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Nanoparticle Size and Coating Chemistry Control Foliar Uptake Pathways, Translocation and Leaf-to-Rhizosphere Transport in Wheat Astrid Avellan, Jie Yun, Yilin Zhang, Eleanor Spielman-Sun, Jason M. Unrine, Juergen Thieme, Jieran Li, Enzo Lombi, Garret Bland, and Gregory V. Lowry ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.8b09781 • Publication Date (Web): 10 May 2019 Downloaded from http://pubs.acs.org on May 10, 2019

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ACS Nano

Nanoparticle Size and Coating Chemistry Control Foliar Uptake Pathways, Translocation and Leaf-to-Rhizosphere Transport in Wheat Astrid Avellan†*, Jie Yun†, Yilin Zhang†, Eleanor Spielman-Sun†, Jason M. Unrine‡, Juergen Thieme§, Jieran Li‡, Enzo Lombi∥, Garret Bland†, Gregory V. Lowry†** †. Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States ‡. Department of Plant and Soil Sciences, University of Kentucky, Lexington, Kentucky 40546, United States §. NSLS-II, Brookhaven National Laboratory, Brookhaven, New York 11973, United States ∥. Future Industries Institute, University of South Australia, Mawson Lakes, South Australia 5095, Australia * [email protected], **[email protected]

TOC

Abstract Nano-enabled foliar-applied agrochemicals can potentially be safer and more efficient than conventional products. However, limited understanding about how nanoparticle properties influence their interactions with plant leaves, uptake, translocation through the mesophyll to the vasculature, and transport to the rest of the plant prevents rational design. This study used a combination of Au quantification and spatial analysis to investigate how size (3, 10 or 50nm) and coating chemistry (PVP- vs citrate-) of gold nanoparticles (AuNPs) influence these processes. Following wheat foliar exposure to AuNPs suspensions (˜280 ng per plant), adhesion on the leaf surface was increased for smaller sizes and PVP-AuNPs compared to citrate-AuNPs. After 2 weeks, there was incomplete uptake of citrate-AuNPs with some AuNPs remaining on the outside of the cuticle layer. However, the fraction of citrate-AuNPs that had penetrated the cuticle was translocated efficiently to the plant vasculature. In contrast, for similar sizes, virtually all of the PVP-AuNPs crossed the cuticle layer after 2 weeks but its transport through the mesophyll cells was lower. As a consequence of PVPAuNP accumulation in the leaf mesophyll, wheat photosynthesis was impaired. Regardless of their ACS Paragon Plus Environment

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coating and sizes, the majority of the transported AuNPs accumulated in younger shoots (10-30%) and in roots (10-25%), and 5-15% of the NPs