With increasing global population, innovations in agriculture will be essential for a sustainable food supply. We compare commercial CuO NP to synthesized Cu 3 (PO 4 ) 2 •3H 2 O nanosheets to determine the influence of coordinating anion, particle morphology, and dissolution profile on Fusarium oxysporum f. sp. niveum induced disease in watermelon. Copper dissolution in organic acid solutions that mimic complexing agents found in plants was increased by 2 orders of magnitude relative to water. Cu 3 (PO 4 ) 2 •3H 2 O nanosheets showed a rapid initial dissolution, with equilibration after 24 h; CuO NP exhibited continuous particle dissolution. In a greenhouse study, Cu 3 (PO 4 ) 2 •3H 2 O nanosheets at 10 mg/L significantly repressed fungal disease as measured by yield and by a 58% decrease in disease progress. Conversely, CuO NP only yielded significant effects on disease at 1000 mg/L. In field studies, similar enhanced disease suppression was noted for Cu 3 (PO 4 ) 2 •3H 2 O nanosheets, although biomass and yield effects were variable. The method of application was a significant factor in treatment success, with the dip method being more effective than foliar spray; this is likely due to homogeneity of coverage during treatment. The data show that Cu-based nanoscale materials can be an effective and sustainable strategy in the crop disease management but that particle characteristics such as morphology, coordination environment, and dissolution profile will be important determinants of success.

There has been a surge of consumer products that incorporate nanoparticles, which are used to improve or impart new functionalities to the products based on their unique physicochemical properties. With such an increase in products containing nanomaterials, there is a need to understand their potential impacts on the environment. This is often done using various biological models that are abundant in the different environmental compartments where the nanomaterials may end up after use. Beyond studying whether nanomaterials simply kill an organism, the molecular mechanisms by which nanoparticles exhibit toxicity have been extensively studied. Some of the main mechanisms include (1) direct nanoparticle association with an organism's cell surface, where the membrane can be damaged or initiate internal signaling pathways that damage the cell, (2) dissolution of the material, releasing toxic ions that impact the organism, generally through impairing important enzyme functions or through direct interaction with a cell's DNA, and (3) the generation of reactive oxygen species and subsequent oxidative stress on an organism, which can also damage important enzymes or an organism's genetic material. This Account reviews these toxicity mechanisms, presenting examples for each with different types of nanomaterials. Understanding the mechanism of nanoparticle toxicity will inform efforts to redesign nanoparticles with reduced environmental impact. The redesign strategies will need to be chosen based on the major mode of toxicity, but also considering what changes can be made to the nanomaterial without impacting its ability to perform in its intended application. To reduce interactions with the cell surface, nanomaterials can be designed to have a negative surface charge, use ligands such as polyethylene glycol that reduce protein binding, or have a morphology that discourages binding with a cell surface. To reduce the nanoparticle dissolution to toxic ions, the toxic species can be replaced with less toxic elements that have similar properties, the nanoparticle can be capped with a shell material, the morphology of the nanoparticle can be chosen to minimize surface area and thus minimize dissolution, or a chelating agent can be co-introduced or functionalized onto the nanomaterial's surface. To reduce the production of reactive oxygen species, the band gap of the material can be tuned either by using different elements or by doping, a shell layer can be added to inhibit direct contact with the core, or antioxidant molecules can be tethered to the nanoparticle surface. When redesigning nanoparticles, it will be important to test that the redesign strategy actually reduces toxicity to organisms from relevant environmental compartments. It is also necessary to confirm that the nanomaterial still demonstrates the critical physicochemical properties that inspired its inclusion in a product or device.

This work investigates the biological impact of LixNiyMnzCo1−y−zO2, a class of cathode materials used in lithium ion batteries.

Current high-throughput approaches evaluating toxicity of chemical agents toward bacteria typically rely on optical assays, such as luminescence and absorbance, to probe the viability of the bacteria. However, when applied to toxicity induced by nanomaterials, scattering and absorbance from the nanomaterials act as interferences that complicate quantitative analysis. Herein, we describe a bacterial viability assay that is free of optical interference from nanomaterials and can be performed in a high-throughput format on 96-well plates. In this assay, bacteria were exposed to various materials and then diluted by a large factor into fresh growth medium. The large dilution ensured minimal optical interference from the nanomaterial when reading optical density, and the residue left from the exposure mixture after dilution was confirmed not to impact the bacterial growth profile. The fractions of viable cells after exposure were allowed to grow in fresh medium to generate measurable growth curves. Bacterial viability was then quantitatively correlated to the delay of bacterial growth compared to a reference regarded as 100% viable cells; data analysis was inspired by that in quantitative polymerase chain reactions, where the delay in the amplification curve is correlated to the starting amount of the template nucleic acid. Fast and robust data analysis was achieved by developing computer algorithms carried out using R. This method was tested on four bacterial strains, including both Gram-negative and Gram-positive bacteria, showing great potential for application to all culturable bacterial strains. With the increasing diversity of engineered nanomaterials being considered for large-scale use, this high-throughput screening method will facilitate rapid screening of nanomaterial toxicity and thus inform the risk assessment of nanoparticles in a timely fashion.

Research at the interface of synthetic materials, biochemistry, and analytical techniques has enabled sensing platforms for applications across many research communities. Herein we review the materials used as affinity agents to create surface-enhanced Raman spectroscopy (SERS) sensors. Our scope includes those affinity agents (antibody, aptamer, small molecule, and polymer) that facilitate the intrinsic detection of targets relevant to biology, medicine, national security, environmental protection, and food safety. We begin with an overview of the analytical technique (SERS) and considerations for its application as a sensor. We subsequently describe four classes of affinity agents, giving a brief overview on affinity, production, attachment chemistry, and first uses with SERS. Additionally, we review the SERS features of the affinity agents, and the analytes detected by intrinsic SERS with that affinity agent class. We conclude with remarks on affinity agent selection for intrinsic SERS sensing platforms.