Reactivity with hydrogen of pure iron oxide and of iron oxides doped with oxides of Mn, Co, Ni and Cu

Using dynamic TG in H2, X-ray powder diffraction and Mössbauer Spectroscopy the reactivities fot hydrogen reduction of Fe2O3 prepared at different temperatures, Fe2O3 doped with oxides of Mn, Co, Ni and Cu prepared at 300DaggerC from nitrate precursors and intermediate spinels derived from above samples during reduction have been explored. The reactivity is higher for finely divided Fe2O3 prepared at 250DaggerC. The reduction is retarded by Mn, marginally affected by Co and accelerated by Ni and Cu, especially at higher (5 at.%) dopant concentration. These reactivities confirmed also by isothermal experiments, are ascribed to the nature of disorder in the metastable intermediate spinels and to hydrogen rsquospill overrsquo effects.

In-Network Computation in Random Wireless Networks: A PAC Approach to Constant Refresh Rates with Lower Energy Costs

We propose a method to compute a probably approximately correct (PAC) normalized histogram of observations with a refresh rate of Theta(1) time units per histogram sample on a random geometric graph with noise-free links. The delay in computation is Theta(root n) time units. We further extend our approach to a network with noisy links. While the refresh rate remains Theta(1) time units per sample, the delay increases to Theta(root n log n). The number of transmissions in both cases is Theta(n) per histogram sample. The achieved Theta(1) refresh rate for PAC histogram computation is a significant improvement over the refresh rate of Theta(1/log n) for histogram computation in noiseless networks. We achieve this by operating in the supercritical thermodynamic regime where large pathways for communication build up, but the network may have more than one component. The largest component however will have an arbitrarily large fraction of nodes in order to enable approximate computation of the histogram to the desired level of accuracy. Operation in the supercritical thermodynamic regime also reduces energy consumption. A key step in the proof of our achievability result is the construction of a connected component having bounded degree and any desired fraction of nodes. This construction may also prove useful in other communication settings on the random geometric graph.

Evaluation of Erosion Resistance of Metallic Materials and the Role of Material Properties in Correlations

A study of the correlations between material properties and normalized erosion resistance (inverse of erosion rates) of various materials tested in the rotating disk and the flow venturi at various intensities indicates that different individual properties influence different stages of erosion. At high and low intensities of erosion, energy properties predominate the phenomenon, whereas at intermediate intensities strength and acoustic properties become more significant. However, both strength and energy properties are significant in the correlations for the entire spectrum of erosion when extensive cavitation and liquid impingement data from several laboratories involving different intensities and hydrodynamic conditions are considered. The use of true material properties improved the statistical parameters by 3 to 37%, depending on the intensity of erosion. It is possible to evaluate qualitatively the erosion resistances of materials based on the true stress-true strain curves.

Towards Explaining the Tasks and Roles of the Boards of Directors

While previous research has helped to improve our understanding of corporate governance and boards of directors, less is known about the factors that affect boards’ tasks and roles and directors’ motivation and engagement. This requires knowledge of how board decisions are being made and the internal and external factors that affect the decision-making process. Large inferential leaps have been made from board demographics to firm performance with equivocal results. This thesis concentrates on how the institutional, behavioral and social identification factors impact the enactment of board roles and tasks. Data used in this thesis were collected in 2009 through a mailed survey to Finnish large and middle-sized corporations. The findings suggest that firstly, the national context of an organization is reflected in board roles and shapes how and for what reasons the board roles are carried out; secondly, the directors’ human and external social capital invariably impacts their engagement in board tasks and that conflicts among directors moderate those relationships; finally, directors’ identification with the organization, its shareholders and its customers affect the directors’ involvement in board tasks. By addressing the impact of organisational context, board-internal behaviour and social identification of board members on board roles and tasks, this thesis firstly complements the shareholder supremacy view as the only reason for the board’s involvement with specific tasks; secondly questions the existence of the board as separate from its institutional context; and thirdly questions the view that a board is a ‘black box’, subject to a selection of input demographic variables and producing quantifiable results. The thesis demonstrates that boards are complex organisational bodies, which involve much interaction among board members. Director behaviour and its influence on board decision making is an important determinant of board tasks and boards are likely subjected to inter-group tensions and are susceptible to the influence of internal and external social forces.

Singlet quenching of tetraphenylporphyrin and its metal derivatives by iron(III) coordination compounds

The quenching of fluorescence of the free-base tetraphenylporphyrin, H2TPP, and its metal derivatives, MgTPP and ZnTPP by diverse iron(III) complexes, [Fe(CN)6]3−, Fe(acac)3, [Fe(mnt)2]−, Fe(Salen)Cl, [Fe4S4(SPh)4]2−·, FeTPPCl and [Fe(Cp)2]+ has been studied both in homogeneous medium (CH3CN) and micellar media, SDS., CTAB and Triton X-100. The quenching efficiencies are analysed in terms of diffusional encounters and it has been possible to separate static quenching components. The quenching constants are dependent on the nature of the ligating atoms around iron(III) and also on the extent of π-conjugation of the ligands. The quenching mechanism has been investigated using steady-state irradiation experiments. Evidence for oxidative quenching by iron(III) complexes was obtained, though the spin multiplicities of the excited electronic states of iron(III) complexes permit both energy and electron transfer mechanisms for quenching of the singlet excited state of the porphyrins.

Kokeellisten aivovaltimoaneurysmien molekulaarinen kuvantaminen

Tutkimuksessa arvioitiin Sinerem-rautananopartikkelivarjoaineen soveltuvuutta aivovaltimoaneurysmiin liittyvän tulehdusreaktion kuvantamiseen. Tutkimuksessa tarkasteltiin 17 kokeellista rotan aivovaltimoaneurysmamallia. Eläimet jaettiin 9 ja 7 rotan sarjoihin, joista 9 rotan sarjasta kaikki ja 7 rotan sarjasta 3 satunnaistettua eläintä saivat varjoainetta. Kaikki eläimet kuvattiin ennen ja jälkeen varjoaineruiskutuksen ja kuvista arvioitiin varjoaineen aiheuttamaa artefaktaa. 7 rotan sarja kuvattiin lisäksi ex vivo. Kaikista aneurysmista tehtiin histologisia ja immunohistokemiallisia värjäyksiä raudan ja makrofagien osoittamiseksi. 9 rotan sarjasta vain 5 oli elossa koesarjan lopussa. 7 rotan sarjasta yksi eläin kuoli kesken koesarjan. Kaikissa 9 rotan sarjan aneurysmissa havaittiin varjoaineen aiheuttamaksi sopivaa artefaktaa. 3 aneurysmassa varsinaisessa koesarjassa havaittiin vastaavaa artefaktaa ja 2 näistä oli saanut varjoainetta. 1 negatiivisessa kontrollissa havaittiin artefaktaa. Ex vivo –kuvissa ei havaittu varjoaineen aiheuttamaksi sopivaa artefaktaa. Kaikissa aneurysmissa havaittiin eri-ikäistä trombia histologiassa. Varjoaineinjektio ei liittynyt negatiivisia kontrolleja suurempaan aneurysman rautapitoisten solujen osuuteen. Tutkimuksessa ei kyetty osoittamaan rautananopartikkelivarjoaineen soveltuvuutta aneurysmaan liittyvän tulehdusreaktion kuvantamisessa. (146 sanaa)

Computer modeling studies on the binding of 2',5'-linked dinucleoside phosphates to ribonuclease T1-influence of subsite interactions on the substrate specificity

The modes of binding of Gp(2',5')A, Gp(2',5')C, Gp(2',5')G and Gp(2',5')U to RNase T1 have been determined by computer modelling studies. All these dinucleoside phosphates assume extended conformations in the active site leading to better interactions with the enzyme. The 5'-terminal guanine of all these ligands is placed in the primary base binding site of the enzyme in an orientation similar to that of 2'-GMP in the RNase T1-2'-GMP complex. The 2'-terminal purines are placed close to the hydrophobic pocket formed by the residues Gly71, Ser72, Pro73 and Gly74 which occur in a loop region. However, the orientation of the 2'-terminal pyrimidines is different from that of 2'-terminal purines. This perhaps explains the higher binding affinity of the 2',5'-linked guanine dinucleoside phosphates with 2'-terminal purines than those with 2'-terminal pyrimidines. A comparison of the binding of the guanine dinucleoside phosphates with 2',5'- and 3',5'-linkages suggests significant differences in the ribose pucker and hydrogen bonding interactions between the catalytic residues and the bound nucleoside phosphate implying that 2',5'-linked dinucleoside phosphates may not be the ideal ligands to probe the role of the catalytic amino acid residues. A change in the amino acid sequence in the surface loop region formed by the residues Gly71 to Gly74 drastically affects the conformation of the base binding subsite, and this may account for the inactivity of the enzyme with altered sequence i.e., with Pro, Gly and Ser at positions 71 to 73 respectively. These results thus suggest that in addition to recognition and catalytic sites, interactions at the loop regions which constitute the subsite for base binding are also crucial in determining the substrate specificity.

Jos olisin viisas niin siivoisin : Lasten luovat prosessit päiväkodissa

It has been found usually to talk in the early childhood education in connection with the creativity about arts and skills and about play. In this treatise, the creativity is approached besides play but also from the point of view of the creativity of the everyday. The starting point for the study is the view according to which the creativity is complex interaction between a creative person and an environment. The theoretical body of the study is the Componential theory of creativity of Amabile (1996). The process which is open and product which is new and suitable or acceptable were defined creative. In the opinion of many researchers, the creativity is a phenomenon that has determined in a certain time and place so the creativity is examined from the point of view of the social constructionism. As creative processes in the day nursery it has been defined pretend play, child´s involvement and children´s agentive perception which is based on the Children´s agentive perception theory of Reunamo (2007). The purpose of the study is to clarify how the child's personal factors and the social environment affect the creative processes of children in the day nursery. This Master's thesis is based on the Children' s agentive perception uncovered study led by Jyrki Reunamo (2010) which was carried out in the spring of 2010 in Keski-Uusimaa and in Hämeenlinna and Taiwan. From the study, a name has also been used "on the sources of Orientation", a research project and development project. The study includes the children's evaluation sector, the observation sector, the children's interview sector and the evaluation sector of the pedagogic environment. 891 Children 1-7 year-old by age participated in the study. All the sectors which belong to the study of Reunamo were utilized in this treatise and the Finnish day nurseries or preschool groups which had participated in the study were marked off as the target group. The main component analysis, sum variables, the correlation coefficients, Mann-Whitney s U-test and Kruskall-Wallas test were used for the statistical examination of the quantitative material. In this treatise it was noticed, both the personal properties of the child and a social environment, that they affected all the examined creative processes which also had a significant connection with each other statistically. The definition of creativity was filled best by the participative answers. However, the number of the participative answers was only 8% in the questions concerning adults. That raised the question whether an attempt should be made to have effect so that the children's better participation also in the interaction with the adults would be possible in the educational culture of the day nursery. In the further study, the conscious building of the social environment which supports the creativity from a social constructionism point of view could indeed be an interesting task. The treatise is suitable for an examination of the interaction between the child's person and a social environment especially from the point of view of the creativity.

Synthesis and photocatalytic properties of AgLi1/3Ru2/3]O-2: A new delafossite oxide

A new delafossite oxide, AgLi1/3Ru2/3]O-2, synthesized by ion-exchanging interlayer-Li+ with Ag+ in layered Li2RuO3, is reported. The transformation of layered Li2RuO3 (monoclinic, space group C2/c) to AgLi1/3Ru2/3]O-2 possessing a delafossite structure (space group R (3) over barm) has been established with powder X-ray diffraction. The successful conversion of LiLi1/3Ru2/3]O-2 to AgLi1/3Ru2/3]O-2 is further confirmed by EDAX analysis. The diffuse reflectance spectrum of AgLi1/3Ru2/3]O-2 shows broad absorption in the UV-visible region suggesting its use as a photocatalyst. The photocatalytic activity of AgLi1/3Ru2/3]O-2 has been investigated by degrading various dyes. It showed significant photocatalytic activity for dye degradation both under UV and solar radiation. (C) 2010 Elsevier B.V. All rights reserved.

Selectivity in Garratt-Braverman Cyclization: An Experimental and Computational Study

Bispropargyl sulfones equipped with aromatic rings of dissimilar nature were synthesized. Under basic conditions, these sulfones isomerized to the bisallenic sulfones, creating a competitive scenario between two alternate Garratt-Braverman (GB) cyclization pathways. The observed product distribution ruled out the involvement of any ionic intermediate and supported the diradical mechanism with greater involvement of the electron-rich aromatic ring via the more nucleophilic radical. DFT-based calculations supported the diradical mechanism along with the observed selectivity.

Dynamic scheduling in manufacturing systems using brownian approximations

Recently, Brownian networks have emerged as an effective stochastic model to approximate multiclass queueing networks with dynamic scheduling capability, under conditions of balanced heavy loading. This paper is a tutorial introduction to dynamic scheduling in manufacturing systems using Brownian networks. The article starts with motivational examples. It then provides a review of relevant weak convergence concepts, followed by a description of the limiting behaviour of queueing systems under heavy traffic. The Brownian approximation procedure is discussed in detail and generic case studies are provided to illustrate the procedure and demonstrate its effectiveness. This paper places emphasis only on the results and aspires to provide the reader with an up-to-date understanding of dynamic scheduling based on Brownian approximations.

Synthesis and properties of tialite, beta-AL2TIO5

Tialite, beta-Al2TiO5, a low expansion material, has been synthesised by the combustion of corresponding metal nitrates and carbohydrazide (CH) or urea redox mixtures at 500-degrees-C. As prepared powders contained tialite, rutile, and corundum in the mole ratios of 50:25:25 (CH) and 20:40:40 (urea). The combustion derived powders, when calcined 30 min at 1300-degrees-C, gave single phase beta-tialite having a surface area of 20-25 m2 g-1 and a particle size of 0.79-1.03 mum.