Mussel-Inspired Nanocellulose Coating for Selective Neodymium Recovery.

Neodymium (Nd) is one of the most in-demand rare earth elements (REEs) for developing the next generation of magnetic medical devices and clean energy. Eco-friendly and sustainable nanotechnology for REE recovery may be highly suitable to address the limited global supply while minimizing the environmental footprints of current practice, such as solvent extraction. Here, we present a novel one-step mussel-inspired nanocellulose coating (MINC) using bifunctional hairy cellulose nanocrystals (BHCNC), bearing dialdehyde and dicarboxylate groups. The dialdehyde groups enable dopamine-mediated orthogonal conjugation of BHCNC to substrates, such as microparticles, while the high content of dicarboxylate groups yields high-capacity and selective Nd removal against ferric, calcium, and sodium ions. To the best of our knowledge, the MINC-treated substrate provides the most rapid selective removal and recovery of Nd ions even at low Nd concentrations with a capacity that is among the highest reported values. We envision that the MINC will provide new opportunities in developing next-generation bio-based materials and interfaces for the sustainable recovery of REEs and other precious elements.

Fabrication of Transparent PEGylated Antifouling Coatings via One-Step Pyrogallol Deposition.

Antifouling coatings are critical for many biomedical devices. A simple and universal technique used to anchor antifouling polymers is important in order to expand its applications. In this study, we introduced the pyrogallol (PG)-assisted immobilization of poly(ethylene glycol) (PEG) to deposit a thin antifouling layer on biomaterials. Briefly, biomaterials were soaked in a PG/PEG solution and PEG was immobilized onto the biomaterial surfaces via PG polymerization and deposition. The kinetics of PG/PEG deposition started with the deposition of PG on the substrates, followed by the addition of a PEG-rich adlayer. However, prolonged coating added a top-most PG-rich layer, which deteriorated the antifouling efficacy. By controlling the amounts of PG and PEG and the coating time, the PG/PEG coating was able to reduce more than 99% of the adhesion of L929 cells and the adsorption of fibrinogen. The ultrathin (tens of nanometers) and smooth PG/PEG coating was easily deposited onto a wide variety of biomaterials, and the deposition was robust enough to survive harsh sterilization conditions. Furthermore, the coating was highly transparent and allowed most of the UV and Vis light to pass through. The technique has great potential to be applied to biomedical devices that need a transparent antifouling coating, such as intraocular lenses and biosensors.

Colloidal aspects of calcium carbonate scaling in water-in-oil emulsions: A fundamental study using droplet-based microfluidics.

HYPOTHESIS: As a mainstream process in the extraction and recovery of crude oil, water is injected into reservoirs in the so-called waterflooding process to facilitate the oil displacement through the wellbore, typically generating water-in-oil (W/O) emulsions. Based on economic considerations, sea water is used in the flooding process; however, the ionic incompatibility between the injected water and the formation water inside the reservoir may precipitate sparingly-soluble inorganic salts (scale). We hypothesize that calcium carbonate (CaCO3) scale dynamically interacts with cationic surfactants in W/O emulsions, resulting in (i) scale growth retardation and (ii) emulsion destabilization. EXPERIMENTS: We developed stable W/O emulsions via combining droplet-based microfluidics with multifactorial optimizations to investigate the influence of emulsion properties, such as surfactant type and concentrations, temperature, and pH, as well as calcium ions on the CaCO3 scaling kinetics and emulsion stability. The CaCO3 scale was characterized based on particle size and charge, lattice structure, interactions with the surfactant, and time-dependent effects on emulsion stability. FINDINGS: The interfacial interactions between the cationic surfactant (cetyltrimethylammonium bromide, CTAB) and CaCO3 retarded scale growth rate, decreased crystal size, and destabilized emulsion within hours as a result of surfactant depletion at the water-oil interface. The surfactant did not affect the crystal structure of scale, which was formed as the most thermodynamically stable crystalline polymorph, calcite, at the ambient condition. This fundamental study may open new opportunities for engineering stable W/O emulsions, e.g., for enhanced oil recovery (EOR), and developing scale-resistant multiphase flows.

Ion Exchange Biomaterials to Capture Daptomycin and Prevent Resistance Evolution in Off-Target Bacterial Populations.

Daptomycin (DAP), a cyclic anionic lipopeptide antibiotic, is among the last resorts to treat multidrug-resistant Gram-positive bacterial infections, caused by vancomycin-resistant Enterococcus faecium or methicillin-resistant Staphylococcus aureus. DAP is administered intravenously, and via biliary excretion, ∼5-10% of the intravenous DAP dose arrives in the gastrointestinal (GI) tract where it drives resistance evolution in the off-target populations of E. faecium bacteria. Previously, we have shown in vivo that the oral administration of cholestyramine, an ion exchange biomaterial (IXB) sorbent, prevents DAP treatment from enriching DAP resistance in the populations of E. faecium shed from mice. Here, we investigate the biomaterial-DAP interfacial interactions to uncover the antibiotic removal mechanisms. The IXB-mediated DAP capture from aqueous media was measured in controlled pH/electrolyte solutions and in the simulated intestinal fluid (SIF) to uncover the molecular and colloidal mechanisms of DAP removal from the GI tract. Our findings show that the IXB electrostatically adsorbs the anionic antibiotic via a time-dependent diffusion-controlled process. Unsteady-state diffusion-adsorption mass balance describes the dynamics of adsorption well, and the maximum removal capacity is beyond the electric charge stoichiometric ratio because of DAP self-assembly. This study may open new opportunities for optimizing cholestyramine adjuvant therapy to prevent DAP resistance, as well as designing novel biomaterials to remove off-target antibiotics from the GI tract.

One-step electrochemical deposition of antifouling polymers with pyrogallol for biosensing applications.

Electrochemical techniques are highly sensitive and label-free sensing methods for the detection of various biomarkers, toxins, or pathogens. An ideal sensing element should be electroconductive, nonfouling, and readily available for conjugation of ligands. In this work, we have developed a facile, one-step electrodeposition method based on pyrogallol polymerization for preparation of a nonfouling and biotinylated surface on indium tin oxide (ITO). A copolymer of sulfobetaine methacrylate and aminoethyl methacrylate (pSBAE) was synthesized and deposited on ITO in the presence of pyrogallol via cyclic voltammetry. The deposition took less than 15 minutes to sufficiently inhibit cell adhesion. Using biotinylated pSBAE, the modified surface resisted nonspecific protein adsorption from the fetal bovine serum solution and detected added avidin concentrations. The results show an efficient platform to fabricate an electrochemical biosensor for the detection of biomarkers. We expect that this facile one-step technology could be applied to conjugate various biosensing elements for nonfouling biosensors.

Conjugation of Polysulfobetaine via Poly(pyrogallol) Coatings for Improving the Antifouling Efficacy of Biomaterials.

Antifouling treatment is critical to certain biomedical devices for their functions and patients' life. Facial, versatile, and universal coating methods to conjugate antifouling materials on a wide variety of biomaterials are beneficial for the fabrication of low-fouling biomedical devices. We developed a simple one-step coating method for surface conjugation of zwitterionic poly(sulfobetaine) via deposition of self-polymerized pyrogallol (PG). Poly(pyrogallol) could deposit copolymers of sulfobetaine methacrylate and aminoethyl methacrylate (pSBAE) on various biomaterials. pSBAE coatings inhibited as high as 99.8% of the adhesion of L929 cells and reduced protein adsorption significantly. The resistance against L929 cell adhesion was increased with increasing coating time and was positively correlated with the surface hydrophilicity and film thickness. Such a coating was robust to resist harsh sterilization conditions and stable for long-term storage in phosphate-buffered saline. We expect that the simple low-fouling pSBAE coating is applicable to the manufacture of medical devices.