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Interfacial Fabrication of Supramolecular Polymer Networks Using Mussel-Inspired Catechol–Iron Complexes
The liquid–liquid interface provides a promising platform to construct supramolecular polymers and materials with advanced functions. However, supramolecular polymerization at the interface usually requires monomers with different or even orthogonal solubilities, which significantly limit the number of usable monomers. Here, in this work, we report a new strategy to construct supramolecular polymer networks at the oil–water interface using a water-soluble catechol–iron complex and an oil-soluble diend-functionalized polymer. Owing to the dynamic catechol–iron coordination bond and imine bond, the resulting supramolecular polymer networks demonstrate excellent dynamic features and responsiveness to different stimuli including the pH, redox, competing ligands, and temperature. With a supramolecular polymer network serving as a building block, emulsions and 2D films can be generated that have potential applications in encapsulation, release, and molecular separation.
A Biosynthetic Hybrid Spidroin-Amyloid-Mussel Foot Protein for Underwater Adhesion on Diverse Surfac
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Hanford Site Freshwater Mussel Monitoring Report for Calendar Year 2024
The U.S. Department of Energy, Hanford Field Office (HFO) conducts ecological monitoring at the Hanford Site to collect and maintain data to ensure compliance with an array of environmental laws, regulations, and policies governing HFO activities. Ecological monitoring data provides baseline information about the plants, animals, and habitats under HFO stewardship at the Hanford Site that is required for decision making under the National Environmental Policy Act of 1969 and the Comprehensive Environmental Response, Compensation, and Liability Act of 1980. In addition, ecological monitoring helps ensure that HFO, its contractors, and other entities conducting activities at the Hanford Site are in compliance with DOE/EIS-0222-F, Final Hanford Comprehensive Land-Use Plan Environmental Impact Statement. HFO places priority on monitoring those plant and animal species or habitats with specific regulatory protections or requirements that are rare and/or declining (i.e., federal or state listed endangered, threatened, or sensitive species) or are of significant interest to federal, state, or tribal governments or the public.
Hanford Site Freshwater Mussel Monitoring Report for Calendar Year 2022
The U.S. Department of Energy, Richland Operations Office (DOE-RL) conducts ecological monitoring on the Hanford Site to collect and maintain data needed to ensure compliance with an array of environmental laws, regulations, and policies governing DOE-RL activities. Ecological monitoring data provides baseline information about the plants, animals, and habitats under DOE-RL stewardship at the Hanford Site that is required for decision making under the National Environmental Policy Act of 1969 and Comprehensive Environmental Response, Compensation, and Liability Act of 1980. In addition, ecological monitoring helps ensure that DOE-RL, its contractors, and other entities conducting activities on the Hanford Site are in compliance with the Hanford Site Comprehensive Land Use Plan (DOE/EIS-0222-F). DOE-RL places priority on monitoring those plant and animal species or habitats with specific regulatory protections or requirements that are rare and/or declining (federal or state listed endangered, threatened, or sensitive species) or are of significant interest to federal, state, or tribal governments or the public.
Modeled sensitivity of Lake Michigan productivity and zooplankton to changing nutrient concentrations and quagga mussels
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Geological evaluation of radar imagery - San Andreas fault zone from Stevens Creek, Santa Clara County to Mussel Rock, San Mateo County, California
Geologic interpretation of side-looking radar imagery using aerial photographs of California
Integration of natural selection across the life cycle stabilizes a marine mussel hybrid zone
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Limitations of Applying Diffusive Gradients in Thin Films to Predict Bioavailability of Metal Mixtures in Aquatic Systems with Unstable Water Chemistries
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Molecular design principles of Lysine-DOPA wet adhesion
The mussel byssus has long been a source of inspiration for the adhesion community. Recently, adhesive synergy between flanking lysine (Lys, K) and 3,4-Dihydroxyphenylalanine (DOPA, Y ) residues in the mussel foot proteins (Mfps) has been highlighted. However, the complex topological relationship of DOPA and Lys as well as the interfacial adhesive roles of other amino acids have been understudied. Herein, we study adhesion of Lys and DOPA-containing peptides to organic and inorganic substrates using single-molecule force spectroscopy (SMFS). We show that a modest increase in peptide length, from K Y to (K Y ) 3 , increases adhesion strength to TiO 2. Surprisingly, further increase in peptide length offers no additional benefit. Additionally, comparison of adhesion of dipeptides containing Lys and either DOPA (K Y ) or phenylalanine (KF) shows that DOPA is stronger and more versatile. We furthermore demonstrate that incorporating a nonadhesive spacer between (K Y ) repeats can mimic the hidden length in the Mfp and act as an effective strategy to dissipate energy.
HydroBio: Hydropower Capacity and Freshwater Biodiversity in Conterminous United States Sub-basins
This dataset summarizes existing and potential hydropower capacity and freshwater biodiversity at the sub-basin level throughout the conterminous United States (CONUS). It contains descriptive information regarding each sub-basin (e.g., 8-digit hydrologic unit code identifier, name, states, and size) along with sub-basin-level summaries of: 1) existing hydropower capacity (MW), 2) potential nominal non-powered dam (NPD) capacity (MW), 3) potential capacity of new stream reach development (NSD) (MW), and 4) freshwater biodiversity, including the total richness of fish, crayfish, and mussels and metrics that account for how rare and threatened those species tend to be. Hydropower data were obtained from Oak Ridge National Laboratory data resources (Existing Hydropower Assets, Non-Powered Dam Technical Potential, and New Stream Reach Development). Freshwater biodiversity data were obtained from NatureServe. Sub-basin characteristic information was obtained from the United States Geological Survey. Additionally, long data that provide lists of unique elements within each sub-basin for each constituent data resource (e.g., NatureServe, Existing Hydropower Assets) are provided to enhance dataset utility for users. The dataset provides, for the first time, a national-level assessment of existing and potential hydropower capacity in the context of freshwater biodiversity and is a valuable resource for stakeholders tasked with providing affordable, reliable energy to the American public while maintaining or enhancing invaluable freshwater resources. The dataset contains six data files in comma separated (*.csv) format that are within a zipped file.
Ion‐Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes
Abstract Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.
An algorithm for detecting and quantifying disturbance and recovery in high-frequency time series
Determining when a disturbance has occurred, its severity, and when the system recovered, is important to numerous questions in the aquatic sciences. This problem can be conceptualized as the timing and degree of perturbation from a typical state, and when the system returns to that typical state. We present an algorithm for detecting disturbance and recovery designed for high-frequency time series, e.g., data produced by automated sampling devices in instrumented buoys and flux towers. The algorithm quantifies differences in the empirical cumulative distribution functions of moving windows over reference and evaluation periods, and is sensitive to changes in the mean, variance, and higher statistical moments. Tests on simulated data show it accurately identifies disturbance and recovery. Three case studies illustrate the application of our algorithm in different empirical settings. A case study on dissolved oxygen in a Florida, USA estuary following a hurricane identified the disturbance and recovery 73 d later. A case study on air temperature and net ecosystem exchange in the Florida everglades identified cold snaps coinciding with periods of reduced carbon uptake. A case study on rotifer abundance following zebra mussel invasion in the Hudson River, NY showed rotifer collapse following invasion and recovery over a decade later. Methods such as ours can improve understanding response to disturbance and facilitate comparative and synthetic study of disturbance impacts across ecosystems.
Ionic Liquid Facilitated Solvent‐Phase Polymerization of Ultrasmooth Coatings of Polycatecholamines
Mussel-inspired polycatecholamine coatings and films have proven to be versatile materials for surface modification. However, the progress of chemically modified coatings with tailored properties has been slow due to the lack of definitive evidence of their polymeric structure. Polycatecholamines form aggregates during polymerization, and their formation mechanism has been a subject of debate owing to their insolubility in traditional molecular solvents. Exploiting the capability of ionic liquids (ILs) to exhibit strong electrostatic interactions, herein, the first solution-phase polymerization approach is reported to achieve polymerization of four catecholamines – dopamine (DA), norepinephrine (NE), L-3,4-dihydroxyphenylalanine (L-DOPA), and adrenaline (AD). Kinetic control over the polymerization process in the solution phase enabled it to follow the process with 1 H NMR spectroscopy, revealing the formation of structural features of resulting complex heterogeneous and soluble polymers. The polymers are both covalent and associative in nature. Solution phase polymerization prevented the formation of large aggregates in the solution, thus facilitating the formation of coatings that are ultra-smooth and have root mean square roughness of the order of sub-nm to nm scale.
Bioinspired design toward nanocellulose-based materials
Nature provides lots of inspiration for material and structural design for various applications. Deriving design principles from the investigation of nature can provide a rich source of inspiration for the development of multifunctional materials. The bioinspired design templates mainly include mussels, nacre, and various plant species. As a sustainable and renewable feedstock, nanocellulose can be used to fabricate advanced materials with multifunctional properties through bioinspired designs. However, challenges and opportunities remain for realizing the full potential in the design of novel materials. Here, this article reviewed recent development in the bioinspired nanocellulose based materials and their application. This article summarizes the functions (e.g., surface wetting) and applications (e.g., composite) of bioinspired nanocellulose-based materials. The bioinspired design templates are discussed along with strategies, advantages, and challenges to the development of synthetic mimics. Additionally, mechanisms and processes (e.g., chemical modification, self-assembly) leading to biomimetic design are discussed. Finally, future research directions and opportunities of bioinspired nanocellulose-based materials are highlighted.
Toughening by Nanodroplets: Polymer–Droplet Biocomposite with Anomalous Toughness
The development of new polymer composites is highly dependent on the design of novel fillers that can bring more benefits in the design and control of structure–property–function than conventional solid particles. Here, inspired by the unique coupling structures of tough mussel byssus, we employ nanodroplets of high-boiling-point oligomers as the liquid filler to fabricate a new class of polymer–droplet composites (PDCs). The combination of nanodroplets and chain end/tail modifier in PDCs finally generates soft-coupling structures with chain ends coupled by the nanodroplets. With this strategy, brittle poly(lactic acid) is successfully transformed into a tough bioplastic with toughness improved by over 2000% via a minimal amount of the modifiers (1.5 wt %). Moreover, the composites show unexpected speed-enhanced energy absorption capability. A soft-coupling toughening mechanism is further proposed for the first time to understand the PDCs’ mechanical properties. This work also indicates the potential of nanodroplets as a new tool for tuning the mechanical properties and even functions of polymer composites.
In situ mechanical reinforcement of polymer hydrogels via metal-coordinated crosslink mineralization
Biological organic-inorganic materials remain a popular source of inspiration for bioinspired materials design and engineering. Inspired by the self-assembling metal-reinforced mussel holdfast threads, we tested if metal-coordinate polymer networks can be utilized as simple composite scaffolds for direct in situ crosslink mineralization. Starting with aqueous solutions of polymers end-functionalized with metal-coordinating ligands of catechol or histidine, here we show that inter-molecular metal-ion coordination complexes can serve as mineral nucleation sites, whereby significant mechanical reinforcement is achieved upon nanoscale particle growth directly at the metal-coordinate network crosslink sites.
Low friction bio-inspired polydopamine/polytetrafluoroethylene coating performance in hydrodynamic bearings
Purpose Low friction polymer coatings able to withstand high loadings and many years of continuous operation are difficult to formulate at low cost, but could find many applications in industry. This study aims to analyze and compare friction and wear performance of novel polydopamine/polytetrafluoroethylene (PDA/PTFE) and traditional tin Babbitt coatings applied to an industrial journal bearing. Design/methodology/approach This paper tested PTFE based coating, co-deposited with PDA, a biopolymer allowing sea mussels to adhere to ocean rocks. This coating was deposited on flat steel substrates and on a curved cast iron hydrodynamic journal bearing surface. The flat substrates were analyzed with a tribometer and an optical microscope, while the coated bearing liners were tested in an industrial laboratory setting at different speeds and different radial loads. Findings PDA/PTFE coating showed 2-3 times lower friction compared to traditional tin Babbitt for flat substrates, but higher friction in the bearing liners. PDA/PTFE also showed considerable wear through coating delamination and abrasion in the bearing liners. Research limitations/implications Five future modifications to mitigate coating flaws are provided, which include modifications to coating thickness and its surface finish. Originality/value While the novel coating showed excellent results on flat substrates, coating performance in a large scale bearing was found to be poor. This study shows that coating preparation needs to be improved to avoid frictional losses and unwanted damage to bearings. We provide several routes that could improve coating performance in industrial applications.