Q1Report for CADWR Project: Desalination Using Carbon NAnotube Membranes

In this research and development project, LLNL will leverage the process for fabrication of the membranes developed by our internally funded effort (LLNL Laboratory Directed Research and Development). LLNL will then employ chemical manipulations to modify charge at the ends of the nanotubes and make the membranes more selective to either positive or negative ions through a combination of size and charge selectivity. LLNL's goal is to demonstrate ion exclusion while preserving high permeabilities and low energy use. Success of this research and development project may warrant further developments in the fabrication of membranes

Diffusion through Carbon Nanotube Semipermeable membranes

The goal of this project is to measure transport through CNTs and study effects of confinement at molecular scale. This work is motivated by several simulation papers in high profile journals that predict significantly higher transport rates of gases and liquids through carbon nanotubes as compared with similarly-sized nanomaterials (e.g. zeolites). The predictions are based on the effects of confinement, atomically smooth pore walls and high pore density. Our work will provide the first measurements that would compare to and hopefully validate the simulations. Gas flux is predicted to be >1000X greater for SWNTs versus zeolitesi. A high flux of 6-30 H2O/NT/ns {approx} 8-40 L/min for a 1cm{sup 2} membrane is also predicted. Neutron diffraction measurements indicate existence of a 1D water chain within a cylindrical ice sheet inside carbon nanotubes, which is consistent with the predictions of the simulation. The enabling experimental platform that we are developing is a semipermeable membrane made out of vertically aligned carbon nanotubes with gaps between nanotubes filled so that the transport occurs through the nanotubes. The major challenges of this project included: (1) Growth of CNTs in the suitable vertically aligned configuration, especially the single wall carbon nanotubes; (2) Development of a process for void-free filling gaps between CNTs; and (3) Design of the experiments that will probe the small amounts of analyte that go through. Knowledge of the behavior of water upon nanometer-scale confinement is key to understanding many biological processes. For example, the protein folding process is believed to involve water confined in a hydrophobic environment. In transmembrane proteins such as aquaporins, water transport occurs under similar conditions. And in fields as far removed as oil recovery and catalysis, an understanding of the nanoscale molecular transport occurring within the nanomaterials used (e.g. zeolites) is the key to process optimization. Furthermore, advancement of many emerging nanotechnologies in chemistry and biology will undoubtedly be aided by an understanding confined water transport, particularly the details of hydrogen bonding and solvation that become crucial on this length scale. We can envision several practical applications for our devices, including desalination, gas separations, dialysis, and semipermeable fabrics for protection against CW agents etc. The single wall carbon nanotube membranes will be the key platform for applications because they will allow high transport rates of small molecules such as water and eliminate solvated ions or CW agents

Development of a Fast Microfluidic Mixer for Studies of Protein Folding KineticsFinal Report Cover Page

We designed and fabricated mixing devices that will help us elucidate the mechanisms of protein folding through measurements of folding reaction rates. These devices can be used in studying of other biological systems and are compatible with various spectroscopic observation methods. The project involved development of fabrication processes and setup of a laboratory for assembly and characterization of microfluidic devices, as well as measurements of protein folding kinetics. We produced three variants of the mixer: (1) The ultra fast mixer for Foerster Resonance Energy Transfer measurements (described by Anal. Chem. Article UCRL-JRNL-206676) and MicroTAS Conference Proceedings article (UCRL-JC-153057 ) included in the report; (2) The ultra fast mixer for UV measurements (described by the poster presented at MicroTAS conference (UCRL-POST-207476) included in the report); and (3) The mixer for single molecule measurements (described by the Science article UCRL-JC-153057) included in the report. In these mixers, the channels are narrow, ranging from a few to hundreds of {micro}m, so that the flow is laminar and all of the mixing is achieved through diffusion. Our goal is to develop robust microfluidic mixer with at least 100 times lower consumption rate, shorter dead time and time resolution than commercially available mixers that would be compatible with most commonly used spectroscopic methods. We are also developing mixers that can be used in combination with single molecule spectroscopy. The mixers are used to study kinetics of fast protein folding reactions using bulk fluorescence and single molecule fluorescence resonance energy transfer techniques. Capabilities for microfluidic have been developed at BSNL that will be useful for studies of interactions of DNA with proteins and other projects such as the single molecule detector for detection of low concentration of toxins

Fabrication and Characterization of Suspended Carbon Nanotube Devices in Liquid

Suspended carbon nanotube devices are a promising platform for future bio-electronic applications. Suspended carbon nanotube transistors have been previously fabricated in air; however all previous attempts to bring them into liquid failed. We analyze forces acting on the suspended nanotube devices during immersion into liquids and during device operation and show that surface tension forces acting on the suspended nanotubes during transfer into the liquid phase are responsible for the nanotube damage. We have developed a new strategy that circumvents these limitations by coating suspended nanotubes with a rigid inorganic shell in the gas phase. The coating reinforces the nanotubes and allows them to survive transfer through the interface. Subsequent removal of the coating in the solution phase restores pristine suspended nanotubes. We demonstrate that devices fabricated using this technique preserve their original electrical characteristics

MICROFLUIDIC MIXERS FOR THE INVESTIGATION OF PROTEIN FOLDING USING SYNCHROTRON RADIATION CIRCULAR DICHROISM SPECTROSCOPY

The purpose of this study is to design, fabricate and optimize microfluidic mixers to investigate the kinetics of protein secondary structure formation with Synchrotron Radiation Circular Dichroism (SRCD) spectroscopy. The mixers are designed to rapidly initiate protein folding reaction through the dilution of denaturant. The devices are fabricated out of fused silica, so that they are transparent in the UV. We present characterization of mixing in the fabricated devices, as well as the initial SRCD data on proteins inside the mixers

A High-Flux, Flexible Membrane with Parylene-encapsulated Carbon Nanotubes

We present fabrication and characterization of a membrane based on carbon nanotubes (CNTs) and parylene. Carbon nanotubes have shown orders of magnitude enhancement in gas and water permeability compared to estimates generated by conventional theories [1, 2]. Large area membranes that exhibit flux enhancement characteristics of carbon nanotubes may provide an economical solution to a variety of technologies including water desalination [3] and gas sequestration [4]. We report a novel method of making carbon nanotube-based, robust membranes with large areas. A vertically aligned dense carbon nanotube array is infiltrated with parylene. Parylene polymer creates a pinhole free transparent film by exhibiting high surface conformity and excellent crevice penetration. Using this moisture-, chemical- and solvent-resistant polymer creates carbon nanotube membranes that promise to exhibit high stability and biocompatibility. CNT membranes are formed by releasing a free-standing film that consists of parylene-infiltrated CNTs, followed by CNT uncapping on both sides of the composite material. Thus fabricated membranes show flexibility and ductility due to the parylene matrix material, as well as high permeability attributed to embedded carbon nanotubes. These membranes have a potential for applications that may require high flux, flexibility and durability

Nanofiltration of Electrolyte Solutions by Sub-2nm Carbon Nanotube Membranes

Both MD simulations and experimental studies have shown that liquid and gas flow through carbon nanotubes with nanometer size diameter is exceptionally fast. For applications in separation technology, selectivity is required together with fast flow. In this work, we use pressure-driven filtration experiments to study ion exclusion in silicon nitride/sub-2-nm CNT composite membranes as a function of solution ionic strength, pH, and ion valence. We show that carbon nanotube membranes exhibit significant ion exclusion at low salt concentration. Our results support a rejection mechanism dominated by electrostatic interactions between fixed membrane charges and mobile ions, while steric and hydrodynamic effects appear to be less important. Comparison with commercial nanofiltration membranes for water softening reveals that our carbon nanotube membranes provides far superior water fluxes for similar ion rejection capabilities