Synthesis, characterization and thermal behaviour of solid-state compounds of 4-methoxybenzoate with lanthanum (III) and trivalent lighter lanthanides

Solid-state M-4-MeO-Bz compounds, where M stands for trivalent La, Ce, Pr, Nd and Sm and 4-MeO-Bz is 4-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, polymorphic transformation, ligand's denticity, thermal behaviour and thermal decomposition of the isolated compounds.

Magnetic, thermal and spectral behaviour of 3-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II)

Physico-chemical properties of 3-chloro-2-nitrobenzoates of Co(II), Ni(II) and Cu(II) were synthesized and studied. The complexes were obtained as mono- and dihydrates with a metal ion to ligand ratio of 1 : 2. All analysed 3-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II) and blue for Cu(II) complexes. Their thermal decomposition was studied in the range of 293 ­ 523 K, because it was found that on heating in air above 523 K 3-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10-4 ­ 10-2 mol / dm³. The magnetic moment values of Co2+, Ni2+ and Cu2+ ions in 3-chloro-2-nitrobenzoates experimentally determined at 76 ­ 303 K change from 3.67µB to 4.61µB for Co(II) complex, from 2.15µB to 2.87µB for Ni(II) 3-chloro-2-nitrobenzoate and from 0.26µB to 1.39µB for Cu(II) complex. 3-Chloro-2-nitrobenzoates of Co(II) and Ni(II) follow the Curie-Weiss law. Complex of Cu(II) forms dimer.

Synthesis, characterization and thermal behaviour on solid pyruvates of light trivalent lanthanides

Solid State Ln-L compounds, where Ln stands for light trivalent lanthanides (La - Gd) and L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-Ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, ligand denticity, thermal behaviour and thermal decomposition of the isolated compounds.

Synthesis, characterization and thermal behaviour on solid pyruvates of some bivalent metal ions

Solid state M-L compounds, were M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn and L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-Ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, ligand denticity, and thermal decomposition of the isolated compounds.

Synthesis, characterization and thermal behaviour of solid 2-methoxycinnamylidenepyruvate of some bivalent metal ions in CO2 and N2 atmospheres

Solid State M-2-MeO-CP compounds, where M stands for bivalent metals (Mn, Fe, Co, Ni, Cu and Zn) and 2-MeO-CP is 2-methoxycinnamylidenepyruvate, were synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), elemental analysis and complexometry were used to establish the stoichiometry and to study the thermal behaviour of these compounds in CO2 and N2 atmospheres. The results were consistent with the general formula: M(L)2∙H2O. In both atmospheres (CO2, N2) the thermal decomposition occurs in consecutive steps which are characteristic of each compound. For CO2 atmosphere the final residues were: Mn3O4, Fe3O4, Co3O4, NiO, Cu2O and ZnO, while under N2 atmosphere the thermal decomposition is still observed at 1000 º C.

Synthesis, characterization and thermal behaviour of heavy trivalent lanthanide malonates

Solid-state Ln-L compounds, where Ln stands for heavy trivalent lanthanides (Tb-Lu) and L is malonate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry were used to characterize and to study the thermal behaviour of these compounds. The dehydration of the compounds begins at 303 K and the anhydrous compounds are stable up to 548 K. The results also provided information concerning the ligand's denticity, thermal behaviour and identification of some gaseous products evolved during the thermal decomposition of these compounds.

Social capital, coping and information behaviour of long-term unemployed people in Finland

Avhandlingen studerar hur långtidsarbetslösa klarar av sin situation, hurdant socialt kapital och informationsbeteende de har, samt granskar hur de ovannämnda faktorerna är relaterade till varandra. Därtill undersöks om det finns skillnader mellan finsk- och svenskspråkiga långtidsarbetslösa på de här tre livsområdena. I undersökningen består socialt kapital av sociala relationer, deltagande i organisatoriska aktiviteter samt känslan av tillhörighet med olika grupper och samfund. Gällande informationsbeteende är fokus på vardaglig informationssökning, vilka källor som används, och hurdana problem man stöter på när man söker information. Som mest påfrestande upplevdes arbetslösheten av män, som var i början eller mitten av sin arbetskarriär. De äldre (över 55 år) verkade på många sätt klara av arbetslöshetssituationen bättre än de yngre, som drabbades hårdare av ekonomiska problem och stress. Kvinnor kunde bättre än män bibehålla en positiv inställning, de hade t.ex. starkare sociala nätverk som stöd, medan mäns sociala relationer i högre grad verkade vila på en arbetsgemenskap, som blev allt svagare i och med utdragen arbetslöshet. Yngre män upplevde också ofta att deras hälsa hade försämrats, när den för kvinnor och äldre arbetslösa i genomsnitt blev bättre. När arbetslösas bemästring av arbetslöshetssituationen, sociala relationer och informationssökning granskades, framgick att människor som var aktiva på ett livsområde också var aktiva på andra livsområden. I de flesta fall framkom inte några större skillnader mellan finsk- och svenskspråkiga arbetslösa. Beträffande informationssökning var de upplevda problemen ändå av diametralt motsatt karaktär – för svenskspråkiga åsamkade för lite tillgänglig information ofta problem, medan problemet för de finskspråkiga var att hitta det väsentliga i informationsflödet. Finskspråkiga kände sig också mera fast anknutna till sin boendemiljö och det finska samhället i stort, svenskspråkiga hade däremot i genomsnitt bredare och tätare sociala nätverk.

The left ventricular contractility of the rat heart is modulated by changes in flow and a1-adrenoceptor stimulation

Myocardial contractility depends on several mechanisms such as coronary perfusion pressure (CPP) and flow as well as on a1-adrenoceptor stimulation. Both effects occur during the sympathetic stimulation mediated by norepinephrine. Norepinephrine increases force development in the heart and produces vasoconstriction increasing arterial pressure and, in turn, CPP. The contribution of each of these factors to the increase in myocardial performance needs to be clarified. Thus, in the present study we used two protocols: in the first we measured mean arterial pressure, left ventricular pressure and rate of rise of left ventricular pressure development in anesthetized rats (N = 10) submitted to phenylephrine (PE) stimulation before and after propranolol plus atropine treatment. These observations showed that in vivo a1-adrenergic stimulation increases left ventricular-developed pressure (P<0.05) together with arterial blood pressure (P<0.05). In the second protocol, we measured left ventricular isovolumic systolic pressure (ISP) and CPP in Langendorff constant flow-perfused hearts. The hearts (N = 7) were perfused with increasing flow rates under control conditions and PE or PE + nitroprusside (NP). Both CPP and ISP increased (P<0.01) as a function of flow. CPP changes were not affected by drug treatment but ISP increased (P<0.01). The largest ISP increase was obtained with PE + NP treatment (P<0.01). The results suggest that both mechanisms, i.e., direct stimulation of myocardial a1-adrenoceptors and increased flow, increased cardiac performance acting simultaneously and synergistically.

Genesis and Evolution of Brittle Structures In Southwestern Finland and Western South Africa. Insights into Fault Reactivation, Fluid Flow and Structural Maturity in Precambrian Cratons

The bedrock of old crystalline cratons is characteristically saturated with brittle structures formed during successive superimposed episodes of deformation and under varying stress regimes. As a result, the crust effectively deforms through the reactivation of pre-existing structures rather than by through the activation, or generation, of new ones, and is said to be in a state of 'structural maturity'. By combining data from Olkiluoto Island, southwestern Finland, which has been investigated as the potential site of a deep geological repository for high-level nuclear waste, with observations from southern Sweden, it can be concluded that the southern part of the Svecofennian shield had already attained structural maturity during the Mesoproterozoic era. This indicates that the phase of activation of the crust, i.e. the time interval during which new fractures were generated, was brief in comparison to the subsequent reactivation phase. Structural maturity of the bedrock was also attained relatively rapidly in Namaqualand, western South Africa, after the formation of first brittle structures during Neoproterozoic time. Subsequent brittle deformation in Namaqualand was controlled by the reactivation of pre-existing strike-slip faults.In such settings, seismic events are likely to occur through reactivation of pre-existing zones that are favourably oriented with respect to prevailing stresses. In Namaqualand, this is shown for present day seismicity by slip tendency analysis, and at Olkiluoto, for a Neoproterozoic earthquake reactivating a Mesoproterozoic fault. By combining detailed field observations with the results of paleostress inversions and relative and absolute time constraints, seven distinctm superimposed paleostress regimes have been recognized in the Olkiluoto region. From oldest to youngest these are: (1) NW-SE to NNW-SSE transpression, which prevailed soon after 1.75 Ga, when the crust had sufficiently cooled down to allow brittle deformation to occur. During this phase conjugate NNW-SSE and NE-SW striking strike-slip faults were active simultaneous with reactivation of SE-dipping low-angle shear zones and foliation planes. This was followed by (2) N-S to NE-SW transpression, which caused partial reactivation of structures formed in the first event; (3) NW-SE extension during the Gothian orogeny and at the time of rapakivi magmatism and intrusion of diabase dikes; (4) NE-SW transtension that occurred between 1.60 and 1.30 Ga and which also formed the NW-SE-trending Satakunta graben located some 20 km north of Olkiluoto. Greisen-type veins also formed during this phase. (5) NE-SW compression that postdates both the formation of the 1.56 Ga rapakivi granites and 1.27 Ga olivine diabases of the region; (6) E-W transpression during the early stages of the Mesoproterozoic Sveconorwegian orogeny and which also predated (7) almost coaxial E-W extension attributed to the collapse of the Sveconorwegian orogeny. The kinematic analysis of fracture systems in crystalline bedrock also provides a robust framework for evaluating fluid-rock interaction in the brittle regime; this is essential in assessment of bedrock integrity for numerous geo-engineering applications, including groundwater management, transient or permanent CO2 storage and site investigations for permanent waste disposal. Investigations at Olkiluoto revealed that fluid flow along fractures is coupled with low normal tractions due to in-situ stresses and thus deviates from the generally accepted critically stressed fracture concept, where fluid flow is concentrated on fractures on the verge of failure. The difference is linked to the shallow conditions of Olkiluoto - due to the low differential stresses inherent at shallow depths, fracture activation and fluid flow is controlled by dilation due to low normal tractions. At deeper settings, however, fluid flow is controlled by fracture criticality caused by large differential stress, which drives shear deformation instead of dilation.

Effects of algal turbidity on foraging and antipredator behaviour of the three-spined stickleback (Gasterosteus aculeatus)

The aim of this thesis was to examine how aquatic organisms, such as fish, behave in an altered environmental condition. Many species of fish use vision as their primary tool to gain information about their surrounding environment. The visual conditions of aquatic habitats are often altered as a result of anthropogenic disturbance, such as eutrophication that initiates algal turbidity. In general, turbidity reduces the visibility and can be hypothesized to have an influence on the behaviour of fish. I used the three-spined stickleback (Gasterosteus aculeatus) as a model species and conducted four studies in the laboratory to test how algal turbidity affects its behaviour. In this thesis, two major behavioural aspects are discussed. The first is antipredator behaviour. In study I, the combined effects of turbidity and shoot density on habitat choice (shelter vs open) behaviour was tested on a group of sticklebacks (20 fish) in the presence and absence of piscivorous perch (Perca fluviatilis). In study II, I examined the behavioural responses of feeding sticklebacks when they were exposed to the sudden appearance of an avian predator (the silhouette of a common tern, Sterna hirundo). The study was done in turbid and clear water using three different groups sizes (1, 3 and 6 fish). The second aspect is foraging behaviour. Study III & IV focused on the effects of algal turbidity on the foraging performance of sticklebacks. In study III, I conducted two separate experiments to examine the effects of turbidity on prey consumption and prey choice of sticklebacks. In this experiment turbidity levels and the proportion of large and small prey (Daphnia spp.) were manipulated. In study IV, I studied whether a group of six sticklebacks can distribute themselves according to food input at two feeding stations in a way that provided each fish with the same amount of food in clear and turbid water. I also observed whether the fish can follow changes in resource distribution between the foraging patches. My results indicate an overall influence of algal turbidity on the antipredator and foraging behaviour of sticklebacks. In the presence of a potential predator, the use of the sheltered habitat was more pronounced at higher turbidity. Besides this, sticklebacks reduced their activity levels with predator presence at higher turbidity and shoot density levels, suggesting a possible antipredator adaptation to avoid a predator. When exposed to a sudden appearance of an avian predator, sticklebacks showed a weaker antipredator response in turbid water, which suggests that turbidity degrades the risk assessment capabilities of sticklebacks. I found an effect of group size but not turbidity in the proportion of sticklebacks that fled to the shelter area, which indicates that sticklebacks are able to communicate among group members at the experimental turbidity levels. I found an overall negative effect of turbidity on food intake. Both turbidity and changes in the proportion of prey sizes played a significant role in a stickleback’s prey selection. At lower turbidity levels (clear <1 and 5 NTU) sticklebacks showed preferences for large prey, whereas in more turbid conditions and when the proportion of large to small prey increased sticklebacks became increasingly random in their prey selection. Finally, my results showed that groups of sticklebacks disperse themselves between feeding stations according to the reward ratios following the predictions of the ideal free distribution theory. However, they took a significantly longer time to reach the equilibrium distribution in turbid water than in clear water. In addition, they showed a slower response to changes in resource distribution in a turbid environment. These findings suggest that turbidity interferes with the information transfer among group foragers. It is important to understand that aquatic animals are often exposed to a degraded environment. The findings of this thesis suggest that algal turbidity negatively affects their behavioural performance. The results also shed light on the underlying behavioural strategies of sticklebacks in turbid conditions that might help them adapt to an altered environmental situation and increase their survival. In conclusion, I hold that although algal turbidity has detrimental effects on the antipredator and foraging behaviour of sticklebacks, their behavioural adjustment might help them adapt to a changing environment.

Foraging ecology and parental behaviour in the common tern (Sterna hirundo)

One component of successful parenting is related to efficiency in foraging behaviour. The relationships among chick feeding, the size and type of food package, and length of parental foraging trips has not been well studied in seabirds. In addition, relatively few data have been collected on the activities of seabirds when foraging away from the nest site. The objectives of this study were: (1) to contrast productivity, feeding rate, and attendance patterns of individuals carrying a novel transmitter with a control group of birds; (2) to use radio-telemetry to assess the variability in foraging locations within and between individual male Common Terns; (3) to determine the seasonal variation in chick diet; (4) to determine for each transmittered bird, the relationships among the foraging patterns, parental behaviour, and seasonal reproductive success. The study took place over two years (1990-91) on a concrete breakwater 1 km offshore on Lake Erie near Port Colbome, Ontario. Ten pairs of terns in 1990 and 12 pairs in 1991 were radio-tracked by boat or car during the chick rearing stage. Concurrent behavioural observations documented the time each sex spent foraging or at the nest. The frequency and prey species composition of feeds to chicks were also recorded. The transmitters had negligible effects on the feeding frequency and brood attendance patterns of transmitter carrying birds. Peak nesting transmittered birds in 1990 and 1991 exhibited some inter-individual variability in foraging locations, however intraindividual variability was low. Birds foraged primarily to the west and northwest of the colony. Late nesters exhibited greater inter-individual variability, however intra-individual variability remained low for most birds. Neither group demonstrated sufficient variability to support the regular use of this colony as an "information centre". Individual transmittered birds had unique and predictable foraging patterns, and corresponding differences in feeding frequencies and brood attendance patterns, yet productivity was essentially equal between nests due to the impact and importance of stochastic events. Individuals that were recaptured in 1991 exhibited very similar foraging patterns to 1990, suggesting littie variability between years. Conservation of foraging patterns between years may have potential implications for mate choice decisions in future breeding seasons. Prey species delivered to chicks differed between morning and evening for peak and late nesters in 1990, but not 1991. Peak nesters in 1990 fed significantiy more Rainbow Smelt fOsmerus mordM) than Emerald Shiner (Notropis atherinoidesV this trend was reversed for late nesters who also fed large numbers of unidentified larval fish. No significant differences were found in 1991. Seasonal changes in prey species delivered to chicks is believed to be attributable to the temperature tolerances of the smelt and shiners, and the presence of large schools of larval fish during the late nesting season.

Effect of citrate on the redox properties of cytochrome C and its kinetic and binding behaviour with cytochrome oxidase /

Increasing citrate concentration, at constant ionic strength (30 mM) decreases the rate of cytochrome ~ reduction by ascorbate. This effect is also seen at both high (600 mM) and low (19 mM) ionic strengths, and the Kapp for citrate increases with increasing ionic strength. Citrate binds d both ferri -and ferrocytochrome ~, but with a lower affinity for the latter form (Kox . .red d = 2 mM, Kd = 8 mM) as shown by an equilibrium assay with N,N,N',N', Tetramethyl E- phenylenediamine. The reaction of ferricytochrome ~with cyanide is also altered in the presence of citrate: citrate increases the K~PP for cyanide. Column chromatography of cytochrome ~-cytochrome oxidase mixtures shows citrate increases the dissociation constant of the complex. These results are confirmed in kinetic assays for the "loose"site (Km = 20 pM) only. The effect of increasing citrate observable at the "tight" site (Km = 0.25 pM) is on the turnover number and not on the K . These results suggest a mechanism m where anion binding to cytochrome £ at the tight site affects the equilibrium between two forms of cytochrome c bound cytochrome oxidase: an active and an inactive one.

The association of faculty's teaching philosophy and teaching behaviour, and critical thinking and self- direction in learning

The intent in this study was to investigate in what ways teachers· beliefs about education and teaching are expressed in the specific teaching behaviours they employ, and whether teaching behaviours, as perceived by their students, are correlated with students· critical thinking and self-directed learning. To this end the relationships studied were: among faCUlty members· philosophy of teaching, locus of control orientation, psychological type, and observed teaching behaviour; and among students· psychological type, perceptions of teaching behaviour, self-directed learning readiness, and critical thinking. The overall purpose of the study was to investigate whether the implicit goals of higher education, critical thinking and self-direction, were actually accounted for in the university classroom. The research was set within the context of path-goal theory, adapted from the leadership literature. Within this framework, Mezirow·s work on transformative learning, including the influences of Habermas· writings, was integrated to develop a theoretical perspective upon which to base the research methodology. Both qualitative and quantitative methodologies were incorporated. Four faCUlty and a total of 142 students participated in the study. Philosophy of teaching was described through faCUlty interviews and completion of a repertory grid. Faculty completed a descriptive locus of control scale, and a psychological type test. Observations of their teaching behaviour were conducted. Students completed a Teaching Behaviour Assessment Scale, the Self-Directed Learning Readiness Scale, a psychological type test, and the Watson-Glaser Critical Thinking Appraisal. A small sample of students were interviewed. Follow-up discussions with faculty were used to validate the interview, observation, teaching behaviour, and repertory grid data. Results indicated that some discrepancies existed between faculty's espoused philosophy of teaching and their observed teaching behaviour. Instructors' teaching behaviour, however, was a function of their personal theory of practice. Relationships were found between perceived teaching behaviour and students· self-directed learning and critical thinking, but these varied across situations, as would be predicted from path-goal theory. Psychological type of students and instructor also accounted for some of the variability in the relationships studied. Student psychological type could be shown as a partial predictor of self-directed learning readiness. The results were discussed in terms of theory development and implications for further research and practice.