WCC (SC), inaugurated in Harare, worked during the period 1999 2002 to solve the crisis and to secure the Orthodox participation in the WCC. The purpose of this study is: 1) to clarify the theological motives for the inauguration of the SC and the theological argumentation of the Orthodox criticism; 2) to write a reliable history and analysis of the SC; 3) to outline the theological argumentation, which structures the debate, and 4) to investigate the ecclesiological questions that arise from the SC material. The study spans the years 1998 to 2006, from the WCC Harare Assembly to the Porto Alegre Assembly. Hence, the initiation and immediate reception of the Special Commission are included in the study. The sources of this study are all the material produced by and for the SC. The method employed is systematic analysis. The focus of the study is on theological argumentation; the historical context and political motives that played a part in the Orthodox-WCC relations are not discussed in detail. The study shows how the initial, specific and individual Orthodox concerns developed into a profound ecclesiological discussion and also led to concrete changes in WCC practices, the best known of which is the change to decision-making by consensus. The Final Report of the SC contains five main themes, namely, ecclesiology, decision-making, worship/common prayer, membership and representation, and social and ethical issues. The main achievement of the SC was that it secured the Orthodox membership in the WCC. The ecclesiological conclusions made in the Final Report are twofold. On the one hand, it confirms that the very act of belonging to the WCC means the commitment to discuss the relationship between a church and churches. The SC recommended that baptism should be added as a criterion for membership in the WCC, and the member churches should continue to work towards the mutual recognition of each other s baptism. These elements strengthen the ecclesiological character of the WCC. On the other hand, when the Final Report discusses common prayer, the ecclesiological conclusions are much more cautious, and the ecclesiological neutrality of the WCC is emphasized several times. The SC repeatedly emphasized that the WCC is a fellowship of churches. The concept of koinonia, which has otherwise been important in recent ecclesiological questions, was not much applied by the SC. The comparison of the results of the SC to parallel ecclesiological documents of the WCC (Nature and Mission of the Church, Called to Be the One Church) shows that they all acknowledge the different ecclesiological starting points of the member churches, and, following that, a variety of legitimate views on the relation of the Church to the churches. Despite the change from preserving the koinonia to promises of eschatological koinonia, all the documents affirm that the goal of the ecumenical movement is still full, visible unity.

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.

Diakoniatyön paikka ihmisten arjessa

This study examines the diaconia work of the Finnish Evangelical Lutheran Church from the standpoint of clients. The role of diaconia work has grown since the early 1990s recession, and since it established itself as one of the actors along with other social organizations. Previous studies have described the changing role of diaconal work, especially from the standpoint of diaconia workers and co-operators. This research goes back to examine, beyond the activities of the diaconia work of everyday practices, its relations of ruling which are determining practices. The theoretical and methodological framework rises from the thinking of Dorothy E. Smith, the creator of institutional ethnography. Its origins are in feminism, Marxism, phenomenology, etnomethodology, and symbolic interactionism. However, it does not represent any school. Unlike the objectivity-based traditional sociology, institutional ethnography has its starting point in everyday life, and people s subjective experience of it. Everyday life is just a starting point, and is used to examine everyday life s experiences of hidden relations of ruling, linking people and organizations. The level of generalization is just on the relations of ruling. The research task is to examine those meanings of diaconia work which are embedded in its clients experiences. The research task is investigated with two questions: how diaconia work among its clients takes shape and what kinds of relations of ruling exist in diaconia work. The meanings of diaconia work come through an examination of the relations of ruling, which create new forms of diaconal work compared with previous studies. For the study, two kinds of data were collected: a questionnaire and ethnographic fieldwork. The first data set was collected from diaconal workers using the questionnaire. It gives background information of the diaconia work process from the standpoint of the clients. In the ethnographic study there were two phases. The first ethnographic material was collected from one local parish by observing, interviewing clients and diaconal workers and gathering documents. The number of observations was 36 customer appointments, and 29 interviews. The second ethnographic material was included as a part of the analysis, in which ruling relations in people s experiences were collected from the transcribed data. Close reading and narrative analysis are used as analysing methods. The analysis has three phases. First, the experiences are identified with close reading; the following step is to select some of the institutional processes that are shaping those experiences and are relevant for the research. At the third stage, those processes are investigated in order to describe analytically how they determine people s experience. The analysis produces another narrative about diaconia work, which provides tools for examining the diaconal work from a new perspective. Through the analysis it is possible to see diaconia as an exchange ratio, in which the exchange takes place between a client and a diaconia worker, but also more broadly with other actors, such as social workers, shop clerks, or with other parishioners. The exchange ratio is examined from the perspective of power which is embedded in the client s experiences. The analysis reveals that the most important relations of ruling are humiliation and randomness in the exchange ratio of diaconia work; valuating spirituality above the bodily being; and replacing official social work. The results give a map about the relations of ruling of diaconia work which gives tools to look at diaconia work s meanings to the clients. The hidden element of humiliation in the exchange ratio breaks the current picture of diaconia work. The ethos of the holistic encounters and empathic practices are shown to be of another kind when spirituality is preferred to the bodily being. Nevertheless, diaconia appears to be a place for a respectful encounter, especially in situations where the public sector s actors are retreating on liability or clients are in a life crisis. The collapse of the welfare state structures imposes on diaconia work tasks that have not previously belonged to it. At the local level, clients receive partners from diaconia workers in order to advocate them in the welfare system. Actions to influence the wider societal structures are not reached because of lacking resources. An awareness of the oppressive practices of diaconia work and their critical reviewing are the keys to the development of diaconia work, since there are such practices even in holistic and respectful diaconia work. While the research raises new information for the development of diaconia work, it also opens up new aspects for developing other kinds of social work by emphasizing the importance of taking people s experiences seriously. Keywords: diaconia work, institutional ethnography, Dorothy E. Smith, experience, customer, relations of ruling.