Cu(OH) 2 nanorods undergo sulfidation in water: in situ formation of CuO nanorods as intermediates and enhanced toxicity

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ORIGINAL PAPER

Cu(OH)2 nanorods undergo sulfidation in water: in situ formation of CuO nanorods as intermediates and enhanced toxicity to Escherichia coli Heming Su1 · Xiaoting Qian1 · Zhouhang Gu2 · Zhenlan Xu3 · Haijin Lou1 · Xinyun Bian1 · Tao Zeng4 · Daohui Lin5 · Juliane Filser6 · Lingxiangyu Li1  Received: 5 April 2020 / Accepted: 11 June 2020 © Springer Nature Switzerland AG 2020

Abstract Fate and risk of nanomaterials in the environment have attracted wide attention over the years. Copper hydroxide (Cu(OH)2) nanorods have been used as antibacterial nanomaterials in agricultural products, leading to their release into the environment. Yet, knowledge about the transformation of Cu(OH)2 nanorods is currently scarce, representing a potential for the environment. Here we investigated the sulfidation process of Cu(OH)2 nanorods by dissolved sulfide ­(Na2S) in aqueous solutions with varied molar ratios of Cu(OH)2 nanorods versus ­Na2S. The solid products were characterized with focus on the roles of dissolved oxygen (DO) and dissolved sulfide on CuS formation. The impact of sulfidation on the toxicity of Cu(OH)2 nanorods for Escherichia coli was also investigated. Copper oxide (CuO) nanorods with comparable morphology to Cu(OH)2 nanorods were identified as the intermediate of Cu(OH)2 nanorods sulfidation. We proposed that in situ formation of selfassembly CuS nanorods was achieved through an anion-exchange reaction between ­O2− of CuO and ­S2− of ­Na2S. We found that sulfidation enhanced the toxicity of Cu(OH)2 nanorods to E. coli: the inhibition of E. coli growth increased from 1.2 to 22.6% with increasing sulfidation due to an increase of dissolved Cu concentration. Keywords Cu(OH)2 nanorods · Sulfidation · In situ transformation · Dissolved oxygen · Escherichia coli

Electronic supplementary material  The online version of this article (https​://doi.org/10.1007/s1031​1-020-01035​-4) contains supplementary material, which is available to authorized users. * Lingxiangyu Li [email protected] 1



Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, China

2



Key Laboratory of Plant Secondary Metabolism and Regulation of Zhejiang Province, College of Life Sciences and Medicine, Zhejiang Sci-Tech University, Hangzhou 310018, China

3

Institute of Quality and Standard of Agro‑Products, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China

4

College of Environment, Zhejiang University of Technology, Hangzhou 310014, China

5

Department of Environmental Science, Zhejiang University, Hangzhou 310058, China

6

UFT‑Centre for Environmental Research and Sustainable Technology, Department General and Theoretical Ecology, Faculty 2 (Biology/Chemistry), University of Bremen, Bremen 28359, Germany



Introduction Over the past decades, copper hydroxide (Cu(OH) 2) nanorods have been used as antibacterial nanomaterials in agricultural products, for instance, nanopesticides Kocide 3000 (Zhang et al. 2019). Cu(OH)2 nanorods are thus inevitably released into the environment. Altho

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