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Synthetic routes to aza and diaza bioisosteres related to the anthracene-9,10-dione, mitoxantrone, have been developed. The antitumor properties of these chemotypes are compared with those exhibited by the corresponding carbocyclic analogues. The sensitivity of the expressed cytotoxicities on the position(s) of the nitrogen atom(s) are discussed in terms of potential cellular targets. Several analogues show potential for clinical evaluations.
Toxic compounds which belong to PAHs are generated during all types of combustion of fuels and other substances as well as a result of natural processes (mineralisation). Products which appear during the above processes eventually reach soil, where they accumulate. The objective of this study has been to evaluate the effect of anthracene and pyrene accumulated in soil on yield, concentration of macronutrients (N, P, K, Mg, Ca, Na) and their uptake by cv. Vilmorin butter lettuce (Lactuca sativa L.) grown under the minimum and 3-fold enriched abundance of substrate. A pot experiment in four replicates was carried out twice in a greenhouse at the University of Warmia and Mazury in Olsztyn, in the spring of 2007 and 2008. Supplementary fertilisation was applied before planting butter lettuce. At the first rate of fertilisation, nitorgen was introduced in a full dose before planting lettuce, but at the triple rate of nutrients in substrate, it was divided into 2/3 of the dose before planting and the remaining 1/3 applied to soil 10 days after planting. Soil contamination with anthracene (ANT) and pyrene (PYR) or their mixture started 10 days after planting lettuce. Soil application of the two PAHs was performed 5 times at five-day intervals until the end of the growing season of lettuce. Determination of macronutrients (N, P, K, Mg, Ca, Na) was accomplished with standard methods after mineralisation (H2SO4 + H2O2) of the plant material dried at 60oC. The determinations were peformed in comparison to certified material (CTA-VTL-2). Increasing the abundance of substrate in nutrients (N, P, K, Mg, Na, Cl) by three-fold led to a 13.7% increase in yield of lettuce heads. The PAH compounds present in the substrate depressed lettuce yield. This tendency was more evident when anthracene rather than pyrene contaminated soil. ANT and PYR depressed the concentration of nitrogen but raised the concentration of calcium in substrate less abundant in nutrients.
The capacity of anthracene uptake by plants of two varieties of pea: Kwestor and Sześciotygodniowy, from soil and its effect on growth and development of the plants were determined in a model experiment. The anthracene levels applied were 0.1 and 0.3 g/kg of soil and its concentrations in the soil and the plants were determined with the absorption and emission spectrophotometry. After harvest, anthracene was present in all pea plant organs with its greatest amount in the roots. Depending on plant variety, age and the applied concentration of anthracene, changes in the stem and root length, biomass, and dry matter as well as the course of the proper leaf and nodule formation, were observed during the vegetation period.
PAHs (polycyclic aromatic hydrocarbons) are widespread in the natural environment. They are suspected to have mutagenic, carcinogenic and teratogenic effect on our organisms. Production of wholesome and high quality vegetables does not necessarily involve selection of adequate farmlands or substrates used for vegetable growing. Combustion processes are a source of PAHs in the soil and air. Excessive levels of PAHs are accumulated when the balance between their decomposition in soil and supply from other sources is disrupted. The objective of the present research has been to evaluate the effect of anthracene and pyrene on the concentration of selected trace elements in butter lettuce (Lactuca sativa L.), cultivar Vilmorin, grown on substrates with different nutrient abundance. A pot experiment in four replications was carried out twice in the spring of 2007 and 2008. The pots were maintained in a greenhouse at the University of Warmia and Mazury in Olsztyn. Lettuce was grown under the minimum (optimum) and triple (II fertilization level) substrate abundance in nutrients. In the second variant o the experiment, when the nutrient abundance was elevated, nitrogen was split into two doses: 2/3 of the whole rate were added before planting lettuce seedlings, and 1/3 of the rate was introduced 10 days afterwards. In the first variant, when the nutrient abundance was minimal, all of the nitrogen was added in a single dose. Spraying the lettuce plants with anthracene (ANT), pyrene (PYR0 or their mixture started 10 days after planting. Foliar introduction of the tested PAHs continued for 25 days (in the amount of 1.8 cm3 day–1 at a concentration of 100 mg dm–3) until the vegetative season finished. At the same time, an identical total amount of the PAHs was added to soil as aqueous solution, at 7-day intervals, according to the same pattern. Determinations of the concentrations of heavy metals (Cd, Cu, Ni, Cr, Zn, Mn) was performed with the ASA method, having first mineralised (HClO4+HCl+HNO3) the plant material which had been dried at 60oC. The determinations were compared with certified material (CTA-VTL-2). Concentrations of the trace elements in butter lettuce were significantly varied depending on the experimental factors. A more abundant substrate significantly raised the levels of Cd, Zn and Mn, but had no effect on concentrations of Cu, Ni and Cr. The way the PAHs were applied did not have any influence on modifications in the determined levels of the metals. Out of the two analysed PAHs, anthracene, especially when applied to soil, increased the concentrations of Zn nd Cr in lettuce leaves.
Binding affinities of ten polycyclic aromatic hydrocarbons to albumin were determined: anthracene, its eight oxy-derivatives: anthraquinone, 9-anthracenemethanol, 9-anthraldehyde, 9-anthracenecarboxylic acid, 1,4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone, 1,8-dihydroxyanthraquinone, 2,6-dihydroxyanthraquinone and benzo[a]pyrene. The quenching of albumin fluorescence was used to measure the PAH — protein interaction. The theoretical curve of calculated fluorescence was fitted to experimental data after necessary corrections regarding PAHs fluorescence and inner filter effect. From the numerical fitting the final association constants were calculated. Anthracene and anthraquinone failed to quench the albumin fluorescence. 9-anthracenecarboxylic acid showed the highest, while 9-anthracenemethanol the weakest albumin binding affinity. The affinity constants determined for 9-anthraldehyde and benzo[a]pyrene were of the same magnitude and indicated low-affinity binding to albumin. The constants obtained for the four dihydroxyanthraquinones were higher, but dissimilar, which suggests that the position of the functional group in anthracene molecule influences the binding constant. Moreover, this study suggests that the type of substituent plays a significant role in PAH-albumin complex formation. The carboxylic group increases the binding affinity of the anthracene molecule the most rather than the presence of both carbonyl and hydroxyl groups. The lowest affinity constants were obtained for aldehyde, methyl and carbonyl substituents.
Urease activity was determined in soil contaminated with four polycyclic aromatic hydrocarbons (PAHs): naphthalene, phenanthrene, anthracene, and pyrene in the amount of 0, 1,000, 2,000, and 4,000 mg·kg⁻¹ DM soil. Organic materials – cellulose, sucrose, and compost – were applied to the samples in the amount of 0 and 9 g·kg⁻¹ DM soil. The experiment was carried out in a laboratory, and soil samples consisted of loamy sand. Soil resistance (RS) and soil resilience (RL) were determined. Soil contamination with PAHs had an adverse effect on urease activity, and naphthalene had the most inhibitory impact on the studied enzyme. Urease activity was significantly determined by the dose of PAH, soil incubation time, and the type of organic material. Soil resistance to PAHs decreased with an increase in contamination levels. The addition of sucrose, cellulose, and compost increased soil's resistance to the toxic effects of naphthalene and phenanthrene. Soil resilience values indicate that polycyclic aromatic hydrocarbons cause long-term impairment of urease activity.
Przeprowadzone badania miały na celu określenie wpływu trójpierścieniowego węglowodoru aromatycznego (antracenu), podawanego dolistnie i do podłoża piaskowego, na wzrost i plonowanie łubinu żółtego. Po 21 dniach od wykiełkowania antracen podawano przez 79 dni roślinom rosnącym w warunkach szklarniowych. Zaobserwowano, iż związek podawany na część nadziemną roślin powodował znaczne zmniejszenie suchej masy łodygi (o ok. 28%) oraz suchej masy nasion (o ok. 10%). Na podstawie otrzymanych wyników można przypuszczać, że zmniejszenie wydajności fotosyntezy wskutek długotrwałej ekspozycji części nadziemnej na działanie związku, spowodowało ograniczenie przemieszczania asymilatów do pędu i nasion. Z kolei, podanie ANT do podłoża miało niewielki wpływ na rozwój części nadziemnej łubinu. Natomiast obserwowano obniżenie suchej masy korzenia (o ok. 18%) oraz jego długości (o ok. 10%).
The purpose of this study has been to evaluate the effect of foliar application of PAH organic chemical compounds (anthracene, pyrene) on yield, chemical composition and uptake of nutrients by cv. Vilmorin butterhead lettuce (Lactuca sativa L.). Lettuce was grown under minimum and three-fold higher abundance of substrate in nutrients, as determined according to threshold amounts. A pot trial was established in four replicates and performed twice, in the spring of 2008 and 2009, in a greenhouse at the University of Warmia and Mazury in Olsztyn. Lettuce seedlings were planted in pots containing 10 dm3 of mineral substrate. Fertilization (N, P, K, Mg, Na and Cl) was carried out prior to the planting of lettuce. Under the minimum nutrient abundance of the substrate, all the dose of nitrogen was supplied as a pre-sowing treatment, whereas when the abundance in nutrients was raised three-fold, the nitrogen dose was divided (2/3 pre-sowing and 1/3 10 days after planting). Contamination of lettuce plants with anthracene (ANT) or pyrene (PYR) and their mixture started 10 days after planting lettuce. Foliar application of either of the PAHs continued for 25 days until the vegetative growth of lettuce terminated. Determination of the concentration of macronutrients (N, P, K, Mg, Ca and Na) was performed using standard methods on the mineralised (H2SO4+H2O2), previously dried at 60ºC lettuce plant material. The determinations were completed by referring to certified material (CTA-VTL-2). The amount of fresh mass of butterhead lettuce depended primarily on the abundance of the substrate in nutrients. The three-fold increase in the substrate’s abundance in N, P, K, Mg, Na and Cl caused an increment in the yield of lettuce head mass by 13.3%. Foliar application of ANT and PYR caused an increase in the yield of lettuce head mass. The concentration of N, K, Na, Mg, Ca and Mg in lettuce was modified first of all by the abundance of the substrate and, to a lesser degree, by the applied PAHs.
Degradation of polycyclic aromatic hydrocarbons (PAH) such as phenanthrene, anthracene, fluoran-thene, pyrene, benzo[a]anthracene, chryzene, benzo[b]fluoranthene, benzo[e]pyrene, benzo[k]fluoranthene and benzo[a]pyrene) in the surface layer (5 cm) of soil polluted with aircraft fuel in an amount of 10 ml/kg was analyzed. The direct influence of solubility in water on the degree of its loss was proven. The clear influence of the soil type – directly related, among other things, to organic matter content and contribution of alluvial fraction – on the decomposition of 5-ring PAHs. Half-lives ranged from 152 to 313 for 3-ring PAHs and from 117 to 492 for 4- and 5-ring PAHs.
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