Domino syntheses of bioactive tetronic and tetramic acids

Natural products containing tetronic acid or tetramic acid moieties continue to attract the interest of chemists, biologists, and physicians due to their challenging structures and to the wide range of biological activities they display. This review portrays the structural varieties of tetronic and tetramic acids and the spectrum of possible therapeutically relevant effects in man for exemplary derivatives. Their biosynthetic origin from α-amino and α-hydroxy acids is briefly discussed as is the relationship between their structures and their modes of interaction with biochemical effectors such as metal cations or enzymes. A short overview of laboratory syntheses of the heterocyclic core structures of tetramic and tetronic acids is provided with an emphasis on those emulating the biosynthesis. A synthesis from the α-amino or α-hydroxy esters and the cumulated phosphorus ylide Ph₃PCCO based upon a domino addition–intra-Wittig alkenation sequence is presented with applications to the preparation of the antibiotics reutericyclin and tenuazonic acid, the cytotoxic melophlin B, and the enzyme inhibitor RK-682. Procedural advantages of immobilizing either starting component by attaching it to a resin and its exploitation in the parallel synthesis of libraries of potential drug candidates are described. The basic domino reaction can even be extended by further C–C bond forming steps when starting from suitable α-hydroxy or α-amino allyl esters. Depending on the chosen reaction conditions, bioactive intermediates of formally three to seven step long cascades can be obtained. Among them, herbicidal 3-alkyltetronic acids and lactone endoperoxides with antiplasmodial activity exceeding that of the natural antimalarial lead artemisinin. Hence, this domino reaction gives access to diversely functionalized derivatives of tetronic and tetramic acids. As it can also be ported to solid phase, it is ideally suited for parallel and combinatorial processing. Future developments might include running such domino sequences in continuous mode in arrays of “labs on microchips”.     

Impr?gnierte Filterpapiere für die Wasserreinigung

Mit impr?gnierten Filtermaterialien ist es m?glich, die Schwermetalle Blei, Kupfer und Nickel sowie Arsen durch Sorption bzw. chemische Bindung aus Wasser zu entfernen. Bei 24stündiger Einwirkungszeit wurden Reduktionsraten von 97% bis>99,9% erreicht.     

Use of metal-reducing bacteria for bioremediation of soil contaminated with mixed organic and inorganic pollutants

Mixed contamination by organic and inorganic compounds in soil is a serious problem for remediation. Most laboratory studies and field-scale trials focused on individual contaminant in the past. For concurrent bioremediation by biodegradation and bioleaching processes, we tested metal-reducing microorganism, Geobacter metallireducens. In order to prove the feasibility of the coupled process, multiple-contaminated soil was prepared. Mineralogical analyses have shown the existence of labile forms of As(V) as amorphous and/or weakly sorbed phases in the secondary Fe oxides. In the biotic experiment using G. metallireducens, biodegradation of toluene and bioleaching of As by bacteria were observed simultaneously. Bacteria accelerated the degradation rate of toluene with reductive dissolution of Fe and co-dissolution of As. Although there have been many studies showing each individual process, we have shown here that the idea of concurrent microbial reaction is feasible. However, for the practical use as a remediation technology, more details and multilateral evaluations are required in future studies.

     

Metal fractionation in a contaminated soil after reforestation: Temporal changes versus spatial variability

In a lysimeter experiment, topsoils were polluted with filter dust from a non-ferrous metal smelter and then planted with trees. Sequential extractions were used to follow the changes in metal fractionation of Cu, Zn, Cd, and Pb over 42 months. Plant-free and uncontaminated soils served as reference. In the contaminated and planted soils, the largest changes in speciation occurred within the first 6 months. The relative amounts of certain metal fractions were linearly related to each other, indicating systematic redistribution between fractions. The results indicate that under natural conditions with high heterogeneity in total metal contents spatial differences are more important than temporal variations in determining the fractionation and solubility of metals in contaminated soils. In the absence of plants soils exhibited a completely different fractionation 30 months after pollution, with much higher proportions in the more refractory phases. This suggests that plant activity kept the metals in a more soluble form.     

Landfill aeration within the scope of post-closure care and its completion

The time frame required for post-closure care of Municipal Solid Waste (MSW) landfills is often assessed over several decades or centuries. One possibility to significantly shorten this period and, at the same time, improve the emission behavior exists with in situ aeration. Positive effects in connection with this method for biological stabilization have been investigated and published elsewhere. However, until today neither generally accepted monitoring guidelines nor completion criteria have been defined. With the paper on hand the authors propose a methodology for the assessment of both, total and remaining stabilization periods for aerated landfills. The central component of this methodology is a carbon balance. The latter is based on a detailed waste characterization in combination with online monitoring of the emissions (gas and leachate). The methodology is exemplarily demonstrated by means of data derived from a full scale project in Northern Germany. Here it could be shown that the predicted aeration period of approximately 6.4 years was sufficient to bio-stabilize the landfill.Furthermore, proposals for the completion of landfill aeration are presented. In this connection, carbon balance is of particular importance since the amount of biodegradable organic carbon mainly determines the emission potential. Additional parameters, aiming at a validation of the state of biological stabilization achieved during aeration are proposed and described.