Kemian ylioppilaskokeen tehtävät summatiivisen arvioinnin välineenä

The main purpose of the research was to illustrate chemistry matriculation examination questions as a summative assessment tool, and represent how the questions have evolved over the years. Summative assessment and its various test item classifications, Finnish goal-oriented curriculum model, and Bloom’s Revised Taxonomy of Cognitive Objectives formed the theoretical framework for the research. The research data consisted of 257 chemistry questions from 28 matriculation examinations between 1996 and 2009. The analysed test questions were formulated according to the national upper secondary school chemistry curricula 1994, and 2003. Qualitative approach and theory-driven content analysis method were employed in the research. Peer review was used to guarantee the reliability of the results. The research was guided by the following questions: (a) What kinds of test item formats are used in chemistry matriculation examinations? (b) How the fundamentals of chemistry are included in the chemistry matriculation examination questions? (c) What kinds of cognitive knowledge and skills do the chemistry matriculation examination questions require? The research indicates that summative assessment was used diversely in chemistry matriculation examinations. The tests included various test item formats, and their combinations. The majority of the test questions were constructed-response items that were either verbal, quantitative, or experimental questions, symbol questions, or combinations of the aforementioned. The studied chemistry matriculation examinations seldom included selected-response items that can be either multiple-choice, alternate choice, or matching items. The relative emphasis of the test item formats differed slightly depending on whether the test was a part of an extensive general studies battery of tests in sciences and humanities, or a subject-specific test. The classification framework developed in the research can be applied in chemistry and science education, and also in educational research. Chemistry matriculation examinations are based on the goal-oriented curriculum model, and cover relatively well the fundamentals of chemistry included in the national curriculum. Most of the test questions related to the symbolism of chemical equation, inorganic and organic reaction types and applications, the bonding and spatial structure in organic compounds, and stoichiometry problems. Only a few questions related to electrolysis, polymers, or buffer solutions. None of the test questions related to composites. There were not any significant differences in the emphasis between the tests formulated according to the national curriculum 1994 or 2003. Chemistry matriculation examinations are cognitively demanding. The research shows that the majority of the test questions require higher-order cognitive skills. Most of the questions required analysis of procedural knowledge. The questions that only required remembering or processing metacognitive knowledge, were not included in the research data. The required knowledge and skill level varied slightly between the test questions in the extensive general studies battery of tests in sciences and humanities, and subject-specific tests administered since 2006. The proportion of the Finnish chemistry matriculation examination questions requiring higher-order cognitive knowledge and skills is very large compared to what is discussed in the research literature.

The kinetics and reactivity of several polyatomic free radicals in reactions with NO2, O2, Cl2, and HCl

In this thesis, the kinetics of several alkyl, halogenated alkyl, and alkenyl free radical reactions with NO2, O2, Cl2, and HCl reactants were studied over a wide temperature range in time resolved conditions. Laser photolysis photoionisation mass spectrometer coupled to a flow reactor was the experimental method employed and this thesis present the first measurements performed with the experimental system constructed. During this thesis a great amount of work was devoted to the designing, building, testing, and improving the experimental apparatus. Carbon-centred free radicals were generated by the pulsed 193 or 248 nm photolysis of suitable precursors along the tubular reactor. The kinetics was studied under pseudo-first-order conditions using either He or N2 buffer gas. The temperature and pressure ranges employed were between 190 and 500 K, and 0.5 45 torr, respectively. The possible role of heterogeneous wall reactions was investigated employing reactor tubes with different sizes, i.e. to significantly vary the surface to volume ratio. In this thesis, significant new contributions to the kinetics of carbon-centred free radical reactions with nitrogen dioxide were obtained. Altogether eight substituted alkyl (CH2Cl, CHCl2, CCl3, CH2I, CH2Br, CHBr2, CHBrCl, and CHBrCH3) and two alkenyl (C2H3, C3H3) free radical reactions with NO2 were investigated as a function of temperature. The bimolecular rate coefficients of all these reactions were observed to possess negative temperature dependencies, while pressure dependencies were not noticed for any of these reactions. Halogen substitution was observed to moderately reduce the reactivity of substituted alkyl radicals in the reaction with NO2, while the resonance stabilisation of the alkenyl radical lowers its reactivity with respect to NO2 only slightly. Two reactions relevant to atmospheric chemistry, CH2Br + O2 and CH2I + O2, were also investigated. It was noticed that while CH2Br + O2 reaction shows pronounced pressure dependence, characteristic of peroxy radical formation, no such dependence was observed for the CH2I + O2 reaction. Observed primary products of the CH2I + O2 reaction were the I-atom and the IO radical. Kinetics of CH3 + HCl, CD3 + HCl, CH3 + DCl, and CD3 + DCl reactions were also studied. While all these reactions possess positive activation energies, in contrast to the other systems investigated in this thesis, the CH3 + HCl and CD3 + HCl reactions show a non-linear temperature dependency on the Arrhenius plot. The reactivity of substituted methyl radicals toward NO2 was observed to increase with decreasing electron affinity of the radical. The same trend was observed for the reactions of substituted methyl radicals with Cl2. It is proposed that interactions of frontier orbitals are responsible to these observations and Frontier Orbital Theory could be used to explain the observed reactivity trends of these highly exothermic reactions having reactant-like transition states.

Eldercare demands, strain, and work engagement: The moderating role of perceived organizational support

Demographic changes give rise to an increasing number of middle-aged employees providing home-based care to an elderly family member. However, the potentially important role of employees' perceptions of organizational support for eldercare has so far not been investigated. The goal of this study was to examine a stressor–strain–outcome model (Koeske & Koeske, 1993) of eldercare strain as a mediator of the relationship between eldercare demands and caregivers' work engagement. Perceived organizational eldercare support was expected to attenuate the positive relationship between eldercare demands and eldercare strain and to buffer the negative relationship between eldercare strain and work engagement. Results of mediation and moderated mediation analyses with data collected from 147 employees providing eldercare supported the hypotheses. The findings suggest that perceived organizational eldercare support is especially beneficial for employees' work engagement when eldercare demands and strain are high.

Inactivation of Aspergillus flavus spores by curcumin-mediated photosensitization

Minimizing fungal infection is essential to the control of mycotoxin contamination of foods and feeds but many potential control methods are not without their own safety concerns for the consumers. Photodynamic inactivation is a novel light-based approach which offers a promising alternative to conventional methods for the control of mycotoxigenic fungi. This study describes the use of curcumin to inactivate spores of Aspergillus flavus, one of the major aflatoxin producing fungi in foods and feeds. Curcumin is a natural polyphenolic compound from the spice turmeric (Curcuma longa). In this study the plant has shown to be an effective photosensitiser when combined with visible light (420 nm). The experiment was conducted in in vitro and in vivo where A. flavus spores were treated with different photosensitiser concentration and light dose both in buffer solution and on maize kernels. Comparison of fungal load from treated and untreated samples was determined, and reductions of fungal spore counts of up to 3 log CFU ml−1 in suspension and 2 log CFU g−1 in maize kernels were obtained using optimal dye concentrations and light dose combinations. The results in this study indicate that curcumin-mediated photosensitization is a potentially effective method to decontaminate A. flavus spores in foods and feeds.

Climate savvy grazing (Developing improved grazing and related practices to assist beef production enterprises across northern Australia to adapt to a changing and more variable climate)

There is uncertainty over the potential changes to rainfall across northern Australia under climate change. Since rainfall is a key driver of pasture growth, cattle numbers and the resulting animal productivity and beef business profitability, the ability to anticipate possible management strategies within such uncertainty is crucial. The Climate Savvy Grazing project used existing research, expert knowledge and computer modelling to explore the best-bet management strategies within best, median and worse-case future climate scenarios. All three scenarios indicated changes to the environment and resources upon which the grazing industry of northern Australia depends. Well-adapted management strategies under a changing climate are very similar to best practice within current climatic conditions. Maintaining good land condition builds resource resilience, maximises opportunities under higher rainfall years and reduces the risk of degradation during drought and failed wet seasons. Matching stocking rate to the safe long-term carrying capacity of the land is essential; reducing stock numbers in response to poor seasons and conservatively increasing stock numbers in response to better seasons generally improves profitability and maintains land in good condition. Spelling over the summer growing season will improve land condition under a changing climate as it does under current conditions. Six regions were included within the project. Of these, the Victoria River District in the Northern Territory, Gulf country of Queensland and the Kimberley region of Western Australia had projections of similar or higher than current rainfall and the potential for carrying capacity to increase. The Alice Springs, Maranoa-Balonne and Fitzroy regions had projections of generally drying conditions and the greatest risk of reduced pasture growth and carrying capacity. Encouraging producers to consider and act on the risks, opportunities and management options inherent in climate change was a key goal of the project. More than 60,000 beef producers, advisors and stakeholders are now more aware of the management strategies which build resource resilience, and that resilience helps buffer against the effects of variable and changing climatic conditions. Over 700 producers have stated they have improved confidence, skills and knowledge to attempt new practices to build resilience. During the course of the project, more than 165 beef producers reported they have implemented changes to build resource and business resilience.

Kinetics of resinification of furfuryl alcohol in aqueous solution

Kinetic information on the resinification of furfuryl alcohol has been derived from the rate of increase of color intensity measured with a photoelectric colorimeter, the resinification being carried out isothermally in Clark-Lubs aqueous buffer solutions in the pH range of 1.0-2.2. The activation energy for polymerization is found to increase exponentially with pH. The time required for emulsification (which is quickly followed by separation of resin layer) to occur in an aqueous solution of furfuryl alcohol also increases exponentially with pH, but it decreases exponentially with temperature. This is described quantitatively by a single expression.

Mode of action of antitumour antibiotics: Spectrophotometric studies on the interaction of chromomycin A3 with DNA and chromatin of normal and neoplastic tissue

The binding of chromomycin A3, an antitumour antibiotic, to various DNA and chromatin isolated from mouse and rat liver, mouse fibrosarcoma and Yoshida ascites sarcoma cells was studied spectrophotometrically at 29°C in 10−2 M Tris-HCl buffer, pH 8.0, containing small amounts of MgCl2 (4.5 · 10−5−25 · 10−5 M). An isobestic point at 415 nm was observed when chromomycin A3 was gradually titrated with Image and its spectrum shifted towards higher wavelength. The rates and extent of these spectral changes were found to be dependent on the concentration of Mg2+. The change in absorbance at 440 nm was used to calculate apparent binding constant (Ka p M−1) and sites per nucleotide (n) from Scatchard plots for various DNA and chromatins. As expected, values of n for chromatin (0.06–0.10) were found to be lower than that found for corresponding DNA (0.10–0.15). Apparently no such correlation exists between binding constants (Ka p M−1 · 10−4) of DNA (6.4–11.2) and of chromatin (3.1–8.3), but Ka p M−1 of chromatin isolated from mouse fibrosarcoma and Yoshida ascites sarcoma are 1.5–3 times higher than that found for mouse and rat liver chromatin. These differences may be taken to indicate structural difference in nucleoprotein complexes caused by neoplasia. The relevance of this finding to tumour suppressive action of chromomycin A3 is discussed.

On the Specificity of Carbohydrate-Lectin Recognition The Interaction of a Lectin from Ricinus communis Beans with Simple Saccharides and Concanavalin A

A galactose-specific protein (RC1) isolated from Ricinus communis beans was found to give a precipitin reaction with concanavalin A. Its carbohydrate content amounted to 8–9% of the total protein and was found to be rich in mannose. The interaction of RC1 with galactose and lactose was measured in 0.05 M phosphate buffer containing 0.2 M NaCl (pH 6.8) by the method of conventional equilibrium dialysis. From the analysis of the binding data according to Scatchard method the association constant (Ka) at 5°C was calculated as 3.8 mM−1 and 1.2 mM−1 for lactose and galactose, respectively. In both cases the number of binding sites per molecule of RC1 with molecular weight of 120000 was found to be 2. From the temperature-dependent Ka values for the binding of lactose, the values of –5.7 kcal/mol and –4.3 cal × mol−1× K−1 were calculated for ΔH and ΔS, respectively. The addition of concanavalin A to RC1 or vice versa led to the formation of the insoluble complex RC1· ConA4 containing one molecule of RC1 and one molecule of tetrameric concanavalin A (ConA4) which could be dissociated upon addition of concanavalin A-specific sugars. The complex formation results in a time-dependent appearance of turbidity in the time range from 10s to 10 min. From the measurement of the time-dependent appearance and disappearance of the turbidity the formation (kf) and dissociation (kd) rate constants were calculated as 3 mM−1× s−1 and 0.07 ks−1 respectively. The ratio kf/kd (43μM −1), that corresponds to the association constant of complex RC1· ConA4, is higher than that of mannoside · ConA4 and thereby suggests that protein-protein interaction contributes significantly in stabilising glycoprotein · lectin complexes. The relevance of this finding to the understanding of the chemical specificities that are involved in a model cell-lectin interaction is discussed.

Purification, properties and induction of a specific benzoate-4-hydroxylase from Aspergillus niger (UBC 814)

An inducible benzoate-4-hydroxylase has been partially purified from crude extracts of the mycelial felts of Aspergillus niger. This enzyme catalyzes the transformation of benzoate to p-hydroxybenzoate with equimolar consumption of NADPH and O2. It requires tetrahydropteridine as a prosthetic group. The optimum activity was found at pH 6.2 with a Km value at 30°C of 1.6 · 10−4 M for NADPH and 1.3 · 10−4 M for benzoate. Fe2+ (iron) is required for the enzyme activity. The enzyme is stabilized by the inclusion of benzoate, EDTA and glutathione in the extracting buffer. The enzyme is specific for benzoate as substrate. Sulfhydryl group(s) are essential for enzyme activity as indicated by p-chloromercuri-benzoate and N-ethylmaleimide inactivation. Benzoate-4-hydroxylase activity is decreased in the mycelial felts of Aspergillus niger grown in the presence of higher concentrations of benzoate. Maximum activity of the enzyme was observed at 36 h after inoculation.

Political transition and structural politicisation : The long shadow of Taiwan's one-party legacy

Väitöskirjatutkimuksessa tarkastellaan Taiwanin politiikkaa ensimmäisen vaalien kautta tapahtuneen vallanvaihdon jälkeen (2000) yhteiskunnan rakenteellisen politisoitumisen näkökulmasta. Koska Taiwanilla siirryttiin verettömästi autoritaarisesta yksipuoluejärjestelmästä monipuoluejärjestelmään sitä on pidetty poliittisen muodonmuutoksen mallioppilaana. Aiempi optimismi Taiwanin demokratisoitumisen suhteen on sittemmin vaihtunut pessimismiin, pitkälti yhteiskunnan voimakkaasta politisoitumisesta johtuen. Tutkimuksessa haetaan selitystä tälle politisoitumiselle. Yhteiskunnan rakenteellisella politisoitumisella tarkoitetaan tilannetta, jossa ”poliittisen” alue kasvaa varsinaisia poliittisia instituutioita laajemmaksi. Rakenteellinen politisoituminen muuttuu helposti yhteiskunnalliseksi ongelmaksi, koska siitä usein seuraa normaalin poliittisen toiminnan (esim. lainsäädännän) jähmettyminen, yhteiskunnan jyrkkä jakautuminen, alhainen kynnys poliittisille konflikteille ja yleisen yhteiskunnallisen luottamuksen alentuminen. Toisin kuin esimerkiksi Itä-Euroopassa, Taiwanissa entinen valtapuolue ei romahtanut poliittisen avautumisen myötä vaan säilytti vahvan rakenteellisen asemansa. Kun valta vaihtui ensimmäisen kerran vaalien kautta, vanha valtapuolue ei ollut valmis luovuttamaan poliittisen järjestelmän ohjaksia käsistään. Alkoi vuosia kestänyt taistelu järjestelmän hallinnasta vanhan ja uuden valtapuolueen välillä, jossa yhteiskunta politisoitui voimakkaasti. Tutkimuksessa Taiwanin yhteiskunnan politisoituminen selitetään useiden rakenteellisten piirteiden yhteisvaikutuksen tuloksena. Tällaisia politisoitumista edistäviä rakentellisia piirteitä ovat hidas poliittinen muutos, joka säilytti vanhat poliittiset jakolinjat ja niihin liittyvät vahvat edut ja intressit; sopimaton perustuslaki; Taiwanin epäselvä kansainvälinen asema ja jakautunut identiteetti; sekä sosiaalinen rakenne, joka helpottaa ihmisten nopeaa mobilisointia poliittiisiin mielenilmauksiin. Tutkimuksessa kiinnitetään huomiota toistaiseksi vähän tutkittuun poliittiseen ilmiöön, joidenkin demokratisoituvien yhteiskuntien voimakkaaseen rakenteelliseen politisoitumiseen. Tutkimuksen pääasiallinen havainto on, että yksipuoluejärjestelmän demokratisoituminen kantaa sisällään rakenteellisen politisoitumisen siemenen, jos entinen valtapuolue ei romahda demokratisoitumisen myötä.

A simple method for large-scale preparation of chick embryo tRNA

A simple method for preparing bulk quantities of tRNA from chick embryo has been developed. In this method chick embryos were homogenized in a buffer of pH 4.5, followed by deproteinization with phenol. The aqueous layer was allowed to separate under gravity. The resulting aqueous layer, after two more phenol treatments, was directly passed through a DEAE-cellulose column and the tRNA eluted therefrom with 1 Image NaCl. The tRNA prepared by this method was as active as the one prepared at neutral pH.

Responses of Scots pine to nickel and copper exposure and herbivory

The goal of this thesis was to examine the ecophysiological responses of Scots pine (Pinus sylvestris L.), with an emphasis on the oxidative enzyme peroxidase and plant phenolics to environmental stresses like elevated levels of nickel (Ni) and copper (Cu), and herbivory. The effects of Ni and Cu were studied in a gradient survey at a sulphur dioxide contaminated site in the Kola Peninsula, and with experiments in which seedlings were exposed to Ni mist or to Ni and Cu amended into the soil. In addition, experimental Ni exposure was combined with disturbance of the natural lichen cover of the forest ground layer. Pine sawfly attack was simulated in the early season defoliation experiment, in which mature Scots pine were defoliated (100 %) during two successive years in a dry, nutrient-poor Scots pine stand. In addition, the effect of previous defoliation on the growth of sawfly (Diprion pini L.) larvae was studied. Apoplastic peroxidase activity was elevated in the needles of pine in a Ni- , Cu- and SO2- polluted environment, which indicated an increased oxidative stress. Increased foliar peroxidase activity due to Ni contamination was shown in the experiment, in which Ni was added as mist. No such response was found in peroxidase acitivity of the roots exposed to elevated Ni and/or Cu in the soil. Elevated Ni in the soil increased the concentration of foliar condensed tannins, which are able to bind heavy metals in the cells. Addition of low levels of Ni in the soil appeared to benefit pine seedlings, which was seen as promoted shoot growth and better condition of the roots. Wet Ni deposition of 2000 mg m-2 reduced growth and survival of pine seedlings, whereas deposition levels 200 mg m-2 or 20 mg m-2 caused no effects in a 2-y lasting experiment. The lichen mat on the forest floor did not act as an effective buffer against the adverse impacts of heavy metals on pine seedlings. However, some evidence was found indicating that soil microbes profited from the lichen mat. Artificial defoliation increased peroxidase activity in the Scots pine needles. In addition, defoliation decreased nitrogen, diamine putrescine and glucose concentrations in the needles and increased the concentrations of several phenolic compounds, starch and sucrose. Previous artificial defoliation led to poor growth of sawfly larvae reared on the pines, suggesting delayed induced resistance in Scots pine. However, there was no consistent relationship between inducibility (proportional increase in a compound following defoliation) and adverse effects on the growth of pine sawfly larvae. The observed inducible responses in needle phenolics due to previous defoliation thus appear to represent non-specific responses against sawflies.

Reactivity of µ-Peroxo-Bridged Dimeric Vanadate in Bromoperoxidation

Diglycyl triperoxodivanadate [V2O2(O2)3(Gly H)2(H2O)2], a synthetic compound with μ-peroxo-bridge derived from H2O2and vanadate, oxidized bromide to a bromination-competent intermediate in phosphate buffer and physiological pH. This is in contrast to the requirement of acid medium with H2O2as the oxidant. Addition of its solid to bromide solution instantly produced a 262-nm-absorbing compound that converted phenol red (a trap) to its 592-nm-absorbing bromo-derivative. The high bromination activity was lost on dissolving this compound in water and the solution showed the presence of peroxovanadates (mono and di) and vanadates (V1and oligomeric V10) in51V-NMR spectrum. Of these, diperoxovanadate and vanadate together supported slow bromination activity by a second set of reactions including bromide-assisted reductive formation of vanadyl. Bromination activity dependent on vanadyl was sensitive to oxidation by excess H2O2and to complexation by EDTA, whereas that of triperoxodivanadate was relatively insensitive. Vanadyl and diperoxovanadate are capable of forming a μ-peroxo-bridged complex that is essentially similar to the synthetic vanadate dimer used in the present experiments. It appears that a μ-peroxo-intermediate is the proximal oxidant of bromide in vanadium-catalyzed bromoperoxidation.

Thermodynamics of metal ion binding and denaturation of a calcium binding protein from Entamoeba histolytica

The thermodynamics of tie binding of calcium and magnesium ions to a calcium binding protein from Entamoeba histolytica was investigated by isothermal titration calorimetry (ITC) in 20 mM MOPS buffer (pH 7.0) at 20 degrees C. Enthalpy titration curves of calcium show the presence of four Ca2+ binding sites, There exist two low-affinity sites for Ca2+, both of which are exothermic in nature and with positive cooperative interaction between them. Two other high affinity sites for Ca2+ exist of which one is endothermic and the other exothermic, again with positive cooperative interaction. The binding constants for Ca2+ at the four sites have been verified by a competitive binding assay, where CaBP competes with a chromophoric chelator 5, 5'-Br-2 BAPTA to bind Ca2+ and a Ca2+ titration employing intrinsic tyrosine fluorescence of the protein, The enthalpy of titration of magnesium in the absence of calcium is single site and endothermic in nature. In the case of the titrations performed using protein presaturated with magnesium, the amount of heat produced is altered. Further, the interaction between the high-affinity sites changes to negative cooperativity. No exchange of heat was observed throughout the addition of magnesium in the presence of 1 mM calcium, Titrations performed on a cleaved peptide comprising the N-terminus and the central linker show the existence of two Ca2+ specific sites, These results indicate that this CaBP has one high-affinity Ca-Mg site, one high-affinity Ca-specific site, and two low-affinity Ca-specific sites. The thermodynamic parameters of the binding of these metal ions were used to elucidate the energetics at the individual site(s) and the interactions involved therein at various concentrations of the denaturant, guanidine hydrochloride, ranging from 0.05 to 6.5 M. Unfolding of the protein was also monitored by titration calorimetry as a function of the concentration of the denaturant. These data show that at a GdnHCl concentration of 0.25 M the binding affinity for the Mg2+ ion is lost and there are only two sites which can bind to Ca2+, with substantial loss cooperativity. At concentrations beyond 2.5 M GdnHCl, at which the unfolding of the tertiary structure of this protein is observed by near UV CD spectroscopy, the binding of Ca2+ ions is lost. We thus show that the domain containing the two low-affinity sites is the first to unfold in the presence of GdnHCl. Control experiments with change in ionic strength by addition of KCI in the range 0.25-1 M show the existence of four sites with altered ion binding parameters.

Growth factor-loaded microparticles for tissue engineering: The discrepancies of in vitro characterization assays

Efficient and effective growth factor (GF) delivery is an ongoing challenge for tissue regeneration therapies. The accurate quantification of complex molecules such as GFs, encapsulated in polymeric delivery devices, is equally critical and just as complex as achieving efficient delivery of active GFs. In this study, GFs relevant to bone tissue formation, vascular endothelial growth factor (VEGF) and bone morphogenetic protein 7 (BMP-7), were encapsulated, using the technique of electrospraying, into poly(lactic-co-glycolic acid) microparticles that contained poly(ethylene glycol) and trehalose to assist GF bioactivity. Typical quantification procedures, such as extraction and release assays using saline buffer, generated a significant degree of GF interactions, which impaired accurate assessment by enzyme-linked immunosorbent assay (ELISA). When both dry BMP-7 and VEGF were processed with chloroform, as is the case during the electrospraying process, reduced concentrations of the GFs were detected by ELISA; however, the biological effect on myoblast cells (C2C12) or endothelial cells (HUVECs) was unaffected. When electrosprayed particles containing BMP-7 were cultured with preosteoblasts (MC3T3-E1), significant cell differentiation into osteoblasts was observed up to 3 weeks in culture, as assessed by measuring alkaline phosphatase. In conclusion, this study showed how electrosprayed microparticles ensured efficient delivery of fully active GFs relevant to bone tissue engineering. Critically, it also highlights major discrepancies in quantifying GFs in polymeric microparticle systems when comparing ELISA with cell-based assays.