Title
GC-TOF-MS based metabolomics and ICP-MS based metallomics of cucumber (: CucumissativusCopper-based nanoparticles have wide application in agriculture as fungicides and bactericides. Due to the rapid increase in their use, it is imperative to understand their environmental impact, especially on agricultural crops. In this study, inductively coupled plasma mass spectrometry (ICP-MS) based metallomics and gas chromatography-time of flight mass spectrometry (GC-TOF-MS) based metabolomics were applied to detect metal and molecular changes in cucumber plants exposed to various environmentally-relevant levels of nano copper (nCu at 0, 200, 400, and 800 mg kg) until full maturity. Metallomics studies showed nCu caused the perturbation of Fe uptake in leaves. In fruit, Ca, K, S, P, Zn and Mg increased after exposure to 400 and 800 mg kg −1 nCu. Metabolomics and partial least-squares discriminant analysis (PLS-DA) revealed that the metabolite profile in cucumber fruits was distinctively altered due to exposure to nCu. A number of metabolites were either up-regulated (proline, glycine, valine, pelargonic acid, arachidic acid, xylose, benzoic acid) or down-regulated (citric acid, myo-inositol, ornithine, 1-kestose) in response to nCu exposure. Biological pathway analysis showed a number of C and N related pathways were changed, especially galactose metabolism and the tricarboxylic acid cycle, indicating C and N metabolism was perturbed by nCu. This study showed GC-TOF-MS based metabolomics combined with ICP-MS based metallomics provide the necessary preliminary data to conduct further mechanistic investigations.Environ. Table S1. A summary of analysis of variance for effect of nCu on the biomass, Cu and Fe content are presented in Table S2. The concentration of metabolites in cucumber fruit analyzed by GC-TOF-MS are shown in Table S3. Effect of nCu on biomass of root, stem, leaf and fruit are shown in Fig. S1. Waterextractable Cu in soil solutions are shown in Fig. S2. Score plot and loading plot of mineral nutrient analyzing by PLS-DA are shown in Fig. S3 and S4; VIP scores and pathway impact are shown in Fig. S5. See DOI: 10.1039/c6en00093b
Nano impactWith the increasing use of copper-containing nano-pesticides in agriculture, a comprehensive understanding of their implications for terrestrial plants, especially edible crops, is needed. GC-TOF-MS based metabolomics and ICP-MS based metallomics were applied to investigate the response at the molecular level of cucumber plants exposed to nano-Cu. Fruit metabolomics revealed that the metabolite profiles were significantly changed due to exposure to nanoCu. Several metabolites, including 1-kestose, xylose, fructose, ornithine, citrulline, glycine, proline, oxoproline, methionine, aspartic acid, citric acid, glutaric acid, shikimic acid, benzoic acid, pelargonic acid, arachidic acid, linolenic acid, and caprylic acid were either down-or up-regulated. Nano-Cu also significantly changed the concentration of Ca, K, S, P, Zn, and Mg. The biological pathway of galactose met...