Modeling and biological investigations of an unusual behavior of novel synthesized acridine-based polyamine ligands in the binding of double helix and G-quadruplex DNA

Three novel 2,7-substituted acridine derivatives were designed and synthesized to investigate the effect of this functionalization on their interaction with double-stranded and G-quadruplex DNA. Detailed investigations of their ability to bind both forms of DNA were carried out by using spectrophotometric, electrophoretic, and computational approaches. The ligands in this study are characterized by an open-chain (L1) or a macrocyclic (L2, L3) framework. The aliphatic amine groups in the macrocycles are joined by ethylene (L2) or propylene chains (L3). L1 behaved similarly to the lead compound m-AMSA, efficiently intercalating into dsDNA, but stabilizing G-quadruplex structures poorly, probably due to the modest stabilization effect exerted by its protonated polyamine chains. L2 and L3, containing small polyamine macrocyclic frameworks, are known to adopt a rather bent and rigid conformation; thus they are generally expected to be sterically impeded from recognizing dsDNA according to an intercalative binding mode. This was confirmed to be true for L3. Nevertheless, we show that L2 can give rise to efficient π-π and H-bonding interactions with dsDNA. Additionally, stacking interactions allowed L2 to stabilize the G-quadruplex structure: using the human telomeric sequence, we observed the preferential induction of tetrameric G-quadruplex forms. Thus, the presence of short ethylene spacers seems to be essential for obtaining a correct match between the binding sites of L2 and the nucleobases on both DNA forms investigated. Furthermore, current modeling methodologies, including docking and MD simulations and free energy calculations, provide structural evidence of an interaction mode for L2 that is different from that of L3; this could explain the unusual stabilizing ability of the ligands (L2>L3>L1) toward G-quadruplex that was observed in this study.     

Glutathione-S-transferase polymorphism, metallothionein expression, and mercury levels among students in Austria

BACKGROUND: Detoxification is an essential process in all living organisms. Humans accumulate heavy metals primarily as a result of lifestyle and environmental contamination. However, not all humans experience the estimated individual exposure. This suggests the presence of genetic regulatory mechanisms. OBJECTIVE: In order to identify genetic factors underlying the inter-individual variance in detoxification capacity for the heavy metal mercury, 192 students were investigated. We focused on the relationship between polymorphisms in glutathione-S-transferase (GST) genes and mercury concentrations in blood, urine, and hair. The correlation between blood mercury levels, GSTT1 and GSTM1 polymorphism, and gene expression of certain metallothionein subgroups (MT1, MT3) was evaluated in a further group of students (N=30). METHODS: Mercury levels in acid digested samples were measured by cold vapor AAS. Genotyping of the GSTT1 and GSTM1-gene deletion polymorphism was performed by means of PCR. Gene expression of several MT genes was analyzed in lymphocytes from fresh peripheral blood by semiquantitative RT-PCR. RESULTS: The following was noted: a) hair mercury concentrations are significantly increased in persons with the double deleted genotype (GSTT1-/- and GSTM1-/-) as compared to persons with the intact genotype, and b) MT1X expression is higher in persons with the intact genotype (GSTT1+/+ and GSTM1+/+). CONCLUSIONS: We conclude that the epistatic effect of the GSTT1 and the GSTM1 deletion polymorphism is a risk factor for increased susceptibility to mercury exposure. The relationship between MT gene expression and GST gene polymorphisms needs further investigation. If MT expression depends on GST polymorphisms it would have important implications on the overall metal detoxification capability of the human organism.     

Baseline water quality and macrophyte assemblages in Pampean streams: a regional approach

Streams of the pampas region (central Argentina) are characterized by the lack of riparian forests and by low current velocities, and receive a large amount of industrial and domestic effluents. Intensive agriculture in the region has greatly increased during the last years; nevertheless, regional studies to determine baseline conditions are not available. Here, we characterized pampean streams considering physico-chemical water features and the composition of macrophyte communities, and we established if the regions proposed by an early hydrological regionalization show differentiated water chemistry and macrophyte assemblages. Forty-one streams were sampled in autumn, spring and summer. Streams were characterized by alkaline waters, with high conductivities and dissolved oxygen concentrations, and they can be classified as eutrophic. A good discrimination among regions was achieved based on streamwater features in all seasons; variables that most contribute to the discrimination were related to pH, eutrophication, and conservative ions. Regional differences may be due to variations in water availability, parent material, and land use practices. The aquatic plant communities reflected the eutrophic state of waters, but macrophyte composition was not useful to differentiate among regions because it is not affected by differences in water chemistry. Macrophyte species grouped according to their growth form and assemblage distribution were related to chemical variables (as conductivity and nitrate) and possibly to flow conditions.     

Adsorption behaviors and mechanisms of porous hypercrosslinked polymers with adjustable functional groups toward doxycycline hydrochloride from water

Imino hypercrosslinked polymers (NH-HCPs), amino hypercrosslinked polymers (NH₂-HCPs), and carboxyl hypercrosslinked polymers (COOH-HCPs) were synthesized through cross-linking and Friedel-Crafts reactions to serve as highly efficient adsorbents for doxycycline hydrochloride (DOX) in water. These polymers, NH-HCPs, NH₂-HCPs, and COOH-HCPs, exhibited specific surface areas measuring 450, 267.576, and 94.39 m²/g, respectively. The adsorption kinetics of DOX onto these polymers were consistent with the pseudo-second-order model, while the adsorption isotherms followed the Langmuir model (NH-HCPs) and Freundlich model (NH₂-HCPs and COOH-HCPs), respectively. The maximum DOX adsorption capacities for NH-HCPs, NH₂-HCPs, and COOH-HCPs were 166.82, 132.43, and 72.07 mg/g, respectively. Simulation results indicated that COOH-HCPs exhibited the strongest adsorption capability due to a substantial presence of oxygen and nitrogen groups on its surface, enabling the formation of hydrogen bonds with DOX. However, its actual adsorption capacity was the lowest among the polymers, indicating that structural adjustments played a more significant role in improving adsorption performance compared to functional adjustments. Adsorption experiments conducted with NH-HCPs and NH₂-HCPs further supported this hypothesis. The primary DOX adsorption mechanism of NH-HCPs, NH₂-HCPs, and COOH-HCPs involved the H-bonding of oxygen and nitrogen functional groups, along with other mechanisms such as π-π conjugated effects, pore-filling effects, electrostatic interactions, and acid–base interactions. Overall, this study demonstrates the effectiveness of NH-HCPs, NH₂-HCPs, and COOH-HCPs in DOX removal from water, highlighting the significant influence of structural adjustments on adsorption performance.     

Composites produced from waste plastic with agricultural and energy sector by-products

A three-stage route to chemically upcycle post-consumer poly(ethylene terephthalate) (PET) to produce high compressive strength composites is reported. This procedure involves initial glycolysis with diethylene glycol to produce a mixture (GPET) comprising oligomers of 2–7 terephthalate units followed by trans/esterification of GPET with fatty acid chains supplied by brown grease, an agricultural by-product of animal fat of relatively low nutritional or fuel value. This process yields PGB comprising a mixture of mono-terephthalate ester derivatives. The olefin units provided by unsaturated fatty acid chains in brown grease were crosslinked by an inverse vulcanization reaction with elemental sulfur to give composites GBS_x (x = wt% S, varied from 80%–90%). The compressive strengths of GBS₈₀ (27.5 ± 2.6 MPa) and GBS₉₀ (19.2 ± 0.8 MPa) exceed the compressive strength required of ordinary Portland cement (17 MPa) for its use in residential building foundations. The current route represents a way to repurpose waste plastic, energy sector by-product sulfur, and agricultural by-product brown grease to give high strength composites with mechanical properties suggesting their possible use to replace less sustainably sourced legacy structural materials.     

Factors influencing the soil-air partitioning and the strength of soils as a secondary source of polychlorinated biphenyls to the atmosphere

Soils are a major reservoir of persistent organic pollutants, and soil-air partitioning and exchange are key processes controlling the atmospheric concentrations and regional fate of pollutants. Here, we report and discuss the concentrations of polychlorinated biphenyls (PCBs) in soils, their measured fugacities in soil, the soil-air partition coefficients (K(SA)) and soil-air fugacity gradients in rural background areas of N-NE Spain and N-NW England. Four sampling campaigns were carried out to assess seasonal and daily variability and differences between sampling sites. K(SA) values were significantly dependent on soil temperature and soil organic matter quantity, and to a minor extent organic matter type. All the PCB congeners in the soil are close to equilibrium with the atmosphere at rural Ebro sites, but soil fugacities tend to be higher than ambient air fugacities in early and late summer, consistent with the influence of temperature on soil-air partitioning. Therefore, during warm periods, soils increment their strength as secondary sources to the atmosphere. The mixture of PCBs found in the atmosphere is clearly strongly influenced by the mixture of PCBs which escape from soil, with significant correlations between them (R(2) ranging between 0.35 and 0.74 and p-level <0.001 for the Ebro sampling sites). Conversely, the close-to-equilibrium to net sink status of rural UK sites, suggest a close coupling of air and soil concentrations, but it is not possible to elucidate the importance of these soils as secondary sources yet, and presumably there are still significant primary sources to the regional/global environment.     

Microbial Abundance in the Schwertmannite Formed in a Mine Water Treatment Plant

Treatment of acidic iron- and sulfate-rich mine waters in a pilot plant at the opencast lignite mining pit Nochten (Lusatia, Germany) involves microbial iron oxidation and subsequent precipitation of the iron-oxyhydroxysulfate schwertmannite. To determine if recirculation of schwertmannite can stabilize and optimize the oxidation process, cell number, viability, and diversity of the bacterial community in schwertmannite precipitated on carrier material and stored schwertmannite were analyzed. In schwertmannite on carrier material, the total cell number decreased slightly with increasing mineral depth, whereas the percentage of viable cells decreased significantly. The microbial community, investigated by fluorescence-in-situ-hybridization (FISH) and terminal restriction fragment length polymorphism (T-RFLP), revealed the presence of the iron-oxidizing bacterium “Ferrovum” sp. and relatives of Gallionella, independent of mineral depth. Analysis of the viability of microorganism in stored schwertmannite indicated an almost constant percentage of viable cells over 42 days.     

Antioxidant activity prediction and classification of some teas using artificial neural networks

In order to characterise and to classify some teas a simple, rapid and economical method based on composition, antioxidant activity and artificial neural networks (ANNs) is proposed. For these purpose two types of ANN based applications have been developed: one for predicting the antioxidant activity and a second one for establishing the class of the teas. The complex relationship between the total antioxidant activity (AA) depending on the total flavonoids content (F), total catechins content (C) and total methyl-xanthines content (MX) of commercial teas was revealed by the first designed feed-forward ANN. Secondly, using a probabilistic ANN, successful tea classification in various classes (green tea, black tea and express black tea) was also performed.     

Well-being and organizational attitudes in alternative employment: The role of contract and job preferences.

This study focuses upon the heterogeneity in the contemporary workforce in relation to well-being and organizational attitudes. This heterogeneity may concern (a) the specific type of contract (permanent full-time vs. alternative arrangements; e.g., permanent part-time, fixed-term, and on-call work), (b) job and contract preferences, or (c) specific combinations of contract type and preferences. The authors argue that working in alternative employment, but also being in a nonpreferred contract or job may imply stress and, hence, strain (i.e., poor well-being). This may lead to withdrawal from the organization (i.e., poor organizational attitudes). A combination of the stressors may strengthen these effects. Analyses of questionnaire data from Sweden collected in 2004 (N = 716) reveal that preferences, particularly preferences for the job and partly also for the contract, were associated with the outcomes. Contract heterogeneity was not informative for well-being, while it was for differences in reported organizational attitudes. Type of employment contract interacted with job and contract preferences: for permanent full-time workers, job preferences displayed stronger associations with well-being and attitudes than for workers in alternative employment. (PsycINFO Database Record (c) 2010 APA, all rights reserved)