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Ion-exchange chromatography (IEX) relies on electrostatic interactions between the adsorbent and the adsorbate, and is used extensively in protein purification. Conventional IEX utilizes ligands that are singly charged and randomly dispersed over the adsorbent, creating a heterogeneous distribution of potential adsorption sites. Clustered-charge ion exchangers exhibit higher affinity, capacity, and selectivity than their dispersed-charge counterparts of the same total charge density. In the present work, we monitored the transport behavior of an anionic protein near clustered-charge adsorbent surfaces using Fluorescence Correlation Spectroscopy. We can resolve protein free diffusion, hindered diffusion and association with bare glass, agarose-coated, and agarose-clustered peptide surfaces, demonstrating that this method can be used to understand and ultimately optimize clustered charge adsorbent and other surface interactions at the molecular scale.

The present work reports on in situ observations of the interaction of organic dye probe molecules and dye-labeled protein with different poly(ethylene glycol) (PEG) architectures (linear, dendron, and bottle brush). Fluorescence correlation spectroscopy (FCS) and single molecule event analysis were used to examine the nature and extent of probe–PEG interactions. The data support a sieve-like model in which size-exclusion principles determine the extent of probe–PEG interactions. Small probes are trapped by more dense PEG architectures and large probes interact more with less dense PEG surfaces. These results, and the tunable pore structure of the PEG dendrons employed in this work, suggest the viability of electrochemically-active materials for tunable surfaces.

Single-molecule fluorescence spectroscopy is employed to reveal 3D details of the mechanisms underpinning ion transport in a polyelectrolyte thin film possessing polymer-brush nanoscale order. The ability to resolve fluorescence emission over three discrete polarization angles reveals that these ordered materials impart 3D orientation to charged, diffusing molecules. The experiments, supported by simulations, report global orientation parameters for molecular transport, track dipole angle progressions over time, and identify a unique transport mechanism: translational diffusion with restricted rotation. In general, realization of this experimental method for translational diffusion in systems exhibiting basic orientation should lend itself to evaluation of transport in a variety of important, ordered, functional materials.

Diffusive transport within complex environments is a critical piece of the chemistry occurring in such diverse membrane systems as proton exchange and bilayer lipid membranes. In the present study, fluorescence correlation spectroscopy was used to evaluate diffusive charge transport within a strong polyelectrolyte polymer brush. The fluorescent cation rhodamine-6G was used as a counterion probe molecule, and the strong polyelectrolyte poly(styrene sulfonate) was the polymer brush. Such strong polyelectrolyte brushes show promise for charge storage applications, and thus it is important to understand and tune their transport efficiencies. The polymer brush demonstrated preferential solvation of the probe counterion as compared to solvation by the aqueous solvent phase. Additionally, diffusion within the polymer brush was strongly inhibited, as evidenced by a decrease in diffusion constant of 4 orders of magnitude. It also proved possible to tune the transport characteristics by controlling the solvent pH, and thus the ionic strength of the solvent. The diffusion characteristics within the charged brush system depend on the brush density as well as the effective interaction potential between the probe ions and the brush. In response to changes in ionic strength of the solution, it was found that these two properties act in opposition to each other within this strong polyelectrolyte polymer brush environment. A stochastic random walk model was developed to simulate interaction of a diffusing charged particle with a periodic potential, to show the response of characteristic diffusion times to electrostatic field strengths. The combined results of the experiments and simulations demonstrate that responsive diffusion characteristics in this brush system are dominated by changes in Coulombic interactions rather than changes in brush density. More generally, these results support the use of FCS to evaluate local charge transport properties within polyelectrolyte brush systems, and demonstrate that the technique shows promise in the development of novel polyelectrolyte films for charge storage/transport materials.

Single-molecule fluorescence spectroscopy is employed to reveal 3-dimensional details of the mechanisms underpinning ion transport in a polyelectrolyte thin film possessing polymer-brush nanoscale order. The ability to resolve fluorescence emission over three discrete polarization angles reveals that these ordered materials impart 3-dimensional orientation to charged, diffusing molecules. The experiments, supported by simulations, report global orientation parameters for molecular transport, track dipole angle progressions over time, and identify a unique transport mechanism: translational diffusion with restricted rotation. Generally, realization of this experimental method for translational diffusion in systems exhibiting basic orientation should lend itself to evaluation of transport in a variety of important, ordered, functional materials.

A novel process has been developed to produce highly concentrated forms of surfactants suitable for chemical Enhanced Oil Recovery (cEOR) in the form of powders. Powders are advantageous for cEOR applications because, through their lower water content (typically 3%), they have the potential to reduce transportation costs and simplify the logistics of transporting surfactants from the production location to field locations. Data are presented showing the properties and advantages of powder cEOR surfactants and how they compare to the more conventional liquid form of surfactants. The manufacturing route first involves the preparation of higher active matter liquids (around 70% active) that are subsequently converted into powders using dedicated, standard mixing equipment, the same type used for the manufacture of laundry powders. In this work, several surfactant powders were produced on a pilot plant scale using a number of internal olefin sulfonates to establish applicability for different cEOR projects. The blended powders are agglomerates of surfactant and sodium carbonate and were made both with and without polymer (termed ASP and AS powders respectively). The AS and ASP powders were found to easily dissolve in brine, eliminating the need for special field equipment for dissolution, and gave faster polymer dissolution in water compared with dissolving the polymer as a separate component. The powders have acceptable physical properties that facilitate transport and dispersion in brine and have been tested at desired ratios of surfactant to alkali. This paper also outlines how higher active matter liquids can be manufactured to avoid gel phases, improve their handleability and lower their viscosity. The surfactant powder approach has the potential to substantially reduce costs for full scale chemical EOR projects where large chemical volumes are manufactured, transported, stored and injected.

Functional polymers have a wide variety of applications ranging from energy storage to drug delivery. For energy storage applications, desirable material properties include low cost, high charge storage and/or mobility, and low rates of degradation. Isotropic thin films have been used for many of these types of applications, but research suggests that different structures such as polymer brushes can improve charge transport by an order of magnitude. Supported polymer brush structures produced by "grafting-from" polymerization methods offer a framework for a controlled study of these materials on the molecular scale. Using these materials, researchers can study the basis of hindered diffusion because they contain a relatively homogeneous polyelectrolyte membrane. In addition, researchers can use fluorescent molecular probes with different charges to examine steric and Coulombic contributions to transport near and within polymer brushes. In this Account, we discuss recent progress in using fluorescence correlation spectroscopy, single-molecule polarization-resolved spectroscopy, and a novel three-dimensional orientational technique to understand the transport of charged dye probes interacting with the strong polyanionic brush, poly(styrene sulfonate). Our preliminary experiments demonstrate that a cationic dye, Rhodamine 6G, probes the brush as a counterion, and diffusion is therefore dominated by Coulombic forces, which results in a 10,000-fold decrease in the diffusion coefficient in comparison with free diffusion. We also support our experimental results with molecular dynamics simulations. Further experiments show that, up to 50% of the time, Rhodamine 6G translates within the brush without significant rotational diffusion, which indicates a strong deviation from Fickian transport mechanisms (in which translational and rotational diffusion are related directly through parameters such as chemical potential, size, solution viscosity, and thermal properties). To understand this oriented transport, we discuss the development of an experimental technique that allows us to quantify the three-dimensional orientation on the time scale of intrabrush transport. This method allowed us to identify a unique orientational transport direction for Rhodamine 6G within the poly(styrene sulfonate) brush and to report preliminary evidence for orientational dye "hopping".

Ion-exchange chromatography relies on electrostatic interactions between the adsorbent and the adsorbate and is used extensively in protein purification. Conventional ion-exchange chromatography uses ligands that are singly charged and randomly dispersed over the adsorbent, creating a heterogeneous distribution of potential adsorption sites. Clustered-charge ion exchangers exhibit higher affinity, capacity, and selectivity than their dispersed-charge counterparts of the same total charge density. In the present work, we monitored the transport behavior of an anionic protein near clustered-charge adsorbent surfaces using fluorescence correlation spectroscopy. We can resolve protein-free diffusion, hindered diffusion, and association with bare glass, agarose-coated, and agarose-clustered peptide surfaces, demonstrating that this method can be used to understand and ultimately optimize clustered-charge adsorbent and other surface interactions at the molecular scale.

In this paper an innovative structure/property approach is used to evaluate several commercially available surfactants in tests relevant to both alkaline-surfactant-polymer (ASP) and surfactant-polymer (SP) floods, in order to gain an understanding of how hydrophobe structure is related to surfactant performance and crude oil composition. The surfactant structural elements considered here include relative branching level and carbon chain length. This has application to chemical EOR implementation in fields over a range of reservoir temperatures and salinity. Phase behavior (giving interfacial tension), and micro-emulsion viscosity tests were carried out for internal olefin sulfonates and mixtures with alcohol propoxy sulfates to identify those that perform well while minimizing or eliminating the use of costly co-solvents. Hydrophobe branching and carbon chain length, characterized by gas chromatography, were used to match surfactants to certain crude oil properties such as natural surfactants, including total acid number (TAN) and asphaltenes, and the ratio of saturates/aromatics. The paper also examines how crude oil sampling influences crude properties and surfactant performance. The approach used and associated data contribute to cost reduction of formulations through a) better matching of commercially produced surfactants to the reservoir and crude oil properties to improve oil recovery efficiency, and b) minimizing or eliminating the use of co-solvents to reduce formulation and logistics costs. In addition, the study demonstrates how binary blends from a few core surfactants can match formulations across regionally different crude oils thereby simplifying formulation selection, and reducing uncertainty and cost.

This study revealed that lead, cadmium, mercury, zinc, arsenic, and selenium can be volatilized from both spiked and actual contaminated soils by heating in inert or reducing atmospheres. Generally oxygen proved to be detrimental to the remediation process. An apparatus capable of rapidly heating soil samples to as high as 1,100 C was designed and built to volatilize toxic inorganic contaminants from 500-mg soil samples while purging with hydrogen, nitrogen, or nitrogen/oxygen mixtures. An average of 93% lead removal was observed for PbSO[sub 4]-, Pb(NO[sub 3])[sub 2]-, PbCO[sub 3]-, Pb[sup 0]-, and PbO-spiked soil samples aged for up to two years with initial lead concentrations of 2,000 mg/kg soil when heated for 20 minutes at 900 C in a flowing stream of hydrogen or nitrogen. About 50% lead removal was achieved at 750 C for all the compounds at these conditions. Similar results were obtained for lead-contaminated soil from a battery waste site. Under the same conditions, a sample containing 8,220 mg Pb/kg soil yielded 93% lead removal in hydrogen or nitrogen, but only 73% lead removal in air. Other toxic metals and metalloids also proved amenable to removal from soil by volatilization. The temperatures required for approximately 90% removalmore » during 10 minutes heating in nitrogen were as follows: mercury 370 C, cadmium 550 C, zinc 850 C, arsenic 500 C, and selenium 700 C. Further experiments with oxygen added to the purge gas showed that as little as 1% oxygen significantly lowered the removal of metals, particularly at the lower volatilization temperatures. These experimental results are encouraging; they suggest that the controlled-temperature-metal-volatilization technique is potentially applicable for the permanent lean up of metal contaminated soil.« less

Fluorescence correlation spectroscopy and single molecule burst analysis were used to measure the effects of glass surface interactions on the diffusion of two common fluorescent dyes, one cationic and one anionic. The effects of dye-surface interactions on measured diffusion rates as a function of distance from the surface were investigated. Use of a three-axis piezo stage, combined with reference calibration measurements, enabled the accurate acquisition of surface-distance-dependent transport data. This analysis reveals attractive interactions between the cationic dye and the surface, which significantly alter the extracted diffusion values and persist in the measurements up to 1.0 microm from the surface. The Coulomb attraction between the cationic dye and the surface also results in rare, long-lived association events that lead to irreproducibility in extracted diffusion values. In addition to an assignment of the association lifetime for these events, this paper demonstrates that, if experiments must be performed with cationic probes near a glass surface, the use of solution electrolytes can eliminate deleterious dye-surface interactions, as the dyes were tested in a variety of environments. Finally, our data demonstrate that a better dye choice is an anionic probe, which exhibits no depth dependence of diffusion characteristics above a glass surface.

Single molecule polarization and fluorescence correlation spectroscopy were used to evaluate heterogeneous transport mechanisms of molecular ions within supported polyelectrolyte brushes. Modes of diffusive transport include periods of significantly restricted rotational motion, often maintained over tens of milliseconds; periods of fast molecular rotation; and occasional adsorption of fluorescent probe molecules in the brush. The studies reveal rapid switching between orientational states during each observed mode of motion. Through quantitative analysis of state occupation times, the rate constants for transitions from weakly associated to strongly associated states were extracted. Additionally, the pH dependence of the ion transport rates in the brush exhibits an abrupt, rather than continuous, trend. These single molecule studies demonstrate the presence of dynamic anisotropic interactions between the charged molecular probe and the polymer brush and provide experimental evidence of stimuli responsive switchable transport functionality in the polyelectrolyte brush.

We have evaluated the effect of varying three key parameters for Fluorescence Correlation Spectroscopy analysis, first in the context of a one species/one environment system, and then in a complex system composed of two species, or conversely, two environments. We establish experimentally appropriate settings for the (1) minimum lag time, (2) maximum lag time, and (3) averaging times over which an autocorrelation is carried out, as a function of expected diffusion decay time for a particular solute, and show that use of appropriate settings plays a critical role in recovering accurate and reliable decay times and resulting diffusion constants. Both experimental and simulated data were used to show that for a complex binary system, to extract accurate diffusion constants for both species, decay times must be bounded by adequate minimum and maximum lag times as dictated by the fast and slow diffusing species, respectively. We also demonstrate that even when constraints on experimental conditions do not permit achieving the necessary lag time limits for both of the species in a binary system, the accuracy of the recovered diffusion constant for the one species whose autocorrelation function is fully time-resolved is unaffected by uncertainty in fitting introduced by the presence of the second species.