Asymmetrical flow field-flow fractionation in the study of water-soluble macromolecules

Asymmetrical flow field-flow fractionation (AsFlFFF) was constructed, and its applicability to industrial, biochemical, and pharmaceutical applications was studied. The effect of several parameters, such as pH, ionic strength, temperature and the reactants mixing ratios on the particle sizes, molar masses, and the formation of aggregates of macromolecules was determined by AsFlFFF. In the case of industrial application AsFlFFF proved to be a valuable tool in the characterization of the hydrodynamic particle sizes, molar masses and phase transition behavior of various poly(N-isopropylacrylamide) (PNIPAM) polymers as a function of viscosity and phase transition temperatures. The effect of sodium chloride salt and the molar ratio of cationic and anionic polyelectrolytes on the hydrodynamic particle sizes of poly (methacryloxyethyl trimethylammonium chloride) and poly (ethylene oxide)-block-poly (sodium methacrylate) and their complexes were studied. The particle sizes of PNIPAM polymers, and polyelectrolyte complexes measured by AsFlFFF were in agreement with those obtained by dynamic light scattering. The molar masses of PNIPAM polymers obtained by AsFlFFF and size exclusion chromatography agreed also well. In addition, AsFlFFF proved to be a practical technique in thermo responsive behavior studies of polymers at temperatures up to about 50 oC. The suitability of AsFlFFF for biological, biomedical, and pharmaceutical applications was proved, upon studying the lipid-protein/peptide interactions, and the stability of liposomes at different temperatures. AsFlFFF was applied to the studies on the hydrophobic and electrostatic interactions between cytochrome c (a basic peripheral protein) and anionic lipid, and oleic acid, and sodium dodecyl sulphate surfactant. A miniaturized AsFlFFF constructed in this study was exploited in the elucidation of the effect of copper (II), pH, ionic strength, and vortexing on the particle sizes of low-density lipoproteins.

"... I want an Ocean between us!" : Letters from Samuel Kahn, devoted father of one of the thousand children brought from Germany to the United States in 1934.

The manuscript contains letters written by Samuel Kahn to his daughter in the USA between 1934 and 1937.

Radical Enhanced Atomic Layer Deposition of Metals and Oxides

Atomic Layer Deposition (ALD) is a chemical, gas-phase thin film deposition method. It is known for its ability for accurate and precise thickness control, and uniform and conformal film growth. One area where ALD has not yet excelled is film deposition at low temperatures. Also deposition of metals, besides the noble metals, has proven to be quite challenging. To alleviate these limitations, more aggressive reactants are required. One such group of reactants are radicals, which may be formed by dissociating gases. Dissociation is most conveniently done with a plasma source. For example, dissociating molecular oxygen or hydrogen, oxygen or hydrogen radicals are generated. The use of radicals in ALD may surmount some of the above limitations: oxide film deposition at low temperatures may become feasible if oxygen radicals are used as they are highly reactive. Also, as hydrogen radicals are very effective reducing agents, they may be used to deposit metals. In this work, a plasma source was incorporated in an existing ALD reactor for radical generation, and the reactor was used to study five different Radical Enhanced ALD processes. The modifications to the existing reactor and the different possibilities during the modification process are discussed. The studied materials include two metals, copper and silver, and three oxides, aluminium oxide, titanium dioxide and tantalum oxide. The materials were characterized and their properties were compared to other variations of the same process, utilizing the same metal precursor, to understand what kind of effect the non-metal precursor has on the film properties and growth characteristics. Both metals were deposited successfully, and silver for the first time by ALD. The films had low resistivity and grew conformally in the ALD mode, demonstrating that the REALD of metals is true ALD. The oxide films had exceptionally high growth rates, and aluminium oxide grew at room temperature with low cycle times and resulted in good quality films. Both aluminium oxide and titanium dioxide were deposited on natural fibres without damaging the fibre. Tantalum oxide was also deposited successfully, with good electrical properties, but at slightly higher temperature than the other two oxides, due to the evaporation temperature required by the metal precursor. Overall, the ability of REALD to deposit metallic and oxide films with high quality at low temperatures was demonstrated.

'I wonder what you know...': Teachers designing requests for factual information

Optimizing the quality of early childhood education (ECE) is an international policy priority. Teacher-child interactions have been identified as the strongest indicator of quality and most potent predictor of child outcomes. This paper presents ethnomethodological and conversation analysis of an interaction between an early childhood educator with two children as they engage with each other, while performing a Web search. Analyses shows that question design can elicit qualitatively different responses with regard to sustained interactions. Understanding the design of teacher questions has pedagogic implications for the work of the teacher and for the broader quality agenda in early childhood education.

Antioxidative long chain alkylresorcinols. Synthesis and deuterium labelling of bioactive compounds present in whole grains

The first synthesis of long chain 5-n-alkylresorcinols (C15-C25) in whole grains and whole grain products by a novel modification of Wittig reaction is described. 5-n-Alkylresorcinols are phenolic lipids that have various effects on biological systems, such as antioxidant activity and interaction with biological membranes. These compounds are considered as biomarkers of whole grain intake, which is connected with reduced risk of cardiovascular diseases and certain cancers. Novel hapten derivatives of 5-n-alkylresorcinols, potential compounds for immunoanalytical techniques, are prepared by the same procedure utilizing microwave catalysed aqueous Wittig reaction as the key step. The synthesised analogues are required by various analytical, metabolism and bioactivity investigations. Four alternative strategies for producing deuterium polylabelled 5-n-alkylresorcinols are explored. Ring-labelled D3-alkylresorcinols were synthesized by acidic H/D exchange. Side chain -labelled D4-derivative was prepared by a total synthesis approach utilizing D2 deuterogenation of a D2-alkene derivative, and deuterogenation of alkynes was investigated in another total synthesis approach. An -D3-labelled alkylresorcinol is isotopically pure and completely stable under all relevant conditions encountered during analytical work. The labelling of another phenolic component of whole grains was explored. The preparation of D3-ferulic acid and related compounds by way of selective methylation of the precursors is described. The deuterated compounds are useful as standards in the quantification of these natural products in various substances, such as food and human fluids. The pure 5-n-alkylresorcinol analogues prepared were used in in vitro experiments on alkylresorcinol antioxidant activity and antigenotoxicity. The in vitro experiments show that alkylresorcinols act as antioxidants, especially when incorporated into biological systems, but possess lower activity in chemical tests (FRAP and DPPH assay). Whole grain alkylresorcinols are shown for the first time to have a protective effect against copper induced oxidation of LDL, and H2O2 or genotoxic faecal water induced damage on HT29 cells.

A quantum chemical investigation of the metal centres in cytochrome c oxidase

Quantum effects are often of key importance for the function of biological systems at molecular level. Cellular respiration, where energy is extracted from the reduction of molecular oxygen to water, is no exception. In this work, the end station of the electron transport chain in mitochondria, cytochrome c oxidase, is investigated using quantum chemical methodology. Cytochrome c oxidase contains two haems, haem a and haem a3. Haem a3, with its copper companion, CuB, is involved in the final reduction of oxygen into water. This binuclear centre receives the necessary electrons from haem a. Haem a, in turn, receives its electrons from a copper ion pair in the vicinity, called CuA. Density functional theory (DFT) has been used to clarify the charge and spin distributions of haem a, as well as changes in these during redox activity. Upon reduction, the added electron is shown to be evenly distributed over the entire haem structure, important for the accommodation of the prosthetic group within the protein. At the same time, the spin distribution of the open-shell oxidised state is more localised to the central iron. The exact spin density distribution has been disputed in the literature, however, different experiments indicating different distributions of the unpaired electron. The apparent contradiction is shown to be due to the false assumption of a unit amount of unpaired electron density; in fact, the oxidised state has about 1.3 unpaired electrons. The validity of the DFT results have been corroborated by wave function based coupled cluster calculations. Point charges, for use in classical force field based simulations, have been parameterised for the four metal centres, using a newly developed methodology. In the procedure, the subsystem for which point charges are to be obtained, is surrounded by an outer region, with the purpose of stabilising the inner region, both electronically and structurally. Finally, the possibility of vibrational promotion of the electron transfer step between haem a and a3 has been investigated. Calculating the full vibrational spectra, at DFT level, of a combined model of the two haems, revealed several normal modes that do shift electron density between the haems. The magnitude of the shift was found to be moderate, at most. The proposed mechanism could have an assisting role in the electron transfer, which still seems to be dominated by electron tunnelling.

Schiff Base Complexes and their Assemblies on Surfaces

Schiff bases and their transition metal complexes are of significant current interest even though they have been prepared for decades. They have been used in various applications such as catalysis, corrosion protection, and molecular sensors. In this study, N-aryl Schiff base ketimine ligands as well as numerous new, differently substituted salen and salophen-type ligands and their cobalt(II), copper(II), iron(II), manganese(II), and nickel(II) complexes were synthesised. New solid state structures of the above compounds and the dioxygen coordination properties of cobalt(II) complexes and catalytic properties of three synthesised binuclear complexes were examined. The prepared complexes were applied in the formation of self-assembled layers on a polycrystalline gold surface and liquid-graphite interface. The effect of metal ion and ligand structure on the as-formed patterns was studied. When studying gold surfaces, a unique thiol-assisted dissolution of elemental gold was observed and a new thin gold foil preparation method was introduced. In the summary, synthesis, structures, and properties of Schiff base ligands and their transition metal complexes are described in detail and the applications of these reviewed. Assemblies of other complexes on a liquid-graphite interface and on a gold surface are also presented, and the surface characterisation methods and surfaces employed are described.

Mechanism of adsorption effects on electrode kinetics: Part I: Selection rules in the case of low coverage by molecular surfactants

It is shown that the effect of adsorption of inert molecules on electrode reaction rates is completely accounted for, by introducing into the rate equation, adsorption-induced changes in both the effective electrode area as well as in the electrostatic potential at the reaction site with an additional term for the noncoulombic interaction between the reactant and the adsorbate. The electrostatic potential at the reaction site due to the adsorbed layer is calculated using a model of discretely-distributed molecules in parallel orientation when adsorbed on the electrode with an allowance for thermal agitation. The resulting expression, which is valid for the limiting case of low coverages, is used to predict the types of molecular surfactants that are most likely to be useful for acceleration and inhibition of electrode reactions.

Motional Averaging of Electric Field Gradients. Temperature Dependence of Nqr in Sodium Chlorate and Copper Chlorate

Es wird die Temperaturabhiingigkeit der CI35-Kernquadrupolresonanz in Natriumchlorat und Kupferchlorat im Temperature von 77 bis 300 °K untersucht. Es wird gezeigt, daß die Annahmen, die in der Theorie von Bayer gemacht werden, fur Chlorate gelten. Die Frequenz der Torsionsschwingungen der ClO3-Gruppe wird folglich mit dieser Theorie berechnet. Der berechnete Wert der Torsionsfrequenz stimmt gut mit vorhandenen Werten der Ramanspektroskopie überein.

Should I stay or should I go?: Rural and remote students in first year university stem courses

Research on the achievement of rural and remote students in science and mathematics is located within a context of falling levels of participation in physical science and mathematics courses in Australian schools, and underrepresentation of rural students in higher education. International studies such as the Programme of International Student Assessment (PISA), have reported lower levels of mathematical and scientific literacy in Australian students from rural and remote schools (Thomson et al, 2011). The SiMERR national survey of science, mathematics and ICT education in rural and regional Australia (Lyons et al, 2006) identified factors affecting student achievement in rural and remote schools. Many of the issues faced by rural and remote students in their schools are likely to have implications on their university enrolments in science, technology, engineering and mathematics (STEM) courses. For example, rural and remote students are less likely to attend university in general than their city counterparts and higher university attrition rates have been reported for remote students nationally. This paper examines the responses of a sample of rural/remote Australian first year STEM students at Australian universities to two questions. These related to their intentions to complete the course; and whether -and if so, why- they had ever considered withdrawing from their course. Results indicated that rural students who were still in their course by the end of first year were no more or less likely to consider withdrawing than were their peers from more populous centres. However, almost 20% of the rural cohort had considered withdrawing at some stage in their course, and their explanations provide insights into the reasoning of those who may not persist with their courses at university. These results, in the context of the greater attrition rate of remote students from university, point to the need to identify factors that positively impact on rural and remote students’ interest and achievement in science and mathematics. It also highlights a need for future research into the particular issues remote students may face in deciding whether or not to do science at the two key transition points of senior school and university/TAFE studies, and whether or not to persist in their tertiary studies. This paper is positioned at the intersection of two problems in Australian education. The first is a context of falling levels of participation in physical science and mathematics courses in Australian universities. The second is persistent inequitable access to, and retention in, tertiary education for students from rural and remote areas. Despite considerable research attention to both of these areas over recent years these problems have thus far proved to be intractable. This paper therefore aims to briefly review the relevant Australian literature pertaining to these issues; that is, declining STEM enrolments, and the underrepresentation and retention of rural/remote students in higher education. Given the related problems in these two overlapping domains, we then explore the views of first year rural students enrolled in courses, in relation to their intentions of withdrawing (or not) and the associated reasons for their views.

Plan U.S.R.R. Melitopol'skogo okruga Genicheskogo raiona poluostrova Chongar vymezhevannogo v poriadke chastichnogo izmeneniia ustroistva kolfonda s ustroistvom poselkov, razbivkoiu na polia sevooborota, gony soglasno nakazu N.K.Z dnia 1927, n 52-2825. Izmerenie v nature proizvedeno i plan etot sostovlen X. partieiu po ustroistvu kolfondov

Digital image

Lätta stabila isotopfraktioner som verktyg i biologisk forskning

Det finns en mätbar entitet i all levande materia, nämligen förhållandet mellan ett atomslags lätta och tunga isotop. Denna entitet divideras med en definierad referens och ett värde erhålls som brukar anges i promille ( ). Värdet är ett mått på isotopfraktionering. Genom att studera ekologi, taxonomi, kretslopp, isotopeffekter, dokumenterad data och metabola effekter kan man skissera över vad isotopfraktionen betyder. Migrationsbeteende, trofinätverk, dieter, miljö- och klimatdata kan rekonstrueras i tid och rum. Vid rekonstruktioner av gången tid har de museala samlingarna en nyckelposition. I litteraturöversikten tas teori, praktik och forskning upp för att påvisa metodens faror och användningsområden.

Kukuruza Raĭony vozdelyvanii︠a︡ kukuruzy : nailuchshie sorta i sredni︠a︡i︠a︡ urozhaĭnost' sukhogo zerna na 1 des. po dannym seti opytnykh uchastkov iuga Rossii i postoi︠a︡nnykh opytnykh uchrezhdenniĭ

Digital image

Plan uchastkov nn 4, 7, 7a i 9 Chongarskogo poluostrova Henicheskogo raiona

Digital image