Light as energy source in chemical reaction. New synthesis of valuable dithienylacetylenes
Photochromism (from Greek φωζ photo “light” and χρωμα chroma “colour”) is determined as reversible transformation between two chemical species, induced by action of light [1]. Herewith, initial form and photoinduced isomer have different physical and chemical properties. The phenomenon is attractive for the design of hi-tech materials, including optical memory elements and molecular switches. Diarylethenes is the most promising class of organic photochromic compounds due to outstanding thermal stability of both isomers and high photostability [2]. The size of so-called ethene bridge significantly affects the photochromic reaction. The photochromic diarylethenes with 4-, 5-, and 6-membered cyclic ethene bridge are known, but there is no example with 3-membered bridge. In this study we report a new approach towards dithienylacetylenes 3 that include the synthesis of diarylcyclopropenones 2 via Friedel-Crafts alkylation of heterocyclic compounds 1 with tetrachlorocyclopropene and following UV-irradiation. It was found that the diarylethenes 2 do not display photochromic properties, but they undergo quantitative photoelimination of carbon monoxide upon UV-irradiation resulting in dithienylacetylene 3. Thus, we have proposed a new synthetic two-step approach to dithienylacetylenes 3 [3], which could be useful synthons in synthesis of photochromic diarylethenes with various ethene bridges.
Reactivity of styrylmalonates as synthetic equivalents of Donor–acceptor cyclopropanes with aldehydes in the presence of BF3•Et2O
Donor–acceptor cyclopropanes (DACs), which can act as sources of 1,2- and 1,3-zwitterions in the presence of Lewis acids, are widely used in organic synthesis for the preparation of various carbo- and heterocyclic compounds, including natural compounds and their analogues. To date, many types of DACs reactivity have been identified. However, the chemistry of styrylmalonates (isomers of DACs, which can be easily generated from DACs) is almost undescribed and has a powerful synthetic potential. The use of styrylmalonates as synthetic equivalents of DACs allows us cardinally change the known reaction pathways of DACs. In this work, a new strategy for cascade assembly of substituted pyrenes based on the reactions of styrylmalonates with aldehydes in the presence of BF3•Et2O has been developed. Generation of formal 1,2-zwitterionic intermediates owing to complexation of dicarboxylate groups with BF3•Et2O is the driving force of the reaction discovered. This method makes it possible to assemble pyrenes or 5,6-dihydro-2H-pyran-2-ones in one synthetic stage from readily available starting compounds with high regio- and diastereoselectivity, and use these pyrenes in futher reactions. We’ve optimized conditions of the reaction and synthesized a number of various substituted pyrenes. Moreover, the reaction shows good results with various aromatic and heteroaromatic substituents. Pyrenes can be easily purified by crystallization. Every product was obtained selectively and determined by full set of physical-chemical methods, including X-ray analysis. 5,6-dihydro-2H-pyran-2-one skeleton is found in various natural compounds demonstrating a broad spectrum of biological activity, such as antiviral and antineoplastic.
Neolema ogloblini- An agent in the biological control of Tradescantia
Tradescantia (Tradescantia fluminensis) is the worst weed in New Zealand. By smothering and shading out seedlings, Tradescantia prevents forest regeneration. Current control methods are ineffective and simultaneously cause harm to native forest. In 2011 Neolema ogloblini, a Brazilian beetle was introduced into New Zealand as a biological control for Tradescantia. To be successful in New Zealand, a country with different environmental factors, the beetles’ ranges of preference (temperature and light intensity) had to be investigated. A gender specific trait also identified, to enable desired sex ratios within founding populations to be selected. [18] This would ensure that the beetles are not released in areas of physiological stress, and can be optimised to have the greatest impact on Tradscantia. To establish how the intensity of light affects the distribution and amount of Tradescantia eaten by N.ogloblini a choice chamber investigation was conducted. Different layers of shade cloth provided a range of light intensities 150-3450Lux (likely to be found under forest canopy where Tradescantia is problematic). Thirty beetles of a range of sizes and approximately same maturity were randomly distributed through the chambers. Each chamber contained a shoot of Tradescantia with 5 leaves. After a 24hour period the number of beetles in each chamber were counted and the amount of surface area of the leaves eaten measured. The effect of temperature on the amount of leaf surface area eaten was investigated by selecting 90 beetles of a range of sizes and withholding food for 24hours. Five beetles were placed in each of three containers containing two leaves. Each trial container was precooled/warmed to the test temperature before the beetles were added. Leaves of a similar size, shape, mass and maturity were used. All leaves were genetically identical and collected from the same location. Sets of three containers were held in the dark at the following temperatures for 24hours: 9°C, 15°C, 20°C, 25°C, 30°C and 35°C. The surface area of leaf eaten at each temperature (mm2) was calculated. Lastly, microscopic dissections were conducted, using 32 beetles ranging in size, to establish if length (measured from the top of the head to the base of the abdomen) could be used as a phenotypic marker to identify beetle gender. While only a very weak positive relationship between increasing light intensity and the number of beetles was found a significantly higher area of leaf was eaten at a light intensity of 3450Lux compared to 150Lux. The amount of leaf area eaten is significantly reduced at temperatures of 15˚C and below, and significantly increased at 35˚C. There is no significant difference in the amount of leaf area eaten when comparing temperatures between 20-30˚C. Females have on average a larger body length (median=4.92mm) than the males (median=4.215mm). Therefore, sites with warmer temperatures in dappled light conditions (3450Lux) should be prioritised for the release of N.ogloblini, as this is the location in New Zealand at which their use as a biological control will be optimised. Beetle length can be confidently used to select desired gender ratios.
Development of a compact, self-stabilizing handheld camera mount
My purpose of the Research was build a small, compact device for the GoPro, which minimizes shocks that are typically caused by running and makes the video stable. The device must fit into a backpack and must be designed for the GoPro. This scenario raised two central questions for me: Which laws of physics are used for the stabilization of the camera? How can those laws of physics constructively be transformed into a working device? I have built four prototypes. To know which prototype was the best, I compared them and gained data into diagrams. The result with the last prototype was very impressive and encouraging, whether your are walking, running or skiing, the videos were no longer shaky. My final prototype consisted of a hollow tube which extended vertically. My conclusions: First the handheld camera mount mustn't be too light, as the inertia of the device is too low. Second it mustn't be too heavy, because you normally have to hold it over a certain time interval. Inertia as well as lever principal were essential to produce a smooth video. The most difficult part to build was the fully gimbaled suspension because it requires as little friction as possible and it must be precise and solid.