Reactions of Bis(oxy)enamines with Transition Metal Halides
Synthesis of halooximes has attracted much attention given their importance as precursors to proline derivatives1, unnatural amino acids2 and a host of alkaloids3. Halooximes have numerous industrial and biological applications 4, for example oxime ethers increases specific channel opening activities, acting as potential targets in drug treatment for various diseases 5, most adrenergic β-receptor blocking compounds also conform to the structure of oxime ethers 6. They also have vitro antifungal activities against certain plants7. A known method for the synthesis of 3 using Me3SiX as a Lewis acid, via intermediate enamines with acyclic/ cyclic bis(oxy)enamines, gives yields between 21-68%. Low yield stems from lack of reaction specificity2. In this work, we investigate coupling nitrogen-oxides with CoBr2 to synthesise halooximes in high yield. Initial cyclic/ acyclic bis(oxy)enamines were prepared by reacting 1 equiv. nitro compound with 2.4 equiv. in excess of dichloromethane under argon atmosphere at a temperature of 0ºC. 2.2 equiv. of TMS-Br was further added and left to stir till thermal equilibrium with room conditions. The cyclic/ acyclic bis(oxy)enamine was isolated upon aqueous work-up, filtration and evaporation. Synthesis of halooximes was carried out by reacting 8mL to 1mmol equiv. of THF and 2 equiv. of CoBr2 under argon atmosphere and left to stir till CoBr2 dissolves. 2mL to 1mmol equiv. of CH2Cl2 was added to 1 equiv. of bis(oxy)enamines. The reaction mixture was left to stir at room temperature for 2 hours, after which aqueous work-up, filtration and evaporation were carried out. Our results are summarized in Table 1. We also obtained relatively high percentage yields for the direct synthesis of bromooximes from cyclic nitronates via a one-pot procedure: Low yield stems from lack of reaction specificity2. In this work, we investigate coupling nitrogen-oxides with CoBr2 to synthesise halooximes in high yield. Initial cyclic/ acyclic bis(oxy)enamines were prepared by reacting 1 equiv. nitro compound with 2.4 equiv. in excess of dichloromethane under argon atmosphere at a temperature of 0ºC. 2.2 equiv. of TMS-Br was further added and left to stir till thermal equilibrium with room conditions. The cyclic/ acyclic bis(oxy)enamine was isolated upon aqueous work-up, filtration and evaporation. Synthesis of halooximes was carried out by reacting 8mL to 1mmol equiv. of THF and 2 equiv. of CoBr2 under argon atmosphere and left to stir till CoBr2 dissolves. 2mL to 1mmol equiv. of CH2Cl2 was added to 1 equiv. of bis(oxy)enamines. The reaction mixture was left to stir at room temperature for 2 hours, after which aqueous work-up, filtration and evaporation were carried out. Our results are summarized in Table 1. We also obtained relatively high percentage yields for the direct synthesis of bromooximes from cyclic nitronates via a one-pot procedure:
Microbial diversity in the Mediterranean hypersaline deep-sea lake Tyro
1. Purpose of the research Characterization of bacterial and viral diversity of brine Tyro using molecular methods of identification. 2. Procedures For bacteria: 1. Amplification or multiplication of 16S rRNA gene (one of the most conservative gene) by polymerase chain reaction (PCR). 2. Agarose gel electrophoresis and purification of PCR product 3. Ligation of purified PCR product into the vector pGEM-T 4. Transformation of plasmids containing an insert into competent cells E.coli XB1 5. Blue-white selection (we need white colonies, they contain the insert of interest) 6. Isolation of plasmids containing an insert of interest 7. Sequencing of inserts 8. Bioinformatics analysis: matching homologues from GeneBank database, construction of phylogenetic trees, statistical analysis. For viruses: The same methods were used for gp23 gene, which code a major head protein of T-even bacteriophages; to amplify gp23 gene a special set of primers was used, along with a standard cloning protocol described above. 3. Data 1) Two libraries of clones were obtained during analysis: lake Tyro (24 operational taxonomic units (OTUs), 10 classes) and sea water (6 OTUs, 2 classes of eubacteria). 2) The most abundant classes were: gamma-, delta-, epsilon- Proteobacteria, which is in agreement with previous reports about bacteria in brines of Mediterranean Sea. 3) The number of clones was not sufficient to obtain stable estimates of diversity, the analysis require additional data. 4) The diversity of bacteria was unexpectedly high in brine but not in the seawater, due to higher and more diverse ion composition. 5) Most of the detected bacteria in the deep-sea lake belonged to the previously undescribed (18,75%) bacteria or had unusual metabolism (43,75%). 4. Conclusions The analysis demonstrated unexpectedly high diversity of halophilic bacteria inhabiting Tyro lake. Most of bacteria presented in brine water had unique and uncommon characteristics based on information about its closest relatives. Therefore, the deep-sea hypersaline lakes of Mediterranean Sea have great potential for further investigations. Preliminary results of diversity of viruses of Tyro lake were obtained during analysis, more complete description is coming soon.
USING IRON-STEEL INDUSTRIAL WASTE SLAGS AS A FERTILIZER
Steel slag, is received from iron and steel production facilities in Turkey, and is up to 25-30% from steel production. These couldn’t have been reclamation for any field of use and free stored in nature. When the structure of this slag examined, it was contained metallic formation (Fe2O3, Al2O3, MnO2, MgO2 etc.) and oxide compositions (SiO2, CaO2 etc.). The aim of this project is investigate metallic content of steel slag used as fertilizer in plants. For this purpose, slag is used to determine the physical and chemical characterization. Then, it is separated from metallic content by using shaking table and multi gravity separative (MGS) method. After these procedures, there are determinate 6 groups with different densities and different grit size. Element analysis was made of these groups by atomic absorption spectrophotometer (AAS) and ICP-OES system. In addition, mineral analysis was determined by XRD device. Thus, within each group minerals have been identified. Slag-soil mixture was prepared for determination the highest yield of using six different slag groups as fertilizer in the plant. Thus, corn crops were grown in different combinations. Then harvested corn plants and done soil analysis of the plants. As a result of experiments, percentage of the most effective slag-soil composition for corn was determined. The highest yield in the slag pot was determined the rate of %12.5 and coarse-grained. Ideally, the slag content found to be chinerals such as merwinite (3CaO-MgO-2SiO2), akermanite (2CaO-MgO-2SiO2), gehlenite (2CaO-Al2O3-SiO2). Thus, it was detected the steel slags can be used as feed material for plants. Hence by maintaining the ecological balance economic contribution to the country was achieved.
Geo Air
1. Purpose: The purpose of this project was to design a theoretical tempered-air system to be integrated into an existing heating system in a home equipped with an air-to-air heat pump. This was to overcome the cost and environmental challenges of heating in cold climates as well as provide an environmentally friendly air-conditioning system in the summer at little to no cost. 2. Procedure: In the winter of 2010 an underground high-density polyethylene (HDPE) pipe (10cm diameter, and 30.5m length) was buried 2.5m underground around the footings of a new residential project. A fan with a flow of 3.4m³/min was attached to the pipe outside, and used to push air underground through the pipe and into the house. The ambient and incoming air temperatures as well as the date and time were recorded daily using a temperature probe with an error margin of ±0.1ºC throughout the summer and winter seasons of 2011. This data was then plotted and analyzed. A number of options to best extract thermal energy for potential use for heating and cooling were examined. Design components were selected to create an air chamber for an air-to-air heat pump to increase its coefficient of performance (COP). 3. Data: Graph 1 Graph 2 Winter Graph (Graph 1): The blue line represents the outdoor ambient temperature and the orange line represents the temperature of the tempered air. These are both arranged chronologically. The grey lines represent one standard deviation on either side of the incoming temperatures. The ambient temperatures vary dramatically, while the incoming temperatures remain quite stable. The lowest recorded temperature was about -9.0ºC, at which point the temperature exiting from the underground pipe was about 10.5ºC. Summer Graph (Graph 2): With dramatically varying ambient temperatures, the temperature of the incoming air consistently stays between 11.1 and 16.2ºC. The highest recorded outdoor temperature was about 30.0ºC, while the incoming temperature at that point was about 15.5ºC. This cold air was used as air conditioning.