Synthetic and structural studies of permethylscandocene and permethyltantalocene derivatives

Cp*_2Sc-H reacts with H_2 and CO at -78°C to yield Cp*_2ScOCH_3. A stepwise reduction of CO to an alkoxide is observed when CO reacts with Cp*_2ScC_6H_4CH_3-p to give the η^2-acyl Cp*_2Sc(CO)C_6H_4CH_3-p, which then reacts with H_2 to produce Cp*_2ScOCH_2C_6H_4CH_3-p. Cp*_2ScCH_3 and Cp*_2ScH(THF) react with CO to give unchar- uncharacterizable products. Cp*_2ScH and Cp*_2ScCH_3 react with Cp_2MCO (M = Mo, W) to give scandoxycarbenes, Cp_2M=C(CH_3)OScCp*_2, while a wide variety of Cp*_2ScX (X = H, CH_3, N(CH_3)_2, CH_2CH_2C_6H_5) reacts with CpM(CO)_2 (M = Co, Rh) to yield similar carbene complexes. An x-ray crystal structure determination of Cp(CO)Co=C(CH_3)- OScCp*_2 revealed a µ^2: η^1, η^1 carbonyl interaction between the Co-CO and Sc.

CO_2 inserts cleanly into Sc-phenyl bonds at -78°C to produce a carboxylate complex, Cp*_2Sc(O_2C)C_6H_4CH_3-p. The structure of this compound was determined by x-ray crystallographic techniques.

Excess C_2H_2 reacts with Cp*_2ScR (R = H, alkyl, aryl, alkenyl, alkynyl, amide) at temperatures below -78°C to form the alkynyl species Cp*_2Sc-C≡C-H, which then reacts with the remaining acetylene to form polyacetylene. Cp*_2Sc-C≡C-H further reacts to yield Cp*_2sc-C≡C-ScCp*_2. This unusual C_2 bridged dimer was characterized by x-ray crystallography.

Attempts were made to model the C-N bond breaking step of hydrodenitrogenation by synthesizing Cp*_2TaH(η^2-H_2C=N(C_6H_4X)) and studying its rearrangement to Cp*_2Ta(=N(C_6H_4X))(CH_3). The 1,2 addition/elimination reactions of Cp*_2Ta(η^2- H_2C=N(CH_3)H and Cp*_2Ta(=X)H (X=O, S, NH, N(C_6H_5)) were investigated. Cp*_2Ta(=NH)H was found to react with D_2 to give Cp*_2Ta(=ND)H, implying a nonsymmetric amide-dihydride intermediate for the addition/elimination process. Cp*_2Ta(=S)H and H_2O equilibrate with Cp*_2Ta(=O)H and H_2S, which allowed determination of the difference in bond strengths for Ta=O and Ta=S. Ta=O was found to be approximately 41 kcals/mole stronger than Ta=S.

Constraining the interpretation of 2-methylhopanoids through genetic and phylogenetic methods

Hopanoids are a class of sterol-like lipids produced by select bacteria. Their preservation in the rock record for billions of years as fossilized hopanes lends them geological significance. Much of the structural diversity present in this class of molecules, which likely underpins important biological functions, is lost during fossilization. Yet, one type of modification that persists during preservation is methylation at C-2. The resulting 2-methylhopanoids are prominent molecular fossils and have an intriguing pattern over time, exhibiting increases in abundance associated with Ocean Anoxic Events during the Phanerozoic. This thesis uses diverse methods to address what the presence of 2-methylhopanes tells us about the microbial life and environmental conditions of their ancient depositional settings. Through an environmental survey of hpnP, the gene encoding the C-2 hopanoid methylase, we found that many different taxa are capable of producing 2-methylhopanoids in more diverse modern environments than expected. This study also revealed that hpnP is significantly overrepresented in organisms that are plant symbionts, in environments associated with plants, and with metabolisms that support plant-microbe interactions; collectively, these correlations provide a clue about the biological importance of 2-methylhopanoids. Phylogenetic reconstruction of the evolutionary history of hpnP revealed that 2-methylhopanoid production arose in the Alphaproteobacteria, indicating that the origin of these molecules is younger than originally thought. Additionally, we took genetic approach to understand the role of 2-methylhopanoids in Cyanobacteria using the filamentous symbiotic Nostoc punctiforme. We found that hopanoids likely aid in rigidifying the cell membrane but do not appear to provide resistance to osmotic or outer membrane stressors, as has been shown in other organisms. The work presented in this thesis supports previous findings that 2-methylhopanoids are not biomarkers for oxygenic photosynthesis and provides new insights by defining their distribution in modern environments, identifying their evolutionary origin, and investigating their role in Cyanobacteria. These efforts in modern settings aid the formation of a robust interpretation of 2-methylhopanes in the rock record.

An annotated bibliography of aquatic sediment traps and trapping methods

This annotated bibliography is intended to give as reasonably complete a review of the existing literature as possible, and to offer some practical guidance in the selection and operation of sediment traps in future monitoring programmes.

Study of thin-film SO2 gas sensors by photometric and ellipsometric methods

Pt-, Pd-, and Zr-doped SnO2 thin films and dopant-free VOx films were fabricated by planar magnetron sputtering. Tests for sensitivity to SO2 for all samples were conducted at 180 degreesC, and the sensitivities were investigated ex situ with photometric and ellipsometric methods at room temperature. It was found that the optical sensitivities as well as the sensitive wavelength region for SnO2 films could be tuned by doping. The Pd-doped SnO2 films had good sensitivity in the visible range, and the Zr-doped in the near IR. The dominant sensitive wavelength region for VOx films fell into the visible range, and the ratio of the sensitivity in the visible to that in the near IR increased with O-2/Ar in the depositing atmosphere. (C) 2001 society of Photo-Optical instrumentation Engineers .

Assessing trends in the density of Atlantic croaker (Micropogonias undulatus): a comparison of passive acoustic and trawl methods

Using data collected simultaneously from a trawl and a hydrophone, we found that temporal and spatial trends in densities of juvenile Atlantic croaker (Micropogonias undulatus) in the Neuse River estuary in North Carolina can be identified by monitoring their sound production. Multivariate analysis of covariance (MA NCOVA) revealed that catch per unit of effort (CPUE) of Atlantic croaker had a significant relationship with the dependent variables of sound level and peak frequency of Atlantic croaker calls. Tests of between-subject correspondence failed to detect relationships between CPUE and either of the call parameters, but statistical power was low. Williamson’s index of spatial overlap indicated that call detection rate (expressed by a 0–3 calling index) was correlated in time and space with Atlantic croaker CPUE. The correspondence between acoustic parameters and trawl catch rates varied by month and by habitat. In general, the calling index had a higher degree of overlap with this species’ density than did the received sound level of their calls. Classification and regression tree analysis identified calling index as the strongest correlate of CPUE. Passive acoustics has the potential to be an inexpensive means of identifying spatial and temporal trends in abundance for soniferous fish species.

Drought frequency analysis for California from observed, synthetic, and proxy data

Drought frequency analysis can be performed with statistical techniques developed for determining recurrence intervals for extreme precipitation and flood events (Linsley et al 1992). The drought analysis method discussed in this paper uses the log-Pearson Type III distribution, which has been widely used in flood frequency research. Some of the difficulties encountered when using this distribution for drought analysis are investigated.

A method for identifying scope and assumptions in developing and selecting methods and tools

This technical report describes a practical method consisting of a checklist and a supporting techniques for those planning or just starting to develop or select design tools and methods. The method helps to summarize and illustrate the envisaged tool or method by identifying its scope and the underlying assumptions. The resulting tool or method description clarifies the problem that is addressed, the approach and the possible implications, and can thus be used by a variety of people involved in assessing a tool or method in an early stage. For the developers themselves the method reveals how realistic the envisaged method or tool is, and whether the scope has to be narrowed.

An assessment of handling and processing methods used for the shrimp fishery by-catch in Kalpitiya, Sri Lanka

The by-catch from the shrimp trawl fishery in Kalpitiya is mainly used for the production of dried fish, which provides an additional source of income for fishermen in the area. It has been observed that current handling practices along the value addition chain are responsible for the poor quality and low price of the end product. This study was aimed at identifying the shortcomings in such handling practices by fishermen and dried fish producers and assessing the quality of shrimp fishery by-catch along the processing chain in order to recommend more efficient utilization methods that will improve the quality of the end product. Fresh fish, dried fish and harbour water samples were tested for total coli forms, faecal coliforms, E. coli and Salmonella in order to assess their microbial quality: In addition, standard plate counts (SPC) of fish samples were also carried out. A survey was carried out from July-October 2006 at Kalpitiya, using a pre-tested questionnaire to collect information from individuals who have been engaged in dried fish processing. Average values obtained for freshly landed and dried fish respectively, were, SPC 9.88x10 super(5) CFU/g and 30.43x10 super(5) CFU/g, total coliforms 23.05 and 24.23 MPN/g and fecal coliforms 8.28 and 9.00 MPN/g. These values exceed the recommendations in the SL standards. A quarter of the landed fresh fish and 38% of dried fish from the producers were positive for E. coli and thus failed to show required end product quality. SPC of harbour water was 14.35x10 super(6) CFU/ml and all samples were found to be contaminated with E. coli. None of the fishermen and dried fish producers were satisfied with the quality of the end product. The reasons for poor quality as indicated by them were: limited availability of ice (75%), lack of infrastructure facilities (65%), uncertainty of markets (52%), lack of emphasis on quality (47%) and poor access to available technologies (41%). Respondents to the questionnaire also identified: unavailability of potable water, insulated boxes, good landing jetty, racks for drying fish, poor cold storage facilities and limitations in dried fish storage facilities, as further factors leading to the loss of quality in their products. Results demonstrate that improvements to the infrastructure facilities and conducting of proper awareness programmes on handling practices could lead for improvements in the quality of value added products prepared from the shrimp fishery by-catch at Kalpitiya.