Ruthenium complexes as potential aqueous romp catalysts

The research described herein relates to studies into the Aqueous Ring-Opening Metathesis Polymerisation (ROMP) of bicyclic monomers using ruthenium complex catalysts. Two monomers were synthesised for the purpose of these studies, namely exo, exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (7-oxanorbornenedicarboxylic acid) and exo, exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (norbornene dicarboxylic acid). A number of ruthenium complexes were synthesised, amongst them a novel complex containing the water soluble phosphine ligand trist(hydroxymethyl)phosphine P(CH2OH)3. Its synthesis and characterisation are described and its physical properties compared and contrasted to analogous compounds of platinum and palladium. Its peculiar properties are ascribed to a trans-placement of the phosphine ligands. Dilatometry was investigated as a technique for the acquisition of kinetic data from aqueous metathesis reactions. For the attempted polymerisation of 7-oxanorbonenedicarboxylic acid the results are explained in terms of a reverse Diels-Alder reaction of the monomer. The reaction between Ru(CO)Cl2(H2O) and 7-oxanorbonenedicarboxylic acid was monitored using UV/Vis spectrometry and kinetic data retrieved. The data are explained in terms of a two stage reaction consisting of consecutive first order processes.The reaction between 7-oxanorbornenedicarboxylic acid and Ru(CO)Cl2(H2O) or Ru(P(CH2OH)3)3Cl2 was found to produce fumaric acid as one of the major products. This reaction is previously unreported in the literature and a mechanism is proposed.

The Synthesis and properties of functionalised polymers

The aim of this project was to synthesise fluorinated polymers that might act as hot material in a guest-host system for use in non-linear optical applications. These polymers would be expected to have the advantage over materials such as poly(vinylidene fluoride) which is known to be incompatible with many nlo active materials. A series of bicyclic fluorinated monomers was prepared by the reaction of fluorinated dienophiles with cyclopentadiene in a series of Diels-Alder reactions. The monomers were purified and then used in ring opening metathesis polymerisation. The materials were then characterised by gel permeation chromatography and nuclear magnetic resonance spectroscopy and cast as films for determination of their activities as nlo materials using a Nd/YAG laser system. The second harmonic intensity of each was measured relative to quartz. However no materials of significant activity were produced. In an attempt to produce polymers that might subsequently be functionalised the polymerisation of 1,2-methylenedioxybenzene and 1,4-benzodioxane was investigated.

Conformational Evaluation of Indol-3-yl-N-alkyl-glyoxalylamides and Indol-3-yl-N,N-dialkyl-glyoxalylamides

Restricted rotation in indol-3-yl-N-alkyl- and indol-3-yl-N,N-dialkyl-glyoxalylamides can in principle give the syn-periplanar and anti-periplanar rotamers. In asymmetrically disubstituted glyoxalylamides, steric effects lead to the occurrence of both rotamers, as observed by NMR spectroscopy. The predominant peak corresponds with the anti rotamer, in which the bulkier alkyl group is orientated trans to the amide carbonyl group. In monoalkylated glyoxalylamides, only one set of peaks is observed, consistent with the presence of only one rotamer. Crystal structures of 5-methoxyindole-3-yl-N-tert-butylglyoxalylamide, indole-3-yl-N-tert-butylglyoxalylamide, and indole-3-yl-N-isopropylglyoxalylamide reported here reveal a syn conformation held by an intramolecular N-HO hydrogen bond.

Synthesis and Properties of a Series of 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes

The work described in this thesis revolves around the 1,1,n,ntetramethyl[n](2,11)teropyrenophanes, which are a series of [n]cyclophanes with a severely bent, board-shaped polynuclear aromatic hydrocarbons (PAH). The thesis is divided into seven Chapters. The first Chapter conatins an overview of the seminal work on [n]cyclophanes of the first two members of the “capped rylene” series of PAHs: benzene and pyrene. Three different general strategies for the synthesis of [n]cyclophanes are discussed and this leads in to a discussion of some slected syntheses of [n]paracyclopahnes and [n](2,7)pyrenophanes. The chemical, structural, spectroscopic and photophysical properties of these benzene and pyrene-derived cyclophanes are discussed with emphasis on the changes that occur with changes in the structure of the aromatic system. Chapter 1 concludes with a brief introduction to [n]cyclophanes of the fourth member of the capped rylene series of PAHs: teropyrene. The focus of the work described in Chapter 2 is the synthesis of of 1,1,n,ntetramethyl[n](2,11)teropyrenophane (n = 6 and 7) using a double-McMurry strategy. While the synthesis 1,1,7,7-tetramethyl[7](2,11)teropyrenophane was successful, the synthesis of the lower homologue 1,1,6,6-tetramethyl[6](2,11)teropyrenophane was not. The conformational behaviour of [n.2]pyrenophanes was also studied by 1H NMR spectroscopy and this provided a conformation-based rationale for the failure of the synthesis of 1,1,6,6-tetramethyl[6](2,11)teropyrenophane. Chapter 3 contains details of the synthesis of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7-9) using a Wurtz / McMurry strategy, which proved to be more general than the double McMurry strategy. The three teropyrenophanes were obtained in ca. 10 milligram quantities. Trends in the spectroscopic properties that accompany changes in the structure of the teropyrene system are discussed. A violation of Kasha’s rule was observed when the teropyrenophanes were irradiated at 260 nm. The work described in the fourth Chapter concentrates on the development of gram-scale syntheses of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) using the Wurtz / McMurry strategy. Several major modifications to the orginal synthetic pathway had to be made to enable the first several steps to be performed comfortably on tens of grams of material. Solubility problems severely limited the amount of material that could be produced at a late stage of the synthetic pathways leading to the evennumbered members of the series (n = 8, 10). Ultimately, only 1,1,9,9- tetramethyl[9](2,11)teropyrenophane was synthesized on a multi-gram scale. In the final step in the synthesis, a valence isomerization / dehydrogenation (VID) reaction, the teropyrenophane was observed to become unstable under the conditions of its formation at n = 8. The synthesis of 1,1,10,10-tetramethyl[10](2,11)teropyrenophane was achieved for the first time, but only on a few hundred milligram scale. In Chapter 5, the results of an investigation of the electrophilic aromatic bromination of the 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) are presented. Being the most abundant cyclophane, most of the work was performed on 1,1,9,9-tetramethyl[9](2,11)teropyrenophane. Reaction of this compound with varying amounts of of bromine revealed that bromination occurs most rapidly at the symmetryrelated 4, 9, 13 and 18 positions (teropyrene numbering) and that the 4,9,13,18- tetrabromide could be formed exclusively. Subsequent bromination occurs selectively on the symmetry-related 6, 7, 15 and 16 positions (teropyrene numbering), but considerably more slowly. Only mixtures of penta-, hexa-, hepta and octabromides could be formed. Bromination reactions of the higher and lower homologues (n = 7, 8 and 10) revealed that the reactivity of the teropyrene system increased with the degree of bend. Crystal structures of some tetra-, hexa-, hepta- and octa-brominated products were obtained. The goal of the work described in Chapter 6 is to use 1,1,9,9- tetramethyl[9](2,11)teropyrenophane as a starting material for the synthesis of warped nanographenophanes. A bromination, Suzuki-Miyaura, cyclodehydrogenation sequence was unsuccessful, as was a C–H arylation / cyclodehydrogenation approach. Itami’s recently-developed K-region-selective annulative -extension (APEX) reaction proved to be successful, affording a giant [n]cyclophane with a C84 PAH. Attempted bay-region Diels-Alder reactions and some cursory host-guest chemistry of teropyrenophanes are also discussed. In Chapter 7 a synthetic approach toward a planar model compound, 2,11-di-tbutylteropyrene, is described. The synthesis could not be completed owing to solubility problems at the end of the synthetic pathway.

Radiocarbon ages and pollen record of a sediment core from Lake Lyadhej-To

An 1180-cm long core recovered from Lake Lyadhej-To (68°15'N, 65°45'E, 150 m a.s.l.) at the NW rim of the Polar Urals Mountains reflects the Holocene environmental history from ca. 11,000 cal. yr BP. Pollen assemblages from the diamicton (ca. 11,000-10,700 cal. yr BP) are dominated by Pre-Quaternary spores and redeposited Pinaceae pollen, pointing to a high terrestrial input. Turbid and nutrient-poor conditions existed in the lake ca. 10,700-10,550 cal. yr BP. The chironomid-inferred reconstructions suggest that mean July temperature increased rapidly from 10.0 to 11.8 °C during this period. Sparse, treeless vegetation dominated on the disturbed and denuded soils in the catchment area. A distinct dominance of planktonic diatoms ca. 10,500-8800 cal. yr BP points to the lowest lake-ice coverage, the longest growing season and the highest bioproductivity during the lake history. Birch forest with some shrub alder grew around the lake reflecting the warmest climate conditions during the Holocene. Mean July temperature was likely 11-13 °C and annual precipitation-400-500 mm. The period ca. 8800-5500 cal. yr BP is characterized by a gradual deterioration of environmental conditions in the lake and lake catchment. The pollen- and chironomid-inferred temperatures reflect a warm period (ca. 6500-6000 cal. BP) with a mean July temperature at least 1-2 °C higher than today. Birch forests disappeared from the lake vicinity after 6000 cal. yr BP. The vegetation in the Lyadhej-To region became similar to the modern one. Shrub (Betula nana, Salix) and herb tundra have dominated the lake catchment since ca. 5500 cal. yr BP. All proxies suggest rather harsh environmental conditions. Diatom assemblages reflect relatively short growing seasons and a longer persistence of lake-ice ca. 5500-2500 cal. yr BP. Pollen-based climate reconstructions suggest significant cooling between ca. 5500 and 3500 cal. yr BP with a mean July temperature 8-10 °C and annual precipitation-300-400 mm. The bioproductivity in the lake remained low after 2500 cal. yr BP, but biogeochemical proxies reflect a higher terrestrial influx. Changes in the diatom content may indicate warmer water temperatures and a reduced ice cover on the lake. However, chironomid-based reconstructions reflect a period with minimal temperatures during the lake history.

Bulk sediment parameter of three sediment cores from permafrost lowlands, Alaska Arctic Coastal Plain

Arctic lowland landscapes have been modified by thermokarst lake processes throughout the Holocene. Thermokarst lakes form as a result of ice-rich permafrost degradation and they may expand over time through thermal and mechanical shoreline erosion. We studied proximal and distal sedimentary records from a thermokarst lake located on the Arctic Coastal Plain of northern Alaska to reconstruct the impact of catchment dynamics and morphology on the lacustrine depositional environment and to quantify carbon accumulation in thermokarst lake sediments. Short cores were collected for analysis of pollen, sedimentological and geochemical proxies. Radiocarbon and Pb/Cs dating, as well as extrapolation of measured historic lake expansion rates, were applied to estimate a minimum lake age of ~ 1,400 calendar years BP. The pollen record is in agreement with the young lake age as it does not include evidence of the "alder high" that occurred in the region ~ 4.0 cal ka BP. The lake most likely initiated from a remnant pond in a drained thermokarst lake basin (DTLB) and deepened rapidly as evidenced by accumulation of laminated sediments. Increasing oxygenation of the water column as shown by higher Fe/Ti and Fe/S ratios in the sediment indicate shifts in ice regime with increasing water depth. More recently, the sediment source changed as the thermokarst lake expanded through lateral permafrost degradation, alternating from redeposited DTLB sediments, to increased amounts of sediment from eroding, older upland deposits, followed by a more balanced combination of both DTLB and upland sources. The characterizing shifts in sediment sources and depositional regimes in expanding thermokarst lakes were therefore archived in the thermokarst lake sedimentary record. This study also highlights the potential for Arctic lakes to recycle old carbon from thawing permafrost and thermokarst processes.

Tránsito en cuerda fija : Su utilización en ámbitos educativos

El grupo de Investigación en Educación Física y Andinismo ha sido constituido en el Centro Regional Universitario Bariloche de la Universidad Nacional del Comahue como consecuencia de los estudios que en el marco de la carrera Profesorado en Educación Física (PEF) y de su orientación en actividades regionales de montaña, están siendo realizados. El objeto de esta comunicación se inscribe en la línea de trabajo que se comenzó a desarrollar en el año 2010 y a la que hemos denominado: Análisis de las prácticas de andinismo en ámbitos educativos. (Goicoechea Gaona, Palacio, 2014) En esta ocasión se trata de conceptualizar la práctica de tránsito por cuerda fija propia de la escalada. La misma forma parte de los contenidos de las asignaturas de formación docente del PEF Deportes Regionales Estivales I y II (DREI y II). Siguiendo la metodología de trabajo del grupo, se determinarán los aspectos específicos que hacen de dicha práctica un contenido de la Educación Física, es decir, resulta apropiada para ser enseñada y realizada en el ámbito educativo. De este modo damos continuidad a la tarea de sistematización de nuevas prácticas que por estar apareciendo en el contexto escolar requiere del estudio y tratamiento de especialistas en andinismo y educación

Tránsito en cuerda fija : Su utilización en ámbitos educativos

El grupo de Investigación en Educación Física y Andinismo ha sido constituido en el Centro Regional Universitario Bariloche de la Universidad Nacional del Comahue como consecuencia de los estudios que en el marco de la carrera Profesorado en Educación Física (PEF) y de su orientación en actividades regionales de montaña, están siendo realizados. El objeto de esta comunicación se inscribe en la línea de trabajo que se comenzó a desarrollar en el año 2010 y a la que hemos denominado: Análisis de las prácticas de andinismo en ámbitos educativos. (Goicoechea Gaona, Palacio, 2014) En esta ocasión se trata de conceptualizar la práctica de tránsito por cuerda fija propia de la escalada. La misma forma parte de los contenidos de las asignaturas de formación docente del PEF Deportes Regionales Estivales I y II (DREI y II). Siguiendo la metodología de trabajo del grupo, se determinarán los aspectos específicos que hacen de dicha práctica un contenido de la Educación Física, es decir, resulta apropiada para ser enseñada y realizada en el ámbito educativo. De este modo damos continuidad a la tarea de sistematización de nuevas prácticas que por estar apareciendo en el contexto escolar requiere del estudio y tratamiento de especialistas en andinismo y educación

Abundance of tintinnids in waters of the Argentine Shelf and the Drake Passage 2002-2003

The relationship between the abundance and diversity of tintinnids and the concentration of chlorophyll a (Chl a) was contrasted between neritic and oceanic waters of the SW Atlantic during autumn and summer. Chl a and tintinnid abundance and biomass reached maximum values (17.53 µg/L, 2.76 x 10**3 ind./L and 6.29 µg C/L, respectively) in shelf waters during summer, and their mean values generally differed by one order of magnitude between environments. Peaks in species richness (13) and Shannon diversity index (2.12) were found in the shelf-ocean boundary, but both variables showed nonsignificant differences between areas. Species richness correlated significantly with both Chl a and abundance. Such relationships, which followed a negative linear or quadratic function in the shelf and a positive linear function in oceanic waters, are thought to reflect either the competitive dominance of one species or a relatively wide spectrum of tintinnid size-classes, respectively.

Results of the pollen analysis of the Dyanushka peat sediments K7/P2

A 415cm thick permafrost peat section from the Verkhoyansk Mountains was radiocarbon-dated and studied using palaeobotanical and sedimentological approaches. Accumulation of organic-rich sediment commenced in a former oxbow lake, detached from a Dyanushka River meander during the Younger Dryas stadial, at ~12.5 kyr BP. Pollen data indicate that larch trees, shrub alder and dwarf birch were abundant in the vegetation at that time. Local presence of larch during the Younger Dryas is documented by well-preserved and radiocarbon-dated needles and cones. The early Holocene pollen assemblages reveal high percentages of Artemisia pollen, suggesting the presence of steppe-like communities around the site, possibly in response to a relatively warm and dry climate ~11.4-11.2 kyr BP. Both pollen and plant macrofossil data demonstrate that larch woods were common in the river valley. Remains of charcoal and pollen of Epilobium indicate fire events and mark a hiatus ~11.0-8.7 kyr BP. Changes in peat properties, C31/C27 alkane ratios and radiocarbon dates suggest that two other hiatuses occurred ~8.2-6.9 and ~6.7-0.6 kyr BP. Prior to 0.6 kyr BP, a major fire destroyed the mire surface. The upper 60 cm of the studied section is composed of aeolian sands modified in the uppermost part by the modern soil formation. For the first time, local growth of larch during the Younger Dryas has been verified in the western foreland of the Verkhoyansk Mountains (~170km south of the Arctic Circle), thus increasing our understanding of the quick reforestation of northern Eurasia by the early Holocene.

Pollen analysis of sediment profile WO1 from Wollingster See

A palynological study of a 15 m sediment core from the centre of Lake Wollingst (water depth 14,5 m) is presented. The pollen record shows 3 lateglacial thermomers, called Meiendorf, Bölling, Alleröd and the early holocene Friesland-Thermomer. The succession of forest vegetation taking place on the lake surroundings during the Holocene was typical for older moraine soils which are poor in nutrients: forest vegetation started with birch and pine, followed by hazel, oak and elm in the Boreal and by alder, lime and ash-tree in the Atlantic. Beech and hornbeam reached the area during Subboreal. However, due to the poor soils they spread out only after the Iron Age. With the deforestation during the medieval time the lake lost its character of a primeval forest lake. Lake Wollingst was oligotrophic since its origin at the end of the Pleniglacial. After medieval forest-clearing the lake has changed its quality of water particularly in connection with hemp- and flax-rotting. The modem sediments in this profile are completely disturbed. They contain reworked material, a lot of blue-green algae and remains of Bosmina longirostris indicating eutrophic conditions.

Ciliate abundance in waters of the Argentine shelf and the Drake Passage, the south-western Atlantic

Ciliates from sub-surface waters of the Argentine shelf and the Drake Passage under austral summer and autumn conditions were examined and compared for the first time. In both environments, the taxonomic structure of ciliates was related to temperature and salinity, and aloricate oligotrichs dominated in density (80%) over loricate oligotrichs, litostomatids and prostomatids, while the microplanktonic fraction prevailed in terms of biomass (90%) over the nanociliates. Myrionecta rubra was found all along the Argentine shelf only in autumn, but showed isolated peaks of abundance (10**3 ind./L) during summer. Mean values of density and biomass of total ciliates decreased ca. 2-fold from the shelf-slope to oceanic waters, while potential maximum production of aloricate oligotrichs decreased 9-fold, in relation with the drop in chlorophyll a concentration and the latitudinal decline of temperature, also reflected in maximum growth rates. Fifty percent of total ciliate abundance was represented by local increases (maximum: 20 000 ind./L and 25 µg C/L), which were spatially superimposed with ranges of seawater temperature and chlorophyll a concentrations of 10-15°C and 0.6-6 µg/L, respectively and were found in the nearby of fronts located on the shelf and the slope.

Pollen records from Bol'shoy Lyakhovsky Island, Siberia

Cryolithological, ground ice and fossil bioindicator (pollen, diatoms, plant macrofossils, rhizopods, insects, mammal bones) records from Bol'shoy Lyakhovsky Island permafrost sequences (73°20'N, 141°30'E) document the environmental history in the region for the past c. 115 kyr. Vegetation similar to modern subarctic tundra communities prevailed during the Eemian/Early Weichselian transition with a climate warmer than the present. Sparse tundra-like vegetation and harsher climate conditions were predominant during the Early Weichselian. The Middle Weichselian deposits contain peat and peaty soil horizons with bioindicators documenting climate amelioration. Although dwarf willows grew in more protected places, tundra and steppe vegetation prevailed. Climate conditions became colder and drier c. 30 kyr BP. No sediments dated between c. 28.5 and 12.05 14C kyr BP were found, which may reflect active erosion during that time. Herb and shrubby vegetation were predominant 11.6-11.3 14C kyr BP. Summer temperatures were c. 4 °C higher than today. Typical arctic environments prevailed around 10.5 14C kyr BP. Shrub alder and dwarf birch tundra were predominant between c. 9 and 7.6 kyr BP. Reconstructed summer temperatures were at least 4 °C higher than present. However, insect remains reflect that steppe-like habitats existed until c. 8 kyr BP. After 7.6 kyr BP, shrubs gradually disappeared and the vegetation cover became similar to that of modern tundra. Pollen and beetles indicate a severe arctic environment c. 3.7 kyr BP. However, Betula nana, absent on the island today, was still present. Together with our previous study on Bol'shoy Lyakhovsky Island covering the period between about 200 and 115 kyr, a comprehensive terrestrial palaeoenvironmental data set from this area in western Beringia is now available for the past two glacial-interglacial cycles.