Dimethyl sulphoxide complexes of titanyl, zirconyl and thorium perchlorates

TiO·5DMSO(ClO4)2, ZrO·8DMSO(ClO4)2 and Th·12DMSO(ClO4)4 are prepared by reaction of the respective metal perchlorates with an excess of dimethyl sulphoxide. The last two complexes yield ZrO·6DMSO(ClO4)2 and Th·6DMSO(ClO4)4 on heating around 185°C, while the titanyl complex explodes at 190°C. The extra DMSO molecules in the zirconyl and thorium complexes seem to be held in the lattice. In the parent complexes, the co-ordinated DMSO molecules are bonded by oxygen to the metal atoms while in the DMSO complexes of zirconyl and thorium perchlorates, obtained by heating at 185°C, the bonding involves the sulphur, indicating a change in the bonding during the process of heating.

Encouragement and discouragement : Essays on taxation and government expenditure

This thesis consists of an introduction to a topic of optimal use of taxes and government expenditure and three chapters analysing these themes more in depth. Chapter 2 analyses to what extent a given amount of subsidies affects the labour supply of parents. Municipal supplement to the Finnish home care allowance provides exogenous variation to labour supply decision of a parent. This kind of subsidy that is tied to staying at home instead of working is found to have fairly large effect on labour supply decisions of parents. Chapter 3 studies theoretically when it is optimal to provide publicly private goods. In the set up of the model government sets income taxes optimally and provides a private good, if it is beneficial to do so. The analysis results in an optimal provision rule according to which the good should be provided when it lowers the participation threshold into labour force. Chapter 4 investigates what happened to prices and demand when hairdressers value added tax was cut in Finland from 22 per cent to 8 per cent. The pass-through to prices was about half of the full pass-through and no clear indication of increased demand for the services or better employment situation in the sector is found.

Novel insertion and deletion mutants of RpoB that render Mycobacterium smegmatis RNA polymerase resistant to rifampicin-mediated inhibition of transcription

The startling increase in the occurrence of rifampicin (Rif) resistance in the clinical isolates of Mycobacterium tuberculosis worldwide is posing a serious concern to tuberculosis management. The majority of Rif resistance in bacteria arises from mutations in the RpoB subunit of the RNA polymerase. We isolated M. smegmatis strains harbouring either an insertion (6 aa) or a deletion (10 aa) in their RpoB proteins. Although these strains showed a compromised fitness for growth in 7H9 Middlebrook medium, their resistance to Rif was remarkably high. The attenuated growth of the strains correlated with decreased specific activities of the RNA polymerases from the mutants. While the RNA polymerases from the parent or a mutant strain (harbouring a frequently occurring mutation, H442Y, in RpoB) were susceptible to Rif-mediated inhibition of transcription from calf thymus DNA, those from the insertion and deletion mutants were essentially refractory to such inhibition. Three-dimensional structure modelling revealed that the RpoB amino acids that interact with Rif are either deleted or unable to interact with Rif due to their unsuitable spatial positioning in these mutants. We discuss possible uses of the RpoB mutants in studying transcriptional regulation in mycobacteria and as potential targets for drug design.

Doing marriage and parenthood: The division of household labour across two life course events

The current study is a longitudinal investigation into changes in the division of household labour across transitions to marriage and parenthood in the UK. Previous research has noted a more traditional division of household labour, with women performing the majority of housework, amongst spouses and couples with children. However, the bulk of this work has been cross-sectional in nature. The few longitudinal studies that have been carried out have been rather ambiguous about the effect of marriage and parenthood on the division of housework. Theoretically, this study draws on gender construction theory. The key premise of this theory is that gender is something that is performed and created in interaction, and, as a result, something fluid and flexible rather than fixed and stable. The idea that couples ‘do gender’ through housework has been a major theoretical breakthrough. Gender-neutral explanations of the division of household labour, positing rational acting individuals, have failed to explicate why women continue to perform an unequal share of housework, regardless of socio-economic status. Contrastingly, gender construction theory situates gender as the key process in dividing household labour. By performing and avoiding certain housework chores, couples fulfill social norms of what it means to be a man and a woman although, given the emphasis on human agency in producing and contesting gender, couples are able to negotiate alternative gender roles which, in turn, feed back into the structure of social norms in an ever-changing societal landscape. This study adds extra depth to the doing gender approach by testing whether or not couples negotiate specific conjugal and parent roles in terms of the division of household labour. Both transitions hypothesise a more traditional division of household labour. Data comes from the British Household Panel Survey, a large, nationally representative quantitative survey that has been carried out annually since 1991. Here, data tracks the same 776 couples at two separate time points – 1996 and 2005. OLS regression is used to test whether or not transitions to marriage and parenthood have a significant impact on the division of household labour whilst controlling for host of relevant socio-economic factors. Results indicate that marriage has no significant effect on how couples partition housework. Those couples making the transition from cohabitation to marriage do not show significant changes in housework arrangements from those couples who remain cohabiting in both waves. On the other hand, becoming parents does lead to a more traditional division of household labour whilst controlling for socio-economic factors which accompany the move to parenthood. There is then some evidence that couples use the site of household labour to ‘do parenthood’ and generate identities which both use and inform socially prescribed notions of what it means to be a mother and a father. Support for socio-economic explanations of the division of household labour was mixed although it remains clear that they, alone, cannot explain how households divide housework.

Energy landscape view of phase transitions and slow dynamics in thermotropic liquid crystals

Thermotropic liquid crystals are known to display rich phase behavior on temperature variation. Although the nematic phase is orientationally ordered but translationally disordered, a smectic phase is characterized by the appearance of a partial translational order in addition to a further increase in orientational order. In an attempt to understand the interplay between orientational and translational order in the mesophases that thermotropic liquid crystals typically exhibit upon cooling from the high-temperature isotropic phase, we investigate the potential energy landscapes of a family of model liquid crystalline systems. The configurations of the system corresponding to the local potential energy minima, known as the inherent structures, are determined from computer simulations across the mesophases. We find that the depth of the potential energy minima explored by the system along an isochor grows through the nematic phase as temperature drops in contrast to its insensitivity to temperature in the isotropic and smectic phases. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures; the inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the isotropic-nematic transition. We find that this breakdown occurs at a temperature below which the system explores increasingly deeper potential energy minima.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Developing and Integrating HRM Practices in MNC Subsidiaries in China

Whilst previous research on Human Resource Management (HRM) in subsidiaries of multinational companies (MNCs) has focused extensively on the HRM practices that exist in foreign subsidiaries and the extent to which they resemble MNC home country and/or local host country practices, considerably less attention has been directed at the question of how these practices come to exist. Accordingly, this thesis aims to shed light on the processes that shape HRM practices and capabilities in MNC subsidiaries. The main contribution of the thesis is the focus on how; how HRM practices are integrated in MNC subsidiaries, and how subsidiary HRM capabilities are developed through involvement in social networks. Furthermore, this thesis includes a time aspect which, despite not being purely longitudinal, provides an indication of the ongoing changes in HRM in MNC subsidiaries in China. Data for this study were collected in 2005-2006 through structured face to face interviews with 153 general managers and HR managers in 87 subsidiaries of European MNCs located in China. Five of the six thesis papers build on this questionnaire data and one paper builds on qualitative data collected at the same time. Two papers build on dual data sets, meaning that they in addition to the abovementioned data include quantitative questionnaire data from 1996 and 1999 respectively. The thesis focuses on the following four sub-questions i) To what extent do subsidiary HRM practices resemble parent MNC and host country practices? How has this changed over time and why? ii) How are HRM practices integrated into MNC subsidiaries and why are certain integration mechanisms used? iii) How does involvement in internal and external social networks influence subsidiary HRM capabilities? iv) What factors influence the strategic role of the subsidiary HR department? Regarding the first sub-question the findings indicate that the HRM practices of MNC subsidiaries in China are converging with both local company practices and parent MNC practices. This is interesting in the sense that it suggests that the isomorphic pressures the subsidiary faces from the MNC and from its local host environment are not always in conflict with each other. Concerning the question of how HRM practices are integrated into MNC subsidiaries and why certain integration mechanisms are used, the thesis provides a fine-grained examination of four mechanisms that MNCs use to integrate HRM practices in subsidiaries. The findings suggest that MNCs use a variety of different integration mechanisms as complements rather than as substitutes for each other. Furthermore, it is apparent that different contextual factors in the subsidiary and the subsidiary-headquarters relationship influence why certain mechanisms are or are not used. The most interesting contribution of the thesis in regard to the third question is that it highlights the importance of network involvement for learning about HRM practices in the Chinese context. Networks with other MNCs in China clearly emerged as particularly important contributors to enhanced HRM capabilities. Finally, concerning the fourth sub-question the findings indicate that the role of the HR department in MNC subsidiaries in China had become more strategic between 1999 and 2006.

A unified model for auxiliary switch commutated DC-DC converters

A novel ZVS auxiliary switch commutated variation for all DGDC converter topologies has been proposed in 2006. With proper designation of the circuit variables (throw current I and the pole voltage V), all these converters are seen to be governed by an identical set of equations. With idealized switches, the steady-state performance is obtainable in an analytical form. The conversion ratio of the converter topologies is obtained. A generalized equivalent circuit emerges for all these converters from the steady-state conversion ratio. It also provides a dynamic model as well. With these generalized steady-state equivalent circuits, small signal analysis of these converters may be carried out readily. It enables one to use the familiar state space averaged results of the standard PWM DGDC converters for the resonant counterparts. Th dc and ac models reveals that dc and low frequency behaviour of the proposed family of converters is similiar to that of its PWM parent

Reversible cation/anion extraction from K2La2Ti3O10: Formation of new layered titanates, KLa2Ti3O9.5 and La2Ti3O9

A new soft-chemical transformation of layered perovskite oxides is described wherein K2O is sequentially extracted from the Ruddlesden-Popper (R-P) phase, K2La2Ti3O10 (I), yielding novel anion-deficient KLa2Ti3O9.5 (II) and La2Ti3O9 (III). The transformation occurs in topochemical reactions of the R-P phase I with PPh4Br and PBu4Br (Ph = phenyl; Bu = n-butyl). The mechanism involves the elimination of KBr accompanied by decomposition of PR4+ (R = phenyl or n-butyl) that extracts oxygen from the titanate. Analysis of the organic products of decomposition reveals formation of Ph3PO, Ph3P, and Ph-Ph for R = phenyl, and Bu3PO, Bu3P along with butane, butene, and octane for R = butyl. The inorganic oxides II and III crystallize in tetragonal structures (II: P4/mmm, a = 3.8335(1) angstrom, c = 14.334(1) angstrom; III: /4/ mmm, a = 3.8565(2) angstrom, c = 24.645(2) angstrom) that are related to the parent R-P phase. II is isotypic with the Dion-Jacobson phase, RbSr2Nb3O10, while III is a unique layered oxide consisting of charge-neutral La2Ti3O9 anion-deficient perovskite sheets stacked one over the other without interlayer cations. Interestingly, both II and III convert back to the parent R-P phase in a reaction with KNO3. While transformations of the R-P phases to other related layered/three-dimensional perovskite oxides in ion-exchange/metathesis/dehydration/reduction reactions are known, the simultaneous and reversible extraction of both cations and anions in the conversions K2La2Ti3O10 reversible arrow KLa2Ti3O9.5 reversible arrow La2Ti3O9 is reported here for the first time.

The Formation, Numbers And Radio Output Of Giant Radio Galaxies

The numbers and mean radio luminosities of giant radio galaxies (GRGs) have been calculated for redshifts up to z = 0.6, assuming a sensitivity limit of 1 Jy at 1 GHz for the observations. The estimates are obtained with a model for the beam propagation, first through the hot gaseaous halo around the parent galaxy, and thereafter, through the even hotter but less dense intergalactic medium. The model is able to accurately reproduce the observed numbers and mean radio luminosities of GRGs at redshifts of less than 0.1, and it predicts that a somewhat larger number of GRGs should be found at redshifts of greater than 0.1.

Chlorine-35 nuclear quadrupole resonance study of molecular torsional motion in some chloropyridine-N-oxides and chloroquinoline-N-oxides

Chlorine has been substituted at the 2- and 4-positions in the pyridine and quinoline rings of the corresponding N-oxides and 35Cl n.q.r. spectra have been studied in the temperature range 77–300 K. The change in the n.q.r. frequencies in N-oxides as compared to their parent compounds are interpreted in terms of the conjugative effect and the inductive effect of the N+—O– group. The negative temperature coefficients of the resonance frequencies in chloropyridine-N-oxides have been analysed using the Bayer, Kushida and Brown equations. The calculated torsional frequencies, which are in the range 52–78 cm–1, are found to be only slightly temperature dependent.

pH mediated delamination of anionic clay-like nickel-zinc hydroxysalt in water through intercalation of zwitterionic p-aminobenzoate ions

p-aminobenzoate could be intercalated into the anionic clay, Ni3Zn2(OH)(8)(OAc)(2)center dot 2H(2)O at a high pH (similar to 10). When the pH was reduced to similar to 7 while washing colloidal dispersion due to delamination was observed. The development of partial positive charge on the amine end of the intercalated anion causes repulsion between the layers leading to delamination and colloidal dispersion of monolayers in water. The layers could be restacked from the colloid to form the parent solid either by increasing the pH or by evaporation.

Manganese-mediated ferromagnetism in La2Fe1-xMn2xCr1-xO6 perovskite oxides

We have investigated the structure and magnetic properties of the perovskite oxides of the formula La2Fe1-xMn2xCr1-xO6 (0 < x < 1.0). For 0 < x <= 0.5, the members adopt the orthorhombic (Pbnm) structure, where the transition metal atoms are disordered at the 4b sites and the MO6 (M = Fe, Mn, Cr) octahedra become increasingly distorted with increasing x. For 0.65 <= x < 1.0, the members adopt the rhombohedral (R-3c) structure that is similar to LaMnO3+delta (delta >= 0.1) where the MO6 octahedra are undistorted. While the magnetic properties of the latter series are largely similar to the parent LaMnO3+delta arising from the double-exchange (DE) between mixed valent Mn-III/Mn-IV, the magnetic properties of the orthorhombic members show a distinct (albeit weak) ferromagnetism (T-C similar to 200 K) that seems to arise from a Mn-III-mediated superexchange (SE) between Fe-III/Cr-III in the disordered perovskite structure containing Fe-III, Mn-III and Cr-III.

Molecular structure-activity relationship study of some non-steroidal antiinflammatory agents using electrostatic potential mapping

A series of 6,11-dihydro-11-oxodibenz[b,e]oxepin-2-acetic acids (DOAA) which are known to be anti-inflammatory agents were studied. The geometries of some of the molecules obtained from X-ray crystallography were used in the calculations as such while the geometries of their derivatives were obtained by local, partial geometry optimization around the Sites of substitution employing the AMI method, keeping the remaining parts of the geometries the same as those in the parent molecules. Molecular electrostatic potential (MEP) mapping was performed for the molecules using optimized hybridization displacement charges (HDC) combined with Lowdin charges, as this charge distribution has been shown earlier to yield near ab initio quality results. A good correlation has been found between the MEP values near the oxygen atoms of the hydroxyl groups of the carboxy groups of the molecules and their anti-inflammatory activities. The result is broadly in agreement with the model proposed earlier by other authors regarding the structure-activity relationship for other similar molecules.