Low potency toxins reveal dense interaction networks in metabolism

Background The chemicals of metabolism are constructed of a small set of atoms and bonds. This may be because chemical structures outside the chemical space in which life operates are incompatible with biochemistry, or because mechanisms to make or utilize such excluded structures has not evolved. In this paper I address the extent to which biochemistry is restricted to a small fraction of the chemical space of possible chemicals, a restricted subset that I call Biochemical Space. I explore evidence that this restriction is at least in part due to selection again specific structures, and suggest a mechanism by which this occurs. Results Chemicals that contain structures that our outside Biochemical Space (UnBiological groups) are more likely to be toxic to a wide range of organisms, even though they have no specifically toxic groups and no obvious mechanism of toxicity. This correlation of UnBiological with toxicity is stronger for low potency (millimolar) toxins. I relate this to the observation that most chemicals interact with many biological structures at low millimolar toxicity. I hypothesise that life has to select its components not only to have a specific set of functions but also to avoid interactions with all the other components of life that might degrade their function. Conclusions The chemistry of life has to form a dense, self-consistent network of chemical structures, and cannot easily be arbitrarily extended. The toxicity of arbitrary chemicals is a reflection of the disruption to that network occasioned by trying to insert a chemical into it without also selecting all the other components to tolerate that chemical. This suggests new ways to test for the toxicity of chemicals, and that engineering organisms to make high concentrations of materials such as chemical precursors or fuels may require more substantial engineering than just of the synthetic pathways involved

Food web effects of titanium dioxide nanoparticles in an outdoor freshwater mesocosm experiment

<p>Over the course of 78 days, nine outdoor mesocosms, each with 1350 L capacity, were situated on a pontoon platform in the middle of a lake and exposed to 0 μg L⁻¹ TiO₂, 25 μg L⁻¹ TiO₂ or 250 μg L⁻¹ TiO₂ nanoparticles in the form of E171 TiO₂ human food additive five times a week. Mesocosms were inoculated with sediment, phytoplankton, zooplankton, macroinvertebrates, macrophytes and fish before exposure, ensuring a complete food web. Physicochemical parameters of the water, nutrient concentrations, and biomass of the taxa were monitored. Concentrations of 25 μg L⁻¹ TiO₂ and 250 μg L⁻¹ TiO₂ caused a reduction in available soluble reactive phosphorus in the mesocosms by 15 and 23%, respectively, but not in the amount of total phosphorus. The biomass of Rotifera was significantly reduced by 32 and 57% in the TiO₂ 25 μg L⁻¹ and TiO₂ 250 μg L⁻¹ treatments, respectively, when compared to the control; however, the biomass of the other monitored groups—Cladocera, Copepoda, phytoplankton, macrophytes, chironomids and fish—remained unaffected. In conclusion, environmentally relevant concentrations of TiO₂ nanoparticles may negatively affect certain parameters and taxa of the freshwater lentic aquatic ecosystem. However, these negative effects are not significant enough to affect the overall function of the ecosystem, as there were no cascade effects leading to a major change in its trophic state or primary production.</p

Designing ionic liquids: the chemical structure role in the toxicity

Ionic liquids (ILs) are a novel class of solvents with interesting physicochemical properties. Many different applications have been reported for ILs as alternatives to organic solvents in chemical and bioprocesses. Despite the argued advantage of having low vapor pressure, even the most hydrophobic ILs show some degree of solubility in water, allowing their dispersion into aquatic systems and raising concerns on its pollutant potential. Moreover, nowadays most widespread notion concerning the ILs toxicity is that there is a direct relationship with their hydrophobicity/lipophilicity. This work aims at enlarging the currently limited knowledge on ILs toxicity by addressing negative impacts in aquatic ecosystems and investigating the possibility of designing hydrophobic ILs of low ecotoxicity, by the manipulation of their chemical structures. The impact of aromaticity on the toxicity of different cations (pyridinium, piperidinium, pyrrolidinium and imidazolium) and hydrophobic anions (bis(trifluoromethylsulfonyl)imide [NTf2] and hexafluorophosphate [PF6]) was analysed. Concomitantly, several imidazolium-based ILs of the type [C (n) C (m) C (j) im][NTf2] were also studied to evaluate the effects of the position of the alkyl chain on the ILs' toxicity. For that purpose, standard assays were performed using organisms of different trophic levels, Vibrio fischeri, Pseudokirchneriella subcapitata and Daphnia magna, allowing to evaluate the consistency of the structure-activity relationships across different biological targets. The results here reported suggest the possibility of designing ILs with an enhanced hydrophobic character and lower toxicity, by elimination of their aromatic nature