• Conway Buchanan posted an update 1 week, 3 days ago

    Microbiological measurements, chemical water quality data, and dye tracer tests provide evidence of human fecal contamination in the private wells studied, suggesting that household septic systems are the source of this contamination.The reaction between trans-[AuF2(pyridine)2]+ and [PhI(pyridine)2]2+ results in the formation of PhIF2 and [Au(pyridine)4]3+. Investigation of the reaction pathway using model Pd and Pt analogues of the gold complex indicate that the most likely mechanism is attack by the Au-F onto the I(III), rather than a redox process. This demonstrates that the Au(III)-F fragment can behave in a nucleophilic manner even in a relatively electron-poor cationic complex.A series of copper/nitrosoarene complexes was created that mimics several steps in biomimetic O2 activation by copper(I). The reaction of the copper(I) complex of N,N,N’,N’-tetramethypropylenediamine with a series of para-substituted nitrosobenzene derivatives leads to adducts in which the nitrosoarene (ArNO) is reduced by zero, one, or two electrons, akin to the isovalent species dioxygen, superoxide, and peroxide, respectively. The geometric and electronic structures of these adducts were characterized by means of X-ray diffraction, vibrational analysis, ultraviolet-visible spectroscopy, NMR, electrochemistry, and density functional theory (DFT) calculations. The bonding mode of the NO moiety depends on the oxidation state of the ArNO moiety κN for ArNO, mononuclear η2-NO and dinuclear μ-η2η1 for ArNO•-, and dinuclear μ-η2η2 for ArNO2-. 15N isotopic labeling confirms the reduction state by measuring the NO stretching frequency (1392 cm-1 for κN-ArNO, 1226 cm-1 for η2-ArNO•-, 1133 cm-1 for dinuclear μ-η2η1-ArNO•-, and 875 cm-1 for dinuclear μ-η2η2 for ArNO2-). The 15N NMR signal disappears for the ArNO•- species, establishing a unique diagnostic for the radical state. Electrochemical studies indicate reduction waves that are consistent with one-electron reduction of the adducts and are compared with studies performed on Cu-O2 analogues. DFT calculations were undertaken to confirm our experimental findings, notably to establish the nature of the charge-transfer transitions responsible for the intense green color of the complexes. In fine, this family of complexes is unique in that it walks through three redox states of the ArNO moiety while keeping the metal and its supporting ligand the same. This work provides snapshots of the reactivity of the toxic nitrosoarene molecules with the biologically relevant Cu(I) ion.This work reports the first bioplatform able to determine electrochemically 5-hydroxymethylcytosine (5-hmC) methylation events at localized sites and single-base sensitivity. The described bioplatform relies on a specific antibody (anti-5-hmC), further conjugated with commercial bioreagents loaded with multiple horseradish peroxidase (HRP) molecules, recognizing the epimark in a target DNA, captured through hybridization onto streptavidin-magnetic microbeads (Strep-MBs) modified with a complementary DNA capture probe. The electrochemical detection is performed by amperometry (-0.20 V vs Ag pseudoreference electrode) at disposable screen-printed carbon electrodes (SPCEs) in the presence of H2O2/hydroquinone (HQ) upon magnetic capture of the modified MBs onto the SPCE. The use of the commercial bioreagents ProtA-polyHRP80 and Histostar, very scarcely explored so far in electrochemical biosensors, provides high sensitivities for a synthetic target DNA sequence with a unique 5-hmC in the promoter region of MGMT tumor suppressor gene. Amplification factors of 43.6 and 55.2 were achieved using ProtA-polyHRP80 or Histostar, respectively, compared to the conventional secondary antibody labeling. This amplification was crucial to detect methylation events at single-nucleotide resolution achieving limits of detection (LODs) of 23.0 and 13.2 pM, respectively, without any target DNA amplification. The ProtA-polyHRP80-based bioplatform, selected as a compromise between sensitivity and cost per determination, exhibited full discrimination toward the target 5-hmC against the closely related 5-mC. In addition, the bioplatform detected 5-hmC at the regional level (MGMT promoter region) in just 10 ng of genomic DNA (gDNA, ∼2700 genomes) extracted from cancer cells and tissues from colorectal cancer (CRC) patients within 60 min.Eutrophication mitigation is an ongoing priority for aquatic ecosystems. However, the current eutrophication control strategies (phosphorus (P) and/or nitrogen (N)) are guided mainly by nutrient addition experiments in small waters without encompassing all in-lake biogeochemical processes that are associated largely with lake morphological characteristics. Omecamtiv mecarbil ATPase activator Here, we use a global lake data set (573 lakes) to show that the relative roles of N vs P in affecting eutrophication are underpinned by water depth. Mean depth and maximum depth relative to mixing depth were used to distinguish shallow (mixing depth > maximum depth), deep (mixing depth less then mean depth), and transitional (mean depth ≤ mixing depth ≤ maximum depth) lakes in this study. TN/TP ratio (by mass) was used as an indicator of potential lake nutrient limitation, i.e., N only limitation if N/P less then 9, N + P colimitation if 9 ≤ N/P less then 22.6, and P only limitation if N/P ≥ 22.6. The results show that eutrophication is favored in shallow lakes, frequently (66.2%) with N limitation while P limitation predominated (94.4%) in most lakes but especially in deep ones. The importance of N limitation increases but P limitation decreases with lake trophic status while N and P colimitation occurs primarily (59.4%) in eutrophic lakes. These results demonstrate that phosphorus reduction can mitigate eutrophication in most large lakes but a dual N and P reduction may be needed in eutrophic lakes, especially in shallow ones (or bays). Our analysis helps clarify the long debate over whether N, P, or both control primary production. While these results imply that more resources be invested in nitrogen management, given the high costs of nitrogen pollution reduction, more comprehensive results from carefully designed experiments at different scales are needed to further verify this modification of the existing eutrophication mitigation paradigm.