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1. Nanoscale Interactions: Evaluating the Ecotoxicity of Engineered Nanoparticles on the Dynamics of Commercially Important Microalgal Strains

   Louime, Clifford J. ; Diaz-Vazquez, Liz M. ; Perez, Abner ; Torres-Díaz, Marielys ; Rojas-Perez, Arnulfo ; Vázquez-López, Juan C. ; Davilla Aguer, Catalina ; Malca Reyes, Carlos A. ( April 2020 , International journal of science and engineering investigations)

   Society has long been exposed to naturally-occurring nanoparticles. Due to their ubiquitous nature, biological systems have adapted and built protection against their potential effects. However, for the past decades, there have been onslaughts of newly engineered nanoparticles being released in the environment with no known effects on ecosystems. Although these materials offer distinct advantages in manufacturing processes, such as odor-free fabric or controlled drug delivery, their fate in nature has yet to be thoroughly investigated. As the size of an already-large NPs market is expected to grow, due to advances in synthetic biology, it is vital that we increase our understanding of their impacts on human, food and natural ecosystems. Recent studies have shown that NPs affect phytoplankton biomass and diversity in the ocean, solely by regulating micronutrients bioavailability. These types of changes could ultimately impact several biogeochemical cycles, as phytoplankton are responsible for almost half of the primary production on earth. Consequently, this study was designed to evaluate the impact of various concentrations (0µM, 20µM, 40µM, 80µM and 100µM) of several manufactured nanoparticles (gold, carbon and iron) on the dynamics of four economically important microalgae strains. Responses, such as chlorophyll content, protein, lipid content, lipid profile, biomass and cell morphology were monitored over a period of two weeks. No significant acute toxicity was exhibited within the first 24 hours of exposure. However, after 4 days, a remarkably high mortality rate was detected with increasing NPs concentrations of Fe60, C80 and Au60. Iron suspensions were found to be more toxic to the microalgae strains tested than those of Gold and Carbon under comparable regimes. Further investigations with other, either positively or negatively charged nanoparticles, should provide a deeper understanding on the impacts on these engineered materials in our ecosystems. 

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2. Lipophilicity of Cationic Ligands Promotes Irreversible Adsorption of Nanoparticles to Lipid Bilayers

   https://doi.org/10.1021/acsnano.0c09732  

   Lochbaum, Christian A. ; Chew, Alex K. ; Zhang, Xianzhi ; Rotello, Vincent ; Van Lehn, Reid C. ; Pedersen, Joel A. ( January 2021 , ACS Nano)

   null (Ed.)

   A mechanistic understanding of the influence of the surface properties of engineered nanomaterials on their interactions with cells is essential for designing materials for applications such as bioimaging and drug delivery as well as for assessing nanomaterial safety. Ligand-coated gold nanoparticles have been widely investigated because their highly tunable surface properties enable investigations into the effect of ligand functionalization on interactions with biological systems. Lipophilic ligands have been linked to adverse biological outcomes through membrane disruption, but the relationship between ligand lipophilicity and membrane interactions is not well understood. Here, we use a library of cationic ligands coated on 2 nm gold nanoparticles to probe the impact of ligand end group lipophilicity on interactions with supported phosphatidylcholine lipid bilayers as a model for cytoplasmic membranes. Nanoparticle adsorption to and desorption from the model membranes were investigated by quartz crystal microbalance with dissipation monitoring. We find that nanoparticle adsorption to model membranes increases with ligand lipophilicity. The effects of ligand structure on gold nanoparticle attachment were further analyzed using atomistic molecular dynamics simulations, which showed that the increase in ligand lipophilicity promotes ligand intercalation into the lipid bilayer. Together, the experimental and simulation results could be described by a two-state model that accounts for the initial attachment and subsequent conversion to a quasi-irreversibly bound state. We find that only nanoparticles coated with the most lipophilic ligands in our nanoparticle library undergo conversion to the quasi-irreversible state. We propose that the initial attachment is governed by interaction between the ligands and phospholipid tail groups, whereas conversion into the quasi-irreversibly bound state reflects ligand intercalation between phospholipid tail groups and eventual lipid extraction from the bilayer. The systematic variation of ligand lipophilicity enabled us to demonstrate that the lipophilicity of cationic ligands correlates with nanoparticle-bilayer adsorption and suggested that changing the nonpolar ligand R group promotes a mechanism of ligand intercalation into the bilayer associated with irreversible adsorption. 

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3. The effect of nanoparticle surface charge on freshwater algae growth, reproduction, and lipid production

   https://doi.org/10.1039/D3EN00353A  

   McKeel, Emma ; Kim, Hye-In ; Jeon, Su-Ji ; Giraldo, Juan Pablo ; Klaper, Rebecca ( January 2024 , Environmental Science: Nano)

   Surface charge is a key characteristic of nanoparticles which has great potential to impact the interactions of nanoparticles and biological systems. Understanding the role charge plays in these interactions is key to determining the ecological risks of nanoparticle exposure and informing sustainable nanoparticle design. In this study, the model freshwater algae Raphidocelis subcapitata was exposed to carbon dots (CDs) functionalized with polymers to have positive, negative, or neutral surface charges to examine the impact of nanoparticle surface charge on nano-algae interactions. Traditional toxicological endpoints of survival and growth inhibition were measured. Additionally, morphological impacts on whole cells, individual organelles, and cellular components were quantified using high-content fluorescence microscopy, demonstrating one of the first uses of high-content imaging in microalgae. Results indicate that PEI functionalized, positively charged CDs are most toxic to green algae (EC50 42.306 μg/L), but that CDs with negative charge induce sublethal impacts on algae. PEI-CD toxicity is hypothesized to be related to electrostatic interactions between CDs and the algal cell wall, which lead to significant cell aggregation. Interestingly, morphological data suggests that exposure to both positively and negatively charged CDs leads to increased neutral lipid droplet formation, a possible indicator of nutrient stress. Further investigation of the mechanisms underlying impacts of nanoparticle surface charge on algae biology can lead to more sustainable nanoparticle design and environmental protections. 

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4. A fiddler crab reduces plant growth in its expanded range

   https://doi.org/10.1002/ecy.4203  

   Martínez‐Soto, Kayla S. ; Johnson, David S. ( December 2023 , Ecology)

   Species across the planet are shifting or expanding their ranges because of climate change. These are climate migrants. Although climate migrants are well documented, their impacts on recipient ecosystems are not. Climate migrants that are also ecosystem engineers (species that modify or create habitats) will likely have profound effects on ecosystems. The Atlantic marsh fiddler crab,Minuca pugnax, is a burrowing crab that recently expanded its range into the northeastern United States. In its historical range,M. pugnaxenhances the aboveground growth of the cordgrassSpartina alterniflora, a plant critical to marsh persistence. In a control‐impact study, however, we found thatSpartinaaboveground biomass was 40% lower whenM. pugnaxwas present. Thus, the positive effect ofM. pugnaxonSpartinaaboveground biomass flipped to a negative one in its expanded range.Spartinabelowground biomass was also 30% lower on average when crabs were present, a finding consistent with what is seen in the historical range. These impacts onSpartinaare likely due to burrowing byM. pugnax.Benthic microalgae was, on average, 45% lower when crabs were present. Fiddler crabs eat benthic microalgae, and these results suggest that fiddler crabs can control algal biomass via grazing. Because fiddler crabs reduced the biomass of foundational primary producers in its expanded range, our results imply thatM. pugnaxcan influence other saltmarsh functions such as carbon storage and accretion as they expand north. Most strikingly, our results suggest that as species expand or shift their range with climate change, not only can they have profound impacts in their new ranges but those impacts can be the inverse of what is seen in their historical ranges.

    

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5. Nutrients associated with terrestrial dissolved organic matter drive changes in zooplankton:phytoplankton biomass ratios in an alpine lake

   https://doi.org/10.1111/fwb.12847  

   Kissman, Carrie E. H. ; Williamson, Craig E. ; Rose, Kevin C. ; Saros, Jasmine E. ( November 2016 , Freshwater Biology)

   Dissolved organic matter (DOM) is increasing in many lakes due to climate change and other environmental forcing. A 21‐day microcosm experiment that manipulated terrestrialDOMwas used to determine the effect ofDOMon zooplankton:phytoplankton biomass ratios (z:p). We predicted that ifDOMadditions increase the amount of fixed carbon available for higher trophic levels through stimulation of the microbial loop and hence zooplankton, the z:p will increase. However, ifDOMadditions increase other nutrients besides fixed carbon, we predict stable or decreasing z:p due to nutrient stimulation of phytoplankton that subsequently enhances zooplankton.

   The effects of experimental additions of terrestrially derivedDOMon zooplankton, phytoplankton, z:p and zooplankton net grazing were assessed in microcosms (sealed bags) incubated in the epilimnion (shallow; 1.5 m) and hypolimnion (deep; 8.0 m) strata of an alpine lake.

   DOMaddition treatments (DOM+) had a 6.0‐ to 7.5‐fold increase in phytoplankton biomass relative to controls, but only a 1.3‐ to 1.5‐fold increase in zooplankton biomass, on day 21 of the experiment. The z:p was, thus, lower in theDOM+ treatments (ratios: 2.3 deep and 4.4 shallow) than in the control treatments (ratios: 13.4 deep and 17.5 shallow), providing evidence thatDOMadditions provide nutrient subsidies besides fixed carbon that stimulate phytoplankton biomass accumulation.

   The increase in zooplankton biomass during the experiment was similar in magnitude to the total amount of dissolved organic carbon (DOC) in theDOMadded in the sealed bags at the beginning of the experiment, which suggests zooplankton biomass stimulation due to increased phytoplankton biomass, and not fromDOMthrough the microbial loop, which would have greater trophic transfer losses. The consumer net grazing effect in theDOM+ treatments was reduced by 2.8‐fold in the shallow stratum and by 2.9‐fold in the deep stratum relative to the control treatments, indicating that zooplankton were unable to exert strong top–down control on the primary producers.

   The role of nutrients needs to be considered when examining the response of pelagic ecosystems to inputs of terrestrialDOM, especially in lakes with lowerDOCconcentrations.

    

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