Sunday, March 16th, 2014

Time	Event
6:00p	Novel membrane reveals water molecules will bounce off a liquid surface Consider the nearest water surface: a half-full glass on your desk, a puddle outside your window, or a lake across town. All of these surfaces represent liquid-vapor interfaces, where liquid meets air. Molecules of water vapor constantly collide with these liquid surfaces: Some make it through the surface and condense, while others simply bounce off. The probability that a vapor molecule will bounce, or reflect, off a liquid surface is a fundamental property of water, much like its boiling point. And yet, in the last century, there has been little agreement on the likelihood that a water molecule will bounce off the liquid surface. “When a water vapor molecule hits a surface, does it immediately go into the liquid? Or does it come off and hit again and again, then eventually go in?” says Rohit Karnik, an associate professor of mechanical engineering at MIT. “There’s a lot of controversy, and there’s no easy way to measure this basic property.” Knowing this bouncing probability would give scientists an essential understanding of a variety of applications that involve water flow: the movement of water through soil, the formation of clouds and fog, and the efficiency of water-filtration devices. This last application spurred Karnik and his colleagues — Jongho Lee, an MIT graduate student in mechanical engineering, and Tahar Laoui, a professor at the King Fahd University of Petroleum and Minerals (KFUPM) in Saudi Arabia — to study water’s probability of bouncing. The group is developing membranes for water desalination; this technology’s success depends, in part, on the ability of water vapor to flow through the membrane and condense on the other side as purified water. By observing water transport through membranes with pores of various sizes, the group has measured a water molecule’s probability of condensing or bouncing off a liquid surface at the nanoscale. The results, published in Nature Nanotechnology, could help in designing more efficient desalination membranes, and may also expand scientists’ understanding of the flow of water at the nanoscale. “Wherever you have a liquid-vapor surface, there is going to be evaporation and condensation,” Karnik says. “So this probability is pretty universal, as it defines what water molecules do at all such surfaces.” Getting in the way of flow One of the simplest ways to remove salt from water is by boiling and evaporating the water — separating it from salts, then condensing it as purified water. But this method is energy-intensive, requiring a great deal of heat. Karnik’s group developed a desalination membrane that mimics the boiling process, but without the need for heat. The razor-thin membrane contains nanoscale pores that, seen from the side, resemble tiny tubes. Half of each tube is hydrophilic, or water-attracting, while the other half is hydrophobic, or water-repellant. As water flows from the hydrophilic to the hydrophobic side, it turns from liquid to vapor at the liquid-vapor interface, simulating water’s transition during the boiling process. Vapor molecules that travel to the liquid solution on the other end of the nanopore can either condense into it or bounce off of it. The membrane allows higher water-flow rates if more molecules condense, rather than bounce. Designing an efficient desalination membrane requires an understanding of what might keep water from flowing through it. In the case of the researchers’ membrane, they found that resistance to water flow came from two factors: the length of the nanopores in the membrane and the probability that a molecule would bounce, rather than condense. In experiments with membranes whose nanopores varied in length, the team observed that greater pore length was the main factor impeding water flow — that is, the greater the distance a molecule has to travel, the less likely it is to traverse the membrane. As pores get shorter, bringing the two liquid solutions closer together, this effect subsides, and water molecules stand a better chance of getting through. But at a certain length, the researchers found that resistance to water flow comes primarily from a molecule’s probability of bouncing. In other words, in very short pores, the flow of water is constrained by the chance of water molecules bouncing off the liquid surface, rather than their traveling across the nanopores. When the researchers quantified this effect, they found that only 20 to 30 percent of water vapor molecules hitting the liquid surface actually condense, with the majority bouncing away. A no-bounce design They also found that a molecule’s bouncing probability depends on temperature: 64 percent of molecules will bounce at 90 degrees Fahrenheit, while 82 percent of molecules will bounce at 140 degrees. The group charted water’s probability of bouncing in relation to temperature, producing a graph that Karnik says researchers can refer to in computing nanoscale flows in many systems. “This probability tells us how different pore structures will perform in terms of flux,” Karnik says. “How short do we have to make the pore and what flow rates will we get? This parameter directly impacts the design considerations of our filtration membrane.” Jan Eijkel, a professor of microfluidics and nanofluidics at the University of Twente in the Netherlands, says the group’s work may be useful in understanding a wide range of phenomena, including the microphysics and chemistry of clouds, fluids, aerosols, and the atmosphere. “Their main contribution is the introduction of an entirely new method, which has the very nice flexibility of being able to adjust the distance between water surfaces down to very short distances,” says Eijkel, who did not contribute to the work. “Also, the innovation of changing the composition of the two solutions independently is elegant.” Lee says that knowing the bouncing probability of water may also help control moisture levels in fuel cells.  “One of the problems with proton exchange membrane fuel cells is, after hydrogen and oxygen react, water is generated. But if you have poor control of the flow of water, you’ll flood the fuel cell itself,” Lee says. “That kind of fuel cell involves nanoscale membranes and structures. If you understand the correct behavior of water condensation or evaporation at the nanoscale, you can control the humidity of the fuel cell and maintain good performance all the time.” The research was funded by the Center for Clean Water and Clean Energy at MIT and KFUPM. (Comment on this)
6:00p	Bionic plants Plants have many valuable functions: They provide food and fuel, release the oxygen that we breathe, and add beauty to our surroundings. Now, a team of MIT researchers wants to make plants even more useful by augmenting them with nanomaterials that could enhance their energy production and give them completely new functions, such as monitoring environmental pollutants. In a new Nature Materials paper, the researchers report boosting plants’ ability to capture light energy by 30 percent by embedding carbon nanotubes in the chloroplast, the plant organelle where photosynthesis takes place. Using another type of carbon nanotube, they also modified plants to detect the gas nitric oxide. Together, these represent the first steps in launching a scientific field the researchers have dubbed “plant nanobionics.” “Plants are very attractive as a technology platform,” says Michael Strano, the Carbon P. Dubbs Professor of Chemical Engineering and leader of the MIT research team. “They repair themselves, they’re environmentally stable outside, they survive in harsh environments, and they provide their own power source and water distribution.” Strano and the paper’s lead author, postdoc and plant biologist Juan Pablo Giraldo, envision turning plants into self-powered, photonic devices such as detectors for explosives or chemical weapons. The researchers are also working on incorporating electronic devices into plants. “The potential is really endless,” Strano says. Supercharged photosynthesis The idea for nanobionic plants grew out of a project in Strano’s lab to build self-repairing solar cells modeled on plant cells. As a next step, the researchers wanted to try enhancing the photosynthetic function of chloroplasts isolated from plants, for possible use in solar cells. Chloroplasts host all of the machinery needed for photosynthesis, which occurs in two stages. During the first stage, pigments such as chlorophyll absorb light, which excites electrons that flow through the thylakoid membranes of the chloroplast. The plant captures this electrical energy and uses it to power the second stage of photosynthesis — building sugars. Chloroplasts can still perform these reactions when removed from plants, but after a few hours, they start to break down because light and oxygen damage the photosynthetic proteins. Usually plants can completely repair this kind of damage, but extracted chloroplasts can’t do it on their own. To prolong the chloroplasts’ productivity, the researchers embedded them with cerium oxide nanoparticles, also known as nanoceria. These particles are very strong antioxidants that scavenge oxygen radicals and other highly reactive molecules produced by light and oxygen, protecting the chloroplasts from damage. The researchers delivered nanoceria into the chloroplasts using a new technique they developed called lipid exchange envelope penetration, or LEEP. Wrapping the particles in polyacrylic acid, a highly charged molecule, allows the particles to penetrate the fatty, hydrophobic membranes that surrounds chloroplasts. In these chloroplasts, levels of damaging molecules dropped dramatically. Using the same delivery technique, the researchers also embedded semiconducting carbon nanotubes, coated in negatively charged DNA, into the chloroplasts. Plants typically make use of only about 10 percent of the sunlight available to them, but carbon nanotubes could act as artificial antennae that allow chloroplasts to capture wavelengths of light not in their normal range, such as ultraviolet, green, and near-infrared. With carbon nanotubes appearing to act as a “prosthetic photoabsorber,” photosynthetic activity — measured by the rate of electron flow through the thylakoid membranes — was 49 percent greater than that in isolated chloroplasts without embedded nanotubes. When nanoceria and carbon nanotubes were delivered together, the chloroplasts remained active for a few extra hours. The researchers then turned to living plants and used a technique called vascular infusion to deliver nanoparticles into Arabidopsis thaliana, a small flowering plant. Using this method, the researchers applied a solution of nanoparticles to the underside of the leaf, where it penetrated tiny pores known as stomata, which normally allow carbon dioxide to flow in and oxygen to flow out. In these plants, the nanotubes moved into the chloroplast and boosted photosynthetic electron flow by about 30 percent. Yet to be discovered is how that extra electron flow influences the plants’ sugar production. “This is a question that we are still trying to answer in the lab: What is the impact of nanoparticles on the production of chemical fuels like glucose?” Giraldo says. Lean green machines The researchers also showed that they could turn Arabidopsis thaliana plants into chemical sensors by delivering carbon nanotubes that detect the gas nitric oxide, an environmental pollutant produced by combustion. Strano’s lab has previously developed carbon nanotube sensors for many different chemicals, including hydrogen peroxide, the explosive TNT, and the nerve gas sarin. When the target molecule binds to a polymer wrapped around the nanotube, it alters the tube’s fluorescence. “We could someday use these carbon nanotubes to make sensors that detect in real time, at the single-particle level, free radicals or signaling molecules that are at very low-concentration and difficult to detect,” Giraldo says. “This is a marvelous demonstration of how nanotechnology can be coupled with synthetic biology to modify and enhance the function of living organisms — in this case, plants,” says James Collins, a professor of biomedical engineering at Boston University who was not involved in the research. “The authors nicely show that self-assembling nanoparticles can be used to enhance the photosynthetic capacity of plants, as well as serve as plant-based biosensors and stress reducers.” By adapting the sensors to different targets, the researchers hope to develop plants that could be used to monitor environmental pollution, pesticides, fungal infections, or exposure to bacterial toxins. They are also working on incorporating electronic nanomaterials, such as graphene, into plants. “Right now, almost no one is working in this emerging field,” Giraldo says. “It’s an opportunity for people from plant biology and the chemical engineering nanotechnology community to work together in an area that has a large potential.” The research was funded primarily by the U.S. Department of Energy. (Comment on this)

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