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.
Antimicrobial and Heavy Metal Sequestration Capacities of Graphene Polymer Nanofilms
Membrane bioreactors (MBR) are important components in the production of effluent in wastewater treatment systems. However, MBR are susceptible to biofouling, a process by which bacteria colonize the surface of the membrane in contact with water. Graphene could be a solution to biofilm formation. In this study, the graphene polymer nanocomposite’s antimicrobial and heavy metal removal properties and the mechanisms behind the properties were investigated. Five different films of nanocomposites with a form of graphene and a polymer were synthesized: Graphene, Graphene Oxide, PVK-GO, PVK-G, PVK. A Büchner funnel and a vacuum pump were used to coat membrane filters with solutions of each nanomaterial. Using the Büchner funnel, E. coli and B. subtilis bacteria were filtered through the filter and both the filtrate and the filter were examined for bacterial content. Similarly, a Pb2+ solution was filtered through the coated filters and percentage removal of the ion was calculated using Atomic Absorbtion Spectrometry. Further analysis from SEM data, ATR-IR, and an Oxidative Stress test revealed that the PVK-GO nanocomposite inactivates bacteria by causing oxidative stress and the carboxyl group binds to lead ions. PVK-GO was most effective at removing the highest percentage of heavy metal and inactivated the most bacteria and displayed the most antimicrobial properties. PVK-GO coatings provide an efficient and economical alternative to the current wastewater industry standard and can save millions of dollars and reduce environmental waste. Also, the coatings have applications in indwelling medical devices and can reduce the risks associated with biofilm formational and bacterial infections.
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.