Browsing by Subject "Kupfer"

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    Ecology of alluvial arable land polluted by copper mine tailings : new insights for restoration
    (2013) Nikolic, Nina; Böcker, Reinhard
    Mining and extraction of metals generates huge amounts of tailings waste (a mixture of water, finely ground ore rock and processing effluents, which remains after removal of mineral concentrate). Unfortunately, accidental release of mine tailings into river systems and their further deposition in floodplains, often over arable land, has been reported from many parts of the world, with environmental implications difficult to predict. Mine tailings from sulphidic metal ores combine high potential for generating soil acidity, and high concentrations of plant available heavy metals, which are the two most intractable issues in restoration of post-mining sites. On the other hand, barren land degraded by mining waste provides an exciting opportunity to reveal some important ecological principles which might not be apparent under ?normal? conditions. Understanding of the process of primary vegetation succession is in particular crucial for the practice of ecological restoration, which is increasingly seen as a preferable alternative to technical reclamation of land degraded by mining. This work addresses the two major issues relevant for ecology and restoration of alluvial arable land polluted by mining waste, which have so far been very poorly understood: Firstly, the long-term fate of contaminants and their actual impact on soil quality and crop production under true field conditions. Secondly, the process of spontaneous revegetation of barren land under the extreme soil conditions and the environmental setup considerably different from the well-studied Central European. The explorative study was undertaken on an exceptional locality created by long-term and large scale-fluvial deposition of sulphidic copper (Cu) tailings over alluvial fields in Eastern Serbia. Comprehensive surveys of spontaneous vegetation, weed assemblages and cereal crops (species cover-abundance; biomass per m2; and foliar mineral analyses), and concomitant surveys of rhizosphere soils (31 physical and chemical parameter) included 297 sampling locations throughout the polluted floodplain (flexible sampling scheme based on visual appearance of vegetation). Data were jointly analysed in a gradient approach framework by different multivariate statistical methods (ordination: NMS, PCA, CCA; classification: agglomerative clustering; group comparisons: MRPP, ISA; habitat modelling: NPMR; and, regression analysis). The results revealed exceptionally strong structure in the vegetation which was highly correlated with the measured soil properties; the regular change of vegetation and soil properties occurred along spatially explicit transects perpendicular to the river channel. The clear gradients observed in this ?field laboratory? research brought forward some new ecological patterns which had not been reported by other relevant studies so far: 1. Severe P deficiency, most likely not amenable by fertilization, is identified as the master limiting soil factor for grains under the multiple abiotic stresses caused by deposition of sulphidic Cu mining waste. Other plausible soil constraints (low pH, excessive concentrations of available Cu and Al, deficiency of N and B; P deficiency-induced increase of As uptake; competition with superior hemicryptophytic weeds), have remained in domain of a ?black-box?. 2. Frequent ploughing accelerates the substitution of high plant available Cu by nutrient deficiency (primarily P and microelements) and excessive exchangeable Al. Thus, agronomic soil quality indicated by crop yield does not improve even when Cu is leached to the background levels. The environmental consequences of intensive land use are however drastic, and increase vulnerability of these soils to further environmental hazards. On the other hand, one type of spontaneously occurring pioneer forests was shown to considerably slow down the oxidative weathering of the tailings deposits and thus prevent Cu leaching via phytostabilization. 3. Although many characteristics of cereal weed assemblages markedly change along the soil pollution gradient, the species? ability to maintain leaf P homeostasis appears to be the key adaptation underlying the observed vegetation structure. The novel associations of unusual species combinations showed a set of functional adaptations which have enabled the leaf N:P homeostasis and thus the uninterrupted survival of weed vegetation along the soil gradient. 4. The proposed conceptual model describes a highly patterned process of spontaneous revegetation of the created barren land under the severe environmental filtering. In this process, the xerothermic surrounding vegetation adapted to calcareous soils has a very limited role. Instead, primary succession relies on novel types of early vegetation which comprise not only novel combinations of species, but also the key role of species which are novel to the affected region, and do not survive outside of the polluted area. We demonstrate for the first time that pollution-induced severe nutrient deficiency can override the well-established importance of both surrounding vegetation and water level gradient for primary succession. Overall, this study implies that severe nutrient deficiency, which is often a neglected issue in studies of metal-polluted sites, can override the effects of Cu toxicity, the role of surrounding vegetation, and even the role of water level gradients, on the process of spontaneous restoration of vegetation cover. It is highly unlikely that spontaneous restoration under the current conditions would allow the reestablishment of the original (or close to original) alluvial vegetation or pre-pollution agricultural land use. Weathering of the substantial residues of sulphides, further acidification and Cu leaching is the major environmental risk; ploughing (or any mechanical soil disturbance with similar effect) of this vast marginalized area should be avoided. Maintenance of the natural flooding regime, which had, bizarrely, caused this vast degradation in the first place, is indicated important for the current spontaneous succession and warrants further research.
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    Neuartige Kupfer-katalysierte und übergangsmetallfreie Methoden zum Aufbau von Heterocyclen
    (2022) Rekowski, Szymon; Beifuss, Uwe
    Heterocycles are the backbones of numerous drugs and are therefore of great importance in medicinal chemistry. As a result, there is an inevitably high demand for methods to synthesize heterocycles. The requirements for new methods for the synthesis of heterocycles are nowadays very high, as they must not only be efficient and selective, but also sustainable. These prerequisites can be met by both transition metal-free and transition metal-catalyzed reactions. Thus, the transition metal-free preparation of a variety of different heterocycles can be achieved by radical, cationic and anionic cyclizations as well as by pericyclic reactions. Recently, the importance of electrochemical and photochemical methods in heterocyclic synthesis has been increasing very rapidly. In transition metal-catalyzed heterocycle synthesis, Pd- and Cu-catalysts in particular play a prominent role. For the Pd-catalyzed assembly of N-heterocycles, the intramolecular Buchwald-Hartwig amination is especially noteworthy. It is now known that many Pd-catalyzed reactions can also be carried out with Cu-catalysts. In view of the fact that Cu-catalysts are much cheaper due to the higher abundance of Cu, and that expensive ligands can usually be omitted to carry out Cu-catalyzed reactions, their enormous importance in heterocyclic synthesis is easy to understand. For example, many N-heterocycles can be prepared by intramolecular Ullmann reactions with excellent yields and high selectivities. Here, bisfunctionalized substrates with two centers of different reactivity play a major role. The aim of the present work was to develop new efficient and highly selective synthetic methods for the construction of relevant N- or O-heterocycles. In particular, Cu-catalyzed reactions with bisfunctionalized substrates were to be developed. The investigation included determining whether the corresponding reactions can also be carried out in the absence of transition metal catalysts. Benzodioxines and 2,3-dihydrobenzodioxines exhibit many interesting biological properties, but the possibilities available nowadays for their synthesis are limited. Therefore, the first part of this dissertation deals with the development of a new method for the diastereospecific construction of (Z)-2-arylidene-2,3-dihydrobenzodioxines (Z)-80 (Scheme 50) by reacting 3-aryl-substituted (Z)-1,2-dibromoarylpropenes (Z)-82 with catechols 83. While the model substrate (Z)-82a (R1 = Ph) can be prepared by reduction and subsequent bromination of a-bromocinnamaldehyde, the remaining substrates (Z)-82 were prepared in three steps from the corresponding benzaldehydes. Subsequent optimization of the model reaction under a wide variety of reaction conditions showed that the best results could be obtained under transition metal-free conditions. The highest yield of (Z)-80a was obtained when 1 equivalent of (Z)-82a (R1 = Ph, R2 = H) was reacted with two equivalents of 83a (R2 = H) in the presence of four equivalents of Cs2CO3 in DMF for 18 h at 140 °C. Remarkably, this transition metal-free domino reaction, which consists of an intermolecular O-allylation followed by an intramolecular O-vinylation, is highly diastereospecific: the use of (Z)-1,2-dibromo-3-phenyl-2-propene [(Z)-82a] exclusively delivers (Z)-2-benzylidene-2,3-dihydrobenzodioxines [(Z)-80a]. This high diastereospecifity was also observed in the reactions of all other substrates (Z)-82. The 2-arylidene-2,3-dihydrobenzodioxins (Z)-80 were obtained in yields up to 89%. This method tolerates different substituents on the aromatic moiety of (Z)-82 as well as different disubstituted catechols 83. DFT calculations conducted in collaboration with Prof. Bharatham, NIPER Nagar (Mohali), suggest that the intramolecular O-vinylation proceeds via an alkene intermediate rather than an alkyne intermediate. The diastereoselective conversion of the E-configured substrate (E)-82a (R1 = Ph) to the corresponding (E)-2-benzylidene-2,3-dihydrobenzodioxine [(E)-80a] supports this assumption. The second part of this work is devoted to the intramolecular Cu(I)-catalyzed cyclization of o-haloarylideneguanylhydrazone salts (E)-86 for the direct construction of N-1 unsubstituted 1H-indazoles 84 (Scheme 51). The synthesis of indazoles of this type is of particular interest to medicinal chemistry because they form the backbone of some important anticancer drugs. Substrates (E)-86 were prepared by condensation of o-halobenzaldehydes with aminoguanidine hydrochloride in yields up to 90%. Subsequent cyclization using 10 mol% CuI, 30 mol% DMEDA and 0.5 equivalents of Cs2CO3 afforded the 1H-indazoles 84 in yields up to 75%. The reactions were carried out at 120 °C in DMF for 5 h in a sealed glass tube. The method tolerated a full range of substituents on the aromatic moiety of the substrates. Based on DFT calculations done in collaboration with Prof. Bharatham, NIPER Nagar (Mohali), it is reasonable to assume that E/Z isomerization of substrate 86 occurs first, followed by metal complexation with subsequent C,N bond formation. The final hydrolysis of the 1H-indazole-1-carboximidamide yields the N-1 unsubstituted 1H-indazole 84.
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    The importance of soil microorganisms and cover crops for copper remediation in vineyards
    (2014) Mackie, Kathleen; Kandeler, Ellen
    The historical use of copper fungicides, as a plant protection agent, has moderately polluted agricultural topsoils across Europe. Organic agriculture, in particular, continues to be limited to the use of copper fungicides due to a lack of permitted alternative plant protection agents. In recent years, the effects of copper accumulation in the soil have been observed. Studies on the negative effects of copper in agricultural soils show a decrease in ecosystem services, which rely on macro- and micro-organisms. Thus, there is the question of how to remediate copper polluted crop fields. Although this topic has more recently been investigated in the laboratory, currently, there are no experiments available in the field. Viticulture is one of the largest perennial crops in Europe that utilize copper fungicides. Therefore, this dissertation was designed to investigate copper remediation strategies in vineyards, in order to best understand potential solutions for a growing problem, as well as their effect on ecosystem services. Understanding the reaction of and support by soil microorganisms will help determine which strategy has the best potential. The main project was implemented using two field experiments, each of which analyzed copper availability, microbial abundance, function and community composition to determine the overall outcome of copper remediation. The dissertation is presented in four papers. The first paper is a review on copper in vineyards, which focused specifically on cutting-edge remediation strategies currently being studied. This paper also provided information on knowledge gaps in the literature. The second paper showed the spatial distribution of copper and soil microorganisms at the plot scale, providing a better understanding of copper and microbial distribution as well as a foundation for subsequent papers. The third paper analyzed copper phytoextraction by single species and mixed species cover crop plots and the microbial community that may support it. The fourth paper was aimed at observing the ability of biochar and biochar-compost to immobilize copper and improve ecosystem services. The studies utilized classic soil biological methods (enzyme activities, microbial C and N, ergosterol) and modern molecular techniques (quantitative polymerase chain reaction (qPCR) of 16S rRNA and taxa specific bacteria genes and phospholipid fatty acid analysis (PLFA)) as well as determination of chemical soil properties and copper fractions.