Biological effects of oxidized carbon nanomaterials (1D versus 2D) on Spodoptera frugiperda: Material dimensionality influences on the insect development, performance and nutritional physiology.

In this work, we developed an integrative experimental design to investigate the long-term effects of two important classes of carbon nanomaterials with different dimensionalities (i.e., 1D oxidized multiwalled carbon nanotube, ox-MWCNT, and 2D graphene oxide, GO) on the development of the generalist insect Spodoptera frugiperda (Lepidoptera: Noctuidae). Insects are exciting in vivo biological models for investigating the impact of nanomaterials on nanobio-ecological interactions. S. frugiperda larvae were reared from egg hatching to pupation on diets containing ox-MWCNT and GO at different concentrations (0, 10, 100 and 1000 µg g-1 of dry mass of diet). Several aspects of larval and adult performance were measured under controlled conditions. The effects of the carbon nanomaterial (CNM)-containing diets on the nutritional physiology and digestive enzymatic activities of S. frugiperda larvae were also evaluated. The results showed that the type and concentration of CNMs in the diet negatively affected the reproductive parameters and the digestive and metabolic efficiency of S. frugiperda. The diet containing the highest concentration of GO significantly reduced the fecundity and fertility of S. frugiperda compared to the effects of other treatments. S. frugiperda larvae showed decreased efficiency of food conversion into biomass and maximal approximate digestibility when fed diets containing GO at higher concentrations. However, quantitative differences in digestive enzyme activities were not observed between all treatments. These findings highlighted the critical influence of CNM dimensionality on the general performance and nutritional physiology of the moth. This work contributes to the safety evaluation and future applications of CNMs in agri-environmental nanotechnology.

Covalent functionalization of graphene oxide with d-mannose: evaluating the hemolytic effect and protein corona formation.

In this work, graphene oxide (GO) was covalently functionalized with d-mannose (man-GO) using mannosylated ethylenediamine. XPS (C1s and N1s) confirmed the functionalization of GO through the binding energies at 288.2 eV and 399.8 eV, respectively, which are attributed to the amide bond. ATR-FTIR spectroscopy showed an increase in the amine bond intensity, at 1625 cm-1 (stretching C[double bond, length as m-dash]O), after the functionalization step. Furthermore, the man-GO toxicity to human red blood cells (hemolysis) and its nanobiointeractions with human plasma proteins (hard corona formation) were evaluated. The mannosylation of GO drastically reduced its toxicity to red blood cells. SDS-PAGE analysis showed that the mannosylation process of GO also drastically reduced the amount of the proteins in the hard corona. Additionally, proteomics analysis by LC-MS/MS revealed 109 proteins in the composition of the man-GO hard corona. Finally, this work contributes to future biomedical applications of graphene-based materials functionalized with active biomolecules.

Feeding on Host Plants with Different Concentrations and Structures of Pyrrolizidine Alkaloids Impacts the Chemical-Defense Effectiveness of a Specialist Herbivore.

Sequestration of chemical defenses from host plants is a strategy widely used by herbivorous insects to avoid predation. Larvae of the arctiine moth Utetheisa ornatrix feeding on unripe seeds and leaves of many species of Crotalaria (Leguminosae) sequester N-oxides of pyrrolizidine alkaloids (PAs) from these host plants, and transfer them to adults through the pupal stage. PAs confer protection against predation on all life stages of U. ornatrix. As U. ornatrix also uses other Crotalaria species as host plants, we evaluated whether the PA chemical defense against predation is independent of host plant use. We fed larvae from hatching to pupation with either leaves or seeds of one of eight Crotalaria species (C. incana, C. juncea, C. micans, C. ochroleuca, C. pallida, C. paulina, C. spectabilis, and C. vitellina), and tested if adults were preyed upon or released by the orb-weaving spider Nephila clavipes. We found that the protection against the spider was more effective in adults whose larvae fed on seeds, which had a higher PA concentration than leaves. The exceptions were adults from larvae fed on C. paulina, C. spectabilis and C. vitellina leaves, which showed high PA concentrations. With respect to the PA profile, we describe for the first time insect-PAs in U. ornatrix. These PAs, biosynthesized from the necine base retronecine of plant origin, or monocrotaline- and senecionine-type PAs sequestered from host plants, were equally active in moth chemical defense, in a dose-dependent manner. These results are also partially explained by host plant phylogeny, since PAs of the host plants do have a phylogenetic signal (clades with high and low PA concentrations in leaves) which is reflected in the adult defense.