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Creators/Authors contains: "Maldarelli, Charles"

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  1. Peptide surfactants (PEPS) are studied to capture and retain rare earth elements (REEs) at air–water interfaces to enable REE separations. 
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  2. Rare earth elements (REEs) are critical materials to modern technologies. They are obtained by selective separation from mining feedstocks consisting of mixtures of their trivalent cation. We are developing an all-aqueous, bioinspired, interfacial separation using peptides as amphiphilic molecular extractants. Lanthanide binding tags (LBTs) are amphiphilic peptide sequences based on the EF-hand metal binding loops of calcium-binding proteins which complex selectively REEs. We study LBTs optimized for coordination to Tb3+using luminescence spectroscopy, surface tensiometry, X-ray reflectivity, and X-ray fluorescence near total reflection, and find that these LBTs capture Tb3+in bulk and adsorb the complex to the interface. Molecular dynamics show that the binding pocket remains intact upon adsorption. We find that, if the net negative charge on the peptide results in a negatively charged complex, excess cations are recruited to the interface by nonselective Coulombic interactions that compromise selective REE capture. If, however, the net negative charge on the peptide is −3, resulting in a neutral complex, a 1:1 surface ratio of cation to peptide is achieved. Surface adsorption of the neutral peptide complexes from an equimolar mixture of Tb3+and La3+demonstrates a switchable platform dictated by bulk and interfacial effects. The adsorption layer becomes enriched in the favored Tb3+when the bulk peptide is saturated, but selective to La3+for undersaturation due to a higher surface activity of the La3+complex. 
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  3. A colloidal motor driven by surface tension forces is theoretically designed by encapsulating an active Janus particle in a liquid drop which is immiscible in the suspending medium. The Janus particle produces an asymmetric flux of a solute species which induces surface tension gradients along the liquid–liquid interface between the drop and the surrounding fluid. The resulting Marangoni forces at the interface propel the compound drop/Janus particle system. The propulsion speeds of the motor are evaluated for a range of relative sizes and positions of the drop and the particle and across a range of transport properties of the drop and the suspending medium. It is demonstrated that the proposed design can produce higher propulsion velocities than the traditional Janus-particle-based colloidal motors propelled by neutral diffusiophoresis. 
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  4. Colloid-sized particles (10 nm–10 μm in characteristic size) adsorb onto fluid interfaces, where they minimize their interfacial energy by straddling the surface, immersing themselves partly in each phase bounding the interface. The energy minimum achieved by relocation to the surface can be orders of magnitude greater than the thermal energy, effectively trapping the particles into monolayers, allowing them freedom only to translate and rotate along the surface. Particles adsorbed at interfaces are models for the understanding of the dynamics and assembly of particles in two dimensions and have broad technological applications, importantly in foam and emulsion science and in the bottom-up fabrication of new materials based on their monolayer assemblies. In this review, the hydrodynamics of the colloid motion along the surface is examined from both continuum and molecular dynamics frameworks. The interfacial energies of adsorbed particles is discussed first, followed by the hydrodynamics, starting with isolated particles followed by pairwise and multiple particle interactions. The effect of particle shape is emphasized, and the role played by the immersion depth and the surface rheology is discussed; experiments illustrating the applicability of the hydrodynamic studies are also examined. Expected final online publication date for the Annual Review of Fluid Mechanics, Volume 54 is January 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates. 
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  5. Colloids which adsorb to and straddle a fluid interface form monolayers that are paradigms of particle dynamics on a two dimensional fluid landscape. The dynamics is typically inertialess (Stokes flows) and dominated by interfacial tension so the interface is undeformed by the flow, and pairwise drag coefficients can be calculated. Here the hydrodynamic interaction between identical spherical colloids on a planar gas/liquid interface is calculated as a function of separation distance and immersion depth. Drag coefficients (normalized by the coefficient for an isolated particle on the surface) are computed numerically for the four canonical interactions. The first two are motions along the line of centres, either with the particles mutually approaching each other or moving in the same direction (in tandem). The second two are motions perpendicular to the line of centres, either oppositely directed (shear) or in the same direction (tandem). For mutual approach and shear, the normalized coefficients increase with a decrease in separation due to lubrication forces, and become infinite on contact when the particle is more than half immersed. However, they remain bounded at contact when the particles are less than half immersed because they do not contact underneath the liquid. For in-tandem motion, the normalized coefficients decrease with a decrease in separation; they collapse, for all immersion depths, to the dependence of the drag coefficient on separation for two particles moving in tandem in an infinite medium. The coefficients are used to compute separation against time for colloids driven together by capillary attraction. 
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  6. The interaction of monoclonal antibodies (mAbs) with air/water interfaces plays a crucial role in their overall stability in solution. We aim to understand this behavior using pendant bubble measurements to track the dynamic tension reduction and x-ray reflectivity to obtain the electron density profiles (EDPs) at the surface. Native immunoglobulin G mAb is a rigid molecule with a flat, “Y” shape, and simulated EDPs are obtained by rotating a homology construct at the surface. Comparing simulations with experimental EDPs, we obtain surface orientation probability maps showing mAbs transition from flat-on Y-shape configurations to side-on or end-on configurations with increasing concentration. The modeling also shows the presence of β sheets at the surface. Overall, the experiments and the homology modeling elucidate the orientational phase space during different stages of adsorption of mAbs at the air/water interface. These finding will help define new strategies for the manufacture and storage of antibody-based therapeutics. 
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