The role of impurities in the shape, structure and physical properties of semiconducting oxide nanostructures grown by thermal evaporation

A thermal evaporation method developed in the research group enables to grow and design several morphologies of semiconducting oxide nanostructures, such as Ga_2O_3, GeO_2 or Sb_2O_3, among others, and some ternary oxide compounds (ZnGa_2O_4, Zn_2GeO_4). In order to tailor physical properties, a successful doping of these nanostructures is required. However, for nanostructured materials, doping may affect not only their physical properties, but also their morphology during the thermal growth process. In this paper, we will show some examples of how the addition of impurities may result into the formation of complex structures, or changes in the structural phase of the material. In particular, we will consider the addition of Sn and Cr impurities into the precursors used to grow Ga_2O_3, Zn_2GeO_4 and Sb_2O_3 nanowires, nanorods or complex nanostructures, such as crossing wires or hierarchical structures. Structural and optical properties were assessed by electron microscopy (SEM and TEM), confocal microscopy, spatially resolved cathodoluminescence (CL), photoluminescence, and Raman spectroscopies. The growth mechanisms, the luminescence bands and the optical confinement in the obtained oxide nanostructures will be discussed. In particular, some of these nanostructures have been found to be of interest as optical microcavities. These nanomaterials may have applications in optical sensing and energy devices.

Meiofauna and the structure of the benthic community in the Iberian deep sea basin

1. On the cruises 3 and 15 of R.V. "Meteor" 6 grab samples, and 6 hauls with the 6 m Agassiztrawl were taken and at 2 stations the deep sea camera was lowered. This material gave quantitative results on the meiofauna and minimum counts of the macrofauna. 2. The nematodes constitute nearly 95% of the meiofauna, the copepoda only 2%. With increasing sediment depth the density of animals decrease gradually. In the uppermost centimeter of sediment 42.6% of the meiofauna are found while only 3.7% live in layer 6-7 cm. Meiofauna weight ranges from 0.6-5.7 mg/25 m**2 surface i.e. 0.24-2.8 g/m**2. 3. Mean numbers of individuals and weights show standard errors of 20-30 %. As an approximate average values for further considerations the weight of the meiofauna in the area was taken as 1 g/m**2 4. Quantitative information on the macrofauna is derived from the trawls and the photographs for the actinia Chitonanthus abyssorum only, which is found in the rate of 1 individual/36-72 m**2, but seems to be less abundant generally. 5. Animal density does not decrease steadily from nearshore to offshore biocoenoses, i.e. generally with increasing depth. The decrease is more pronounced for macro- than for meiofauna. For the deep sea the weight proportion of macrofauna : meiofauna is of the order of 1 : 1. 6. With the assumption, that adaptation of metabolism to deep sea conditions is similar in macro- and meiofauna total metabolism of invertebrates is ascribed to meiofauna to more than 80%. 7. The structure of the biocoenosis of the deep sea floor is characterized by the meiofauna living on and in the sediment and by the dominance of sediment feeders in the macrofauna. 8. Considering the large numbets and high partition rates of bacteria a comparative large part of the metabolism in the deep sea sediment must be ascribed to bacteria. This favours the hypothesis, that with increasing depth and decreasing addition of organic material to the sediment, the importance of meiofauna and microorganisms for total metabolism increases. 9. Considering the different modes of food transport to the deep sea environment, i.e. sinking of dead particles, transport by vertical migration of organisms, aggregation of organic particles, adsorption of dissoloved organic substance to inorganic particles, and heterotrophy, the sediment may be assumed to contain more food for invertebrates than the water above the bottom. 10. Suspensions feeders of macrofauna are fixed to hard substrates in the sediment surface. Some of them are shown to bend themselves down to the bottom in underwater photographs. This suggests the idea that some deep sea suspension feeders partly depend on food from the sediment surface, on which they feed directly.

Investigating sea level rise due to global warming in the teaching laboratory using Archimedes’ principle

A teaching laboratory experiment is described that uses Archimedes’ principle to precisely investigate the effect of global warming on the oceans. A large component of sea level rise is due to the increase in the volume of water due to the decrease in water density with increasing temperature. Water close to 0 °C is placed in a beaker and a glass marble hung from an electronic balance immersed in the water. As the water warms, the weight of the marble increases as the water is less buoyant due to the decrease in density. In the experiment performed in this paper a balance with a precision of 0.1 mg was used with a marble 40.0 cm3 and mass of 99.3 g, yielding water density measurements with an average error of -0.008 ± 0.011%.

A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Genetic diversity and microcystin production by Anabaena in the Gulf of Finland, Baltic Sea

Syanobakteerit (sinilevät) ovat olleet Itämeressä koko nykymuotoisen Itämeren ajan, sillä paleolimnologiset todisteet niiden olemassaolosta Itämeren alueella ovat noin 7000 vuoden takaa. Syanobakteerien massaesiintymät eli kukinnat ovat kuitenkin sekä levinneet laajemmille alueille että tulleet voimakkaimmiksi viimeisten vuosikymmenien aikana. Tähän on osasyynä ihmisten aiheuttama kuormitus, joka rehevöittää Itämerta. Suomenlahti, jota tämä tutkimus käsittelee, on kärsinyt tästä rehevöitymiskehityksestä muita Itämeren altaita enemmän. Syanobakteerit muodostavat jokakesäisiä kukintoja Suomenlahdella - niin sen avomerialueilla kuin rannoillakin. Yleisimmät kukintoja muodostavat syanobakteerisuvut ovat Nodularia, Anabaena ja Aphanizomenon. Kukinnat aiheuttavat paitsi esteettistä haittaa myös terveydellisen riskitekijän. Niiden myrkyllisyys liitetään usein Nodularia-suvun tuottamaan nodulariini-maksamyrkkyyn. Itämeren Aphanizomenon-suvun on todettu olevan myrkytön. Vaikka Itämeren kukintoja aiheuttavista Nodularia- ja Aphanizomenon-syanobakteereista tiedetään varsin paljon, on molekyylimenetelmiin pohjautuva syanobakteeritutkimus ohittanut Itämeren Anabaena-suvun monelta osin. Tämän työn tarkoituksena oli syventää käsitystämme Itämeren Anabaena-syanobakteerista, sen mahdollisesta myrkyllisyydestä, geneettisestä monimuotoisuudesta ja fylogeneettisista sukulaisuussuhteista. Tässä työssä eristettiin 49 planktista Anabaena-kantaa, joista viisi tuottivat mikrokystiinejä. Tämä oli ensimmäinen yksiselitteinen todiste, että Itämeren Anabaena tuottaa maksamyrkyllisiä mikrokystiini-yhdisteitä. Jokainen eristetty myrkyllinen Anabaena-kanta tuotti useita mikrokystiini-variantteja. Lisäksi mikrokystiinejä löydettiin kukintanäytteistä, joissa oli myrkkyä syntetisoivia geenejä sisältäneitä Anabaena-syanobakteereita. Myrkkyjä löydettiin molempina tutkimusvuosina 2003 ja 2004. Myrkkyjen esiintyminen ei siten ollut vain yksittäinen ilmiö. Tässä työssä saimme viitteitä siitä, että maksamyrkyllinen Anabaena-syanobakteeri esiintyisi vähäsuolaisissa vesissä. Tämä riippuvuussuhde jää kuitenkin tulevien tutkimuksien selvitettäväksi. Tässä työssä havaittiin mikrokystiinisyntetaasi-geenien inaktivoituminen Itämeren Anabaena-kannassa ja kukintanäytteissä. Kuvasimme Anabaena-kannan mikrokystiinisyntetaasigeenien sisältä insertioita, jotka hyvin todennäköisesti inaktivoivat myrkyntuoton. Insertion sisältäneeltä kannalta löysimme kuitenkin kaikki mikrokystiinisyntetaasigeenit osoittaen, että geenien olemassaolo ei välttämättä varmista kannan mikrokystiinintuottoa. Mielenkiintoista oli se, että inaktivaation aiheuttavia insertioita löytyi kukintanäytteistä molemmilta tutkimusvuosilta. Vastaavia insertioita ei kuitenkaan löydetty makean veden Anabaena-kannoista tai järvinäytteistä. On yleistä, että syanobakteerikukinnoista löytyy usean syanobakteerisuvun edustajia. Myrkyllisiä sukuja tai lajeja ei voida kuitenkaan erottaa mikroskooppisesti myrkyttömistä. Käsillä olevassa tutkimuksessa kehitettiin molekyylimenetelmä, jolla on mahdollista määrittää kukinnan mahdollisesti maksamyrkylliset syanobakteerisuvut. Tätä menetelmää sovellettiin Itämeren kukintojen tutkimiseen. Itämeren pintavesistä ja ranta-alueiden pohjasta eristetyt Anabaena-kannat osoittautuivat geneettisesti monimuotoisiksi. Tämä Anabaena-syanobakteerien geneettinen monimuotoisuus vahvistettiin monistamalla geenejä suoraan kukintanäytteistä ilman kantojen eristystä. Makeiden vesien ja Itämeren Anabaena-kannat ovat geneettisesti hyvin samankaltaisia. Geneettisissä vertailuissa kävi kuitenkin ilmi, että pohjassa elävien Anabaena-kantojen geneettinen monimuotoisuus oli suurempaa kuin pintavesistä eristettyjen kantojen. Itämeren Anabaena-kantojen sekvenssit muodostivat omia ryhmiä sukupuun sisällä, jolloin on mahdollista, että nämä edustavat Itämeren omia Anabaena-ekotyyppejä. Tämä tutkimus oli ensimmäinen, jossa uusin molekyylimenetelmin systemaattisesti selvitettiin Itämeren Anabaena-syanobakteerin geneettistä populaatiorakennetta, fylogeniaa ja myrkyntuottoa. Tulevaisuudessa monitorointitutkimuksissa on otettava huomioon myös Itämeren Anabaena-syanobakteerin mahdollinen maksamyrkyntuotto – erityisesti vähäsuolaisemmilla rannikkovesillä.

Mechanisms of the impact of a weed (grader grass, Themeda quadrivalvis) on reptile assemblage structure in a tropical savannah

Invasive grasses are among the worst threats to native biodiversity, but the mechanisms causing negative effects are poorly understood. To investigate the impact of an invasive grass on reptiles, we compared the reptile assemblages that used native kangaroo grass (Themeda triandra), and black spear grass (Heteropogon contortus), to those using habitats invaded by grader grass (Themeda quadrivalvis). There were significantly more reptile species, in greater abundances, in native kangaroo and black spear grass than in invasive grader grass. To understand the sources of negative responses of reptile assemblages to the weed, we compared habitat characteristics, temperatures within grass clumps, food availability and predator abundance among these three grass habitats. Environmental temperatures in grass, invertebrate food availability, and avian predator abundances did not differ among the habitats, and there were fewer reptiles that fed on other reptiles in the invaded than in the native grass sites. Thus, native grass sites did not provide better available thermal environments within the grass, food, or opportunities for predator avoidance. We suggest that habitat structure was the critical factor driving weed avoidance by reptiles in this system, and recommend that the maintenance of heterogeneous habitat structure, including clumping native grasses, with interspersed bare ground, and leaf litter are critical to reptile biodiversity.

Mechanisms of the impact of a weed (grader grass, Themeda quadrivalvis) on reptile assemblage structure in a tropical savannah

Invasive grasses are among the worst threats to native biodiversity, but the mechanisms causing negative effects are poorly understood. To investigate the impact of an invasive grass on reptiles, we compared the reptile assemblages that used native kangaroo grass (Themeda triandra), and black spear grass (Heteropogon contortus), to those using habitats invaded by grader grass (Themeda quadrivalvis). There were significantly more reptile species, in greater abundances, in native kangaroo and black spear grass than in invasive grader grass. To understand the sources of negative responses of reptile assemblages to the weed, we compared habitat characteristics, temperatures within grass clumps, food availability and predator abundance among these three grass habitats. Environmental temperatures in grass, invertebrate food availability, and avian predator abundances did not differ among the habitats, and there were fewer reptiles that fed on other reptiles in the invaded than in the native grass sites. Thus, native grass sites did not provide better available thermal environments within the grass, food, or opportunities for predator avoidance. We suggest that habitat structure was the critical factor driving weed avoidance by reptiles in this system, and recommend that the maintenance of heterogeneous habitat structure, including clumping native grasses, with interspersed bare ground, and leaf litter are critical to reptile biodiversity.

Human genetic variation in the Baltic Sea region: Features of population history and natural selection

In this thesis, the genetic variation of human populations from the Baltic Sea region was studied in order to elucidate population history as well as evolutionary adaptation in this region. The study provided novel understanding of how the complex population level processes of migration, genetic drift, and natural selection have shaped genetic variation in North European populations. Results from genome-wide, mitochondrial DNA and Y-chromosomal analyses suggested that the genetic background of the populations of the Baltic Sea region lies predominantly in Continental Europe, which is consistent with earlier studies and archaeological evidence. The late settlement of Fennoscandia after the Ice Age and the subsequent small population size have led to pronounced genetic drift, especially in Finland and Karelia but also in Sweden, evident especially in genome-wide and Y-chromosomal analyses. Consequently, these populations show striking genetic differentiation, as opposed to much more homogeneous pattern of variation in Central European populations. Additionally, the eastern side of the Baltic Sea was observed to have experienced eastern influence in the genome-wide data as well as in mitochondrial DNA and Y-chromosomal variation – consistent with linguistic connections. However, Slavic influence in the Baltic Sea populations appears minor on genetic level. While the genetic diversity of the Finnish population overall was low, genome-wide and Y-chromosomal results showed pronounced regional differences. The genetic distance between Western and Eastern Finland was larger than for many geographically distant population pairs, and provinces also showed genetic differences. This is probably mainly due to the late settlement of Eastern Finland and local isolation, although differences in ancestral migration waves may contribute to this, too. In contrast, mitochondrial DNA and Y-chromosomal analyses of the contemporary Swedish population revealed a much less pronounced population structure and a fusion of the traces of ancient admixture, genetic drift, and recent immigration. Genome-wide datasets also provide a resource for studying the adaptive evolution of human populations. This study revealed tens of loci with strong signs of recent positive selection in Northern Europe. These results provide interesting targets for future research on evolutionary adaptation, and may be important for understanding the background of disease-causing variants in human populations.

Benthic-pelagic coupling in the northern Baltic Sea: importance of bioturbation and benthic predation

Benthic-pelagic coupling describes processes that operate across and between the seafloor and open-water ecosystems. In soft-sediment communities, bioturbation by sediment-dwelling and epibenthic organisms may strongly shape habitat characteristics and influence processes, e.g. biogeochemical cycling, which supplies bioavailable nutrients to pelagic primary producers. In addition, benthic fauna may mediate benthic-pelagic coupling by affecting the survival and hatching of zooplankton dormant eggs in the sediment. In the shallow waters and seasonally fluctuating environment of the Baltic Sea, emergence from the seafloor essentially contributes to the dynamics of zooplankton pelagic populations. In this thesis, I examine how benthic organisms with different functional traits affect the link between the benthic and pelagic systems in the northern Baltic Sea. By means of experimental laboratory studies, the effects of sediment-dwelling (Monoporeia affinis, Macoma balthica and Marenzelleria spp.) and nectobenthic (Mysis spp.) taxa on the survival and hatching of zooplankton benthic eggs and on benthic nutrient fluxes and sediment structure were investigated. In the predation studies, the nectobenthic mysids Mysis spp. preyed upon benthic eggs of the cladoceran Bosmina longispina maritima (syn. B. coregoni maritima), both in pelagic and benthic environments. Of the sediment-dwelling species, the amphipod M. affinis and the bivalve M. balthica reduced the number of cladoceran eggs in the sediment, whereas the polychaetes Marenzelleria spp. had no effects on cladoceran eggs. Both M. balthica and M. affinis also increased the mortality rates of benthic eggs of copepods and rotifers. It was estimated that zooplankton eggs provide an additional carbon source for food-limited benthic communities. The results indicate that predation pressure on zooplankton benthic eggs may be strong, but varies widely depending on the season and the functional characteristics of the macrofauna. Macoma balthica buried cladoceran eggs and a fluorescent tracer from the sediment surface to a depth of 3 4 cm, indicating efficient sediment mixing. In contrast, the other taxa had fewer effects on particle distributions. In addition to organic matter mineralization, particle mixing is crucial to the success of benthic recruitment of zooplankton, since only eggs close to the sediment surface may hatch. Macoma balthica and M. affinis altered the patterns of zooplankton emergence from the sediment. In general, the highest emergence rates were observed in the absence of macroscopic fauna, and M. balthica exerted a stronger suppressive effect than M. affinis. Moreover, copepods were less severely affected than cladocerans, while only one species (Temora longicornis) clearly benefited from the presence of the macrofauna. These differences probably result from species-specific differences in the resistance of eggs to disturbances. The results show that benthic fauna may considerably alter the patterns of zooplankton emergence from the seafloor, thereby shaping zooplankton pelagic populations. The semi-motile M. balthica and Marenzelleria spp. increased the fluxes of phosphate and ammonium from the sediment to the water, whereas the motile M. affinis and Mysis mixta had a contrasting effect. In the eutrophied Baltic Sea, efficient internal cycling of bioavailable nutrients forms a strong feedback inhibiting the recovery of the ecosystem. Based on the results, a change in species dominance from the two motile taxa, susceptible to oxygen deficiency, to the more tolerant semi-motile taxa provides additional feedback, strengthening internal nutrient cycling and accelerating eutrophication, with deteriorating near-bottom oxygen conditions and changes in the benthic communities. In shallow-water ecosystems, benthic nutrient regeneration plays a key role in determining the overall productivity of the ecosystem. In addition, the results of this study show that the communities in the benthos may essentially contribute to the structure of those in the plankton.

Allelopathic effects of filamentous cyanobacteria on phytoplankton in the Baltic Sea

Eutrophication and enhanced internal nutrient loading of the Baltic Sea are most clearly reflected by increased late-summer cyanobacterial blooms, which often are toxic. In addition to their toxicity to animals, phytoplankton species can be allelopathic, which means that they produce chemicals that inhibit competing phytoplankton species. Such interspecific chemical warfare may lead to the formation of harmful phytoplankton blooms and the spread of exotic species into new habitats. This is the first report on allelopathic effects in brackish-water cyanobacteria. The experimental studies presented in this thesis showed that the filamentous cyanobacteria Anabaena sp., Aphanizomenon flos-aquae and Nodularia spumigena are capable of decreasing the growth of other phytoplankton species, especially cryptophytes, but also diatoms. The detected allelopathic effects are rather transitory, and some co-occurring species show tolerance to them. The allelochemicals are excreted during active growth and they decrease cell numbers, chlorophyll a content and carbon uptake of the target species. Although the more specific modes of action or chemical structures of the allelochemicals remain to be studied, the results clearly indicate that the allelopathic effects are not caused by the hepatotoxin, nodularin. On the other hand, cyanobacteria stimulated the growth of bacteria, other cyanobacteria, chlorophytes and flagellates in a natural phytoplankton community. In a long-term data analysis of phytoplankton abundances and hydrography of the northern Baltic Sea, a clear change was observed in phytoplankton community structure, together with a transition in environmental factors, between the late 1970s and early 2000s. Surface water salinity decreased, whereas water temperature and the concentration of dissolved inorganic nitrogen increased. In the phytoplankton community, the biomass of cyanobacteria, chrysophytes and chlorophytes significantly increased, and the late-summer phytoplankton community became increasingly cyanobacteria-dominated. In contrast, the biomass of cryptophytes decreased. The increased temperature and nutrient concentrations probably explain most of the changes in phytoplankton, but my results suggest that the possible effect of chemically mediated biological interactions should also be considered. Cyanobacterial allelochemicals can cause additional stress to other phytoplankton in the nutrient-depleted late-summer environment and thus contribute to the formation and persistence of long-lasting cyanobacterial mass occurrences. On the other hand, cyanobacterial blooms may either directly or indirectly promote the growth of some phytoplankton species. Therefore, a further increase in cyanobacteria will probably shape the late-summer pelagic phytoplankton community by stimulating some species, but inhibiting others.

Fast- and drift-ice communities in the Bothnian Bay and the impact of UVA radiation on the Baltic Sea ice ecology

The aim of this thesis was to study ecology of Baltic Sea ice from two perspectives. In the first two studies, sea-ice ecology from riverine-influenced fast ice to drift ice in the Bothnian Bay was investigated, whereas the last two studies focus on the sensitivity of sea-ice bacteria and algae to UVA examined in situ. The seasonal sea ice cover is one of the main characteristics of the Baltic Sea, and despite the brackish parental water, the ice structure is similar to polar ice with saline brine inclusions, the sea ice habitat. The decreasing seawater salinity from the northern Baltic Sea to the Bothnian Bay translates to decreasing brine volumes along the gradient, governing the size and community structure of the food webs in ice. However, the drift and fast ice in the Bothnian Bay may differ greatly in this sense, as drift ice may have been formed at more southern locations. Rafting and the formation of snow ice are common processes in the ice field of the Bothnian Bay. As evidenced in this thesis, rafting altered the vertical distribution of organisms and snow-ice formation provided habitable space in the better-illuminated, nitrogen-rich surface layer. The divergence between fast and drift ice became apparent at the more advanced stages, and chlorophyte biomass decreased from fast to drift ice, while the opposite held true for protozoan and metazoan biomass. The brine volumes affected the communities somewhat, and a higher percentage of flagellate species was generally linked to lower brine volumes, whereas chain-forming diatoms were mostly concentrated in layers with larger brine volumes. These results add to knowledge of the ecological significance of the ice cover lasting up to 7 months per year in this area. Sea-ice food webs are generally light-limited, but while increasing light irradiances typically enhance the primary production and further, the secondary production in sea ice, any increase in solar radiation also includes an increase in harmful UVA radiation. The Baltic Sea ice microbial communities were clearly sensitive to UVA and the responses were strongly linked to the earlier light history, as well as to the solar irradiances they were exposed to. The increased biomass of chlorophytes and pennate diatoms, when UVA was excluded, indicates that their normally minor contribution to the biomass in the upper layers of sea ice might be partly dictated by UVA. The effects of UVA on bacterial production in Baltic Sea ice mostly followed the responses in algal growth, but occasionally the exposure to UVA even enhanced the bacterial production. The dominant bacterial class, Flavobacteria, seemed to be UVA-tolerant, whereas all the Alpha-, Beta- and Gammaproteobacteria present in the surface layer showed UVA sensitivity. These results indicate that changes in the light field of ice may alter the community structure and affect the functioning of ice food webs, and are of importance when the effects of thinning of the ice cover are assessed.

Origin of the plateau in the low-temperature thermal conductivity of silica

Thermal conductivities of glasses at low temperatures show strikingly similar behavior irrespective of their chemical composition. While for T<1 K the thermal conductivity can be understood in the phenomenological tunneling model; the ‘‘universal plateau’’ in the temperature interval 15>T>2 K is totally unexplained. While Rayleigh scattering of phonons by structural disorder should be the natural cause for limiting the mean free path of phonons in this temperature range, it has been concluded before that in glasses a strong enough source of such scattering does not exist. In this study we show by a proper structural analysis in at least one material (namely, silica) that a strong enough source of Rayleigh scattering of phonons in glasses does exist so that the ‘‘universal plateau’’ can be explained without invoking any new mechanism. This may be for the first time that the low-temperature property of a structural glass has been correlated to its structure.

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.

Intraloop and Interloop Interactions in the Folded-G Quartet Structure of Oxytricha Telomeric Sesquence

The antiparallel intramolecular G quartet structure for the 3.5 copy Oxytricha telomeric sequence d(G(4)T(4))(3)G4 has been established using a combination of spectroscopic and chemical probing methods. In the presence of Naf ions, this sequence exhibits a circular dichroism spectrum with a positive band at 295 nm and a negative band around 265 nm, characteristic of an antiparallel G quartet structure. Further, we show that d(G(4)T(4))(3)G(4) adopts an antiparallel intramolecular G quartet structure even in K+ unlike d(G(4)T(4)G(4)). KMnO4 probing experiments indicated the existence of intra and interloop interactions in the Na+ induced structure. We have found that K+ not only increases the thermal stability of,G quartet structure but also binds to the loop region and disrupts stacking and interloop interactions. Biological consequences of such cation-dependent conformational micro-heterogeneity in the loop region of G quartet structures is also discussed.

The role of lysine-256 in the structure and function of sheep liver recombinant serine hydroxymethyltransferase

The active site lysine residue, K256, involved in Schiffs base linkage with pyridoxal-5'-phosphate (PEP) in sheep liver recombinant serine hydroxymethyltransferase (rSHMT) was changed to glutamine or arginine by site-directed mutagenesis. The purified K256Q and K256R SHMTs had less than 0.1% of catalytic activity with serine and H(4)folate as substrates compared to rSHMT. The mutant enzymes also failed to exhibit the characteristic visible absorbance spectrum (lambda(max) 425 nm) and did not produce the quinonoid intermediate (lambda(max) 495 nm) upon the addition of glycine and H(4)folate. The mutant enzymes were unable to catalyze aldol cleavage of beta-phenylserine and transamination of D-alanine. These results suggested that the mutation of the lysine had resulted in the inability of the enzyme to bind to the cofactor. Therefore, the K256Q SHMT was isolated as a dimer and the K256R SHMT as a mixture of dimers and tetramers which were converted to dimers slowly. On the other hand, rSHMT was stable as a tetramer for several months, further confirming the role of PLP in maintenance of oligomeric structure. The mutant enzymes also failed to exhibit the increased thermal stability upon the addition of serine, normally observed with rSHMT. The enhanced thermal stability has been attributed to a change in conformation of the enzyme from open to closed form leading to reaction specificity. The mutant enzymes were unable to undergo this conformational change probably because of the absence of bound cofactor.