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Keywords: Hydration of ions, gates, values. Abstract: In conventional desalination process called reverse osmosis in which brine Is filtrated by a fine membrane so that pure water passes through and the ions are left behind. However, this requires large amount of energy to pump the water through the membrane, which is the reason desalinated water is expensive. But by using an array of short carbon nanotubes with each one just 0.8 nm across, packed side by side as a membrane then water immediately flowed down the nanotubes. Whats the surprise was the speed was ten thousand times faster than predicted and it experiences virtually no friction. The Nacl ions are not flowed down because they are hydrated.But here in the process molecular pumps, gates and values are required to make the process user-friendly.
It’s a review paper(Its taken from the Newscientist journal)
GERHARD HUMMER was pondering a serious plumbing problem. He was trying to unravel the inner workings of tiny proteins called aquaporins, which are found in the walls of living cells. Each aquaporin is threaded by a narrow pore that helps control the flow of water into the cell. The pore is a complex thing, narrow in parts and wide in others, lined with a variety of chemical groups that mostly repel water. But it is basically a pipe. And that realisation made Hummer, working at the US National Institutes of Health in Bethesda, Maryland, turn his attention to carbon nanotubes. Consisting of curled-up sheets of carbon and just nanometres wide, they are essentially smooth pipes of waterrepelling graphite. Hummer hoped that their simple structure might offer new insights into the way that water travels through aquaporins. It proved a smart move. Nanotubes have not only helped researchers like Hummer understand water flow in proteins, but they are also enabling scientists to devise a host of nanoscale plumbing parts - such as molecular pumps, gates and valves - capable of moving and filtering everything from salty water and hydrocarbon fuels to gases such as carbon dioxide. It seems that these humble tubes could hold the key to cheap desalinated water, better fuel cells and new strategies to tackle global warming. Hummer's study of fluid flow in nanotubes kicked off around a decade ago when along with two colleagues he created a detailed computer simulation of the way water moves inside a carbon nanotube just 0.8 nanometres wide. When they dunked the tube into a tiny tank of virtual water, the researchers found that a thin thread of water molecules rushed into the interior of the tube. This was surprising, given the narrowness of the nanotube's pore and the water-repelling nature of its carbon surface. Then when they tweaked the simulation, slightly increasing the repulsion between the water molecules and the carbon atoms of the nanotube, they were surprised to see that the tube emptied almost instantaneously. When they decreased the strength of the repulsion, the tube filled
again. The ease with which they could fill or empty the tube was unexpected, and their results published in the journal. Implied that just small changes in charge or even tube geometry might be used to move water through real nanotubes. Hummer and his colleagues then simulated an array of short carbon nanotubes, again each one just 0.8 nanometres across, packed side by side in a membrane. When pure water was added to one side of the membrane and brine to the other, water immediately flowed down the nanotubes into the brine, driven by the difference in salt concentration. What surprised the researchers was the speed of the flow: it seemed that the chain of water molecules passing through each nanotube experiences virtually no friction, moving nearly ten thousand times faster than theory predicts. What's more, Hummer's team found that ions could not get through the pores in either direction. In principle, the nanotubes were wide enough to let the ions through, but it seems they could not make it when the water was confined by the tube. The reason for this behaviour is actually straightforward (see diagram). Charged ions, like those in brine, are surrounded by a network of water molecules in a so-called "hydration shell". But there is no space to accommodate this network inside a nanotube. Instead, each water molecule is hydrogen-bonded to just two others, one in front and one behind, forming a continuous, organised chain. For an ion to enter a nanotube, its hydration shell must be stripped away. Hummer's results suggest this costs too much energy, so the ions stay put. This, in effect, is what occurs in a conventional desalination process called reverse osmosis in which brine is filtered by a fine membrane so that pure water passes through and the ions are left behind. However, this process requires large amounts of energy to pump the water through the membrane, which is one reason why desalinated water is expensive. The high flow-rates measured by Hummer suggested that desalination would be more efficient if it could harness the ion-blocking properties of nanotube membranes.
Constructing membranes from parallel nanotubes is a huge technical challenge. But it can be done: in 2006, Olgica Bakajin of the Lawrence Livermore National Laboratory in California and her co-workers grew nanotubes with inner diameters of about 1.6 nanometres, organised in a parallel arrangement, like the pile in a carpet. Then they embedded the nanotubes in a thin but strong film of the ceramic silicon nitride. In experiments, these membranes permitted much the same super-fast water flow as Hummer had observed - the water rushed through the nanotubes up to 100 times as fast as through conventional porous membranes with far wider pores.
Yet the nanotubes must be even narrower if they are to be effective for desalination. With a diameter of more than 1 nanometre, ions can start to sneak through, says Hummer. "Keeping the pore diameter below this value is important for efficient salt exclusion," he says. According to a recent paper by Ben Corry at the University of Western Australia in Perth, nanotubes measuring 0.93 nanometres across block out 95 per cent of ions. This is good enough to make drinking water, and such a membrane should perform around five times as efficiently as current designs, purifying tens of thousands of litres per square metre per day, Corry says. Corry is now collaborating with chemists to construct nanotube arrays in an altogether different membrane structure. He reckons that silicon nitride is too brittle to be useful, so he is trying to embed the nanotubes in flexible polymers like the polycarbonates used in conventional desalination membranes. Hummer is hopeful that such efforts will pay off. "This is a rapidly evolving field," he says. "I am quite optimistic that densely packed, narrow nanotube membranes can be made, and will be made soon." In some water-purification applications, it would also be useful to have control over the flow through the narrow channels: to be able to turn it on and off as required, for example. For tricks like this, researchers are again turning to nature for inspiration. Take the membrane protein MscS, which controls the transport of ions in bacteria. MscS contains a water channel about 1 nanometre wide that can be closed by stretching the cell membrane in which the protein sits. This distorts the protein, and constricts the pore just enough to keep water out. Engineers are starting to wonder if they can mimic this behaviour in water-filtration membranes by adding chemical groups to carbon nanotubes to create valves and filters. "Clearly, biology provides an amazing array of nanoscale solutions, including those for gated flow," says Hummer. He admits that it is hard to tamper with the rather inaccessible surface inside a nanotube. "But a lot of interesting chemistry has already been done at the rims." Bruce Hinds and his colleagues at the University of Kentucky in Lexington have begun to explore the idea of controllable nanotube membranes. They have taken advantage of the reactivity of carbon atoms at the ends of the nanotube to tether a small organic molecule called a biotin. Biotin, also known as vitamin B7, selectively binds to a protein called streptavidin, and when the nanotubes in the membrane are exposed to a solution of streptavidin, the protein sticks to the openings, reducing the flow to just one-fifteenth of its former rate. Hind's team is now exploring more sophisticated ways of adding gates. For instance, they have grafted an electrically charged molecule onto the mouth of a tube. Applying an electric field to the nanotube moves the molecule into the entrance, obstructing fluid flow. They have even created a gate made from a synthetic peptide that can be closed by a molecule of ATP, the energy-carrier in human cells. The ATP triggers a reaction in
which a large antibody binds to the peptide, blocking the pore. This gating method was inspired by the kinds of chemical switches used to control ion flow and other processes in cells, says Hinds. He suggests that it might also be possible to use ATP or other energy sources to power a molecular motor at each nanotube's entrance to pump fluid through. This would be an important step towards a nanoscale desalination system, says Hinds. It might be possible to pump fluid using an ATP-powered molecular motor at each nanotube's entrance Haiping Fang and his colleagues at the Shanghai Institute of Applied Physics in China are already moving towards this goal. In simulations they showed that three positive charges placed outside a carbon nanotube at specific points along its length can pull water molecules through the tube in one direction. These could be provided by charged groups attached to the outside of the nanotube - which is much easier to modify than the inside or even by small electrodes. The asymmetry of the charge distribution is what causes a preference for flow in one direction. The design mimics the way charged amino acid groups are arranged in the water channel of aquaporins, Fang points out.
Though still purely theoretical, this nanopump works thanks to the charge distribution on water molecules as they line up inside the narrow channel. The pump would not require any external pressure to drive the water through, and combined with the salt-excluding properties of nanotubes, it would offer a simple nanoscale desalinator. Yet it will require a source of energy to run, because energy is needed to hold the charges in place: water molecules moving through the channel will exert a force on them, and try to drag them out of position as they pass. The precise positioning and control of the charges will be difficult, Fang admits, but he hopes to find experimentalists who are up for the challenge. If they succeed, these gates and pumps could be useful in all kinds of ways. Hummer, for example, envisages using nanotubes as channels, gates, valves and pumps in nanofluidic circuits. These could move tiny quantities of chemical solutions around on chip-sized devices for medical and environmental diagnostics. They might also be useful for extracting or transporting hydrogen ions, perhaps to increase the efficiency with which fuel cells generate energy. Modifications of the nanotubes at the insides or ends will be the best way to produce controllable gating and filtration, says Bakajin. "We'll eventually use the nanotubes as the highways, and we will use some kind of gate at the end that blocks whatever it is that we want to exclude." Bakajin has also discovered that her nanotube membranes can transport gases as well as liquids, and will selectively admit smaller molecules like hydrogen and nitrogen rather than carbon dioxide. "By modifying the chemistry of the pore it may be possible to make this differentiation much greater and to target it so that the membranes can be used for molecular separation or molecular sensors," Corry says. Eventually, it might be possible to build nanotube membranes that can separate mixtures of hydrocarbon gases, filter CO2 from a power plant chimney, say, or even extract the gas directly from the air.
Conclusions: They might also be useful for extracting or transporting hydrogen ions to increase the efficiency with which fuel cells generate energy. The membranes can be modified and can be used for molecular separation or molecular sensors. These can also be used to separate mixtures of hydrocarbon gases, filter carbon-di-oxide from a power plant chimney or even extract the gas directly from the air. References
Nature in 2001 (vol 414, p 156) [1 & 2]
(Science, vol 312, p 1034) [1 & 2] Journal of Physical Chemistry B (vol 112, p 1427) [1 & 2]
Nature Nanotechnology (vol 2, p 709) in November 2007 [1 & 2] Newscientist journal (vol.1, issue 07, p 63) [1 & 2]
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