DNA Is Blueprint, Contractor And Construction Worker For New Structures

Daily Science Journal (Feb. 4, 2008) — DNA is the blueprint of all life, giving instruction and function to organisms ranging from simple one-celled bacteria to complex human beings. Now Northwestern University researchers report they have used DNA as the blueprint, contractor and construction worker to build a three-dimensional structure out of gold, a lifeless material.

Computer rendition of a structure created by using DNA to assemble nanoparticles into well-defined crystal lattices. (Credit: Northwestern University)

Using just one kind of nanoparticle (gold) the researchers built two common but very different crystalline structures by merely changing one thing -- the strands of synthesized DNA attached to the tiny gold spheres. A different DNA sequence in the strand resulted in the formation of a different crystal.

The technique, to be published in the journal Nature, and reflecting more than a decade of work, is a major and fundamental step toward building functional "designer" materials using programmable self-assembly. This "bottom-up" approach will allow scientists to take inorganic materials and build structures with specific properties for a given application, such as therapeutics, biodiagnostics, optics, electronics or catalysis

Most gems, such as diamonds, rubies and sapphires, are crystalline inorganic materials. Within each crystal structure, the atoms have precise locations, which give each material its unique properties. Diamond's renowned hardness and refractive properties are due to its structure -- the precise location of its carbon atoms.

In the Northwestern study, gold nanoparticles take the place of atoms. The novel part of the work is that the researchers use DNA to drive the assembly of the crystal. Changing the DNA strand's sequence of As, Ts, Gs and Cs changes the blueprint, and thus the shape, of the crystalline structure. The two crystals reported in Nature, both made of gold, have different properties because the particles are arranged differently.

"We are now closer to the dream of learning, as nanoscientists, how to break everything down into fundamental building blocks, which for us are nanoparticles, and reassembling them into whatever structure we want that gives us the properties needed for certain applications," said Chad A. Mirkin, one of the paper's senior authors and George B. Rathmann Professor of Chemistry in the Weinberg College of Arts and Sciences, professor of medicine and professor of materials science and engineering. In addition to Mirkin, George C. Schatz, Morrison Professor of Chemistry, directed the work.

By changing the type of DNA on the surface of the particles, the Northwestern team can get the particles to arrange differently in space. The structures that finally form are the ones that maximize DNA hybridization. DNA is the stabilizing force, the glue that holds the structure together. "These structures are a new form of matter," said Mirkin, "that would be difficult, if not impossible, to make any other way."

He likens the process to building a house. Starting with basic materials such as bricks, wood, siding, stone and shingles, a construction team can build many different types of houses out of the same building blocks. In the Northwestern work, the DNA controls where the building blocks (the gold nanoparticles) are positioned in the final crystal structure, arranging the particles in a functional way. The DNA does all the heavy lifting so the researchers don't have to.

Mirkin, Schatz and their team just used one building block, gold spheres, but as the method is further developed, a multitude of building blocks of different sizes can be used -- with different composition (gold, silver and fluorescent particles, for example) and different shapes (spheres, rods, cubes and triangles). Controlling the distance between the nanoparticles is also key to the structure's function.

"Once you get good at this you can build anything you want," said Mirkin, director of Northwestern's International Institute for Nanotechnology.

"The rules that govern self-assembly are not known, however," said Schatz, "and determining how to combine nanoparticles into interesting structures is one of the big challenges of the field."

The Northwestern researchers started with gold nanoparticles (15 nanometers in diameter) and attached double-stranded DNA to each particle with one of the strands significantly longer than the other. The single-stranded portion of this DNA serves as the "linker DNA," which seeks out a complementary single strand of DNA attached to another gold nanoparticle. The binding of the two single strands of linker DNA to each other completes the double helix, tightly binding the particles to each other.

Each gold nanoparticle has multiple strands of DNA attached to its surface so the nanoparticle is binding in many directions, resulting in a three-dimensional structure -- a crystal. One sequence of linker DNA, programmed by the researchers, results in one type of crystal structure while a different sequence of linker DNA results in a different structure.

"We even found a case where the same linker could give different structures, depending on the temperatures at which the particles were mixed," said Schatz.

Using the extremely brilliant X-rays produced by the Advanced Photon Source synchrotron at Argonne National Laboratory in combination with computational simulations, the research team imaged the crystals to determine the exact location of the particles throughout the structure. The final crystals have approximately 1 million nanoparticles.

"It took scientists decades of work to learn how to synthesize DNA," said Mirkin. "Now we've learned how to use the synthesized form outside the body to arrange lifeless matter into things that are useful, which is really quite spectacular."

The Nature paper, entitled "DNA-programmable nanoparticle crystallization" is to be published January 31, 2008. In addition to Mirkin and Schatz, other authors are Sung Yong Park, a former postdoctoral fellow in Schatz's lab and now at the University of Rochester (lead author); graduate student Abigail K. R. Lytton-Jean, Northwestern University; Byeongdu Lee, Advanced Photon Source, Argonne National Laboratory; and Steven Weigand, Northwestern's DND-CAT Synchrotron Research Center at Argonne's Advanced Photon Source.

Adapted from materials provided by Northwestern University, via EurekAlert!, a service of AAAS.

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New Nanotube Findings Give Boost To Potential Biomedical Applications

Daily Science Journal (Feb. 4, 2008) — Carbon nanotubes-cylinders so tiny that it takes 50,000 lying side by side to equal the width of a human hair-are packed with the potential to be highly accurate vehicles for administering medicines and other therapeutic agents to patients. But a dearth of data about what happens to the tubes after they discharge their medical payloads has been a major stumbling block to progress.

A representation of a carbon nanotube accessorized with a coating of branched PEG. (Credit: Courtesy of Hongjie Dai)

Now, Stanford researchers, who spent months tracking the tiny tubes inside mice, have found some answers.

Studies in mice already had shown that most nanomaterials tend to accumulate in organs such as the liver and spleen, which was a concern because no one knew how long they could linger. But fears that the tiny tubes might be piling up in vital organs, like discarded refrigerators at the bottom of a rural ravine, can now be put to rest, said Hongjie Dai, the J. G. Jackson and C. J. Wood Professor of Chemistry at Stanford, whose research team has demonstrated that the nanotubes exit the organs.

Dai and his group found that the carbon nanotubes leave the body primarily through the feces, with some by way of the urine. ''That's nice to know,'' Dai said. ''This now proves that they do get out of the system.''

The full extent of the news, which is scheduled to be published the week of Jan. 28 in Proceedings of the National Academy of Sciences Online Early Edition (PNAS), is even better than that: The three-month-long study also allays worries that the nanotubes, by simply remaining in the organs for a long time, would prove toxic to the mouse.

''None of the mice died or showed any anomaly in the blood chemistry or in the main organs,'' said Dai, senior author on the PNAS paper. ''They appear very healthy, and they are gaining weight, just like normal mice. There's no obvious toxicity observed.'' The lack of toxicity of nanotubes in mice is consistent with a previous pilot study done by Sanjiv Gambhir, a professor of radiology at Stanford, and his research group in collaboration with Dai's group.

''This is the first time anyone has done a systematic circulation and excretion study like this for nanotubes, and data on other nano particles is also scarce,'' Dai said. ''The excretion pathway may apply to other nano materials and may need to be looked at closely like this also.''

Previous research published by Dai's group has demonstrated the potential for using nanotubes in treating cancerous cells and targeting tumors in mice.

His group used Raman spectroscopy, a method of applying light from a laser beam that effectively ''illuminates'' the presence of the target molecules in the organs of the mice.

Being hit with light from the beam causes a detectable change in the state of a molecule's energy. Carbon nanotubes, composed entirely of carbon atoms that are mostly arranged in linked hexagonal rings, give off a strong signal in response to the beam. This allowed the researchers to pinpoint the position of the chosen molecules, as well as ascertain their abundance in the blood or organs.

Previous detection methods that relied on attaching fluorescent labels or spectroscopic tags to the nanotubes had yielded unreliable results. The attachments tended to either come loose from the tubes or decay over time spans ranging from a few days to only a few hours-far too short to reveal the ultimate fate of the nanotubes.

While knowing the carbon nanotubes will move through the digestive system at a healthy pace is critical to future practical applications, it is also crucial that the nanotubes not enter the digestive system too soon after being injected; they need to spend enough time in the circulatory system to find their way to their target location.

The key to fine-tuning the carbon nanotubes' speed of circulation turns on how the basic, bare-bones floor model is chemically accessorized.

''You can make the nanotubes circulate a very long time in the blood, if the chemistry is done right,'' Dai said. The researchers found that coating their carbon nanotubes with polyethylene glycol (PEG), a common ingredient in cosmetics, worked best.

They used a form of PEG with three little limbs sprouting off a central trunk. ''Those provide better shielding to the nanotube than just a single branch. Therefore, they interact less with the biological molecules around them,'' Dai said.

The team stuffed the PEG liberally into the linked hexagonal rings that compose the nanotubes, prompting Dai to describe the end result as resembling rolled-up chicken wire with feathers sticking out all over.

Though they may sound less than gorgeous visually, the feathery nanotubes turned in a beautiful performance in practical terms, Dai said. The coating of PEG made the nanotubes highly water soluble, which helped them to stay in the blood instead of being absorbed.

''They circulate in the blood for about 10 hours or so in mice, which seems to be a good length of time,'' Dai said.

The right chemical coating on nanotubes also can help ease them out of the mouse in a timely fashion, and the three-branched PEG was effective there, too.

Dai's earlier research demonstrated that nanotubes have promise for treating cancer with two different approaches. Once they have zeroed in on the target cells, shining light on the nanotubes causes them to generate heat, which can kill cancer cells. The other method is to rig the nanotubes to accumulate at targeted sites, where they can deliver medication from within the tubes.

''[Carbon nanotubes] seem to be promising for biomedical applications and for potentially treating cancer, either using drugs or using the physical properties,'' Dai said. ''This is the reason we carried out the study of the fate of nanotubes in mice. I think this is really a very fundamental issue.''

The research was funded by the Cancer Center for Nanotechnology Excellence, which is funded by the National Institutes of Health and the National Cancer Institute. The first author of the PNAS paper is Zhuang Liu, graduate student in chemistry. The paper's other authors, all affiliated with Stanford University, are Xiaoyuan ''Shawn'' Chen, assistant professor in radiology; Dr. Corrine Davis of the Veterinary Service Center in the Department of Comparative Medicine; Weibo Cai, postdoctoral scholar in radiology; and Lina He, formerly a technician in Chen's research group.

Adapted from materials provided by Stanford University.

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New Polymer Could Improve Semiconductor Manufacturing, Packaging

Daily Science Journal (Feb. 2, 2008) — Researchers at Rensselaer Polytechnic Institute and Polyset Company have developed a new inexpensive, quick-drying polymer that could lead to dramatic cost savings and efficiency gains in semiconductor manufacturing and computer chip packaging.

Researchers from Rensselaer Polytechnic Institute's Department of Physics and Center for Integrated Electronics have developed a new inexpensive, quick-drying polymer that could lead to dramatic cost savings and efficiency gains in semiconductor manufacturing and computer chip packaging. In this series of scanning electron microscope images of the new PES polymer in a UV-imprint lithography application, the well-defined pattern indicates the material’s potential for use in next-generation chip making techniques. (Credit: Rensselaer Polytechnic Institute)

Along with allowing enhanced performance and cost savings for conventional photolithography processes, the new material, called polyset epoxy siloxane (PES), should also enable a new generation of lower-cost, on-chip nanoimprinting lithography technology, according to the researchers.

"With this new material, chip manufacturers will be able to trim several steps from their production and packaging processes, and in turn realize a cost savings," said Toh-Ming Lu, the R.P. Baker Distinguished Professor of Physics at Rensselaer, who oversaw the study. "PES is cheaper and more reliable."

The widely adopted technique of photolithography involves using a mix of light and chemicals to generate intricate micro- and nano-scale patterns on tiny areas of silicon. As part of the process, a thin polymer film -- called a redistribution layer, and crucial to the effectiveness of device -- is deposited onto the silicon wafer, in order to ease the signal propagation delay and to protect the chip from different environmental and mechanical factors.

The new PES material developed by Lu's group and Polyset Company is one such thin polymer film, and it offers several advantages over the incumbent materials typically used in the semiconductor manufacturing industry. In addition, their new PES material can also be used as a thin polymer film for ultraviolet (UV) on-chip nanoimprinting lithography technology, which is still in the early phases of development. The consistency of using PES in conventional technology, and then continuing to use PES while academia and industry test and gradually migrate to the next generation of devices, should help ease the transition, Lu said.

"Having the ability to use one material -- our new PES -- for both photolithography and imprint will be very attractive to manufacturers," Lu said. "At its core, our project is basic research, but it also has important industry implications. It's very exciting."

Manufacturers today typically use benzocyclobutene and polyimide as polymers for redistribution layers, because of their low water absorption, thermal stability, low curing temperature, low thermal expansion, low dielectric constant, and low leakage current. Lu said PES offers significant advantages to these materials, particularly in the areas of cure temperature and water uptake.

PES cures, or dries and hardens, at 165 degrees Celsius, about 35 percent cooler than the other two materials. The need for less heat should translate directly into lower overhead costs for manufacturers, Lu said. Another advantage of PES is its low water uptake rate of less than 0.2 percent, less than the other materials. Additionally, PES adheres well to copper and can easily be made less brittle if needed. All of these attributes make PES a promising candidate for redistribution layer application and UV imprint lithography.

"The results demonstrate that PES is feasible to be used as UV-curable resist for both the redistribution application for electronic packaging and micro/nano imprint lithography," said Rensselaer Research Associate Pei-I Wang, co-author of the new paper, published recently in the Journal of Vacuum Science and Technology B.

Along with photolithography and on-chip nanoimprinting lithography, PES holds the potential for applications in other optical devices, flat-panel display, biotechnology devices, and microelectromechanical systems, Wang said.

In addition to Lu and Wang, co-authors on the paper include Rensselaer materials science and engineering professor Omkaram Nalamasu, who is also chief technical officer of Applied Materials Inc. in Santa Clara, Calif.; Rajat Ghoshal and Ram Ghoshal of Polyset Co. Inc. in Mechanicville, N.Y.; Charles Schaper of Transfer Devices Inc. in Santa Clara, Calif.; and Andrew Li of Applied Materials.

The project was funded through the New York State Foundation for Science, Technology and Innovation.

Adapted from materials provided by Rensselaer Polytechnic Institute.

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New Method For Creating Self-Assembling, Nanoscale Materials

Daily Science Journal (Feb. 2, 2008) — While biomedical, electronics, and other branches of research are marching steadily into the realm of the smaller-than-small nanometer scale, building needed materials at this scale has been problematic.

Recently, however, a team from The Scripps Research Institute unveiled a novel approach to the problem that yields a material with novel properties, which some might find reminiscent of Flubber. The material is produced using naturally occurring proteins as templates for uniform, self-assembled, nano-scale construction.

The material, an organic polymer described in today's early, online edition of the Proceedings of the National Academy of Sciences (PNAS), could one day find application in everything from screening for disease to microelectronics.

Using Nature's Tricks

Nature is replete with examples of molecules such as DNA that self-assemble with uniform patterns on the nanoscale, but until now researchers have had limited success duplicating such processes. The new study, however, provides one synthetic method that has effectively mimicked the templating strategy used in nature for nanoscale construction in the lab.

To create the new material, the Scripps Research team, led by Scripps Research President Richard Lerner and Assistant Professor Tobin Dickerson, began with a natural nanoscale product, a bacterial virus or phage. A nanometer is one billionth of a meter, or the width of a few average atoms.

Specifically, the product the team worked with was a phage known as M13. If scaled up, the phage is proportionally equivalent to a 4-foot-long pencil, with the tip and eraser roughly representing the active parts of the phage that infect bacteria. Other proteins that are biologically inert and analogous to the wood body of the pencil provide the filamentous phage's structure.

Having worked with phage extensively in other applications, the team decided to explore the possibility of using those structural proteins as a potential template for nanoscale construction. To do so, the team chemically modified molecular protrusions on the proteins so they would attract and bind with the components needed to form strands of polyacrylamide, a common polymer used to make laboratory gels.

The resulting polymer-phage combination, which twists into helices like DNA and RNA molecules, takes on the shape of a comb with the polymers as the teeth. These teeth in turn interlock to form a strangely resilient, rubbery solid.

Shocking Flexibility

Once the new material, known as a protein-polymer bioconjugate, was created, the group was shocked to find that it was almost impossible to break a sample apart. It could be sliced, but no matter how hard researchers compressed or squeezed it, it always bounced back to its original state, because the stable phage proteins act like rebar in concrete to provide strength.

Further analyses uncovered additional important characteristics. The combs do not grow completely uniformly—some combs grow more teeth than others, for instance, before interlocking with a nearby comb. But the combs can only be a prescribed distance apart for the chemical interlocking to occur, which leads to uniform size for the pores between the comb teeth. The pores proved to be about 4 nanometers wide and greater than 1 micrometer (one millionth of a meter) in length.

This uniformity is in stark contrast with experiments which showed that simply mixing the phages with polymers without the templating procedure produces a chaotic hodge podge at the molecular level.

Interestingly, after creating the material, the group discovered that a British scientist had done theoretical calculations about how flexible rods—like the phages—would pack together using the least amount of energy.

"It was extremely gratifying to see that the mathematics had exactly predicted what we were observing," says Dickerson

Putting It to Use

Although the work was intended mainly as a proof of concept for using the phages as templates, the researchers have a number of potential applications in mind. The phage can be produced easily and cheaply in very large quantities, and the polymer components are readily available and simple to combine to create the final material. These characteristics would make commercial application possible.

"In essence, bacteriophage-derived materials are a renewable resource," says Dickerson.

The defined channels established by the pores in the material might be adapted as pathways for electrons for use in microelectronics. Or, the pores might be used as a filter for certain molecules, for example to test blood samples for proteins whose presence is tied to particular diseases. More complex potential uses might include altering the biologically active portions of the phage to attract specific molecules, forcing them into the polymers' pores, or to block others.

"These tools can be visualized like Tinkertoys ® or Legos ®," says Dickerson of the possibilities. "You can think about this really in engineering terms using macroscopic analogs such as baskets, or lids, or holes."

To add to the list of potential applications, the team has already begun exploring additional materials that might be created using the basic phage construction scheme.

In addition to Dickerson and Lerner, authors on the paper, entitled "Biologically templated organic polymers with nanoscale order," were Bert Willis, Lisa Eubanks, Malcolm Wood, and Kim Janda, all of Scripps Research. See http://www.pnas.org/cgi/content/abstract/0711308105v1.

The work was supported by the Skaggs Institute for Chemical Biology, Worm Institute for Research and Medicine, and a National Institutes of Health Kirschstein National Research Service Award.

Adapted from materials provided by Scripps Research Institute.

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New Kind Of Transistor Radios Shows Capability Of Nanotube Technology

Daily Science Journal (Jan. 30, 2008) — Carbon nanotubes have a sound future in the electronics industry, say researchers who built the world's first all-nanotube transistor radios to prove it.

Schematic exploded view of a radio-frequency transistor that uses parallel, aligned arrays of carbon nanotubes for the semiconductor. (Credit: Images courtesy John Rogers)

The nanotube radios, in which nanotube devices provide all of the active functionality in the devices, represent "important first steps toward the practical implementation of carbon-nanotube materials into high-speed analog electronics and other related applications," said John Rogers, a Founder Professor of Materials Science and Engineering at the University of Illinois.

Rogers is a corresponding author of a paper* that describes the design, fabrication and performance of the nanotube-transistor radios, which were achieved in a close collaboration with radio frequency electronics engineers at Northrop Grumman Electronics Systems in Linthicum, Md.

"These results indicate that nanotubes might have an important role to play in high-speed analog electronics, where benchmarking studies against silicon indicate significant advantages in comparably scaled devices, together with capabilities that might complement compound semiconductors," said Rogers, who also is a researcher at the Beckman Institute and at the university's Frederick Seitz Materials Research Laboratory.

Practical nanotube devices and circuits are now possible, thanks to a novel growth technique developed by Rogers and colleagues at the U. of I., Lehigh and Purdue universities, and described last year in the journal Nature Nanotechnology.

The growth technique produces linear, horizontally aligned arrays of hundreds of thousands of carbon nanotubes that function collectively as a thin-film semiconductor material in which charge moves independently through each of the nanotubes. The arrays can be integrated into electronic devices and circuits by conventional chip-processing techniques.

"The ability to grow these densely packed horizontal arrays of nanotubes to produce high current outputs, and the ability to manufacture the arrays reliably and in large quantities, allows us to build circuits and transistors with high performance and ask the next question," Rogers said. "That question is: 'What type of electronics is the most sensible place to explore applications of nanotubes"' Our results suggest that analog RF (radio frequency) represents one such area."

As a demonstration of the growth technique and today's nanotube analog potential, Rogers and collaborators at the U. of I. and Northrop Grumman fabricated nanotube transistor radios, in which nanotube devices provided all of the key functions.

The radios were based on a heterodyne receiver design consisting of four capacitively coupled stages: an active resonant antenna, two radio-frequency amplifiers, and an audio amplifier, all based on nanotube devices. Headphones plugged directly into the output of a nanotube transistor. In all, seven nanotube transistors were incorporated into the design of each radio.

In one test, the researchers tuned one of the nanotube-transistor radios to WBAL-AM (1090) in Baltimore, to pick up a traffic report.

"We were not trying to make the world's tiniest radios," Rogers said. "The nanotube radios are a demonstration, an important milestone toward building the technology into a form that ultimately would be commercially competitive with entrenched approaches."

*The paper has been accepted for publication in the Proceedings of the National Academy of Sciences, and is to be published in PNAS Online Early Edition in the first week in February, 2008.

The work was funded by the National Science Foundation and the U.S. Department of Energy.

Adapted from materials provided by University of Illinois at Urbana-Champaign.

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Nanotubes Help Advance Brain Tumor Research

Daily Science Journal (Jan. 30, 2008) — The potential of carbon nanotubes to diagnose and treat brain tumors is being explored through a partnership between NASA's Jet Propulsion Laboratory, Pasadena, Calif., and City of Hope, a leading cancer research and treatment center in Duarte, Calif.

Benham Badie, M.D., director of the Department of Neurosurgery and the Brain Tumor program at City of Hope, performs a minimally invasive procedure to surgically remove a pituitary tumor. Nanotube technology may help in the development of new treatments that would require only minimally invasive procedures no matter the location of the brain tumor. (Credit: City of Hope)

Nanotechnology may help revolutionize medicine in the future with its promise to play a role in selective cancer therapy. City of Hope researchers hope to boost the brain's own immune response against tumors by delivering cancer-fighting agents via nanotubes. A nanotube is about 50,000 times narrower than a human hair, but it length can extend up to several centimeters.

If nanotube technology can be effectively applied to brain tumors, it might also be used to treat stroke, trauma, neurodegenerative disorders and other disease processes in the brain, said Dr. Behnam Badie, City of Hope's director of neurosurgery and of its brain tumor program.

"I'm very optimistic of how this nanotechnology will work out," he said. "We are hoping to begin testing in humans in about five years, and we have ideas about where to go next."

The Nano and Micro Systems Group at JPL, which has been researching nanotubes since about 2000, creates these tiny, cylindrical multi-walled carbon tubes for City of Hope.

City of Hope researchers, who began their quest in 2006, found good results: The nanotubes, which they used on mice, were non-toxic in brain cells, did not change cell reproduction and were capable of carrying DNA and siRNA, two types of molecules that encode genetic information.

JPL's Nano and Micro Systems Group grows the nanotubes on silicon strips a few square millimeters in area. The growth process forms them into hollow tubes as if by rolling sheets of graphite-like carbon.

Carbon nanotubes are extremely strong, flexible, heat-resistant, and have very sharp tips. Consequently, JPL uses nanotubes as field-emission cathodes -- vehicles that help produce electrons -- for various space applications such as x-ray and mass spectroscopy instruments, vacuum microelectronics and high-frequency communications.

"Nanotubes are important for miniaturizing spectroscopic instruments for space applications, developing extreme environment electronics, as well as for remote sensing," said Harish Manohara, the technical group supervisor for JPL's Nano and Micro Systems Group.

Nanotubes are a fairly new innovation, so they are not yet routinely used in current NASA missions, he added. However, they may be used in gas-analysis or mineralogical instruments for future missions to Mars, Venus and the Jupiter system.

JPL's collaboration with City of Hope began last year, after Manohara, Badie and Dr. Babak Kateb, City of Hope's former director of research and development in the brain tumor program, discussed using nanostructures to better diagnose and treat brain cancer. Badie said his team's nanomedical research continues, and the next goal will be to functionalize and attach inhibitory RNA to the nanotubes and deliver it to specific areas of the brain.

The JPL and City of Hope teams published the results of the study earlier this year in the journal NeuroImage.

Badie says that JPL's contribution to City of Hope's nanomedicine research has been invaluable.

"The fact that we can get pristine and really clean nanotubes from Manohara's department is unique," he said. "The fact that we are both collaborating for biological purposes is also really unique."

The collaboration between JPL and City of Hope is conducted under NASA's Innovative Partnership Program, designed to bring benefits of the space program to the public.

Adapted from materials provided by NASA/Jet Propulsion Laboratory.

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Using Carbon Nanotubes To Seek And Destroy Anthrax Toxin And Other Harmful Proteins

Daily Science Journal (Dec. 13, 2007) — Researchers at Rensselaer Polytechnic Institute have developed a new way to seek out specific proteins, including dangerous proteins such as anthrax toxin, and render them harmless using nothing but light. The technique lends itself to the creation of new antibacterial and antimicrobial films to help curb the spread of germs, and also holds promise for new methods of seeking out and killing tumors in the human body.

Transmission electron microscope images show carbon nanotubes conjugated with anthrax toxin before (a, b) and after (c, d) exposure to ultraviolet light. This light caused the adsorbed toxin to deactivate and fall off the nanotube, which is why the structures in pictures c and d are smaller in diameter than those in pictures a and b. (Credit: Rensselaer/Ravi Kane)

Scientists have long been interested in wrapping proteins around carbon nanotubes, and the process is used for various applications in imaging, biosensing, and cellular delivery. But this new study at Rensselaer is the first to remotely control the activity of these conjugated nanotubes.

A team of Rensselaer researchers led by Ravi S. Kane, professor of chemical and biological engineering, has worked for nearly a year to develop a means to remotely deactivate protein-wrapped carbon nanotubes by exposing them to invisible and near-infrared light. The group demonstrated this method by successfully deactivating anthrax toxin and other proteins.

"By attaching peptides to carbon nanotubes, we gave them the ability to selectively recognize a protein of interest -- in this case anthrax toxin -- from a mixture of different proteins," Kane said. "Then, by exposing the mixture to light, we could selectively deactivate this protein without disturbing the other proteins in the mixture."

By conjugating carbon nanotubes with different peptides, this process can be easily tailored to work on other harmful proteins, Kane said. Also, employing different wavelengths of light that can pass harmlessly through the human body, the remote control process will also be able to target and deactivate specific proteins or toxins in the human body. Shining light on the conjugated carbon nanotubes creates free radicals, called reactive oxygen species. It was the presence of radicals, Kane said, that deactivated the proteins.

Kane's new method for selective nanotube-assisted protein deactivation could be used in defense, homeland security, and laboratory settings to destroy harmful toxins and pathogens. The method could also offer a new method for the targeted destruction of tumor cells. By conjugating carbon nanotubes with peptides engineered to seek out specific cancer cells, and then releasing those nanotubes into a patient, doctors may be able to use this remote protein deactivation technology as a powerful tool to prevent the spread of cancer.

Kane's team also developed a thin, clear film made of carbon nanotubes that employs this technology. This self-cleaning film may be fashioned into a coating that -- at the flip of a light switch -- could help prevent the spread of harmful bacteria, toxins, and microbes.

"The ability of these coatings to generate reactive oxygen species upon exposure to light might allow these coatings to kill any bacteria that have attached to them," Kane said. "You could use these transparent coatings on countertops, doorknobs, in hospitals or airplanes -- essentially any surface, inside or outside, that might be exposed to harmful contaminants."

Kane said he and his team will continue to hone this new technology and further explore its potential applications.

Details of the project are outlined in the article "Nanotube-Assisted Protein Deactivation" in the December issue of Nature Nanotechnology.

Co-authors of the paper include Department of Chemical and Biological Engineering graduate students Amit Joshi and Shyam Sundhar Bale; postdoctoral researcher Supriya Punyani; Rensselaer Nanotechnology Center Laboratory Manager Hoichang Yang; and professor Theodorian Borca-Tasciuc of the Department of Mechanical, Aerospace, and Nuclear Engineering.

The group has filed a patent disclosure for their new selective nanotube-assisted protein deactivation technology. The research project was funded by the U.S. National Institutes of Health and the National Science Foundation.

Adapted from materials provided by Rensselaer Polytechnic Institute, via EurekAlert!, a service of AAAS.

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Radio Waves Fire Up Nanotubes Embedded In Tumors, Destroying Liver Cancer

Daily Science Journal (Nov. 3, 2007) — Cancer cells treated with carbon nanotubes can be destroyed by non-invasive radio waves that heat up the nanotubes while sparing untreated tissue, a research team led by scientists at The University of Texas M. D. Anderson Cancer Center and Rice University has shown in preclinical experiments.

Researchers show that the technique completely destroyed liver cancer tumors in rabbits. There were no side effects noted. However, some healthy liver tissue within 2-5 millimeters of the tumors sustained heat damage due to nanotube leakage from the tumor.

"These are promising, even exciting, preclinical results in this liver cancer model," says senior author Steven Curley, M.D., professor in M. D. Anderson's Department of Surgical Oncology. "Our next step is to look at ways to more precisely target the nanotubes so they attach to, and are taken up by, cancer cells while avoiding normal tissue."

Targeting the nanotubes solely to cancer cells is the major challenge in advancing the therapy, Curley says. Research is under way to bind the nanotubes to antibodies, peptides or other agents that in turn target molecules expressed on cancer cells. To complicate matters, most such molecules also are expressed in normal tissue.

Curley estimates that a clinical trial is at least three to four years away.

Curley conducted the research at M. D. Anderson in collaboration with nanotechnology experts at Rice University and with Erie, Pennsylvania, entrepreneur John Kanzius of ThermMed LLC, who invented the experimental radiofrequency generator used in the experiments. Kanzius is a cancer survivor and former radio station owner whose insights into the potential of targeted radio waves inspired this line of research.

At Rice, the work was begun by Nobel laureate Richard Smalley, several months before his untimely death from cancer in October 2005. Smalley was the founder of Rice's Carbon Nanotechnology Laboratory and one of the world's foremost experts on carbon nanotubes. He shared the Nobel Prize for the 1985 discovery of fullerenes, the family of carbon molecules that includes nanotubes. His research in 2005 was concentrated largely on the radiofrequency cancer research project.

Rice materials scientist professor Boris Yakobson, Ph.D., a co-author on the paper, recalled meeting with Smalley in his hospital room at M. D. Anderson five days before his death.

"He looked very ill, breathing heavily through the oxygen mask, but all he wanted to do was talk about the physics of this very phenomenon," Yakobson said. "Oblivious of his ebbing health, Rick was focused in the future. He had told Congress in 1999 that nanotechnology would help revolutionize cancer treatment, and he was a scientist wanting to know whether this technology might be one of the things that would make that possible."

In the liver cancer experiment, a solution of single-walled carbon nanotubes was injected directly into the tumors. Four treated rabbits were then exposed to two minutes of radiofrequency treatment, resulting in thermal destruction of their tumors.

Carbon nanotubes are hollow cylinders of pure carbon that measure about a billionth of a meter, or one nanometer, across.

Control group tumors that were treated only by radiofrequency exposure or only by nanotubes were undamaged.

In lab experiments, two lines of liver cancer cells and one pancreatic cancer cell line were destroyed after being incubated with nanotubes and exposed to the radiofrequency field.

"I'm humbled by the results of this research," says Kanzius. "I realize it's early in the race, but Dr. Curley and his team have moved on this carefully with utmost speed. I look forward to continuing to work with them and hopefully to watching the first person be treated with this procedure. The race isn't over but it needs to be taken to the finish line."

Radiofrequency energy fields penetrate deeply into tissue, so it would be possible to deliver heat anywhere in the body if targeted nanotubes or other nanoparticles can be delivered to cancerous cells, Curley says. Without such a target, radio waves will pass harmlessly through the body.

An invasive technique known as radio frequency ablation is used to treat some malignant tumors, the authors note. It requires insertion of needle electrodes directly into the tumors. ncomplete tumor destruction occurs in 5 to 40 percent of cases, normal tissue is damaged and complications arise in 10 percent of patients who suffer such damage. Radiofrequency ablation is limited to liver, kidney, breast, lung and bone cancers.

This research appeared online ahead of December publication in the journal Cancer.

The research was supported by an American Association of Cancer Research Littlefield Grant, NASA and the Houston-based Alliance for NanoHealth, the National Science Foundation, the Center for Biological and Environmental Nanotechnology and the Fulbright Foundation.

Co-authors with Curley, Smalley, Kanzius and Yakobson are first authors Christopher J. Gannon, M.D., also of M. D. Anderson's Department of Surgical Oncology, and Paul Cherukuri, Ph.D. of Rice's Carbon Nanotechnology Laboratory and Department of Chemistry; Carter Kittrell, Ph.D., R. Bruce Weisman, Ph.D., Matteo Pasquali, Ph.D., and Howard K. Schmidt, Ph.D., all of Rice; and Laurent Cognet, Ph.D., of Rice and the Centre de Physique Moléculaire Optique et Hertzienne, Université Bordeaux, France.

Adapted from materials provided by University of Texas M. D. Anderson Cancer Center.

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First Fully-functional Radio From A Single Carbon Nanotube Created

Daily Science Journal (Oct. 31, 2007) — Make way for the real nanopod and make room in the Guinness World Records. A team of researchers with the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) and the University of California at Berkeley have created the first fully functional radio from a single carbon nanotube, which makes it by several orders of magnitude the smallest radio ever made.

This image, taken by a transmission electron microscope, shows a single carbon nanotube protruding from an electrode. This nanotube is less than a micron long and only 10 nanometers wide, or 10,000 times thinner than the width of a single human hair. When a radio wave of a specific frequency impinges on the nanotube, it begins to vibrate vigorously. An electric field applied to the nanotube forces electrons to be emitted from its tip. This electrical current may be used to detect the mechanical vibrations of the nanotube, and thus listen to the radio waves. (The waves shown in this image were added for visual effect, and are not part of the original microscope image.) (Credit: Courtesy Zettl Research Group, Lawrence Berkeley National Laboratory and University of California at Berkeley)

Wielding a single carbon nanotube 10,000 times smaller than a human hair, this is definitely the smallest radio yet. The nanotube vibrates at radio frequencies to receive the signal, then acts as both amplifier and demodulator. With only a battery and sensitive earphones, it can pick up AM or FM. With such a small receiver or transmitter, you could put a tracking collar on a bacterium.

“A single carbon nanotube molecule serves simultaneously as all essential components of a radio — antenna, tunable band-pass filter, amplifier, and demodulator,” said physicist Alex Zettl, who led the invention of the nanotube radio. “Using carrier waves in the commercially relevant 40-400 MHz range and both frequency and amplitude modulation (FM and AM), we were able to demonstrate successful music and voice reception.”

Given that the nanotube radio essentially assembles itself and can be easily tuned to a desired frequency band after fabrication, Zettl believes that nanoradios will be relatively easy to mass-produce. Potential applications, in addition to incredibly tiny radio receivers, include a new generation of wireless communication devices and monitors. Nanotube radio technology could prove especially valuable for biological and medical applications.

“The entire radio would easily fit inside a living cell, and this small size allows it to safely interact with biological systems,” Zettl said. “One can envision interfaces with brain or muscle functions, or radio-controlled devices moving through the bloodstream.”

It is also possible that the nanotube radio could be implanted in the inner ear as an entirely new and discrete way of transmitting information, or as a radically new method of correcting impaired hearing.

Zettl holds joint appointments with Berkeley Lab's Materials Sciences Division (MSD) and the UC Berkeley Physics Department where he is the director of the Center of Integrated Nanomechanical Systems. In recent years, he and his research group have created an astonishing array of devices out of carbon nanotubes - hollow tubular macromolecules only a few nanometers (billionths of a meter) in diameter and typically less than a micron in length – including sensors, diodes and even a motor. The nanotube radio, however, is the first that – literally – rocks!

“When I was a young kid, I got a transistor radio as a gift and it was the greatest thing I could imagine - music coming from a box I could hold in my hand!” Zettl said. “When we first played our nanoradio, I was just as excited as I was when I first turned on that transistor radio as a kid.”

The carbon nanotube radio consists of an individual carbon nanotube mounted to an electrode in close proximity to a counter-electrode, with a DC voltage source, such as from a battery or a solar cell array, connected to the electrodes for power. The applied DC bias creates a negative electrical charge on the tip of the nanotube, sensitizing it to oscillating electric fields. Both the electrodes and nanotube are contained in vacuum, in a geometrical configuration similar to that of a conventional vacuum tube.

Kenneth Jensen, a graduate student in Zettl’s research group, did the actual design and construction of the radio.

“We started out by making an exceptionally sensitive force sensor,” Jensen said.“Nanotubes are like tiny cat whiskers.Small forces, on the order of attonewtons, cause them to deflect a significant amount.By detecting this deflection, you can infer what force was acting on the nanotube. This incredible sensitivity becomes even greater at the nanotube’s flexural resonance frequency, which falls within the frequencies of radio broadcasts, cell phones and GPS broadcasting. Because of this high resonance frequency, Alex (Zettl) suggested that nanotubes could be used to make a radio.”

Although it has the same essential components, the nanotube radio does not work like a conventional radio. Rather than the entirely electrical operation of a conventional radio, the nanotube radio is in part a mechanical operation, with the nanotube itself serving as both antenna and tuner.

Incoming radio waves interact with the nanotube’s electrically charged tip, causing the nanotube to vibrate. These vibrations are only significant when the frequency of the incoming wave coincides with the nanotube’s flexural resonance frequency, which, like a conventional radio, can be tuned during operation to receive only a pre-selected segment, or channel, of the electromagnetic spectrum.

Amplification and demodulation properties arise from the needle-point geometry of carbon nanotubes, which gives them unique field emission properties. By concentrating the electric field of the DC bias voltage applied across the electrodes, the nanotube radio produces a field-emission current that is sensitive to the nanotube’s mechanical vibrations. Since the field-emission current is generated by the external power source, amplification of the radio signal is possible. Furthermore, since field emission is a non-linear process, it also acts to demodulate an AM or FM radio signal, just like the diode used in traditional radios.

“What we see then is that all four essential components of a radio receiver are compactly and efficiently implemented within the vibrating and field-emitting carbon nanotube,” said Zettl. “This is a totally different approach to making a radio - the exploitation of electro-mechanical movement for multiple functions. In other words, our nanotube radio is a true NEMS (nano-electro-mechanical system) device.”

Because carbon nanotubes are so much smaller than the wavelengths of visible light, they cannot be viewed with even the highest powered optical microscope. Therefore, to observe the critical mechanical motionof their nanotube radio, Zettl and his research team, which in addition to Jensen, also included post-doc Jeff Weldon and graduate student Henry Garcia, mounted their nanotube radio inside a high resolution transmission electron microscope (TEM). A sine-wave carrier radio signal was launched from a nearby transmitting antenna and when the frequencies of the transmitted carrier wave matched the nanotube resonance frequency, radio reception became possible.

“To correlate the mechanical motions of the nanotube to an actual radio receiver operation, we launched an FM radio transmission of the song Good Vibrations by the Beach Boys,” said Zettl. “After being received, filtered, amplified, and demodulated all by the nanotube radio, the emerging signal was further amplified by a current preamplifier, sent to an audio loudspeaker and recorded. The nanotube radio faithfully reproduced the audio signal, and the song was easily recognizable by ear.”

When the researchers deliberately detuned the nanotube radio from the carrier frequency, mechanical vibrations faded and radio reception was lost. A “lock” on a given radio transmission channel could be maintained for many minutes at a time, and it was not necessary to operate the nanotube radio inside a TEM. Using a slightly different configuration, the researchers successfully transmitted and received signals across a distance of several meters.

“The integration of all the electronic components of a radio happened naturally in the nanotube itself,” said Jensen. “Within a few hours of figuring out that our force sensor was in fact a radio, we were playing music!”

Added Zettl, “Our nanotube radio is sophisticated and elegant in the physics of its operation, but sheer simplicity in technical design. Everything about it works perfectly, without additional patches or tricks.”

Berkeley Lab’s Technology Transfer Department is now seeking industrial partners to further develop and commercialize this technology.

A paper on this work is now on-line at the Nano Letters Website. It will also be published in the November 2007 print edition of Nano Letters. The paper is entitled “Nanotube Radio” and the co-authors are Zettl, Jensen, Weldon and Garcia. In that same print edition, there appears a paper by Peter Burke and Chris Rutherglen of UC Irvine, reporting on the use of a carbon nanotube as a demodulator.

The nanotube radio research was supported by the U.S. Department of Energy and by the National Science Foundation within the Center of Integrated Nanomechanical Systems.

Berkeley Lab is a U.S. Department of Energy national laboratory located in Berkeley, California. It conducts unclassified scientific research and is managed by the University of California.

Adapted from materials provided by DOE/Lawrence Berkeley National Laboratory.

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You Thought Your Nano Was Small: Nano-sized Detector Turns Radio Waves Into Music

Daily Science Journal (Oct. 19, 2007) — Researchers in California report development of the world's first working radio system that receives radio waves wirelessly and converts them to sound signals through a nano-sized detector made of carbon nanotubes.

The "carbon nanotube radio" device is thousands of times smaller than the diameter of a human hair. The development marks an important step in the evolution of nano-electronics and could lead to the production of the world's smallest radio, the scientists say.

Peter Burke and Chris Rutherglen developed a carbon nanotube "demodulator" that is capable of translating AM radio waves into sound. In a laboratory demonstration, the researchers incorporated the detector into a complete radio system and used it to successfully transmit classical music wirelessly from an iPod to a speaker several feet away from the music player.

Although other researchers have developed nano-sized radio wave detectors in the past, the current study marks the first time that a nano-sized detector has been demonstrated in an actual working radio system, the scientists say. The study demonstrates the feasibility of making other radio components at the nanoscale in the future and may eventually lead to a "truly integrated nanoscale wireless communications system," they say. Such a device could have numerous industrial, commercial, medical and other applications.

Their findings appeared online October 17 and are scheduled for publication in the Nov. 14 print edition of ACS' Nano Letters.

Adapted from materials provided by American Chemical Society, via EurekAlert!, a service of AAAS.

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