Multiplexable and Scalable Aqueous Synthesis Platform for Oleate-Based, Bilayer-Coated Gold Nanoparticles.

Despite gold-based nanomaterials having a unique role in nanomedicine, among other fields, synthesis limitations relating to reaction scale-up and control result in prohibitively high gold nanoparticle costs. In this work, a new preparation procedure for lipid bilayer-coated gold nanoparticles in water is presented, using sodium oleate as reductant and capping agent. The seed-free synthesis not only allows for size precision (8-30 nm) but also remarkable particle concentration (10 mm Au). These reaction efficiencies allow for multiplexing and reaction standardization in 96-well plates using conventional thermocyclers, in addition to simple particle purification via microcentrifugation. Such a multiplexing approach also enables detailed spectroscopic investigation of the nonlinear growth process and dynamic sodium oleate/oleic acid self-assembly. In addition to scalability (at gram-level), resulting gold nanoparticles are stable at physiological pH, in common cell culture media, and are autoclavable. To demonstrate the versatility and applicability of the reported method, a robust ligand exchange with thiolated polyethylene glycol analogues is also presented.

Total organic carbon measurements reveal major gaps in petrochemical emissions reporting.

Anthropogenic organic carbon emissions reporting has been largely limited to subsets of chemically speciated volatile organic compounds. However, new aircraft-based measurements revealed total gas-phase organic carbon emissions that exceed oil sands industry-reported values by 1900% to over 6300%, the bulk of which was due to unaccounted-for intermediate-volatility and semivolatile organic compounds. Measured facility-wide emissions represented approximately 1% of extracted petroleum, resulting in total organic carbon emissions equivalent to that from all other sources across Canada combined. These real-world observations demonstrate total organic carbon measurements as a means of detecting unknown or underreported carbon emissions regardless of chemical features. Because reporting gaps may include hazardous, reactive, or secondary air pollutants, fully constraining the impact of anthropogenic emissions necessitates routine, comprehensive total organic carbon monitoring as an inherent check on mass closure.

Harnessing the potential of in-situ, electrically generated microbubbles via nickel foam for enhanced, low energy membrane fouling control.

For membrane-based, water treatment technologies, fouling remains a significant challenge for pressure-driven processes. While many antifouling strategies have been proposed, there remains significant room for improved efficiency. Direct application of microbubbles (MBs) at a membrane surface offers a promising approach for managing interfacial fouling through continuous physical interaction(s). Despite such potential, to date, integration and optimization of in-situ generated MBs at the membrane interface that are both highly antifouling with minimal energy inputs and unwanted side reactions remains mostly outstanding. Here we demonstrate the application of conductive, porous nickel foam for electrolysis-based generation of hydrogen microbubbles at an ultra-filtration (UF) membrane interface, which significantly mitigates membrane fouling for a range of model foulants. System characterization and optimization includes comparison of metal foams (Ni, Cu, Ti), faradic efficiencies, hydrogen evolution reaction (HER) curves, cyclic voltammetry, and quantification of hydrogen gas flux and bubble size, as a function of applied current. When optimized, we report rapid (<5 min) and near complete (∼99 %) flux recovery for three classes of foulants, including calcium alginate, humic acid (HA), and SiO2 particles. For all, the described MB-based approach is orders of magnitude more energy efficient when compared to conventional cleaning strategies. Finally, we demonstrate the MB-based regeneration/cleaning process is stable and repeatable for ten cycles and also highly effective for a challenge water (as a model oilfield brine). Taken together, this work presents a novel and efficient approach for the application of in-situ electrically generated MBs to support sustainable pressure-driven membrane processes.

Nanobubble Reactivity: Evaluating Hydroxyl Radical Generation (or Lack Thereof) under Ambient Conditions.

Nanobubble (NB) generation of reactive oxygen species (ROS), especially hydroxyl radical (·OH), has been controversial. In this work, we extensively characterize NBs in solution, with a focus on ROS generation (as ·OH), through a number of methods including degradation of ·OH-specific target compounds, electron paramagnetic resonance (EPR), and a fluorescence-based indicator. Generated NBs exhibit consistent physical characteristics (size, surface potential, and concentration) when compared with previous studies. For conditions described, which are considered as high O2 NB concentrations, no degradation of benzoic acid (BA), a well-studied ·OH scavenger, was observed in the presence of NBs (over 24 h) and no EPR signal for ·OH was detected. While a positive fluorescence response was measured when using a fluorescence probe for ·OH, aminophenyl fluorescein (APF), we provide an alternate explanation for the result. Gas/liquid interfacial characterization indicates that the surface of a NB is proton-rich and capable of inducing acid-catalyzed hydrolysis of APF, which results in a false (positive) fluorescence response. Given these negative results, we conclude that NB-induced ·OH generation is minimal, if at all, for conditions evaluated.

Microbial Reductive Dechlorination by a Commercially Available Dechlorinating Consortium Is Not Inhibited by Perfluoroalkyl Acids (PFAAs) at Field-Relevant Concentrations.

Perfluoroalkyl acids (PFAAs) have been shown to inhibit biodegradation (i.e., organohalide respiration) of chlorinated ethenes. The potential negative impacts of PFAAs on microbial species performing organohalide respiration, particularly Dehalococcoides mccartyi (Dhc), and the efficacy of in situ bioremediation are a critical concern for comingled PFAA-chlorinated ethene plumes. Batch reactor (no soil) and microcosm (with soil) experiments, containing a PFAA mixture and bioaugmented with KB-1, were completed to assess the impact of PFAAs on chlorinated ethene organohalide respiration. In batch reactors, PFAAs delayed complete biodegradation of cis-1,2-dichloroethene (cis-DCE) to ethene. Maximum substrate utilization rates (a metric for quantifying biodegradation rates) were fit to batch reactor experiments using a numerical model that accounted for chlorinated ethene losses to septa. Fitted values for cis-DCE and vinyl chloride biodegradation were significantly lower (p < 0.05) in batch reactors containing ≥50 mg/L PFAAs. Examination of reductive dehalogenase genes implicated in ethene formation revealed a PFAA-associated change in the Dhc community from cells harboring the vcrA gene to those harboring the bvcA gene. Organohalide respiration of chlorinated ethenes was not impaired in microcosm experiments with PFAA concentrations of 38.7 mg/L and less, suggesting that a microbial community containing multiple strains of Dhc is unlikely to be inhibited by PFAAs at lower, environmentally relevant concentrations.

In-situ sequestration of perfluoroalkyl substances using polymer-stabilized ion exchange resin.

Remediation of groundwater impacted by per- and polyfluoroalkyl substances (PFAS) is challenging due to the strength of the carbon-fluorine bond and the need to achieve nanogram per liter drinking water targets. Previous studies have shown that ion exchange resins can serve as effective sorbents for the removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) in conventional water treatment systems. The objectives of this study were to evaluate the in situ delivery and PFAS sorption capacity of a polymer-stabilized ion exchange resin (S-IXR) consisting of Amberlite® IRA910 beads and Pluronic® F-127 in a quartz sand. At concentrations below 100 µg/L, individual and mixed PFAS adsorption on resin beads exhibited linear isotherms with no apparent competitive effects. However, at concentrations up to 100 mg/L, PFAS adsorption isotherms were non-linear and a mixture of six PFAS exhibited strong competitive effects. In columns packed with 40-50 mesh Ottawa sand, injection of the S-IXR suspension created a uniform sorptive zone that increased PFOA or PFOS retention by more than five orders-of-magnitude compared to untreated control columns. Multi-solute column studies revealed earlier breakthrough of shorter-chain length PFAS, which was consistent with the mixed PFAS adsorption data. These findings indicate that injectable ion exchange resins could provide an effective in situ remediation strategy for PFAS-impacted groundwater plumes.

Photoactive Polyethylenimine-Coated Graphene Oxide Composites for Enhanced Cr(VI) Reduction and Recovery.

The application of positively charged polymers is a common treatment strategy for the sorption and separation of dissolved hexavalent chromium Cr(VI). In particular, polyethylenimine (PEI) has been demonstrated as an effective polymer for Cr treatment due to abundant amine groups and cost-effectiveness. However, PEI as a photoactive polymer has not been previously explored for Cr treatment. Toward this, we demonstrate the significant photoactive potential of PEI for Cr sorption and reduction [to Cr (III)], delineating amine structure-function relationships. Overall, Cr(VI) photoreduction is enhanced dramatically as a function of amine group density. Additionally, among the types of amine groups evaluated, tertiary amines are observed to be the most reactive followed by secondary and primary amines. When PEI is incorporated onto graphene oxide (GO) as a stabilizing scaffold, mass loading of PEI is a key variable for Cr(VI) treatment performance, which is observed to be a function of PEI molecular weight and oxidation extent of GO. Finally, when combined with magnetic nanomaterials, low energy, high efficiency separation, and reuse are demonstrated. For these, sorption-based separation processes maintained excellent performance over five cycles. Taken together, this work demonstrates that PEI can serve as highly effective, multifunctional material coating(s) not only for chromium treatment but potentially for other oxidized aqueous species as well.

Yale School of Public Health Symposium: An overview of the challenges and opportunities associated with per- and polyfluoroalkyl substances (PFAS).

On December 13, 2019, the Yale School of Public Health hosted a symposium titled "Per- and Polyfluoroalkyl Substances (PFAS): Challenges and Opportunities" in New Haven, Connecticut. The meeting focused on the current state of the science on these chemicals, highlighted the challenges unique to PFAS, and explored promising opportunities for addressing them. It brought together participants from Yale University, the National Institute of Environmental Health Sciences, the University of Massachusetts Amherst, the University of Connecticut, the Connecticut Agricultural Experiment Station, the Connecticut Departments of Public Health and Energy and Environmental Protection, and the public and private sectors. Presentations during the symposium centered around several primary themes. The first reviewed the current state of the science on the health effects associated with PFAS exposure and noted key areas that warranted future research. As research in this field relies on specialized laboratory analyses, the second theme considered commercially available methods for PFAS analysis as well as several emerging analytical approaches that support health studies and facilitate the investigation of a broader range of PFAS. Since mitigation of PFAS exposure requires prevention and cleanup of contamination, the third theme highlighted new nanotechnology-enabled PFAS remediation technologies and explored the potential of green chemistry to develop safer alternatives to PFAS. The fourth theme covered collaborative efforts to assess the vulnerability of in-state private wells and small public water supplies to PFAS contamination by adjacent landfills, and the fifth focused on strategies that promote successful community engagement. This symposium supported a unique interdisciplinary coalition established during the development of Connecticut's PFAS Action Plan, and discussions occurring throughout the symposium revealed opportunities for collaborations among Connecticut scientists, state and local officials, and community advocates. In doing so, it bolstered the State of Connecticut's efforts to implement the ambitious initiatives that its PFAS Action Plan recommends.

Pharmacological Comparison of Mitragynine and 7-Hydroxymitragynine: In Vitro Affinity and Efficacy for µ-Opioid Receptor and Opioid-Like Behavioral Effects in Rats.

Relationships between µ-opioid receptor (MOR) efficacy and effects of mitragynine and 7-hydroxymitragynine are not fully established. We assessed in vitro binding affinity and efficacy and discriminative stimulus effects together with antinociception in rats. The binding affinities of mitragynine and 7-hydroxymitragynine at MOR (Ki values 77.9 and 709 nM, respectively) were higher than their binding affinities at κ-opioid receptor (KOR) or δ-opioid receptor (DOR). [35S]guanosine 5'-O-[γ-thio]triphosphate stimulation at MOR demonstrated that mitragynine was an antagonist, whereas 7-hydroxymitragynine was a partial agonist (Emax = 41.3%). In separate groups of rats discriminating either morphine (3.2 mg/kg) or mitragynine (32 mg/kg), mitragynine produced a maximum of 72.3% morphine-lever responding, and morphine produced a maximum of 65.4% mitragynine-lever responding. Other MOR agonists produced high percentages of drug-lever responding in the morphine and mitragynine discrimination assays: 7-hydroxymitragynine (99.7% and 98.1%, respectively), fentanyl (99.7% and 80.1%, respectively), buprenorphine (99.8% and 79.4%, respectively), and nalbuphine (99.4% and 98.3%, respectively). In the morphine and mitragynine discrimination assays, the KOR agonist U69,593 produced maximums of 72.3% and 22.3%, respectively, and the DOR agonist SNC 80 produced maximums of 34.3% and 23.0%, respectively. 7-Hydroxymitragynine produced antinociception; mitragynine did not. Naltrexone antagonized all of the effects of morphine and 7-hydroxymitragynine; naltrexone antagonized the discriminative stimulus effects of mitragynine but not its rate-decreasing effects. Mitragynine increased the potency of the morphine discrimination yet decreased morphine antinociception. Here we illustrate striking differences in MOR efficacy, with mitragynine having less than 7-hydroxymitragynine. SIGNIFICANCE STATEMENT: At human µ-opioid receptor (MOR) in vitro, mitragynine has low affinity and is an antagonist, whereas 7-hydroxymitragynine has 9-fold higher affinity than mitragynine and is an MOR partial agonist. In rats, intraperitoneal mitragynine exhibits a complex pharmacology including MOR agonism; 7-hydroxymitragynine has higher MOR potency and efficacy than mitragynine. These results are consistent with 7-hydroxymitragynine being a highly selective MOR agonist and with mitragynine having a complex pharmacology that combines low efficacy MOR agonism with activity at nonopioid receptors.

Graphene oxide/mussel foot protein composites for high-strength and ultra-tough thin films.

Graphene oxide (GO)-based composite materials have become widely popular in many applications due to the attractive properties of GO, such as high strength and high electrical conductivity at the nanoscale. Most current GO composites use organic polymer as the matrix material and thus, their synthesis suffers from the use of organic solvents or surfactants, which raise environmental and energy-consumption concerns. Inspired by mussel foot proteins (Mfp) secreted by the saltwater mussel, Mytilus galloprovincialis and by recent advances in microbial protein production, we developed an aqueous-based green synthesis strategy for preparing GO/Mfp film composites. These GO/Mfp films display high tensile strength (134-158 MPa), stretchability (~ 26% elongation), and high toughness (20-24 MJ/m3), beyond the capabilities of many existing GO composites. Renewable production of Mfp proteins and the facile fabrication process described provides a new avenue for composite material synthesis, while the unique combination of mechanical properties of GO/Mfp films will be attractive for a range of applications.

Intrapore energy barriers govern ion transport and selectivity of desalination membranes.

State-of-the-art desalination membranes exhibit high water-salt selectivity, but their ability to discriminate between ions is limited. Elucidating the fundamental mechanisms underlying ion transport and selectivity in subnanometer pores is therefore imperative for the development of ion-selective membranes. Here, we compare the overall energy barrier for salt transport and energy barriers for individual ion transport, showing that cations and anions traverse the membrane pore in an independent manner. Supported by density functional theory simulations, we demonstrate that electrostatic interactions between permeating counterion and fixed charges on the membrane substantially hinder intrapore diffusion. Furthermore, using quartz crystal microbalance, we break down the contributions of partitioning at the pore mouth and intrapore diffusion to the overall energy barrier for salt transport. Overall, our results indicate that intrapore diffusion governs salt transport through subnanometer pores due to ion-pore wall interactions, providing the scientific base for the design of membranes with high ion-ion selectivity.

Delineating the Relationship between Nanoparticle Attachment Efficiency and Fluid Flow Velocity.

The ability to fundamentally describe nanoparticle (NP) transport in the subsurface underpins environmental risk assessment and successful material applications, including advanced remediation and sensing technologies. Despite considerable progress, our understanding of NP deposition behavior remains incomplete as there are conflicting reports regarding the effect of fluid flow velocity on attachment efficiency. To directly address this and more accurately describe NP attachment behavior, we have developed a novel protocol using a quartz crystal microbalance with dissipation monitoring (QCM-D) to separate and individually observe deposition mechanisms (diffusion and sedimentation), providing in situ, real-time information about particle diffusion (from the bulk liquid to solid surface). Through this technique, we have verified that the approaching velocity of NPs via diffusion increases (0.8-6.7 µm/s) with increasing flow velocity (6.1-106.0 µm/s), leading to an increased NP kinetic energy, thus affecting deposition processes. Further, in the presence of a secondary energy minimum associated with organic surface coatings, secondary minimum deposition decreases and primary minimum deposition increases with the flow velocity. NPs deposited at the primary minimum are relatively more resistant to hydrodynamic energies (including detachment associated energies), resulting in an increase of observed attachment efficiencies. Taken together, this work not only describes a novel method to delineate and quantify physical processes underpinning particle behavior but also provides direct measurements regarding key factors defining the relationship(s) of flow velocity and particle attachment. Such insight is valuable for next-generation fate and transport model accuracy, especially under unfavorable attachment regimes, which is a current and critical need for subsurface material applications and implication paradigms.

Surface-Engineered Nanomaterials in Water: Understanding Critical Dynamics of Soft Organic Coatings and Relative Aggregation Density.

Inorganic-organic nanocomposites, typically as an inorganic core with surface organic coating(s), have received interest as potential platform materials for sensor, catalyst, sorbent, and environmental applications, among others. Here, we describe the critical role of organic surface coatings with regard to the colloidal stability of engineered manganese oxide nanoparticles (MnxOy NPs). Specifically, we prepared libraries of monodisperse MnxOy NPs with a serial selection of surface coatings (stearic acid (SA), oleic acid (OA), poly(maleic anhydride-alt-1-octadecene) (PMAO), linear polyethyleneimine (LPEI), and multibranched polyethyleneimine (BPEI)), which were chosen based on comparable structure(s) and functional group(s). We systematically evaluated the role of surface organic coatings via critical coagulation concentrations (CCCs), which were compared with theoretical calculations (Schulze-Hardy rule). Through a newly developed light scattering protocol, we observed that the effective density of nanoclusters can exceed NPs' primary (bulk) density depending on the open space(s) within organic coatings. Interestingly, PMAO-coated NPs were more stable at the point of zero charge (PZC) than at neutral pH (pH 7), despite the loss of effective surface charge potential. CCC was 334 mM in NaCl and 1.5 mM in CaCl2 at pH 7, compared to CCC values of 807 mM in NaCl and 210 mM in CaCl2 at PZC. This increase in stability is due to polymer (re)configuration (at PZC), which was further confirmed with a quartz crystal microbalance-based technique to evaluate surface-based polymer dynamics. Taken together, this work quantifies the role of organic coating dynamics, including structure, grafting density, and configuration on the colloidal stability of organic-coated NPs.

Formation and Transport of Cr(III)-NOM-Fe Colloids upon Reaction of Cr(VI) with NOM-Fe(II) Colloids at Anoxic-Oxic Interfaces.

Natural organic matter-iron (NOM-Fe) colloids are ubiquitous at anoxic-oxic interfaces of subsurface environments. Fe(II) or NOM can chemically reduce Cr(VI) to Cr(III), and the formation of Cr(III)-NOM-Fe colloids can control the fate and transport of Cr. We explored the formation and transport of Cr(III)-humic acid (HA)-Fe colloids upon reaction of Cr(VI) with HA-Fe(II) colloids over a range of environmentally relevant conditions. Cr(VI) was completely reduced by HA-Fe(II) complexes under anoxic conditions, and the formation of Cr(III)-HA-Fe colloids depended on HA concentration (or molar C/Fe ratio) and redox conditions. No colloids formed at HA concentrations below 3.5 mg C/L (C/Fe ratio below 1.6), but Cr(III)-HA-Fe colloids formed at higher HA concentrations. In column experiments, Cr(III)-HA-Fe(III) colloids formed under oxic conditions were readily transported through sand-packed porous media. Colloidal stability measurements further suggest that Cr(III)-HA-Fe colloids are highly stable and persist for at least 20 days without substantial change in particle size. This stability is attributed to the enrichment of free HA adsorbed on the Cr(III)-HA-Fe colloid surfaces, intensifying the electrostatic and/or steric repulsion interactions between particles. The new insights provided here are important for evaluating the long-term fate and transport of Cr in organic-rich redox transition zones.

Cr(VI) Adsorption on Engineered Iron Oxide Nanoparticles: Exploring Complexation Processes and Water Chemistry.

Surface-functionalized magnetic nanoparticles are promising adsorbents due to their large surface areas and ease of separation after contaminant removal. In this work, the affinity of Cr(VI) adsorption to 8 nm surface-functionalized superparamagnetic magnetite nanoparticles was determined for surface coatings with amine (trimethyloctadecylammonium bromide, CTAB) and carboxyl (stearic acid, SA) functional groups. Cr(VI) adsorbed more strongly to the CTAB-coated nanoparticles than to the SA-coated materials due to electrostatic interactions between positively charged CTAB and anionic Cr(VI) species. The adsorption of Cr(VI) by CTAB- and SA-coated nanoparticles increased with decreasing pH (4.5-10), which could be simulated by a surface complexation model. Cr(VI) removal performance by the nanocomposite was evaluated for two realistic drinking water compositions. The co-occurrence of divalent cations (Ca2+ and Mg2+) and Cr(VI) resulted in decreased Cr(VI) adsorption as particles were destabilized, leading to the aggregation and lower effective surface area, confirming the importance of the overall water composition on the performance of novel engineered nanomaterials for water treatment applications.

Elucidating the Role of Sulfide on the Stability of Ferrihydrite Colloids under Anoxic Conditions.

While the reaction mechanisms between ferrihydrite and sulfide are well-documented, the role of redox reactions on the particle-particle stability of ferrihydrite colloids is largely overlooked. Such reactions are critical for a number of (bio)geochemical processes governing ferrihydrite-based colloid processing and their associated role in nutrient and contaminant subsurface dynamics. Taking a fundamental colloid chemistry approach, along with a complementary suite of characterization techniques, here, we explore the stability mechanisms of ferrihydrite colloids over a wide range of environmentally relevant sulfide concentrations at pH 6.0. Results show that sulfide lowered the stability of both ferrihydrite colloids in a concentration-dependent fashion. At lower sulfide concentrations (15.6-62.5 µM), ferrihydrite colloids are apparently stable, but their critical coagulation concentration (CCC) in NaCl linearly decreases with increasing sulfide concentration. This is attributed to the formation of negatively charged elemental sulfur (S(0)) nanoparticles on the surfaces of positively charged ferrihydrite, intensifying the electrostatic attractions between oppositely charged regions on adjacent ferrihydrite surfaces. Further increasing sulfide concentration generates more S(0) attaching to the ferrihydrite surface. This results in effective surface charge neutralization and then subsequent charge reversal, leading to extensive aggregation of ferrihydrite (core) colloids. Interestingly, for the ferrihydrite colloids with higher hydrodynamic diameter, aggregation rates linearly decreases with increasing sulfide concentration from 156.3 to 312.5 µM, which is likely due to the formation of substantial amounts of negatively charged S(0) and FeS. Findings highlight the significance of sulfidation products in controlling the stability of ferrihydrite colloids in sulfidic environments.

Engineering Graphene Oxide Laminate Membranes for Enhanced Flux and Boron Treatment with Polyethylenimine (PEI) Polymers.

In this work, we have developed and characterized flux-enhanced graphene oxide laminate (GOL) membranes by increasing interlayer (layer-to-layer) spacing using multibranched polyethylenimine (PEI) polymers with varied molecular weights and by controlling the graphene oxide (GO) oxidation extent. For these assemblies, water flux was demonstrated to increase by as much as ca. 30-fold compared to GO only laminate controls. PEI-embedded GOL membranes also had better methyl orange (MO) rejection performance than GO laminate controls due to the dilution effects (i.e., water is transported through the assembly much faster than MO). Further, boron removal is demonstrated via functionalized PEI with d-glucono-1,5-lactone, containing a high density of boron chelating groups, which can also be recycled/recovered with high efficiency.

Formation and stability of NOM-Mn(III) colloids in aquatic environments.

Soluble Mn(III) species stabilized by natural organic matter (NOM) plays a crucial role in a number of biogeochemical processes. To date, current understanding of these phenomena has been primarily concerned on the occurrence and chemistry of soluble NOM-Mn(III) complexes; much less is known regarding the formation and stability of NOM-Mn(III) colloids in the environment. This presents a critical knowledge gap with regard to biogeochemical cycling of manganese and associated carbon, and for predicting the fate and transport of colloid-associated contaminants, nutrients, and trace metals. In this work, we have characterized the chemical and physical properties of humic acid based (HA)-Mn(III) colloids formed over a range of environmentally relevant conditions and quantified their subsequent aggregation and stability behaviors. Results show that molar C/Mn ratios and HA types (Aldrich HA (AHA) and Pahokee peat soil HA (PPSHA)) are critical factors influencing HA-Mn(III) colloidal properties. Both the amount and the stability of HA-Mn(III) colloids increased with increasing initial molar C/Mn ratios, regardless of HA type. The correlation between the critical coagulation concentration (CCC) and zeta potential (R2 > 0.97) suggests that both Derjaguin-Landau-Verwey-Overbeek (DLVO) type and non-DLVO interactions are responsible for enhanced stability of HA-Mn(III) colloids. For a given C/Mn ratio, PPSHA-Mn(III) colloids are significantly more stable against aggregation than AHA-Mn(III) colloids, which is likely due to stronger electrostatic interactions, hydration interactions, and steric hindrance. Further examination in real-world waters indicates that the HA-Mn(III) colloids are highly stable in surface river water, but become unstable (i.e. extensive aggregation) in solutions representing a groundwater-seawater interaction zone. Overall, this study provides new insights into the formation and stability of NOM-Mn(III) colloids which are critical for understanding Mn-based colloidal behavior(s), and thus Mn cycling processes, in aquatic systems.

Microbially Synthesized Repeats of Mussel Foot Protein Display Enhanced Underwater Adhesion.

Mussels strongly adhere to a variety of surfaces by secreting byssal threads that contain mussel foot proteins (Mfps). Recombinant production of Mfps presents an attractive route for preparing advanced adhesive materials. Using synthetic biology strategies, we synthesized Mfp5 together with Mfp5 oligomers containing two or three consecutive, covalently-linked Mfp5 sequences named Mfp5(2) and Mfp5(3). The force and work of adhesion of these proteins were measured underwater with a colloidal probe mounted on an atomic force microscope and the adsorption was measured with a quartz crystal microbalance. We found positive correlations between Mfp5 molecular weight and underwater adhesive properties, including force of adhesion, work of adhesion, protein layer thickness, and recovery distance. DOPA-modified Mfp5(3) displayed a high force of adhesion (201 ± 36 nN µm-1) and a high work of adhesion (68 ± 21 fJ µm-1) for a cure time of 200 s, which are higher than those of previously reported Mfp-mimetic adhesives. Results presented in this study highlight the power of synthetic biology in producing biocompatible and highly adhesive Mfp-based materials.

Real-time evaluation of natural organic matter deposition processes onto model environmental surfaces.

Natural organic matter (NOM) is ubiquitous in aqueous systems and dynamically partitions onto/from environmental surfaces. However, such interfacial processes have not been uniformly quantified in situ and in real time. In this work, adsorption and deposition processes of Suwannee River humic acid (SRHA) and Suwannee River fulvic acid (SRFA), as model NOM, were evaluated for a series of environmentally relevant interfaces. Real-time, interfacial phenomenon, including deposition, release, and adlayer viscoelastic properties, were quantified over a variety of water chemistries via quartz crystal microbalance with dissipation monitoring (QCM-D). Specifically, adlayer mass and deposition rates of SRHA and SRFA were evaluated as a function of NOM concentration/molecular weight (fraction), pH, electrolyte composition (type and concentration), and collector surface type. For these, the adsorption of SRHA onto aluminum oxide (Al2O3) and polystyrene (PS) surfaces follows the Langmuir isotherm model. Rapid, near-monolayer formation of SRHA/SRFA adlayers were observed on Al2O3, hydroxyapatite (HAP), and poly (l-lysine) (PLL) surfaces, but not on PS or iron oxide (Fe3O4) surfaces. The presence of divalent cations (Ca2+/Mg2+) at relatively low concentrations (0.5-5.0 mM) significantly enhances the mass of SRHA/SRFA deposited onto the surfaces of silica (SiO2), Al2O3, and PS. Viscoelastic properties of the adsorbed layer based on the ratio of dissipation to frequency revealed a relatively unique adlayer structure for SRHA in the presence of 5.0 mM Ca2+.