Researchers with the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) and the University of California (UC) Berkeley have developed a solution-based method for inducing the self-assembly of flexible polymer membranes with highly aligned subnanometer channels. Fully compatible with commercial membrane-fabrication processes, this new technique is believed to be the first example of organic nanotubes fabricated into a functional membrane over macroscopic distances.
“We’ve used nanotube-forming cyclic peptides and block co-polymers to demonstrate a directed co-assembly technique for fabricating subnanometer porous membranes over macroscopic distances,” says Ting Xu, a polymer scientist who led this project. “This technique should enable us to generate porous thin films in the future where the size and shape of the channels can be tailored by the molecular structure of the organic nanotubes.”Ting Xu holds joint appointments with Berkeley Lab’s Materials Sciences Division and UC Berkeley's Departments of Materials Sciences and Engineering, and Chemistry. (Photo by Roy Kaltschmidt, Berkeley Lab Public Affairs)
Xu, who holds joint appointments with Berkeley Lab’s Materials Sciences Division and the University of California Berkeley’s Departments of Materials Sciences and Engineering, and Chemistry, is the lead author of a paper describing this work, which has been published in the journal ACS Nano. The paper is titled “Subnanometer Porous Thin Films by the Co-assembly of Nanotube Subunits and Block Copolymers.”
Co-authoring the paper with Xu were Nana Zhao, Feng Ren, Rami Hourani, Ming Tsang Lee, Jessica Shu, Samuel Mao, and Brett Helms, who is with the Molecular Foundry, a DOE nanoscience center hosted at Berkeley Lab.
Channeled membranes are one of nature’s most clever and important inventions. Membranes perforated with subnanometer channels line the exterior and interior of a biological cell, controlling – by virtue of size – the transport of essential molecules and ions into, through, and out of the cell. This same approach holds enormous potential for a wide range of human technologies, but the challenge has been finding a cost-effective means of orienting vertically-aligned subnanometer channels over macroscopic distances on flexible substrates.
“Obtaining molecular level control over the pore size, shape, and surface chemistry of channels in polymer membranes has been investigated across many disciplines but has remained a critical bottleneck,” Xu says. “Composite films have been fabricated using pre-formed carbon nanotubes and the field is making rapid progess, however, it still presents a challenge to orient pre-formed nanotubes normal to the film surface over macroscopic distances.”Schematic drawing depicts process by which a polymer is tethered to cyclic peptides (8CP)then blended with block copolymers (BCPs) to make a membrane permeated with subnanometer channels in the form of organic nanotubes.
For their subnanometer channels, Xu and her research group used the organic nanotubes naturally formed by cyclic peptides – polypeptide protein chains that connect at either end to make a circle. Unlike pre-formed carbon nanotubes, these organic nanotubes are “reversible,” which means their size and orientation can be easily modified during the fabrication process. For the membrane, Xu and her collaborators used block copolymers – long sequences or “blocks” of one type of monomer molecule bound to blocks of another type of monomer molecule. Just as cyclic peptides self-assemble into nanotubes, block copolymers self-assemble into well-defined arrays of nanostructures over macroscopic distances. A polymer covalently linked to the cyclic peptide was used as a “mediator” to bind together these two self-assembling systems
“The polymer conjugate is the key,” Xu says. “It controls the interface between the cyclic peptides and the block copolymers and synchronizes their self-assembly. The result is that nanotube channels only grow within the framework of the polymer membrane. When you can make everything work together this way, the process really becomes very simple.”
Xu and her colleagues were able to fabricate subnanometer porous membranes measuring several centimeters across and featuring high-density arrays of channels. The channels were tested via gas transport measurements of carbon dioxide and neopentane. These tests confirmed that permeance was higher for the smaller carbon dioxide molecules than for the larger molecules of neopentane. The next step will be to use this technique to make thicker membranes.
“Theoretically, there are no size limitations for our technique so there should be no problem in making membranes over large area,” Xu says. “We’re excited because we believe this demonstrates the feasibility of synchronizing multiple self-assembly processes by tailoring secondary interactions between individual components. Our work opens a new avenue to achieving hierarchical structures in a multicomponent system simultaneously, which in turn should help overcome the bottleneck to achieving functional materials using a bottom-up approach.”
This research was supported by DOE’s Office of Science and by the U.S. Army Research Office. Measurements were carried out on beamlines at Berkeley Lab’s Advanced Light Source and at the Advanced Photon Source of Argonne National Laboratory.
Lawrence Berkeley National Laboratory is a U.S. Department of Energy (DOE) national laboratory managed by the University of California for the DOE Office of Science. Berkeley Lab provides solutions to the world’s most urgent scientific challenges including sustainable energy, climate change, human health, and a better understanding of matter and force in the universe. It is a world leader in improving our lives through team science, advanced computing, and innovative technology. Visit our at www.lbl.gov
For more information on the research of Ting Xu, visit her Website at http://www.mse.berkeley.edu/groups/xu/index.htm
A copy of the paper in ACS Nano paper “Subnanometer Porous Thin Films by the Co-assembly of Nanotube Subunits and Block Copolymers” is available at http://pubs.acs.org/doi/abs/10.1021/nn103083t
Lynn Yarris | EurekAlert!
Novel sensors could enable smarter textiles
17.08.2018 | University of Delaware
Quantum material is promising 'ion conductor' for research, new technologies
17.08.2018 | Purdue University
There are currently great hopes for solid-state batteries. They contain no liquid parts that could leak or catch fire. For this reason, they do not require cooling and are considered to be much safer, more reliable, and longer lasting than traditional lithium-ion batteries. Jülich scientists have now introduced a new concept that allows currents up to ten times greater during charging and discharging than previously described in the literature. The improvement was achieved by a “clever” choice of materials with a focus on consistently good compatibility. All components were made from phosphate compounds, which are well matched both chemically and mechanically.
The low current is considered one of the biggest hurdles in the development of solid-state batteries. It is the reason why the batteries take a relatively long...
New design tool automatically creates nanostructure 3D-print templates for user-given colors
Scientists present work at prestigious SIGGRAPH conference
Most of the objects we see are colored by pigments, but using pigments has disadvantages: such colors can fade, industrial pigments are often toxic, and...
Scientists at the University of California, Los Angeles present new research on a curious cosmic phenomenon known as "whistlers" -- very low frequency packets...
Scientists develop first tool to use machine learning methods to compute flow around interactively designable 3D objects. Tool will be presented at this year’s prestigious SIGGRAPH conference.
When engineers or designers want to test the aerodynamic properties of the newly designed shape of a car, airplane, or other object, they would normally model...
Researchers from TU Graz and their industry partners have unveiled a world first: the prototype of a robot-controlled, high-speed combined charging system (CCS) for electric vehicles that enables series charging of cars in various parking positions.
Global demand for electric vehicles is forecast to rise sharply: by 2025, the number of new vehicle registrations is expected to reach 25 million per year....
17.08.2018 | Event News
08.08.2018 | Event News
27.07.2018 | Event News
20.08.2018 | Information Technology
20.08.2018 | Life Sciences
20.08.2018 | Information Technology