Charred seeds in Mikkeli Orijärvi : A study of subsistence strategies of an Iron Age settlement in East Finland

In this study the over 350 macrofossil samples, containing over 2300 charred plant remains from an Iron Age settlement containing fossil fields in Mikkeli Orijärvi Kihlinpelto, were studied archaeobotanically. The aim was to get more information about subsistence strategies, especially agriculture and study differences in the plant combinations in the different structures and use the archaeobotanical theory to interpret these structures. The methodological question was to study the taphonomy of the charred plant material. The results gave a diverse impression of the agriculture and subsistence strategies of the settlement in Orijärvi, where barley was the most important cereal with rye, wheat and oat cultivated as minor crops. The arable weed assemblage indicates that the fields were situated in different kinds of soils and the crops were cultivated when different kind of weather conditions were prevailing. Ergot was found with the cereals, and it was growing on some of the arable crops and it also indicates wet climate. Hemp and flax were cultivated and wild plants were collected. The meadow and wetland plants found in the material derive most probably from animal fodder. Tubers of bulbous oat-grass were interesting, because they are usually found in graves. Comparison with other Iron Age settlements and graves indicates that the plant material found from the ancient field layers derives most probably from dwellings and graves, which were taken into cultivation.

Zeta Potential Studies On Some Iron-Ore Minerals In The Presence Of Starches

Authors perform zeta potential studies on hematite, corundum, and quartz samples using starches to understand the adsorption behavior of polymeric starch flocculants at the oxide mineral-solution interface and to correlate this information with their flocculation characteristics and investigate effects of pH and CaCl#72 on zeta potential of Fe ore minerals.

Interaction of metal ions with nucleic acids and related compounds. II. Studies on Au(III)-nucleic acid system

The nature of interaction of Au(III) with nucleic acids was studied by using methods such as uv and ir spectrophotometry, viscometry, pH titrations, and melting-temperature measurements. Au(III) is found to interact slowly with nucleic acids over a period of several hours. The uv spectra of native calf-thymus DNA 9pH 5.6 acetate buffer containing (0.01M NaCIO4) showed a shift in λ max to high wavelengths and an increase in optical density at 260 nm. There was a fourfold decrease in viscosity (expressed as ηsp/c). The reaction was faster at pH 4.0 and also with denatured DNA (pH 5.6) and whole yeast RNA (pH 5.6). The order of preference of Au(III) (as deduced from the time of completion of reaction) for the nucleic acids in RNA > denatured DNA > DNA. The reaction was found to be completely reversible with respect KCN. Infrared spectra of DNA-Au(III) complexes showed binding to both the phosphate and bases of DNA. The same conclusions were also arrived at by melting-temperature studies of Au(III)-DNA system. pH titrations showed liberation of two hydroxylions at r = 0.12 [r = moles of HAuCl4 added per mole of DNA-(P)] and one hydrogen ion at r = 0.5. The probable binding sites could be N(1)/N(7) of adenine, N(7) and/or C(6)O of guanine, N(3) of cytosine and N(3) of thymine. DNAs differing in their (G = C)-contents [Clostridium perfingens DNA(G = C, 29%), salmon sperm DNA (G + C, 42%) and Micrococcus lysodeikticus DNA(G + C, 29%), salmon sperm DNA (G = C, 72%)] behaved differently toward Au(III). The hyperchromicity observed for DNAs differing in (G + C)-content and cyanide reversal titrations indicate selectivity toward ( A + T)-rich DNA at lw values of r. Chemical analysis and job's continuous variation studies indicated the existence of possible complexes above and below r = 1. The results indicate that Au(III) ions probably bind to hte phosphate group in the initial stages of the reaction, particularly at low values of r, and participation of the base interaction also increases. Cross-linking of the two strands by Au(III) may take place, but a complete collapse of the doulbe helix is not envisaged. It is probable that tilting of the bases or rotaiton of the bases around the glucosidic bond, resulting in a significant distrotion of the double helix, might take place due to binding of Au(III) to DNA.

Protein Kinase C and Anaplastic Lymphoma Kinase Targeted Compounds

The protein kinases (PKs) belong to the largest single family of enzymes, phosphotransferases, which catalyze the phosphorylation of other enzymes and proteins and function primarily in signal transduction. Consequently, PKs regulate cell mechanisms such as growth, differentiation, and proliferation. Dysfunction of these cellular mechanisms may lead to cancer, a major predicament in health care. Even though there is a range of clinically available cancer-fighting drugs, increasing number of cancer cases and setbacks such as drug resistance, constantly keep cancer research active. At the commencement of this study an isophthalic acid derivative had been suggested to bind to the regulatory domain of protein kinase C (PKC). In order to investigate the biological effects and structure-activity relationships (SARs) of this new chemical entity, a library of compounds was synthesized. The best compounds induced apoptosis in human leukemia HL-60 cells and were not cytotoxic in Swiss 3T3 fibroblasts. In addition, the best apoptosis inducers were neither cytotoxic nor mutagenic. Furthermore, results from binding affinity assays of PKC isoforms revealed the pharmacophores of these isophthalic acid derivatives. The best inhibition constants of the tested compounds were measured to 210 nM for PKCα and to 530 nM for PKCδ. Among natural compounds targeting the regulatory domain of PKC, the target of bistramide A has been a matter of debate. It was initially found to activate PKCδ; however, actin was recently reported as the main target. In order to clarify and to further study the biological effects of bistramide A, the total syntheses of the natural compound and two isomers were performed. Biological assays of the compounds revealed accumulation of 4n polyploid cells as the primary mode of action and the compounds showed similar overall antiproliferative activities. However, each compound showed a distinct distribution of antimitotic effect presumably via actin binding, proapoptotic effect presumably via PKCδ, and pro-differentiation effect as evidenced by CD11b expression. Furthermore, it was shown that the antimitotic and proapoptotic effects of bistramide A were not secondary effects of actin binding but independent effects. The third aim in this study was to synthesize a library of a new class of urea-based type II inhibitors targeted at the kinase domain of anaplastic lymphoma kinase (ALK). The best compounds in this library showed IC50 values as low as 390 nM for ALK while the initial low cellular activities were successfully increased even by more than 70 times for NPM-ALK- positive BaF3 cells. More importantly, selective antiproliferative activity on ALK-positive cell lines was achieved; while the best compound affected the BaF3 and SU-DHL-1 cells with IC50 values of 0.5 and 0.8 μM, respectively, they were less toxic to the NPM-ALK-negative human leukemic cells U937 (IC50 = 3.2 μM) and BaF3 parental cells (IC50 = 5.4 μM). Furthermore, SAR studies of the synthesized compounds revealed functional groups and positions of the scaffold, which enhanced the enzymatic and cellular activities.

A convenient and high-yield synthesis for pyridinium and metal hexafluorocomplexes of vanadium, chromium, iron and cobalt

Pyridinium poly(hydrogen fluoride) reacts with the oxide of vanadium(V) and chlorides of chromium(III), iron (III) and Co(II) at room temperature forming the pyridinium salts of hexafluoro vanadate(V), hexafluorochromate(III), hexafluoroferrate(III) and hexafluorocobaltate(II) in near quantitative yields (80%). These pyridinium salts are the precursors for the preparation of the alkali metal hexafluorometallates by metathetic reactions in acetonitrile medium with the corresponding metal chlorides. The prepared salts have been identified by their infrared spectral data and elemental analysis.

A XANES study of the K-absorption edge of copper in some of its compounds and use of the same in the determination of bond length

XANES in the K-edge of copper in the systems CuO, Cu(OH)2, La2CuO4, Cu3AsO4 and CuOHF have been investigated and transitions have been assigned to the observed structures. The measurements have been used for calculating the first coordination bond distance in the above systems. It is observed that the values so determined agree fairly well with crystallographic values.

Wire-cylinder corona discharge with the wire at positive potential studies of iron oxides

A wire-cylinder corona discharge was studied in nitrogen and dry air in crossed electric and magnetic fields for values of magnetic field ranging from 0 to 3000 G with the wire at positive potential. In the absence of a magnetic field pre-onset streamers and pulses were observed in nitrogen. In both nitrogen and dry air breakdown streamers were observed just before spark breakdown of the gap. Furthermore, experiments in dry air at atmospheric pressure in an electric field indicate regular pre-onset streamers appearing at time intervals of 19.5 µs. The appearance of regular pre-onset streamers suggests that it is not possible for negative ions to form a sheath close to the anode as postulated by Hermstein (1960) for the formation of steady or glow corona in a point-plane gap.

Chemoenzymatic Synthesis of Chiral Organosulfur Compounds

This thesis is primarily concerned with the enzyme- catalysed synthesis of sulfoxides using reductase and dioxygenase enzymes. Chapter 1 provides an introduction to the topic of redox chemistry with particular emphasis on the application of reductase and dioxygenase enzymes in organosulfur chemistry. Earlier literature methods for the production of enantiopure sulfoxides are reviewed. A brief discussion of the methods used for the determination of enantiomeric excess and absolute configuration is provided. Chapter 2 contains results obtained using a range of whole-cell bacteria each using a dimethyl sulfoxide reductase enzyme. The synthesis of a series of racemic sulfoxides and the development of appropriate CSPHPLC analytical methods is discussed. Kinetic resolutions of a series of sulfoxides have been achieved. Chapter 3 contains a presentation of results using dioxygenase enzymes as biocatalysts for the asymmetric sulfoxidation of dialkyl sulfoxides including thioacetal sulfoxides. A new range of monosulfoxides, cis-dihydrodiols and cis- dihydrodiol sulfoxides have been isolated in enantiopure form. Chapter 4 is focussed on the application of chiral sulfoxides in synthesis. A new chemoenzymatic route to diol sulfoxide enantiomers and the derived enantiopure phenols and catechols is discussed. The application of chemically synthesised sulfoxide enantiomers in the production of hydroxy sulfoxides is reported. Chapter 5 provides a full experimental section where the synthesis of sulfides and racemic sulfoxides is included. The methods used in the isolation and characterisation of bioproducts from the biotransformation are discussed and full experimental details given.

Low-Temperature Fluorination Of Some Nonmetals And Nonmetal Compounds With Fluorine

Low temperature fluorination with elemental fluorine of elemental phosphorus, sulphur, silicon, amorphous carbon and phosphorus trichloride, phosphorus pentoxide, triphenylphosphine, hexafluorodisilane, hexachlorodisilane, hexabromodisilane, tetrasulphur tetranitride, sulphur dioxide, thionyl chloride and sulphuryl chloride has been carried out in freon-11 medium. The corresponding fluoro compounds have been isolated in near quantitative yields, purified by low temperature fractional condensation and characterised by IR spectroscopy and elemental analysis.

Open-circuit potential—time transients of alkaline porous iron electrodes at various states-of-charge

Open-circuit potential—time transients during the discharge of alkaline porous iron electrodes at various states-of-charge have been studied. From this, it has been possible to arrive at a correlation between the parameters of self-discharge kinetics of the electrode and observed open-circuit potential—recovery time constants. The study provides a method of estimate the state-of-charge of the rechargeable iron electrodes. As a hydrogen evolution reaction inevitably occurs on alkaline iron electrodes, the kinetics of the reaction have also been investigated.

Preparation, characterization, spectral and thermal analyses of (N2H5)2MCl4·2H2O (M = Fe, Co, Ni and Cu); crystal structure of the iron complex

Hydrazinium metal chlorides, (N2H5)2MCl4·2H2O (where M = Fe, Co, Ni and Cu), have been prepared from the aqueous solutions of the respective metal chlorides and hydrazine hydrochloride (N2H4·HCl or N2H4·2HCl) and investigated by spectral and thermal analyses. The crystal structure of the iron complex has been determined by direct methods and refined by full-matrix least-squares to an R of 0.023 and Rw of 0.031 for 1495 independent reflections. The structure shows ferrous ion in an octahedral environment bonded by two hydrazinium cations, two chloride anions and two water molecules. In the complex cation [Fe(N2H5)2(H2O)2Cl2]2+, the coordinated groups are in trans positions.

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.

Putative neuroprotective compounds in in vitro models of dopaminergic neurodegeneration

Parkinson´s disease (PD) is a debilitating age-related neurological disorder that affects various motor skills and can lead to a loss of cognitive functions. The motor symptoms are the result of the progressive degeneration of dopaminergic neurons within the substantia nigra. The factors that influence the pathogenesis and the progression of the neurodegeneration remain mostly unclear. This study investigated the role of various programmed cell death (PCD) pathways, oxidative stress, and glial cells both in dopaminergic neurodegeneration and in the protective action of various drugs. To this end, we exposed dopaminergic neuroblastoma cells (SH-SY5Y cells) to 6-OHDA, which produces oxidative stress and activates various PCD modalities that result in neuronal degeneration. Additionally, to explore the role of glia, we prepared rat midbrain primary mixed-cell cultures containing both neurons and glial cell types such as microglia and astroglia and then exposed the cultures to either MPP plus or lipopolysaccharide. Our results revealed that 6-OHDA activated several PCD pathways including apoptosis, autophagic stress, lysosomal membrane permeabilization, and perhaps paraptosis in SH-SY5Y cells. Furthermore, we found that minocycline protected SH-SY5Y cells from 6-OHDA by inhibiting both apoptotic and non-apoptotic PCD modalities. We also observed an inconsistent neuroprotective effect of various dietary anti-oxidant compounds against 6-OHDA toxicity in vitro in SH-SY5Y cells. Specifically, quercetin and curcumin exerted neuroprotection only within a narrow concentration range and a limited time frame, whereas resveratrol and epigallocatechin 3-gallate provided no protection whatsoever. Lastly, we found that molecules such as amantadine may delay or even halt the neurodegeneration in primary cell cultures by inhibiting the release of neurotoxic factors from overactivated microglia and by enhancing the pro-survival actions of astroglia. Together these data suggest that the strategy of dampening oxidative species with anti-oxidants is less effective than preventing the production of toxic factors such as oxidative and pro-inflammatory molecules by pathologically activated microglia. This would subsequently prevent the activation of various PCD modalities that cause neuronal degeneration.

A new general method for the introduction of the aldehyde function in aromatic compounds

Side chain bromination of aromatic amidomethylated compounds yields aldehydes.

Peeking through the Iron Curtain: Memories of Watching Finnish Television in Estonia during Soviet Occupation

The present study analyses the memories of watching Finnish television in Estonia during the last decades of the Soviet occupation from the late 1960s until the beginning of 1990s. The study stems from a culturalist approach, perceiving television as a relevant aspect in the audiences’ everyday lives. It explores the significance of Finnish television on the society of occupied Estonia from the point of view of its historical audiences. The literature review concentrates on concepts such as the power of television, transnational media, historical audience reception and memory as an object of research. It also explains the concept of spillover, which refers to the unintentional bilateral flow of television signals from one country to another. Despite the numerous efforts of the Soviet authorities to prevent the viewing of the "bourgeois television", there still remained a small gap in the Iron Curtain. The study describes the phenomenon of watching Finnish television in Estonia. It provides understanding about the significance of watching Finnish television in Soviet Estonia through the experiences of its former audience. In addition, it explores what do people remember about watching Finnish television, and why. The empirical data was acquired from peoples’ personal memories through the analysis of private interviews and written responses during the period from February 2010 to February 2011. A total of 85 responses (5 interviews and 83 written responses) were analysed. The research employed the methods of oral history and memory studies. The main theoretical sources of the study include the works of Mati Graf and Heikki Roiko-Jokela, Hagi Šein, Sonia Livingstone, Janet Staiger and Emily Keightley. The study concludes that besides fulfilling the role of an entertainer and an informer, Finnish television enabled its Estonian audiences to gain entry into the imaginary world. Access to this imaginary world was so important, that the viewers engaged in illegal activities and gained special skills, whereby a phenomenon of "television tourism" developed. Most of the memories about Finnish television are vivid and similar. The latter indicates both the reliability and the collectiveness of such memories, which in return give shape to collective identities. Thus, for the Estonian viewers, the experience of watching Finnish television during the Soviet occupation has became part of their identity.