Intermolecular interactions in pi -conjugated systems: Application to polyenes

A computational scheme has been developed for strongly interacting systems wherein the intermolecular interaction is introduced as a charge-induced-dipole term. Within this approximation, the model Hamiltonian is exactly solved using a valence-bond basis. The validity of the scheme has been checked by use of exact calculations on small model systems. The method has been applied to finite polyenes to study the shifts in the ground-state energies and dipole-allowed excited-state energies in the presence of neighbors. Our calculations show a red shift in the optical gap of the infinite polyene by 0.124 eV, which is rather small compared to the experimental red shift. This is traced to the larger inaccuracy in the calculated shift in the excited state. The calculated shift in the ground-state energies are more accurate and hence the method is better suited for studying the effect of intermolecular interactions on the properties of the ground state.

Methyl ethyl ketone plus water plus secondary butyl alcohol: A potential system for the exploration of a quadruple critical point

We report preliminary experiments on the ternary-liquid mixture, methyl ethyl ketone (MEK)+water (W)+secondary butyl alcohol (sBA)-a promising system for the realization of the quadruple critical point (QCP). The unusual tunnel-shaped phase diagram shown by this system is characterized and visualized by us in the form of a prismatic phase diagram. Light-scattering experiments reveal that (MEK+W+sBA) shows near three-dimensional-Ising type of critical behavior near the lower critical solution temperatures, with the susceptibility exponent (gamma) in the range of 1.217 <=gamma <= 1.246. The correlation length amplitudes (xi(o)) and the critical exponent (nu) of the correlation length (xi) are in the ranges of 3.536 <=xi(o)<= 4.611 A and 0.619 <=nu <= 0.633, respectively. An analysis in terms of the effective susceptibility exponent (gamma(eff)) shows that the critical behavior is of the Ising type for MEK concentrations in the ranges of 0.1000 <= X <= 0.1250 and X >= 0.3000. But, for the intermediate range of 0.1750 <= X < 0.3000, the system shows a tendency towards mean-field type of critical behavior. The advantages of the system (MEK+W+sBA) over the system (3-methylpyridine+water+heavy water+potassium Iodide) for the realization of a QCP are outlined.

Critical behavior of the aqueous electrolytic system 3-methylpyridine+D2O+NaBr

The system 3-methylpyridine(3MP)+water(H2O)+NaBr has been the subject of an intense scientific debate since the work of Jacob [Phys. Rev. E. 58, 2188 (1988)] and Anisimov [Phys. Rev. Lett. 85, 2336 (2000)]. The crossover critical behavior of this system seemed to show remarkable sensitivity to the weight fraction (X) of the ionic impurity NaBr. In the range X <= 0.10 the system displayed Ising behavior and a pronounced crossover to mean-field behavior in the range 0.10 <= X <= 0.16. A complete mean-field behavior was observed at X=0.17, a result that was later attributed to the existence of long-living nonequilibrium states in this system [Kostko , Phys. Rev. E. 70, 026118 (2004)]. In this paper, we report the near-critical behavior of osmotic susceptibility in the isotopically related ternary system, 3MP+heavy water(D2O)+NaBr. Detailed light-scattering experiments performed at exactly the same NaBr concentrations as investigated by Jacob reveal that the system 3MP+D2O+NaBr shows a simple Ising-type critical behavior with gamma similar or equal to 1.24 and nu similar or equal to 0.63 over the entire NaBr concentration range 0 <= X <= 0.1900. The crossover behavior is predominantly nonmonotonic and is completed well outside the critical domain. An analysis in terms of the effective susceptibility exponent (gamma(eff)) reveals that the crossover behavior is nonmonotonic for 0 <= X <= 0.1793 and tends to become monotonic for X > 0.1793. The correlation length amplitude xi(o), has a value of similar or equal to 2 A for 0.0250 <= X <= 0.1900, whereas for X=0, xi(o)similar or equal to 3.179 A. Since isotopic H -> D substitution is not expected to change the critical behavior of the system, our results support the recent results obtained by Kostko [Phys. Rev. E. 70, 026118 (2004)] that 3MP+H2O+NaBr exhibits universal Ising-type critical behavior typical for other aqueous solutions.

On the Discursive Construction of Corruption: A Critical Analysis of Media Texts

While extant studies have greatly advanced our understanding of corruption, we still know little of the processes through which specific practices or events come to be labeled as corruption. In a time when public attention devoted to corruption and other forms of corporate misbehavior has exploded, this thesis raises – and seeks to answer – crucial questions related to how the phenomenon is socially and discursively constructed. What kinds of struggles are manifested in public disputes about corruption? How do constructions of corruption relate with broader conceptions of (il)legitimacy in and around organizations? What are the discursive dynamics involved in the emergence and evolution of corruption scandals? The thesis consists of four essays that each employ different research designs and tackle these questions in slightly different theoretical and methodological ways. The empirical focus is on the media coverage of a number of significant and widely discussed scandals in Norway in the period 2003-2008. By illuminating crucial processes through which conceptions of corruption were constructed, reproduced, and transformed in these scandals, the thesis seeks to paint a more nuanced picture of corruption than what is currently offered in the literature. In particular, the thesis challenges traditional conceptions of corruption as a dysfunctional feature of organizations in and of itself by emphasizing the ambiguous, temporal, context-specific, and at times even contradictory features of corruption in public discussions.

Transfer of F- in the reaction of SF6- with SOF4: Implications for SOF4 production in corona discharges

The temperature (T) and electric field-to-gas pressure (E/P) dependences of the rate coefficientk for the reaction SF 6 � +SOF4rarrSOF 5 � +SF5 have been measured. ForT<270>k approaches a constant of 2.1×10�9 cm3/s, and for 433>T>270 K,k decreases withT according tok (cm3/s)=0.124 exp [�3.3 lnT(K)]. ForE/Pk has a constant value of about 2.5×10�10 cm3/s, and for 130 V/cm·torr>E/P>60 V/cm·torr, the rate is approximately given byk (cm3/s)sim7.0×10�10 exp (�0.022E/P). The measured rate coefficient is used to estimate the influence of this reaction on SOF4 production from negative, point-plane, glow-type corona discharges in gas mixtures containing SF6 and at least trace amounts of O2 and H2O. A chemical kinetics model of the ion-drift region in the discharge gap is used to fit experimental data on SOF4 yields assuming that the SF 6 � +SOF4 reaction is the predominant SOF4 loss mechanism. It is found that the contribution of this reaction to SOF4 destruction falls considerably below the estimated maximum effect assuming that SF 6 � is the predominant charge carrier which reacts only with SOF4. The results of this analysis suggest that SF 6 � is efficiently deactivated by other reactions, and the influence of SF 6 � +SOF4 on SOF4 production is not necessarily more significant than that of other slower secondary processes such as gas-phase hydrolysis

Microwave driven hydrothermal synthesis of LiMn2O4 nanoparticles as cathode material for Li-ion batteries

Among the various cathode materials studied for Li-ion batteries over the past many years, spinet LiMn2O4 is found to be one of the most attractive materials. Nanoparticles of the electrode materials sustain high rate capability due to large surface to volume ratio and small diffusion path length. Nanoparticles of spinel LiMn2O4 have been synthesized by microwave hydrothermal technique using prior synthesized amorphous MnO2 and LiOH. The phase and purity of spinel LiMn2O4 are confirmed by powder X-ray diffraction. The morphological studies have been investigated using field emission scanning electron microscopy and high-resolution transmission electron microscopy. The electrochemical performances of the material for Li insertion/extraction are evaluated by cyclic voltammetry, galvanostatic charge-discharge cycling and AC impedance studies. The initial discharge capacity is found to be about 89 mAh g(-1) at current density of 21 mA g(-1). (C) 2010 Elsevier B.V. All rights reserved.

Regulation and Function of GATA Transcription Factors in Adrenocortical Tumors and Granulosa Cells

Transcription factors play a key role in tumor development, in which dysfunction of genes regulating tissue growth and differentiation is a central phenomenon. The GATA family of transcription factors consists of six members that bind to a consensus DNA sequence (A/T)GATA(A/G) in gene promoters and enhancers. The two GATA factors expressed in the adrenal cortex are GATA-4 and GATA-6. In both mice and humans, GATA-4 can be detected only during the fetal period, whereas GATA-6 expression is abundant both throughout development and in the adult. It is already established that GATA factors are important in both normal development and tumorigenesis of several endocrine organs, and expression of GATA-4 and GATA-6 is detected in adrenocortical tumors. The aim of this study was to elucidate the function of these factors in adrenocortical tumor growth. In embryonal development, the adrenocortical cells arise and differentiate from a common pool with gonadal steroidogenic cells, the urogenital ridge. As the adult adrenal cortex undergoes constant renewal, it is hypothesized that undifferentiated adrenocortical progenitor cells reside adjacent to the adrenal capsule and give rise to daughter cells that differentiate and migrate centripetally. A diverse array of hormones controls the differentiation, growth and survival of steroidogenic cells in the adrenal gland and the gonads. Factors such as luteinizing hormone and inhibins, traditionally associated with gonadal steroidogenic cells, can also influence the function of adrenocortical cells in physiological and pathophysiological states. Certain inbred strains of mice develop subcapsular adrenocortical tumors in response to gonadectomy. In this study, we found that these tumors express GATA-4, normally absent from the adult adrenal cortex, while GATA-6 expression is downregulated. Gonadal markers such as luteinizing hormone receptor, anti-Müllerian hormone and P450c17 are also expressed in the neoplastic cells, and the tumors produce gonadal hormones. The tumor cells have lost the expression of melanocortin-2 receptor and the CYP enzymes necessary for the synthesis of corticosterone and aldosterone. By way of xenograft studies utilizing NU/J nude mice, we confirmed that chronic gonadotropin elevation is sufficient to induce adrenocortical tumorigenesis in susceptible inbred strains. Collectively, these studies suggest that subcapsular adrenocortical progenitor cells can, under certain conditions, adopt a gonadal fate. We studied the molecular mechanisms involved in gene regulation in endocrine cells in order to elucidate the role of GATA factors in endocrine tissues. Ovarian granulosa cells express both GATA-4 and GATA-6, and the TGF-β signaling pathway is active in these cells. Inhibin-α is both a target gene for, and an atypical or antagonistic member of the TGF-β growth factor superfamily. In this study, we show that GATA-4 is required for TGF-β-mediated inhibin-α promoter activation in granulosa cells, and that GATA-4 physically interacts with Smad3, a TGF-β downstream protein. Apart from the regulation of steroidogenesis and other events in normal tissues, TGF-β signaling is implicated in tumors of multiple organs, including the adrenal cortex. Another signaling pathway found often to be aberrantly active in adrenocortical tumors is the Wnt pathway. As both of these pathways regulate the expression of inhibin-α, a transcriptional target for GATA-4 and GATA-6, we wanted to investigate whether GATA factors are associated with the components of these signaling cascades in human adrenocortical tumors. We found that the expression of Wnt co-receptors LRP5 and LRP6, Smad3, GATA-6 and SF-1 was diminished in adrenocortical carcinomas with poor outcome. All of these factors drive inhibin-α expression, and their expression in adrenocortical tumors correlated with that of inhibin-α. The results support a tumor suppressor role previously suggested for inhibin-α in the mouse adrenal cortex, and offer putative pathways associated with adrenocortical tumor aggressiveness. Unraveling the role of GATA factors and associated molecules in human and mouse adrenocortical tumors could ultimately contribute to the development of diagnostic tools and future therapies for these diseases.

Mutual diffusion coefficients of some binary liquid systems: benzene-n-alkyl alcohol

The mutual diffusion coefficients for binary liquid systems of benzene-n-alkyl alcohol at various compositions have been determined by the diaphragm cell method at 28-degrees-C. The alcohols used were the members of n-paraffinic alcohols ranging from C1 to C8. The maximum possible experimental error is 14%. The data were fitted with a generalized correlation, giving the deviation from the experimental data to within 2.75%, on average.

Korpien ennallistamisen lyhyen aikavälin vaikutukset puustorakenteeseen

Korpien puustorakenteen palautumisen nopeus ja ennallistettujen kohteiden kehitys on huonosti tunnettua. Monet tutkimukset ovat osoittaneet, että korvet ovat lajistollisen monimuotoisuuden keskittymiä boreaalisessa vyöhykkeessä. Korvet ovat usein merkittäviä lahopuukeskittymiä, joten niillä on iso vaikutus lahottajalajistolle. Valtaosa suojelualu- eiden korvista Etelä-Suomessa on ojitettu ja korpien puustorakenne on metsätalouden muovaamaa ja yksipuolistamaa. Korpien puustorakennetta tutkittiin kahdella erillisellä tutkimusalueella, jotka sijaitsevat Etelä-Suomessa. Työn tavoit- teena oli selvittää luonnontilaisten ja ennallistettujen korpien puuston rakenteellista monimuotoisuutta sekä ennallista- mistoimien vaikutuksia Evon suojelumetsässä ja Liesjärven kansallispuistossa. Molemmat alueet ovat olleet aikaisem- min metsänhoidon piirissä. Evolta valittiin tarkasteluun ennallistettuja ja luonnontilaisen kaltaisia korpia: 12 ennallis- tettua koealaa ja 16 luonnontilaisen kaltaista koealaa. Liesjärveltä valittiin tarkasteluun ennallistettu Soukonkorpi, jossa oli 15 koealaa. Koealat olivat pinta-alaltaan neljä aaria. Evon tutkimusalueella maastomittaukset on tehty kesällä 2002 ja 2010. Liesjärven tutkimusalueella maastomittaukset on tehty vuosina 1995–2010. Tarkastellut muuttujat olivat elävän puuston määrä ja puulajisuhteet, lahopuun määrä ja laatu (lahopuutyyppi, läpimittaluokka, lahoaste ja puulaji). Lahopuuston määrää ja laatua sekä lahopuuston ja elävän puuston suhdetta kuvaavien muuttujien välisiä eroja testattiin ei-parametrisellä Kolmogorov-Smirnov-testillä. Evon ja Liesjärven tutkimusalueiden ennallistamistoimien yhtenä tavoitteena oli lahopuumäärien lisääminen ja laho- puun monipuolistaminen. Lahopuun lisäämisessä on onnistuttu molemmilla tutkimusalueilla. Ennallistamisen jälkeen lahopuumäärä kasvoi Evolla kolminkertaiseksi 8 vuodessa. Lahopuuta oli ennallistamisen jälkeen keskimäärin 71 m³/ha. Sen sijaan Evon luonnontilaisen kaltaisissa korvissa lahopuumäärä pysyi keskimäärin samana (28 m³/ha) tar- kastelujakson aikana. Liesjärvellä lahopuumäärä kasvoi ennallistamisen jälkeen noin kuusinkertaiseksi 15 vuodessa. Lahopuuta oli ennallistamisen jälkeen keskimäärin 124 m³/ha. Suuriläpimittaisen (? 30 cm) lahopuun määrä kasvoi huomattavasti ennallistamisen jälkeen molemmilla tutkimusalueilla. Suuriläpimittaisen lahopuun määrä kasvoi Evolla noin 12-kertaiseksi ja Liesjärvellä noin 9-kertaiseksi. Lahopuun määrä ja laatu vaihtelivat suuresti ennallistettujen ja luonnontilaisen kaltaisten korpien välillä. Evolta löytyi lahopuustoltaan runsaita ja monipuolisia korpia, mutta myös korpia, joiden lahopuusto on luonnontilaisiin korpiin ver- rattuna määrältään vähäistä ja laadultaan yksipuolista. Liesjärvellä koealojen lahopuumäärät poikkesivat suuresti toisis- taan. Valtaosalla koealoista lahopuusto oli kuitenkin runsaampaa ja monimuotoisempaa kuin talousmetsissä yleensä. Molemmilla tutkimusalueilla ennallistetut korvet muistuttavat nyt puustorakenteeltaan lahopuun osalta enemmän luon- nontilaisia korpia kuin ennen ennallistamista. Ilman ennallistamistoimia lahopuumäärän kasvu olisi todennäköisesti ollut hidasta. Evolla ennallistettujen ja luonnontilaisen kaltaisten korpien välillä oli tilastollisesti merkitseviä eroja suuriläpimittaisen lahopuun ja tuoreimpien lahoasteiden (1 ja 2) määrässä. Valtaosalla korvista oli lahopuuta vähintään 20 m³/ha. Metsäaluetasolla keskimäärin 20–30 m³/ha järeää, vaihtelevanlaatuista lahopuuta näyttäisi aikaisempien tutkimusten mukaan täyttävän useimpien saproksyylilajien elinympäristövaatimukset Etelä-Suomessa.

Tutkimuksia jätevesilietteen kunnostuksesta ja koneellisesta kuivauksesta

Engl. summary: Studies on conditioning and mechanical dewatering of waste water sludge

Diruthenium(III) compounds, Ru2O(O2CAr)2(MeCN)4(PPh3)2(ClO4)2.cntdot.H2O and Ru2O(O2CAr)4(PPh3)2, with an (Ru2(.mu.-O)(.mu.-O2CAr)22+) core as model systems for the diiron centers in hemerythrin

Diruthenium(II1) compounds, Ru20(02CAr)2(MeCN)4(PPh3)2(C104)(z1~) Hazn0d R U ~ O ( O ~ C A ~ ) ~(2() P(PA~r ~= )P~h,C6H4-p-OMe), were prepared by reacting R U ~ C I ( O ~ CaAnd~ P)P~h 3 in MeCN and characterized by analytical and spectral data. The molecular structures of 1 with Ar = Ph and of 2 with Ar = C&p-OMe were determined by X-ray crystallography. Crystal data for Ru~~(~~CP~)~(M~CN),(PP~(~la)):~ m(oCnIoc~lin,ic), n~/~cH, ~a O= 27.722 (3) A, b = 10.793 (2) A, c = 23.445 ( 2 )A , fi = 124.18 (l)', V = 5803 A3, and 2 = 4. Cr stal data for Ru~O(O~CC~H~-~-O(M2b~): )o~rth(orPhoPm~bi~c, )Pn~n a, a = 22.767 (5) A, b = 22.084 (7) A, c = 12.904 (3) 1, V = 6488 AS; and 2 = 4. Both 1 and 2 have an (Ruz0(02CAr)z2t1 core that is analogous to the diiron core present in the oxidized form of the nonheme respiratory protein hemerythrin. The Ru-Ru distances of 3.237 (1) and 3.199 ( I ) A observed in 1 and 2, respectively, are similar to the M-M distances known in other model systems. The essentially diamagnetic nature of 1 and 2 is due to the presence of two strongly interacting t22 Ru"' centers. The intense colors of 1 (blue) and 2 (purple) are due to the charge-transfer transition involving an ( R ~ ~ ( f i - 0m)o~ie~ty.) The presence of labile MeCN and carboxylato ancillary ligands in I and 2, respectively, makes these systems reactive toward amine and heterocyclic bases.

Sport, body and power: Reassessing the myth of President Kekkonen

Former President of Finland Urho Kekkonen was not only a powerful politician but also a well-known sportsman and keep-fit enthusiast. The president’s sports hobbies were covered and celebrated in the media and thus became an integral part of his public persona. This paper looks at Kekkonen’s athletic and able-bodied image and its significance for his power from the perspective of gender. In his exercise activities, Kekkonen was able to display his bodily prowess and demonstrate his version of masculinity, which emphasized both physical and mental strength. The union of mind and muscle in turn buttressed his political ascendancy. Kekkonen’s athletic body served as a cornerstone of his dominance over his country and, simultaneously, as a shield protecting Finland from both internal and external threats. Furthermore, Kekkonen’s sports performances were essential elements in the myth that was created around the president during his term and which was carefully conserved after his fall from power. Drawing upon scholarship on men and masculinities, this paper reassesses the still-effective mythical image of Kekkonen as an invincible superman. The article reveals the performative nature of his athletic activities and shows that in part, his pre-eminence in them was nothing more than theatre enacted by him and his entourage. Thus, Kekkonen’s superior and super-masculine image was actually surprisingly vulnerable and dependent on the success of the performance. The president’s ageing, in particular, demonstrates the fragility of his displays of prowess, strength and masculinity, and shows how fragile the entanglement of body and power can be.

Reaction of spironaphthalenones with hydroxylamine: Part I. A reinvestigation of the mechanism

Spironaphthalenones 1b–g on reaction with hydroxylamine hydrochloride gave the expected pyrrolotropones 2b–g. Furanotropone 6, postulated as an intermediate in the formation of pyrrolotropones, remained unchanged on reaction with hydroxylamine hydrochloride in ethanol. Reaction of unsymmetrical spironaphthalenones 1h–o with NH2OH.HCl gave the rearranged pyrrolotropones 2h–o.

One protein�many functions

The concept of one enzyme-one activity had influenced biochemistry for over half a century. Over 1000 enzymes are now described. Many of them are highly 'specific'. Some of them are crystallized and their three-dimensional structures determined. They range from 12 to 1000 kDa in molecular weight and possess 124 to several hundreds of amino acids. They occur as single polypeptides or multiple-subunit proteins. The active sites are assembled on these by appropriate tertiary folding of the polypeptide chain, or by interaction of the constituent subunits. The substrate is held by the side-chains of a few amino acids at the active site on the surface, occupying a tiny fraction of the total area. What is the bulk of the protein behind the active site doing? Do all proteins have only one function each? Why not a protein have more than one active site on its large surface? Will we discover more than one activity for some proteins? These newer possibilities are emerging and are finding experimental support. Some proteins purified to homogeneity using assay methods for different activities are now recognized to have the same molecular weight and a high degree of homology of amino acid sequence. Obviously they are identical. They represent the phenomenon of one protein-many functions.