Type II beta-turn conformation of pivaloyl-L-prolyl-alpha-aminoisobutyryl-N-methylamide: Theoretical, spectroscopic, and X-ray studies

Pivaloyl-L-Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD3)2SO solution, by 1H-nmr methods, suggesting the existence of beta -turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II beta-turn conformations are about 2 kcal mol-1 more stable than Type III structures. A crystallographic study has established the Type II beta-turn in the solid state. The molecule crystallizes in the space group P21 with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, beta = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II -turn conformation is stabilized by an intramolecular 4 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are Pro = -57.8°, Pro = 139.3°, Aib = 61.4°, and Aib = 25.1°. The Type II beta-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.

EXAFS studies of arsenic chalcogenide glasses

An EXAFS study at the AsK edge of the ternary glasses As2(S, Se)3 and As2(Se, Te)3 and the binary As2S3, As2Se3 and As2Te3 glasses has been carried out. Radial structure functions show that the environment of As in glasses of intermediate compositions is quite different from that in the binary glasses. In the As2(S, Se)3 system, this might arise from chemical disorder in the network while in the As2(Se, Te)3 system increased ionicity could be the cause of this behaviour. Glasses where the constituent atoms are of similar size seem to exhibit fewer peaks in the radial structure function.

Widening Perspectives of Teacher Education : Studies on theory-practice relationship, reflection, research and professional development

This dissertation examined the research-based teacher education at the University of Helsinki from different theoretical and practical perspectives. Five studies focused on these perspectives separately as well as overlappingly. Study I focused on the reflection process of graduating teacher students. The data consisted of essays the students wrote as their last assignment before graduating, where their assignment was to examine their development as researchers during their MA thesis research process. The results indicated that the teacher students had analysed their own development thoroughly during the process and that they had reflected on theoretical as well as practical educational matters. The results also pointed out that, in the students’ opinion, personally conducted research is a significant learning process. -- Study II investigated teacher students’ workplace learning and the integration of theory and practice in teacher education. The students’ interviews focused on their learning of teacher’s work prior to education. The interviewees’ responses concerning their ‘surviving’ in teaching prior to teacher education were categorized into three categories: learning through experiences, school as a teacher learning environment, and case-specific learning. The survey part of the study focused on integration of theory and practice within the education process. The results showed that the students who worked while they studied took advantage of the studies and applied them to work. They set more demanding teaching goals and reflected on their work more theoretically. -- Study III examined practical aspects of the teacher students’ MA thesis research as well as the integration of theory and practice in teacher education. The participants were surveyed using a web-based survey which dealt with the participants’ teacher education experiences. According to the results, most of the students had chosen a practical topic for their MA thesis, one arising from their work environment, and most had chosen a research topic that would develop their own teaching. The results showed that the integration of theory and practice had taken place in much of the course work, but most obviously in the practicum periods, and also in the courses concerning the school subjects. The majority felt that the education had in some way been successful with regards to integration. -- Study IV explored the idea of considering teacher students’ MA thesis research as professional development. Twenty-three teachers were interviewed on the subject of their experiences of conducting research about their own work as teachers. The results of the interviews showed that the reasons for choosing the MA thesis research topic were multiple: practical, theoretical, personal, professional reasons, as well as outside effect. The objectives of the MA thesis research, besides graduating, were actual projects, developing the ability to work as teachers, conducting significant research, and sharing knowledge of the topic. The results indicated that an MA thesis can function as a tool for professional development, for example in finding ways for adjusting teaching, increasing interaction skills, gaining knowledge or improving reflection on theory and/or practice, strengthening self-confidence as a teacher, increasing researching skills or academic writing skills, as well as becoming critical and being able to read scientific and academic literature. -- Study V analysed teachers’ views of the impact of practitioner research. According to the results, the interviewees considered the benefits of practitioner research to be many, affecting teachers, pupils, parents, the working community, and the wider society. Most of the teachers indicated that they intended to continue to conduct research in the future. The results also showed that teachers often reflected personally and collectively, and viewed this as important. -- These five studies point out that MA thesis research is and can be a useful tool for increasing reflection doing with personal and professional development, as well as integrating theory and practice. The studies suggest that more advantage could be taken of the MA thesis research project. More integration of working and studying could and should be made possible for teacher students. This could be done in various ways within teacher education, but the MA thesis should be seen as a pedagogical possibility.

Maximising the contribution of native-range studies towards the identification and prioritisation of weed biocontrol agents

Effective study in the native range to identify potential agents underpins all efforts in classical biological control of weeds. Good agents that demonstrate both a high degree of host specificity and the potential to be damaging are a very limited resource and must therefore be carefully studied and considered. The overseas component is often operationally difficult and expensive but can contribute considerably more than a list of herbivores attacking a particular target. While the principles underlying this foreign component have been understood for some time, recently developed technologies and methods can make very significant contributions to foreign studies. Molecular and genetic characterisations of both target weed and agent organism can be increasingly employed to more accurately define the identity and phylogeny of them. Climate matching and modelling software is now available and can be utilised to better select agents for particular regions of concern. Relational databases can store collection information for analysis and future enquiry while quantification of sampling effort, employment of statistical survey methods and analysis by techniques such as rarefaction curves contribute to efficient and effective searching. Obtaining good and timely identifications for discovered agent organisms is perhaps the most serious issue confronting the modern explorer. The diminishing numbers of specialist taxonomists employed at the major museums while international and national protocols demand higher standards of identity exacerbates the issue. Genetic barcoding may provide a very useful tool to overcome this problem. Native-range work also offers under-exploited opportunities for contributing towards predicting safety, abundance and efficacy of potential agents in their target environment.

XPES studies of oxides of second- and third-row transition metals including rare earths

X-ray photoelectron spectroscopy has been employed to investigate oxides of second- and third-row transition metals, including those of rare earths. Systematics in the spin—orbit splittings and binding energies of core levels of the metals are described. In most of the cases studied, the dependence of the spin—orbit splittings on the atomic number Z is given by the relation ΔE = a(Z - Z0)4, where a is the quantum defect parameter and Z0 is the effective screening. Core-level binding energies are found to increase with the oxidation state of the metal. Most of the core-level binding energies are related to the atomic number Z by the expression E = x(Z - Z0)2, giving rise to linear plots of ln E versus ln Z. Specific features of individual oxides, with respect to satellites, multiplet structure, configuration mixing, and other properties are also discussed. The spectra of PrO2, Pr6O11, TbO2 and Tb4O7 are reported for the first time.

Auditory - Visual Matching in Learning Disabilities : Intervention Studies from Finland and Sweden

The present thesis discusses relevant issues in education: 1) learning disabilities including the role of comorbidity in LDs, and 2) the use of research-based interventions. This thesis consists of a series of four studies (three articles), which deepens the knowledge of the field of special education. Intervention studies (N=242) aimed to examine whether training using a nonverbal auditory-visual matching computer program had a remedial effect in different learning disabilities, such as developmental dyslexia, Attention Deficit Disorder (ADD) and Specific Language Impairment (SLI). These studies were conducted in both Finland and Sweden. The intervention’s non-verbal character made an international perspective possible. The results of the intervention studies confirmed, that the auditory-visual matching computer program, called Audilex had positive intervention effects. In Study I of children with developmental dyslexia there were also improvements in reading skills, specifically in reading nonsense words and reading speed. These improvements in tasks, which are thought to rely on phonological processing, suggest that such reading difficulties in dyslexia may stem in part from more basic perceptual difficulties, including those required to manage the visual and auditory components of the decoding task. In Study II the intervention had a positive effect on children with dyslexia; older students with dyslexia and surprisingly, students with ADD also benefited from this intervention. In conclusion, the role of comorbidity was apparent. An intervention effect was evident also in students’ school behavior. Study III showed that children with SLI experience difficulties very similar to those of children with dyslexia in auditory-visual matching. Children with language-based learning disabilities, such as dyslexia and SLI benefited from the auditory-visual matching intervention. Also comorbidity was evident among these children; in addition to formal diagnoses, comorbidity was explored with an assessment inventory, which was developed for this thesis. Interestingly, an overview of the data of this thesis shows positive intervention effects in all studies despite learning disability, language, gender or age. These findings have been described by a concept inter-modal transpose. Self-evidently these issues need further studies. In learning disabilities the aim in the future will also be to identify individuals at risk rather than by deficit; this aim can be achieved by using research-based interventions, intensified support in general education and inclusive special education. Keywords: learning disabilities, developmental dyslexia, attention deficit disorder, specific language impairment, language-based learning disabilities, comorbidity, auditory-visual matching, research-based interventions, inter-modal transpose

Studies on the rust Prospodium tuberculatum, a new classical biological control agent released against the invasive alien weed Lantana camara in Australia. 2. Host range

A strain of the rust Prospodium tuberculatum from Brazil was screened as a potential biocontrol agent against 40 Australian Lantana camara forms and 52 closely related, non-target plant species. Results under glasshouse conditions showed that the Brazilian rust strain is pathogenic to only two flower colour forms: pink and pink-edged red. Macro- and microsymptoms were recorded using 11 assessment categories and four susceptibility ratings. No macrosymptoms were observed on any of the non-target plants.

Studies on the reactions of thionyl fluoride

Thionyl fluoride undergoes quantitative oxidation with chloramine-T and reduction with lithium aluminium hydride and sodium borohydride. At elevated temperatures, (>150°C) it reacts with metals such as copper, silver, zinc and lead forming the corresponding metal sulphides, fluorides and sulphur dioxide. With the respective metal oxides, the metal fluorides and sulphur dioxide are formed.

Sustainable native forest management. Case studies in managing private native forest in southeast Queensland.

The introduction describes productive forest in Queensland and summaries the principles of native forest management that achieve optimum productivity. Case study 1 deals with thinning an even-aged regrowth forest. It shows how thinning the stand actively manages the future composition and structure to improve productivity in the best stems and increase the commercial value of the next harvest. Case study 2 describes restoring productivity in a high-graded spotted gum - ironbark forest. It shows that defective and non-saleable trees should be removed so they do not repress the future stand; and that regeneration should be thinned, retaining the best trees in adequate growing space. Case study 3 discusses on-farm value adding for hardwood forests. It shows how long-term viability and maximum productivity and returns depend on the best management practices and knowing how to obtain the best returns from a range of forest products. Case study 4 examines integrated harvesting in a eucalypt forest. It shows how integrating the harvest enables the full range of timber products are harvested and sold for their maximum value while reducing the amount of waste.

Preparation and catalytic studies of palladium nanoparticles stabilized by dendritic phosphine ligand-functionalized silica

Silica is a prominently utilized heterogeneous metal catalyst support. Functionalization of the silica with poly(ether imine) based dendritic phosphine ligand was conducted, in order to assess the efficacy of the dendritic phosphine in reactions facilitated by a silica supported metal catalyst. The phosphinated poly(ether imine) (PETIM) dendritic ligand was bound covalently to the functionalized silica. For this purpose, the phosphinated dendritic ligand containing an amine at the focal point was synthesized initially. Complexation of the dendritic phosphine functionalized silica with Pd(COD)Cl-2 yielded Pd(II) complex, which was reduced subsequently to Pd(0), by conditioning with EtOH. The Pd metal nanoparticle thus formed was characterized by physical methods, and the spherical nanoparticles were found to have >85% size distribution between 2 nm and 4 nm. The metal nanoparticle was tested as a hydrogenation catalyst of olefins. The catalyst could be recovered and recycled more than 10 times, without a loss in the catalytic efficiency.

Studies on characteristics of lightning generated currents in an interconnected lightning protection system

An in-depth knowledge about the characteristics of lightning generated currents will facilitate evaluation of the interception efficacy of lightning protection systems. In addition, it would aid in extraction of valuable statistics (from measured current data) on local lightning parameters. Incidentally, present day knowledge on characteristics of lightning induced current in typical lightning protection systems is rather limited. This is particularly true with closely interconnected protection systems, like the one employed in Indian Satellite Launch Pad-II. This system is taken as a specific example in the present study. Various aspects suggest that theoretical modelling would be the best possible approach for the intended work. From the survey of pertinent literature, it is concluded that electromagnetic modelling of lightning return-stroke with current source at the channel base is best suited for this study. Numerical electromagnetic code was used for the required electromagnetic field solution and Fourier transform techniques were employed for computing time-domain results. A validation for the numerical modelling is provided by laborator experiments on a reduced scale model of the system. Apart from ascertaining the influence of various parameters, salient characteristics of tower base currents for different kinds of events are deduced. This knowledge can be used in identifying the type of event, as well as its approximate location. A method for estimation of injected stroke current has also been proposed.

1H and 19F NMR relaxation time studies in (NH4)2ZrF6 superionic conductor

1H and 19F spin-lattice relaxation times in polycrystalline diammonium hexafluorozirconate have been measured in the temperature range of 10–400 K to elucidate the molecular motion of both cation and anion. Interesting features such as translational diffusion at higher temperatures, molecular reorientational motion of both cation and anion groups at intermediate temperatures and quantum rotational tunneling of the ammonium group at lower temperatures have been observed. Nuclear magnetic resonance (NMR) relaxation time results correlate well with the NMR second moment and conductivity studies reported earlier.

Circular dichroism and nuclear magnetic resonance studies on the complexation of valinomycin with calcium

Complexation of valinomycin (VM) with the divalent cation Ca2+ in a lipophilic solvent, acetonitrile (CH3-CN), has been studied by using circular dichroism and proton and carbon- 13 nuclear magnetic resonance (‘H NMR and I3C NMR). From analyses of the spectral data, it is concluded that VM forms a 2:l (peptideion-peptide) sandwich complex with Ca2+, at low concentration of VM. At moderate conocentrations of the salt, in addition to the sandwich complex, an equimolar (1:l) complex different from those observed for potassium and sodium is also observed. At very large concentrations of the calcium salt, the data suggested a complex with a conformation similar to that of the free VM in polar solvents. Possible conformations for the sandwich and the equimolar VM-calcium complexes are proposed.

Molecularly adsorbed oxygen on metals: electron spectroscopic studies

Oxygen is shown to adsorb molecularly on gold as well as on Ag and Pt. UV and X-ray photoelectron spectroscopy and Auger electron spectroscopy have been employed to investigate electron states of molecularly adsorbed oxygen.