Surface tension between liquids containing antagonistic and regular salts.

We investigate theoretically the surface tension between two immiscible liquids containing antagonistic and regular salts. The mean-field model includes the electrostatic energy and the Gibbs transfer energy of the ions. We find the Donnan potential difference between the liquids and solve the Poisson-Boltzmann equation to calculate the potential and ion density profiles. When the liquids contain only a regular salt, the surface tension increases when compared to the no-salt case; in contrast, the surface tension is reduced when they contain only an antagonistic salt. When both salts are present, the surface tension can either further decrease or increase depending on the preferential solvation of the ions, in agreement with published experimental observations.

Zeolite performance in removal of multicomponent heavy metal contamination from wastewater.

Efficient removal of heavy metal pollutants from wastewater by ion-exchange sorbents requires knowledge and understanding of the interplay between the adsorption patterns of the different components. The present study elucidates the simultaneous adsorption characteristics of six toxic heavy metal cations (Cd2+, Cr3+, Cu2+, Ni2+, Pb2+, and Zn2+) by two synthetic (13X and 4 A) and one natural (clinoptilolite) zeolite from solutions containing equimolar mixtures of the six metals. Equilibrium adsorption isotherms and equilibration dynamics were obtained by ICP-OES and complemented by EDXRF. An order of magnitude lower adsorption efficiency was exhibited by clinoptilolite (maximum of 0.12 mmol ions/g zeolite), relative to that obtained by the synthetic zeolites 13X and 4 A (a maximum of 2.9 and 1.65 mmol ions/g zeolite respectively). The strongest affinities to both zeolites were demonstrated by Pb2+ and Cr3+ (1.5 and 0.85 mmol/g zeolite respectively for 13X, and 0.8 and 0.4 mmol/g zeolite respectively for 4 A adsorbed from the highest solution concentration). The weakest affinities were observed by Cd2+ (0.1 mmol/g for both zeolites), Ni2+ (0.2 and 0.1 mmol/g for 13X and 4 A respectively), and Zn2+ (0.1 mmol/g for both zeolites). Large differences were observed between the two synthetic zeolites in terms of their equilibration dynamics and adsorption isotherms. Pronounced maxima were displayed in the adsorption isotherms for zeolites 13X and 4 A. The decline in adsorption of the weaker adsorbing ions with the increase in total solution concentration was attributed to the thermodynamic equilibrium between the ions adsorbed on the zeolite surface and those in the solution. Regeneration by 3 M KCL eluting solution resulted in considerable reduction in adsorption capacities following each desorption cycle.

Harnessing Peptide Binding to Capture and Reclaim Phosphate.

With rising consumer demands, society is tapping into wastewater as an innovative source to recycle depleting resources. Novel reclamation technologies have been recently explored for this purpose, including several that optimize natural biological processes for targeted reclamation. However, this emerging field has a noticeable dearth of synthetic material technologies that are programmed to capture, release, and recycle specified targets; and of the novel materials that do exist, synthetic platforms incorporating biologically inspired mechanisms are rare. We present here a prototype of a materials platform utilizing peptide amphiphiles that has been molecularly engineered to sequester, release, and reclaim phosphate through a stimuli-responsive pH trigger, exploiting a protein-inspired binding mechanism that is incorporated directly into the self-assembled material network. This material is able to harvest and controllably release phosphate for multiple cycles of reuse, and it is selective over nitrate and nitrite. We have determined by simulations that the binding conformation of the peptide becomes constrained in the dense micelle corona at high pH such that phosphate is expelled when it otherwise would be preferentially bound. However, at neutral pH, this dense structure conversely employs multichain binding to further stabilize phosphate when it would otherwise be unbound, opening opportunities for higher-order conformational binding design to be engineered into this controllably packed corona. With this work, we are pioneering a new platform to be readily altered to capture other valuable targets, presenting a new class of capture and release materials for recycling resources on the nanoscale.

Transport of Flexible, Oil-Soluble Diblock and BAB Triblock Copolymers to Oil/Water Interfaces.

The connection between block copolymer architecture and adsorption at fluid/fluid interfaces is poorly understood. We characterize the interfacial properties of a well-defined series of polyethylene oxide/polydimethyl siloxane (PDMS) diblock and BAB triblock copolymers at the dodecane/water interface. They are oil-soluble and quite flexible because of their hydrophobic PDMS block. Rather than relying on equilibrium interfacial measurements for which it is difficult to mitigate experimental uncertainty during adsorption, we combine measurements of steady-state adsorption, dilatational rheology, and adsorption/desorption dynamics. Steady-state interfacial pressure is insensitive to interfacial curvature and mostly agrees with theory. Adsorption does not occur in the diffusive limit as is the case for many aqueous, small-molecule surfactants. Dilatational rheology reveals differences in behavior between the diblocks and triblocks, and all interfaces possess elasticities below the thermodynamic limit. Desorption dynamics show that material exchange between the interface and the neighboring fluid occurs too slowly to relax dilatational stresses. The mechanism of relaxation occurs at the interface, likely from the reorientation of adsorbed chains.

Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating.

There is a need for the development of antifouling materials to resist adsorption of biomacromolecules. Here we describe the preparation of a novel zwitterionic block copolymer with the potential to prevent or delay the formation of microbial biofilms. The block copolymer comprised a zwitterionic (hydrophilic) section of alternating glutamic acid (negatively charged) and lysine (positively charged) units and a hydrophobic polystyrene section. Cryo-TEM and dynamic-light-scattering (DLS) results showed that, on average, the block copolymer self-assembled into 7-nm-diameter micelles in aqueous solutions (0 to 100 mM NaCl, pH 6). Quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM), and contact angle measurements demonstrated that the block copolymer self-assembled into a brush-like monolayer on polystyrene surfaces. The brush-like monolayer produced from a 100 mg/L block copolymer solution exhibited an average distance, d, of approximately 4-8 nm between each block copolymer molecule (center to center). Once the brush-like monolayer self-assembled, it reduced EPS adsorption onto the polystyrene surface by ∼70% (mass), reduced the rate of bacterial attachment by >80%, and inhibited the development of thick biofilms. QCM-D results revealed that the EPS molecules penetrate between the chains of the brush and adsorb onto the polystyrene surface. Additionally, AFM analyses showed that the brush-like monolayer prevents the adhesion of large (> d) hydrophilic colloids onto the surface via hydration repulsion; however, molecules or colloids small enough to fit between the brush polymers (< d) were able to be adsorbed onto the surface via van der Waals interactions. Overall, we found that the penetration of extracellular organelles, as well as biopolymers through the brush, is critical for the failure of the antifouling coating, and likely could be prevented through tuning of the brush density. Stability and biofilm development testing on multiple surfaces (polypropylene, glass, and stainless steel) support practical applications of this novel block copolymer.

Thermal properties of ruthenium alkylidene-polymerized dicyclopentadiene.

Differential scanning calorimetry (DSC) analysis of ring opening methatesis polymerization (ROMP) derived polydicyclopentadiene (PDCPD) revealed an unexpected thermal behavior. A recurring exothermic signal can be observed in the DSC analysis after an elapsed time period. This exothermic signal was found to be proportional to the resting period and was accompanied by a constant increase in the glass-transition temperature. We hypothesize that a relaxation mechanism within the cross-linked scaffold, together with a long-lived stable ruthenium alkylidene species are responsible for the observed phenomenon.

Controlling the self-assembly of magnetic nanoparticles by competing dipolar and isotropic particle interactions.

Control over the self-assembly of magnetic nanoparticles (MNP) into superstructures due to different types of coupling is of interest in the development of "bottom-up" fabrication schemes. Here we realize a simple strategy for the systematic variation of particle interaction potential in magnetic nanoparticles. This is achieved by varying the effective surface potential by means of a co-surfactant introduced in the course of the synthesis process. As a consequence, the ability to form chain-like assemblies is affected by the resulting balance of attractive and repulsive forces. We use electron microscopy, electron diffraction, and light scattering methods to study a series of cobalt nanoparticles as a characteristic example of ferromagnetic MNP. We demonstrate experimentally and substantiate theoretically that the observed behavior results from a balance between magnetic dipole-dipole, steric, and electrostatic interactions.

On the confocal images and the rheology of whey protein isolated and modified pectins associated complex.

The conditions necessary to form an associated complex between whey protein isolate (WPI) and enzymatically modified pectin in water, at pH values above the isoelectric point of the protein, have been documented. The existence of the complex is not easily verified and its characterization in solution is even more complicated, since the structure is an intermediate entity between the non-interacting, incompatible aqueous soluble mixture of the biopolymers, and a strongly interacting coacervated precipitating complex. Evidence for the formation of this associated complex is provided from confocal laser scanning microscope images and rheological behavior of the aqueous mixtures. The associated complex is characterized by small fluorescent "patches" interpreted as small aggregates. The viscosity of this solution is greater than that of its individual biopolymer constituents, indicating a synergy of attractive interactions that occurs in the solution. While individually, the pectin and the WPI solutions at the studied range of concentrations exhibit moderately non-Newtonian behavior, at specific weight ratios, mixtures of the two behave either as highly entangled polymeric structures or as weak gels. The values of the storage modulus G' are equal to or greater than those of the loss modulus G''. We conclude that the associated complexes are formed at pH 6, and at 4 wt% WPI with a pectin concentration ranging from 0.1 to 0.75 wt%. The influence of the charge distribution (degree of order of the carboxylic groups) of pectin on the associated complex was also investigated, and it was found that the more "ordered" pectin (U63) favors the formation of the associated soluble complex.

Investigation of micelle formation by fluorescence correlation spectroscopy.

We show that noncovalently bound dye molecules can be used as labels in single-molecule fluorescence experiments for the determination of aggregate formation in standard surfactant systems. Aqueous solutions of sulfosuccinic acid bis(2-ethylhexyl) ester sodium salt, hexadecyltrimethylammonium chloride, and pentaethylene glycol monododecyl ether have been studied by fluorescence correlation spectroscopy using commercially available dyes. The translational diffusion coefficient and the critical micelle concentrations have been determined and compare well to values reported in the literature. The respective charges of the surfactant and of the dye molecule are crucial for the effectiveness of the presented method.

Aqueous enantioselective hydrogenation of methyl 2-acetamidoacrylate with Rh-MeDuPHOS occluded in PDMS.

A new chiral heterogeneous catalytic system obtained by occlusion of the Rh-MeDuPHOS complex in a polydimethylsiloxane film was tested in the asymmetric hydrogenation of methyl 2-acetamidoacrylate in aqueous medium.