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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.

The composition, orientation, and conformation of proteins in biomolecular coronas acquired by nanoparticles in biological media contribute to how they are identified by a cell. While numerous stud...

The interaction of lipopolysaccharides (LPS) with metal cations strongly affects the stability and function of the Gram-negative bacterial outer membrane. The sensitivity of deep rough (Re) LPS packing and function to the ionic environment, as affected by cation valency and ionic radius, has been determined using molecular dynamics simulations and Langmuir balance experiments. The degree of LPS aggregation within the LPS models in the presence of different cations is assessed by measuring the effective mean molecular area (

The initial interactions of engineered nanoparticles (NPs) with living cells are governed by physicochemical properties of the NP and the molecular composition and structure of the cell membrane. Eukaryotic cell membranes contain lipid rafts – liquid-ordered nanodomains involved in membrane trafficking and molecular signaling. However, the impact of these membrane structures on cellular interactions of NPs remains unclear. Here we investigate the role of membrane domains in the interactions of primary amine-terminated quantum dots (Qdots) with liquid-ordered domains or lipid rafts in model membranes and intact cells, respectively. Using correlative atomic force and fluorescence microscopy, we found that the Qdots preferentially localized to boundaries between liquid-ordered and liquid-disordered phases in supported bilayers. The Qdots also induced holes at these phase boundaries. Using super resolution fluorescence microscopy (STORM), we found that the Qdots preferentially co-localized with lipid rafts in the membrane of intact trout gill epithelial cells – a model cell type for environmental exposures. Our observations uncovered preferential interactions of amine-terminated Qdots with liquid-ordered domains and their boundaries, possibly due to membrane curvature at phase boundaries creating energetically favorable sites for NP interactions. The preferential interaction of the Qdots with lipid rafts supports their potential internalization via lipid raft-mediated endocytosis and interactions with raft-resident signaling molecules.

Molecular-level understanding of nanomaterial interactions with bacterial cell surfaces can facilitate design of antimicrobial and antifouling surfaces and inform assessment of potential consequences of nanomaterial release into the environment. Here, we investigate the interaction of cationic nanoparticles with the main surface components of Gram-positive bacteria: peptidoglycan and teichoic acids. We employed intact cells and isolated cell walls from wild type Bacillus subtilis and two mutant strains differing in wall teichoic acid composition to investigate interaction with gold nanoparticles functionalized with cationic, branched polyethylenimine. We quantified nanoparticle association with intact cells by flow cytometry and determined sites of interaction by solid-state 31P- and 13C-NMR spectroscopy. We find that wall teichoic acid structure and composition were important determinants for the extent of interaction with cationic gold nanoparticles. The nanoparticles interacted more with wall teichoic acids from the wild type and mutant lacking glucose in its wall teichoic acids than those from the mutant having wall teichoic acids lacking alanine and exhibiting more restricted molecular motion. Our experimental evidence supports the interpretation that electrostatic forces contributed to nanoparticle–cell interactions and that the accessibility of negatively charged moieties in teichoic acid chains influences the degree of interaction. The approaches employed in this study can be applied to engineered nanomaterials differing in core composition, shape, or surface functional groups as well as to other types of bacteria to elucidate the influence of nanoparticle and cell surface properties on interactions with Gram-positive bacteria., Cationic gold nanoparticle interaction with strains of Bacillus subtilis is dictated by wall teichoic acid structure and composition.

Metal nanoparticles (NPs) functionalized with self-assembled monolayers (SAMs) of long alkanethiol ligands are subject to defects in the SAM structure due to the interplay between alkyl chain packi...

Many pharmaceuticals are present in reclaimed wastewater and effluent-dominated water bodies used to irrigate edible crops. Previous research has shown that plants irrigated with reclaimed wastewater can accumulate pharmaceuticals. However, plant-driven processes that contribute to differences in accumulation among compounds are not well understood. Here, we tested the effects of exposure to mixtures on spinach accumulation and metabolism of four psychoactive pharmaceuticals found in reclaimed wastewater: carbamazepine, fluoxetine, amitriptyline, and lamotrigine. Coexposure of plants to carbamazepine and fluoxetine or amitriptyline decreased accumulation of the toxic carbamazepine metabolite 10,11-epoxycarbamazepine. Furthermore, we tested a simple transpiration-based accumulation model and found that transpiration is a strong predictor for accumulation of the studied compounds. Amitriptyline accumulated to a larger extent than predicted from transpiration alone, and we suggest the possibility that a transporter protein may be involved in its uptake. Our findings highlight the need to consider plant physiology and mixture effects in studying accumulation of polar and ionizable organic contaminants and their metabolites.

Understanding the interactions between surface-functionalized gold nanoparticles (NPs) and lipid bilayers is necessary to guide the design of NPs for biomedical applications. Recent experiments found that cationic NPs adsorb more strongly to phase-separated multicomponent lipid bilayers than single-component liquid-disordered bilayers, suggesting that phase separation affects NP-bilayer interactions. In this work, we use coarse-grained molecular dynamics simulations to investigate the effect of lipid phase behavior on the adsorption of small cationic NPs. We first determined the free energy change for adsorbing a NP to one-phase liquid-disordered and one-phase liquid-ordered bilayers. The simulations indicate that NP adsorption depends on a competition between favorable NP-lipid interactions and the unfavorable curvature deformation of the bilayer, resulting in stronger interactions with the liquid-disordered bilayer due to its lower bending modulus. We then measured the free energy change associated with moving a NP across the surface of a phase-separated bilayer and identified a free energy minimum at the phase boundary. The free energy minimum is attributed to the thickness gradient between the two phases that enables favorable NP-lipid interactions without necessitating large curvature deformations. The simulation results thus indicate that the intrinsic curvature present at phase boundaries drives preferential interactions with surface-adsorbed NPs, providing new insight into the forces that drive NP behavior at multicomponent, phase-separated lipid bilayers.

Supported lipid bilayers (SLBs) have proven to be valuable model systems for studying the interactions of proteins, peptides, and nanoparticles with biological membranes. The physicochemical properties (e.g., topography, coating) of the solid substrate may affect the formation and properties of supported phospholipid bilayers, and thus, subsequent interactions with biomolecules or nanoparticles. Here, we examine the influence of support coating (SiO2vs Si3N4) and topography [sensors with embedded vs protruding gold nanodisks for nanoplasmonic sensing (NPS)] on the formation and subsequent interactions of supported phospholipid bilayers with the model protein cytochrome c and with cationic polymer-wrapped quantum dots using quartz crystal microbalance with dissipation monitoring and NPS techniques. The specific protein and nanoparticle were chosen because they differ in the degree to which they penetrate the bilayer. We find that bilayer formation and subsequent non-penetrative association with cytochrome c were not significantly influenced by substrate composition or topography. In contrast, the interactions of nanoparticles with SLBs depended on the substrate composition. The substrate-dependence of nanoparticle adsorption is attributed to the more negative zeta-potential of the bilayers supported by the silica vs the silicon nitride substrate and to the penetration of the cationic polymer wrapping the nanoparticles into the bilayer. Our results indicate that the degree to which nanoscale analytes interact with SLBs may be influenced by the underlying substrate material.

Electrochemical formation of high-energy species such as hydroxyl radicals in aqueous media is inefficient because oxidation of H2O to form O2 is a more thermodynamically favorable reaction. Boron-doped diamond (BDD) is widely used as an electrode material for generating •OH radicals because it has a very large kinetic overpotential for O2 production, thus increasing electrochemical efficiency for •OH production. Yet, the underlying mechanisms of O2 and •OH production at diamond electrodes are not well understood. We demonstrate that boron-doped diamond surfaces functionalized with hydrophobic, polyfluorinated molecular ligands (PF-BDD) have significantly higher electrochemical efficiency for •OH production compared with hydrogen-terminated (H-BDD), oxidized (O-BDD), or poly(ethylene ether)-functionalized (E-BDD) boron-doped diamond samples. Our measurements show that •OH production is nearly independent of surface functionalization and pH (pH = 7.4 vs 9.2), indicating that •OH is produced by oxidation of H2O in an outer-sphere electron-transfer process. In contrast, the total electrochemical current, which primarily produces O2, differs strongly between samples with different surface functionalizations, indicating an inner-sphere electron-transfer process. X-ray photoelectron spectroscopy measurements show that although both H-BDD and PF-BDD electrodes are oxidized over time, PF-BDD showed longer stability (≈24 h of use) than H-BDD. This work demonstrates that increasing surface hydrophobicity using perfluorinated ligands selectively inhibits inner-sphere oxidation to O2 and therefore provides a pathway to increased efficiency for formation of •OH via an outer-sphere process. The use of hydrophobic electrodes may be a general approach to increasing selectivity toward outer-sphere electron-transfer processes in aqueous media.

Summary Although mixing nanoparticles with certain biological molecules can result in coronas that afford some control over how engineered nanomaterials interact with living systems, corona formation mechanisms remain enigmatic. Here, we report results from experiments and computer simulations that provide concrete lines of evidence for spontaneous lipid corona formation without active mixing upon attachment to stationary and suspended lipid bilayer membranes. Experiments show that polycation-wrapped particles disrupt the tails of zwitterionic lipids, increase bilayer fluidity, and leave the membrane with reduced ζ potentials. Computer simulations suggest that the contact ion pairing between the lipid head groups and the polycations' ammonium groups leads to the formation of stable, albeit fragmented, lipid bilayer coronas. The mechanistic insight regarding lipid corona formation can be used to improve control over nano-bio interactions and to help understand why some nanomaterial-ligand combinations are detrimental to organisms but others are not.

Perfluoroalkyl substances (PFAS) are ubiquitous and persistent environmental contaminants, yet knowledge of their biological effects and mechanisms of action is limited. The highest aqueous PFAS concentrations are found in areas where bacteria are relied upon for functions such as nutrient cycling and contaminant degradation, including fire-training areas, wastewater treatment plants, and landfill leachates. This research sought to elucidate one of the mechanisms of action of PFAS by studying their uptake by bacteria and partitioning into model phospholipid bilayer membranes. PFAS partitioned into bacteria as well as model membranes (phospholipid liposomes and bilayers). The extent of incorporation into model membranes and bacteria was positively correlated to the number of fluorinated carbons. Furthermore, incorporation was greater for perfluorinated sulfonates than for perfluorinated carboxylates. Changes in zeta potential were observed in liposomes but not bacteria, consistent with PFAS being incorporated into the phospholipid bilayer membrane. Complementary to these results, PFAS were also found to alter the gel-to-fluid phase transition temperature of phospholipid bilayers, demonstrating that PFAS affected lateral phospholipid interactions. This investigation compliments other studies showing that sulfonated PFAS and PFAS with more than seven fluorinated carbons have a higher potential to accumulate within biota than carboxylated and shorter-chain PFAS.

Bacterial uptake of charged organic pollutants such as the widely used herbicide glyphosate is typically attributed to active transporters, whereas passive membrane permeation as an uptake pathway is usually neglected. For 1-palmitoyl-2-oleoyl-snglycero-3-phosphocholine (POPC) liposomes, the pH-dependent apparent membrane permeation coefficients (P-app) of glyphosate, determined by nuclear magnetic resonance (NMR) spectroscopy, varied from P-app (pH 7.0) = 3.7 (+/- 0.3) x 10(-7) m.s(-1) to P-app (pH 4.1) = 4.2 (+/- 0.1) x 10(-6) m.s(-1). The magnitude of this surprisingly rapid membrane permeation depended on glyphosate speciation and was, at circumneutral pH, in the range of polar, noncharged molecules. These findings point to passive membrane permeation as a potential uptake pathway during glyphosate biodegradation. To test this hypothesis, a Gram-negative glyphosate degrader, Ochrobactrum sp. FrEM, was isolated from glyphosate-treated soil and glyphosate permeation rates inferred from the liposome model system were compared to bacterial degradation rates. Estimated maximum permeation rates were, indeed, 2 orders of magnitude higher than degradation rates of glyphosate. In addition, biodegradation of millimolar glyphosate concentrations gave rise to pronounced carbon isotope fractionation with an apparent kinetic isotope effect, AKIE(carbon), of 1.014 +/- 0.003. This value lies in the range typical of non-masked enzymatic isotope fractionation demonstrating that glyphosate biodegradation was not subject to mass transfer limitations and glyphosate exchange across the cell membrane was rapid relative to enzymatic turnover.

Many ionizable organic contaminants (IOCs) are present in treated wastewater used to irrigate edible crops and accumulate in plants under field conditions. Phytoavailability of IOCs with pKa values between 4 and 9 may be affected by the pH of the rhizosphere (the water and soil within 2–3 mm of the root surface). Plants can alter rhizosphere pH by 2–3 units in either direction in response to nutrient availability. The effects of plant modulation of rhizosphere pH on IOC accumulation have not been previously reported. Here we provide direct evidence that plant-driven changes in rhizosphere pH impact accumulation of an IOC in plant leaves. Using a modified hydroponic system, we found that rhizosphere pH was higher by 1.5–2.4 units when plants received only nitrate rather than a combination of nitrate and ammonium. Plant-driven changes to rhizosphere pH altered accumulation of lamotrigine (pKa = 5.7) but not carbamazepine, a non-ionizable contaminant. Lamotrigine accumulation in leaves correlated strongly wi...

Charge densities of cationic polymers adsorbed to lipid bilayers are estimated from second harmonic generation (SHG) spectroscopy and quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The systems surveyed included poly(vinylamine hydrochloride) (PVAm), poly(diallyldimethylammonium chloride) (PDADMAC), poly-l-lysine (PLL), and poly-l-arginine (PLR), as well as polyalcohol controls. Upon accounting for the number of positive charges associated with each polyelectrolyte, the binding constants and apparent free energies of adsorption as estimated from SHG data are comparable despite differences in molecular masses and molecular structure, with ΔGads values of -61 ± 2, -58 ± 2, -57 ± 1, -52 ± 2, -52 ± 1 kJ mol-1 for PDADMAC400, PDADMAC100, PVAm, PLL, and PLR, respectively. Moreover, we find charge densities for polymer adlayers of approximately 0.3 C m-2 for poly(diallyldimethylammonium chloride) while those of poly(vinylamine) hydrochloride, poly-l-lysine, and poly-l-arginine are approximately 0.2 C m-2. Time-dependent studies indicate that polycation adsorption to supported lipid bilayers is only partially reversible for most of the polymers explored. Poly(diallyldimethylammonium chloride) does not demonstrate reversible binding even over long timescales (>8 hours).

Interactions of functionalized nanomaterials with biological membranes are expected to be governed by not only nanoparticle physiochemical properties but also coatings or "coronas" of biomacromolecules acquired after immersion in biological fluids. Here we prepared a library of 4-5 nm gold nanoparticles (AuNPs) coated with either ω-functionalized thiols or polyelectrolyte wrappings to examine the influence of surface functional groups on the assemblage of proteins complexing the nanoparticles and its subsequent impact on attachment to model biological membranes. We find that the initial nanoparticle surface coating has a cascading effect on interactions with model cell membranes by determining the assemblage of complexing proteins, which in turn influences subsequent interaction with model biological membranes. Each type of functionalized AuNP investigated formed complexes with a unique ensemble of serum proteins that depended on the initial surface coating of the nanoparticles. Formation of protein-nanoparticle complexes altered the electrokinetic, hydrodynamic, and plasmonic properties of the AuNPs. Complexation of the nanoparticles with proteins reduced the attachment of cationic AuNPs and promoted attachment of anionic AuNPs to supported lipid bilayers; this trend is observed with both lipid bilayers comprising 100% zwitterionic phospholipids and those incorporating anionic phosphatidylinositol. Complexation with serum proteins led to attachment of otherwise noninteracting oligo(ethylene glycol)-functionalized AuNPs to bilayers containing phosphatidylinositol. These results demonstrate the importance of considering both facets of the nano-bio interface: functional groups displayed on the nanoparticle surface and proteins complexing the nanoparticles influence interaction with biological membranes as does the molecular makeup of the membranes themselves.

Mechanistic insight into how polycations disrupt and cross cell membranes is needed for understanding and controlling polycation-membrane interactions, yet such information is surprisingly difficult to obtain at the molecular level. We use second harmonic and vibrational sum frequency generation spectroscopies along with quartz crystal microbalance with dissipation monitoring and computer simulations to quantify the interaction of poly(allylamine) hydrochloride (PAH) and its monomeric precursor allylamine hydrochloride (AH) with lipid bilayers. We find PAH adsorption to be reversible and nondisruptive to the bilayer under the conditions of our experiments. With an observed free adsorption energy of -52.7 ± 0.6 kJ/mol, PAH adsorption was found to be surprisingly less favorable relative to AH (-14.6 ± 0.4 kJ/mol) when considering a simple additive model. By experimentally quantifying the number of adsorbates and the average amount of charge carried by each adsorbate, we find that the PAH is associated with only 70% of the positive charges it could hold while the AH remains mostly charged while attached to the membrane. Simulations indicate that PAH pulls in condensed counterions from solution to avoid charge-repulsion along its backbone and with other PAH molecules to attach to, and completely cover, the bilayer surface. In addition, computations indicate that the amine groups shift their pK

The surface charge of nanomaterials determines their stability in solution and interaction with other molecules and surfaces, yet experimental determination of surface charge of complex nanomaterials is not straightforward. We propose a hybrid approach that iteratively integrates explicit solvent molecular dynamics simulations and a multiconformer continuum electrostatic model (MCCE) to efficiently sample the configurational and titration spaces of surface ligands of nanomaterials. Test calculations of model systems indicate that the iterative approach converges rapidly even for systems that contain hundreds of titratable sites, making the approach complementary to more elaborate methods such as explicit solvent-based constant-pH molecular dynamics. The hybrid method is applied to analyze the pKa distribution of alkylamines attached to a carbon-based nanoparticle as a function of ligand density, nanoparticle surface curvature, and ligand heterogeneity. The results indicate that functionalization strategie...

A variety of peptidic and proteinaceous contaminants (e.g., proteins, toxins, pathogens) present in the environment may pose risk to human health and wildlife. Peroxymonosulfate is a strong oxidant (EH0 = 1.82 V for HSO5-, the predominant species at environmental pH values) that may hold promise for the deactivation of proteinaceous contaminants. Relatively little quantitative information exists on the rates of peroxymonosulfate reactions with free amino acids. Here, we studied the oxidation of 19 of the 20 standard proteinogenic amino acids (all except cysteine) by peroxymonosulfate without explicit activation. Reaction half-lives at pH 7 ranged from milliseconds to hours. Amino acids possessing sulfur-containing, heteroaromatic, or substituted aromatic side chains were the most susceptible to oxidation by peroxymonosulfate, with rates of transformation decreasing in the order methionine > tryptophan > tyrosine > histidine. The rate of tryptophan oxidation did not decrease in the presence of an aquatic natural organic matter. Singlet oxygen resulting from peroxymonosulfate self-decomposition, while detected by electron paramagnetic resonance spectroscopy, was unlikely to be the principal reactive species. Our results demonstrate that peroxymonosulfate is capable of oxidizing 19 amino acids without explicit activation and that solvent-exposed methionine and tryptophan residues are likely initial targets of oxidation in peptides and proteins.

Membrane-bound proteins can play a role in the binding of anionic gold nanoparticles (AuNPs) to model bilayers; however, the mechanism for this binding remains unresolved. In this work, we determine the relative orientation of the peripheral membrane protein cytochrome c in binding to a mercaptopropionic acid-functionalized AuNP (MPA-AuNP). As this is nonrigid binding, traditional methods involving crystallographic or rigid molecular docking techniques are ineffective at resolving the question. Instead, we have implemented a computational assay technique using a cross-correlation of a small ensemble of 200 ns long molecular dynamics trajectories to identify a preferred nonrigid binding orientation or pose of cytochrome c on MPA-AuNPs. We have also employed a mass spectrometry-based footprinting method that enables the characterization of the stable protein corona that forms at long time-scales in solution but remains in a dynamic state. Through the combination of these computational and experimental primary results, we have established a consensus result establishing the identity of the exposed regions of cytochrome c in proximity to MPA-AuNPs and its complementary pose(s) with amino-acid specificity. Moreover, the tandem use of the two methods can be applied broadly to determine the accessibility of membrane-binding sites for peripheral membrane proteins upon adsorption to AuNPs or to determine the exposed amino-acid residues of the hard corona that drive the acquisition of dynamic soft coronas. We anticipate that the combined use of simulation and experimental methods to characterize biomolecule-nanoparticle interactions, as demonstrated here, will become increasingly necessary as the complexity of such target systems grows.

International audience; The chemical composition and properties of environmental media determine nanomaterial (NM) transport, fate, biouptake, and organism response. To compare and interpret experimental data, it is essential that sufficient context be provided for describing the physical and chemical characteristics of the setting in which a nanomaterial may be present. While the nanomaterial environmental, health and safety (NanoEHS) field has begun harmonization to allow data comparison and re-use (e.g. using standardized materials, defining a minimum set of required material characterizations), there is limited guidance for standardizing test media. Since most of the NM properties driving environmental behaviour and toxicity are medium-dependent, harmonization of media is critical. A workshop in March 2016 at Duke University identified five categories of test media: aquatic testing media, soil and sediment testing media, biological testing media, engineered systems testing media and product matrix testing media. For each category of test media, a minimum set of medium characteristics to report in all NM tests is recommended. Definitions and detail level of the recommendations for specific standardized media vary across these media categories. This reflects the variation in the maturity of their use as a test medium and associated measurement techniques, variation in utility and relevance of standardizing medium properties, ability to simplify standardizing reporting requirements, and in the availability of established standard reference media. Adoption of these media harmonization recommendations will facilitate the generation of integrated comparable datasets on NM fate and effects. This will in turn allow testing of the predictive utility of functional assay measurements on NMs in relevant media, support investigation of first principles approaches to understand behavioral mechanisms, and support categorization strategies to guide research, commercial development, and policy.

Prions, the etiological agents in transmissible spongiform encephalopathies, exhibit remarkable resistance to most methods of inactivation that are effective against conventional pathogens. Prions are composed of pathogenic conformers of the prion protein (PrPTSE). Some prion diseases are transmitted, in part, through environmental routes. The recalcitrance of prions to inactivation may lead to a persistent reservoir of infectivity that contributes to the environmental maintenance of epizootics. At present, few methods exist to remediate prion-contaminated lands. Here we examined the ability of peroxymonosulfate to degrade PrPTSE as an initial step toward developing an in situ chemical oxidation process to inactivate prions. We find that peroxymonosulfate rapidly degrades PrPTSE from two species. Transition metal-catalyzed decomposition of peroxymonosulfate to produce sulfate radicals appears to enhance degradation. We further demonstrate that exposure to peroxymonosulfate significantly reduced PrPC-to-PrPTSE converting ability as measured by protein misfolding cyclic amplification, used as a proxy for infectivity. Liquid chromatography-tandem mass spectrometry revealed that exposure to peroxymonosulfate results in oxidative modifications to methionine and tryptophan residues. This study indicates that peroxymonosulfate may hold promise for in situ remediation of prion-contaminated surfaces.

Second harmonic generation (SHG) is useful for studying the properties of interfaces, including the surfaces of nanoparticles and the interaction of nanoparticles with biologically relevant surfaces. Gold nanoparticles at the biological membrane represent a particularly interesting system to be probed by SHG spectroscopy given the rich electronic structure of gold nanoparticles and the charged nature of the nano-bio interface. Here we describe the interplay between the resonant and nonresonant components of the second harmonic response as 4 and 14 nm spherical gold nanoparticles (AuNPs) wrapped in the cationic polyelectrolyte poly(allylamine hydrochloride) (PAH) adsorb to negatively charged supported lipid bilayers. In contrast to the SHG response of 4 nm PAH-AuNPs, that we have shown previously to be dominated by resonance enhancement, the SHG response from the adsorption of the 14 nm PAH-AuNPs, with similar hydrodynamic diameters, to a 9:1 DOPC:DOTAP bilayer is dominated by the nonresonant, interfacial,...

Crops irrigated with reclaimed wastewater or grown in biosolids-amended soils may take up pharmaceuticals and personal care product ingredients (PPCPs) through their roots. The uptake pathways followed by PPCPs and the propensity for these compounds to bioaccumulate in food crops are still not well understood. In this critical review, we discuss processes expected to influence root uptake of PPCPs, evaluate current literature on uptake of PPCPs, assess models for predicting plant uptake of these compounds, and provide recommendations for future research, highlighting processes warranting study that hold promise for improving mechanistic understanding of plant uptake of PPCPs. We find that many processes that are expected to influence PPCP uptake and accumulation have received little study, particularly rhizosphere interactions, in planta transformations, and physicochemical properties beyond lipophilicity (as measured by Kow). Data gaps and discrepancies in methodology and reporting have so far hindered development of models that accurately predict plant uptake of PPCPs. Topics warranting investigation in future research include the influence of rhizosphere processes on uptake, determining mechanisms of uptake and accumulation, in planta transformations, the effects of PPCPs on plants, and the development of predictive models.

Antimicrobial silver nanoparticles used in consumer products may be released during fabrication, during product use, or after disposal and may reach terrestrial and aquatic ecosystems, prompting concern about their potential to adversely impact the environment (Benn and Westerhoff, Environ. Sci. Technol., 2008, 42, 4133, DOI: 10.1021/es7032718). Although the toxicity of pristine silver nanoparticles is well studied and understood, silver nanoparticles can undergo transformation during release and in engineered and natural environments. The speciation of silver after release must therefore be explored to deepen understanding of the potential impact of these nanoparticles on the environment. Herein, we highlight three articles which use highly sensitive analytical techniques to define, and in some cases map, silver speciation in situ after exposure to organisms of varying size and complexity. First, we highlight research by Leonardo et al. which explores the transformations of silver acted upon by a microalgae species that is a candidate for heavy metal remediation in water. Next, we highlight research by Stegemeier et al. quantifying and mapping the speciation of silver in alfalfa after exposure to several silver sources, including two silver-based nanoparticles. Finally, we discuss work by Wang et al. on silver speciation in human monocyte cells as observed by synchrotron radiation techniques which leads to mechanistic insights on cytotoxicity.

Quantifying the number of charges on peptides bound to interfaces requires reliable estimates of (i) surface coverage and (ii) surface charge, both of which are notoriously difficult parameters to obtain, especially at solid/water interfaces. Here, we report the thermodynamics and electrostatics governing the interactions of l-lysine and l-arginine octamers (Lys8 and Arg8) with supported lipid bilayers prepared., Quantifying the number of charges on peptides bound to interfaces requires reliable estimates of (i) surface coverage and (ii) surface charge, both of which are notoriously difficult parameters to obtain, especially at solid/water interfaces. Here, we report the thermodynamics and electrostatics governing the interactions of l-lysine and l-arginine octamers (Lys8 and Arg8) with supported lipid bilayers prepared from a 9 : 1 mixture of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-dimyristoyl-sn-glycero-3-phospho-(1′-rac-glycerol) (sodium salt) (DMPG) from second harmonic generation (SHG) spectroscopy, quartz crystal microbalance with dissipation monitoring (QCM-D) and nanoplasmonic sensing (NPS) mass measurements, and atomistic simulations. The combined SHG/QCM-D/NPS approach provides interfacial charge density estimates from mean field theory for the attached peptides that are smaller by a factor of approximately two (0.12 ± 0.03 C m–2 for Lys8 and 0.10 ± 0.02 C m–2 for Arg8) relative to poly-l-lysine and poly-l-arginine. These results, along with atomistic simulations, indicate that the surface charge density of the supported lipid bilayer is neutralized by the attached cationic peptides. Moreover, the number of charges associated with each attached peptide is commensurate with those found in solution; that is, Lys8 and Arg8 are fully ionized when attached to the bilayer. Computer simulations indicate Lys8 is more likely than Arg8 to “stand-up” on the surface, interacting with lipid headgroups through one or two sidechains while Arg8 is more likely to assume a “buried” conformation, interacting with the bilayer through up to six sidechains. Analysis of electrostatic potential and charge distribution from atomistic simulations suggests that the Gouy–Chapman model, which is widely used for mapping surface potential to surface charge, is semi-quantitatively valid; despite considerable orientational preference of interfacial water, the apparent dielectric constant for the interfacial solvent is about 30, due to the thermal fluctuation of the lipid–water interface.

Chronic wasting disease (CWD) is a fatal neurodegenerative disease of deer, elk, moose, and reindeer (cervids) caused by misfolded prion proteins. The disease has been reported across North America and recently discovered in northern Europe. Transmission of CWD in wild cervid populations can occur through environmental routes, but limited ability to detect prions in environmental samples has prevented the identification of potential transmission "hot spots". We establish widespread CWD prion contamination of mineral licks used by free-ranging cervids in an enzootic area in Wisconsin, USA. We show mineral licks can serve as reservoirs of CWD prions and thus facilitate disease transmission. Furthermore, mineral licks attract livestock and other wildlife that also obtain mineral nutrients via soil and water consumption. Exposure to CWD prions at mineral licks provides potential for cross-species transmission to wildlife, domestic animals, and humans. Managing deer use of mineral licks warrants further consideration to help control outbreaks of CWD.

Nanoparticles are frequently modified with polymer layers to control their physical and chemical properties, but little is understood about the morphology and dynamics of these polymer layers. We report here an NMR-based investigation of a model polymer-modified nanoparticle, using multiple NMR techniques including 1H NMR, diffusion-ordered spectroscopy (DOSY), total correlation spectroscopy (TOCSY), and T2 relaxometry to characterize the dynamics of the nanoparticle–polymer interface. Using 5 nm detonation nanodiamond covalently linked to poly(allylamine) hydrochloride as a model system, we demonstrate the use of NMR to distinguish between free and bound polymer and to characterize the degree to which the segments of the nanoparticle-wrapping polymer are mobile (loops and tails) versus immobile (trains). Our results show that the polymer-wrapped nanoparticle contains a large fraction of highly mobile polymer segments, implying that the polymer extends well into solution away from the nanoparticle surface...

Changes to nanoparticle surface charge, colloidal stability, and hydrodynamic properties induced by interaction with natural organic matter (NOM) warrant consideration in assessing the potential for these materials to adversely impact organisms in the environment. Here, we show that acquisition of a coating, or "corona", of NOM alters the hydrodynamic and electrokinetic properties of diamond nanoparticles (DNPs) functionalized with the polycation poly(allylamine HCl) in a manner that depends on the NOM-to-DNP concentration ratio. The NOM-induced changes to DNP properties alter subsequent interactions with model biological membranes and the Gram-negative bacterium Shewanella oneidensis MR-1. Suwannee River NOM induces changes to DNP hydrodynamic diameter and apparent ζ-potential in a concentration-dependent manner. At low NOM-to-DNP ratios, DNPs aggregate to a limited extent but retain a positive ζ-potential apparently due to nonuniform adsorption of NOM molecules leading to attractive electrostatic interactions between oppositely charged regions on adjacent DNP surfaces. Diamond nanoparticles at low NOM-to-DNP ratios attach to model membranes to a larger extent than in the absence of NOM (including those incorporating lipopolysaccharide, a major bacterial outer membrane component) and induce a comparable degree of membrane damage and toxicity to S. oneidensis. At higher NOM-to-DNP ratios, DNP charge is reversed, and DNP aggregates remain stable in suspension. This charge reversal eliminates DNP attachment to model membranes containing the highest LPS contents studied due to electrostatic repulsion and abolishes membrane damage to S. oneidensis. Our results demonstrate that the effects of NOM coronas on nanoparticle properties and interactions with biological surfaces can depend on the relative amounts of NOM and nanoparticles.

With production of carbon nanotubes surpassing billions of tons per annum, concern about their potential interactions with biological systems is growing. Herein, we utilize second harmonic generation spectroscopy, sum frequency generation spectroscopy, and quartz crystal microbalance with dissipation monitoring to probe the interactions between oxidized multiwalled carbon nanotubes (O-MWCNTs) and supported lipid bilayers composed of phospholipids with phosphatidylcholine head groups as the dominant component. We quantify O-MWCNT attachment to supported lipid bilayers under biogeochemically relevant conditions and discern that the interactions occur without disrupting the structural integrity of the lipid bilayers for the systems probed. The extent of O-MWCNT sorption was far below a monolayer even at 100 mM NaCl and was independent of the chemical composition of the supported lipid bilayer.

Geophysical Research Abstracts, 19, ISSN:1029-7006, ISSN:1607-7962

For assistance in the design of the next generation of nanomaterials that are functional and have minimal health and safety concerns, it is imperative to establish causality, rather than correlations, in how properties of nanomaterials determine biological and environmental outcomes. Due to the vast design space available and the complexity of nano/bio interfaces, theoretical and computational studies are expected to play a major role in this context. In this minireview, we highlight opportunities and pressing challenges for theoretical and computational chemistry approaches to explore the relevant physicochemical processes that span broad length and time scales. We focus discussions on a bottom-up framework that relies on the determination of correct intermolecular forces, accurate molecular dynamics, and coarse-graining procedures to systematically bridge the scales, although top-down approaches are also effective at providing insights for many problems such as the effects of nanoparticles on biological membranes.