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Thermally programmable pH buffers

ACS Applied Materials and Interfaces

Van Gough, Dara; Bunker, B.C.; Roberts, Mark E.; Huber, Dale L.; Zarick, Holly F.; Austin, Mariah J.; Wheeler, Jill S.; Moore, Diana; Spoerke, Erik D.

Many reactions in both chemistry and biology rely on the ability to precisely control and fix the solution concentrations of either protons or hydroxide ions. In this report, we describe the behavior of thermally programmable pH buffer systems based on the copolymerization of varying amounts of acrylic acid (AA) groups into N-isopropylacrylamide polymers. Because the copolymers undergo phase transitions upon heating and cooling, the local environment around the AA groups can be reversibly switched between hydrophobic and hydrophilic states affecting the ionization behavior of the acids. Results show that moderate temperature variations can be used to change the solution pH by two units. However, results also indicate that the nature of the transition and its impact on the pH values are highly dependent on the AA content and the degree of neutralization. © 2012 American Chemical Society.

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Targeting proteins to liquid-ordered domains in lipid membranes

Langmuir

Stachowiak, Jeanne C.; Hayden, Carl C.; Sanchez, Mari A.; Wang, Julia W.; Bunker, B.C.; Voigt, James A.; Sasaki, Darryl Y.

We demonstrate the construction of novel protein-lipid assemblies through the design of a lipid-like molecule, DPIDA, endowed with tail-driven affinity for specific lipid membrane phases and head-driven affinity for specific proteins. In studies performed on giant unilamellar vesicles (GUVs) with varying mole fractions of dipalymitoylphosphatidylcholine (DPPC), cholesterol, and diphytanoylphosphatidyl choline (DPhPC), DPIDA selectively partitioned into the more ordered phases, either solid or liquid-ordered (Lo) depending on membrane composition. Fluorescence imaging established the phase behavior of the resulting quaternary lipid system. Fluorescence correlation spectroscopy confirmed the fluidity of the Lo phase containing DPIDA. In the presence of CuCl2, the iminodiacetic acid (IDA) headgroup of DPIDA forms the Cu(II)-IDA complex that exhibits a high affinity for histidine residues. His-tagged proteins were bound specifically to domains enriched in DPIDA, demonstrating the capacity to target protein binding selectively to both solid and Lo phases. Steric pressure from the crowding of surface-bound proteins transformed the domains into tubules with persistence lengths that depended on the phase state of the lipid domains. © 2010 American Chemical Society.

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Nanoporous carbon for electrochemical capacitors

Yelton, William G.; Siegal, Michael P.; Bunker, B.C.; Limmer, Steven J.

Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

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Size effects in Ni/Ni(OH)2 nanomaterials for electrochemical capacitors

Limmer, Steven J.; Yelton, William G.; Bunker, B.C.

Electrochemical capacitors based on redox-active metal oxides show great promise for many energy-storage applications. These materials store charge through both electric double-layer charging and faradaic reactions in the oxide. The dimensions of the oxide nanomaterials have a strong influence on the performance of such capacitors. Not just due to surface area effects, which influence the double-layer capacitance, but also through bulk electrical and ionic conductivities. Ni(OH)2 is a prime candidate for such applications, due to low cost and high theoretical capacity. We have examined the relationship between diameter and capacity for Ni/Ni(OH)2 nanorods. Specific capacitances of up to 511 F/g of Ni were recorded in 47 nm diameter Ni(OH)2 nanorods.

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Nanoporous carbon for electrochemical capacitors

Limmer, Steven J.; Yelton, William G.; Siegal, Michael P.; Overmyer, Donald L.; Bunker, B.C.

Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

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Exploiting interfacial water properties for desalination and purification applications

Cygan, Randall T.; Jiang, Ying B.; Alam, Todd M.; Brinker, C.J.; Bunker, B.C.; Leung, Kevin L.; Nenoff, T.M.; Nyman, M.; Ockwig, Nathan O.; Orendorff, Christopher O.; Rempe, Susan R.; Singh, Seema S.; Criscenti, Louise C.; Stevens, Mark J.; Thurmer, Konrad T.; Van Swol, Frank; Varma, Sameer V.; Crozier, Paul C.; Feibelman, Peter J.; Houston, Jack E.; Huber, Dale L.

A molecular-scale interpretation of interfacial processes is often downplayed in the analysis of traditional water treatment methods. However, such an approach is critical for the development of enhanced performance in traditional desalination and water treatments. Water confined between surfaces, within channels, or in pores is ubiquitous in technology and nature. Its physical and chemical properties in such environments are unpredictably different from bulk water. As a result, advances in water desalination and purification methods may be accomplished through an improved analysis of water behavior in these challenging environments using state-of-the-art microscopy, spectroscopy, experimental, and computational methods.

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Monolayer Engineered Microchannels for Motor Protein Transport

Sandia journal manuscript; Not yet accepted for publication

Bunker, B.C.; Bachand, George B.; Manginell, Ronald P.

Here, self-assembled monolayers (SAMS) have been investigated for their ability to confine the absorption of the motor protein kinesin and direct the movement of microtubule shuttles (MTs) within channels of a lithographically patterned microfluidic device. Channels were made from gold films deposited on a silicon wafer to provide chemically distinct surfaces for the selective formation of a range of alkane thiol monolayers on channel walls. Devices were then exposed to solutions containing casein and kinesin to develop protein monolayers capable of propelling microtubules in the presence of adenosine triphosphate (ATP) fuel. Fluorescence microscopy images were used to observe the attachment of MTs to chemically distinct regions and to evaluate the ability of the various monolayer coatings to confine the movement of MTs within the channel system. Ellipsometry was used to characterize the protein adsorption characteristics of SAMS terminated with different functional groups to help establish confinement mechanisms. Finally, both anti-fouling and cationic monolayers were found to be effective in confining MT movement within the channels by controlling the adsorption or orientation of the casein buffer layers that mediate motor protein attachment and functionality.

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Results 1–25 of 47
Results 1–25 of 47