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Crystallogenesis of Membrane Proteins Mediated by Polymer-Bounded Lipid Nanodiscs
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Tribology review of blended bulk polymers and their coatings for high-load bearing applications
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Targeting Multiple Binding Sites on Cholera Toxin B with Glycomimetic Polymers Promotes the Formation of Protein-Polymer Aggregates
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Low-Temperature Electrochemical Upgrading of Bio-oils Using Polymer Electrolyte Membranes
While bio-oil-derived fuels hold much promise as a replacement for petroleum, transformation of the highly oxygenated mixture has proven challenging. In particular, bio-oils are reactive and difficult to upgrade through catalytic pyrolysis. To reach a stabilized product capable of deep deoxygenation at elevated pressure and temperature, conversion or separation of reactive groups is required. This paper describes an electrochemical process for stabilization and upgrading of bio-oils prior to hydrotreating at high pressure and temperature. This electrolytic process uses a three-compartment cell designed to hydrogenate reactive carbonyl components while separating small acid molecules, such as acetic and formic acids, which act as catalysts for condensation reactions and consume hydrogen gas to produce low-value gases in hydrotreating. To avoid conductivity issues, electrodes are appended to anion- and cation-exchange membranes. The cell was tested using a mixed acetic acid and formic acid surrogate fed to the cathode compartment, where the decrease in the concentration followed the applied charge to the cell. Experiments performed using pine pyrolysis oil demonstrated a significant reduction in the total acid number (TAN), an increase in pH from 2.6 to over 4, and a modest reduction of the carbonyl concentration. Analysis showed the reduction in TAN was primarily due to removal of carboxylic compounds. Experiments observed a decrease in the reactive carbonyl (aldehydes and ketones) concentration that followed applied charge. The results with the newly devised reactor show promise for the electrochemical route for upgrading bio-oils, but significant improvements in TAN removal and carbonyl conversion are needed. Given the distributed nature of biomass, an electrochemical process paired with pyrolysis could be used to densify and stabilize an oil product near the source. The densified liquid could then be shipped to centralized refineries for final upgrading to fuel and/or chemical products.
Influence of Current Velocity on Uranium Adsorption from Seawater Using an Amidoxime-Based Polymer Fiber Adsorbent
Passive adsorption using amidoxime-based polymeric adsorbents is being developed for uranium recovery from seawater. The local oceanic current velocity where the adsorbent is deployed is a key variable in determining locations that will maximize uranium adsorption rates. Two independent experimental approaches using flow-through columns and recirculating flumes were used to assess the influence of linear velocity on uranium uptake kinetics by the adsorbent. Little to no difference was observed in the uranium adsorption rate vs. linear velocity for seawater exposure in flow-through columns. In contrast, adsorption results from seawater exposure in a recirculating flume showed a nearly linear trend with current velocity. The difference in adsorbent performance between columns and flume can be attributed to (i) flow resistance provided by the adsorbent braid in the flume and (ii) enhancement in braid movement (fluttering) with increasing linear velocity.
Two Neptunium(III) Mellitate Coordination Polymers: Completing the Series Np–Cf of Trans-Uranic An(III) Mellitates
For this work, two neptunium(III) mellitates, 237 Np 2 (mell)(H 2 O) 9 ·1.5H 2 O (Np-1α) and 237 Np 2 (mell)(H 2 O) 8 ·2H 2 O (Np-1β), have been synthesized from 237 NpCl 4 (dme) 2 by reduction with KC 8 and subsequent reaction with an aqueous solution of mellitic acid (H 6 mell). Characterization by single-crystal X-ray crystallography and UV–vis–NIR spectroscopy confirms that the neptunium is in its +3 oxidation state and both polymorphs are isostructural to the previously reported plutonium mellitates. Of the two morphologies, Np-1α is indefinitely stable in air, while Np-1β slowly oxidizes over several months. This is due to the change in the energy of the metal-ligand charge-transfer absorption exhibited by these compounds attributed to differing numbers of carboxylate bonds to Np(III), where in Np-1β the energy is low enough to result in spontaneous oxidation.
Ion-Specific Interfacial Crystallization of Polymer-Grafted Nanoparticles
Abstract not provided
High-Pressure Behavior of C 2 I 2 and Polymerization to a Conductive Polymer
Crystalline diiodoacetylene (C 2 I 2 ) was synthesized and then examined under high-pressure conditions using synchrotron X-ray diffraction, Raman/infrared spectroscopies, and first-principles calculations. At ~0.3 GPa, the starting tetragonal (P$_{4_{2}}$/n) phase, which is stabilized by donor-acceptor interactions, changes into a new orthorhombic structure (Cmca) that is more densely packed and analogous to the low-temperature phase of acetylene. Above approximately 4 GPa, compressed C 2 I 2 molecules in the Cmca structure begin to polymerize to form a predominantly sp 2 amorphous carbon network that maintains a significant fraction of C-I bonds. Transport measurements demonstrate that the polymeric material is electrically conducting. The magnitude of the electrical conductivity is similar to Br-doped polyacetylene and undoped trans-polyacetylene at 8 GPa and 1 atm, respectively. Elemental analyses performed on recovered samples show that the iodine concentration varies with specific processing conditions. Optimization of the pressure-induced polymerization pathway could allow for enhanced electrical properties to be realized, in addition to postpolymerization functionalization using the weak C-I bonds.
Effect of Polymer Chain Length on the Superlattice Assembly of Functionalized Gold Nanoparticles
We report on the assembly of gold nanoparticle (AuNPs) superlattices at the liquid/vapor interface and in the bulk of their suspensions. Interparticle distances in the assemblies are achieved on multiple length scales by varying chain lengths of surface grafted AuNPs by polyethylene glycol (PEG) with molecular weights in the range 2000–40,000 Da. Crystal structures and lattice constants in both 2D and 3D assemblies are determined by synchrotron-based surface-sensitive and small-angle X-ray scattering. Here, assuming knowledge of grafting density, we show that experimentally determined interparticle distances are adequately modeled by spherical brushes close to the θ point (Flory–Huggins parameter, x ≈ 1/2) for 2D superlattices at a liquid interface and a nonsolvent (χ = ∞) for the 3D dry superlattices.