Synthesis and Structural Characterization of a Dendrimer Model Compound Based on a Cyclotriphosphazene Core with TEMPO Radicals as Substituents

The synthesis of the 3Gc₀T zero generation dendrimer with a cyclotriphosphazene core functionalized with nitroxyl radicals in its six branches has been performed. The radical units have been used as probes to determine the orientation of the six branches in solution experimentally by Electron Paramagnetic Resonance (EPR) spectroscopy compared with the structure obtained in the solid state by X-ray diffraction. The orientation of the dendrimer branches is the same in solution as in the solid state

Radical Dendrimers: A Family of Five Generations of Phosphorus Dendrimers Functionalized with TEMPO Radicals

Five novel generations of phosphorus dendrimers based on a cyclotriphosphazene core with stable TEMPO radicals end groups have been synthesized and studied by EPR, SQUID, ¹H NMR, ³¹P NMR, FT-IR, and UV–vis spectroscopy. The nitroxyl radicals exhibit a strong exchange interaction, which depends on the dendrimer generation and the temperature. An |Δ<i>m</i>_s| = 2 transition has been observed in each generation in dilution conditions demonstrating the intramolecular origin of the radicals interaction. There exists a direct proportionality between the EPR |Δ<i>m</i>_s| = 2 transition intensity and the number of radicals by generation; consequently, the utility of EPR for the determination of the substitution efficiency on dendrimers by paramagnetic species is quite good. From the UV–vis characterization, we have observed that the molar extinction coefficient value is also proportional to the number of TEMPO groups. The magnetic properties of the zero, first and fourth generation dendrimers studied by SQUID magnetometry show antiferromagnetic interaction between radicals

Environmental Impacts by Fragments Released from Nanoenabled Products: A Multiassay, Multimaterial Exploration by the SUN Approach

Nanoenabled products (NEPs) have numerous outdoor uses in construction, transportation or consumer scenarios, and there is evidence that their fragments are released in the environment at low rates. We hypothesized that the lower surface availability of NEPs fragment reduced their environmental effects with respect to pristine nanomaterials. This hypothesis was explored by testing fragments generated by intentional micronisation (“the SUN approach”; Nowack et al. Meeting the Needs for Released Nanomaterials Required for Further Testing: The SUN Approach. <i>Environmental Science & Technology</i>, <b>2016</b> (<i>50</i>), 2747). The NEPs were composed of four matrices (epoxy, polyolefin, polyoxymethylene, and cement) with up to 5% content of three nanomaterials (carbon nanotubes, iron oxide, and organic pigment). Regardless of the type of nanomaterial or matrix used, it was observed that nanomaterials were only partially exposed at the NEP fragment surface, indicating that mostly the intrinsic and extrinsic properties of the matrix drove the NEP fragment toxicity. Ecotoxicity in multiple assays was done covering relevant media from terrestrial to aquatic, including sewage treatment plant (biological activity), soil worms (<i>Enchytraeus crypticus</i>), and fish (zebrafish embryo and larvae and trout cell lines). We designed the studies to explore the possible modulation of ecotoxicity by nanomaterial additives in plastics/polymer/cement, finding none. The results support NEPs grouping by the matrix material regarding ecotoxicological effect during the use phase. Furthermore, control results on nanomaterial-free polymer fragments representing microplastic had no significant adverse effects up to the highest concentration tested

Environmental Impacts by Fragments Released from Nanoenabled Products: A Multiassay, Multimaterial Exploration by the SUN Approach

Nanoenabled products (NEPs) have numerous outdoor uses in construction, transportation or consumer scenarios, and there is evidence that their fragments are released in the environment at low rates. We hypothesized that the lower surface availability of NEPs fragment reduced their environmental effects with respect to pristine nanomaterials. This hypothesis was explored by testing fragments generated by intentional micronisation (“the SUN approach”; Nowack et al. Meeting the Needs for Released Nanomaterials Required for Further Testing: The SUN Approach. <i>Environmental Science & Technology</i>, <b>2016</b> (<i>50</i>), 2747). The NEPs were composed of four matrices (epoxy, polyolefin, polyoxymethylene, and cement) with up to 5% content of three nanomaterials (carbon nanotubes, iron oxide, and organic pigment). Regardless of the type of nanomaterial or matrix used, it was observed that nanomaterials were only partially exposed at the NEP fragment surface, indicating that mostly the intrinsic and extrinsic properties of the matrix drove the NEP fragment toxicity. Ecotoxicity in multiple assays was done covering relevant media from terrestrial to aquatic, including sewage treatment plant (biological activity), soil worms (<i>Enchytraeus crypticus</i>), and fish (zebrafish embryo and larvae and trout cell lines). We designed the studies to explore the possible modulation of ecotoxicity by nanomaterial additives in plastics/polymer/cement, finding none. The results support NEPs grouping by the matrix material regarding ecotoxicological effect during the use phase. Furthermore, control results on nanomaterial-free polymer fragments representing microplastic had no significant adverse effects up to the highest concentration tested