понедельник, 28 февраля 2011 г.

Metallic molecules to nanotubes: Spread out!

Metallic molecules to nanotubes: Spread out!

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(PhysOrg.com) -- A lab at Rice University has stepped forward with an efficient method to disperse nanotubes in a way that preserves their unique properties -- and adds more.

The new technique allows inorganicwith different functionalities to remain in close contact with single-walled carbon nanotubes while keeping them separated in a solution.

That separation is critical to manufacturers who want to spin fiber from nanotubes, or mix them into composite materials for strength or to take advantage of their. For starters, the ability to functionalize the nanotubes at the same time may advance imaging sensors, catalysis and solar-activated.

Better yet, a batch of nanotubes can apparently stay dispersed in water for weeks on end.

Keeping carbon nanotubes from clumping in aqueous solutions and combining them with molecules that add novel abilities have been flies in the ointment for scientists exploring the use of these highly versatile materials.

They've tried attaching organic molecules to the nanotubes' surfaces to add functionality as well as solubility. But while these techniques can separate nanotubes from one another, they take a toll on the nanotubes' electronic, thermal and mechanical properties.

Angel Marti, a Rice assistant professor of chemistry and bioengineering and a Norman Hackerman-Welch Young Investigator, and his students reported this month in the Royal Society of Chemistry journalthat ruthenium polypyridyl complexes are highly effective at dispersing nanotubes in water efficiently and for long periods. Ruthenium is a rare metallic element.

One key is having just the right molecule for the job. Marti and his team created ruthenium complexes by combining the element with ligands, stable molecules that bind to. The resulting molecular complex is part hydrophobic (the ligands) and part hydrophilic (the ruthenium). The ligands strongly bind to nanotubes while the attached ruthenium molecules interact with water to maintain the tubes in solution and keep them apart from one another.

Another key turned out to be moderation.

Originally, Marti said, he and co-authors Disha Jain and Avishek Saha weren't out to solve a problem that has boggled chemists for decades, but their willingness to"do something crazy"paid off big-time. Jain is a former postdoctoral researcher in Marti's lab, and Saha is a graduate student.

The researchers were eyeing ruthenium complexes as part of a study to track amyloid deposits associated with Alzheimer's disease."We started to wonder what would happen if we modified the metal complex so it could bind to a nanotube,"Marti said."That would provide solubility, individualization, dispersion and functionality."

It did, but not at first."Avishek put this together with purified single-walled carbon nanotubes (created via Rice's HiPco process) and sonicated. Absolutely nothing happened. The nanotubes didn't get into solution -- they just clumped at the bottom.

"That was very weird, but that's how science works -- some things you think are good ideas never work."

Saha removed the liquid and left the clumped nanotubes at the bottom of the centrifuge tube."So I said, 'Well, why don't you do something crazy. Just add water to that, and with the little bit of ruthenium that might remain there, try to do the reaction.' He did that, and the solution turned black."

A low concentration of ruthenium did the trick."We found out that 0.05 percent of the ruthenium complex is the optimum concentration to dissolve nanotubes,"Marti said. Further experimentation showed that simple ruthenium complexes alone did not work. The molecule requires its hydrophobic ligand tail, which seeks to minimize its exposure to water by binding with nanotubes."That's the same thing nanotubes want to do, so it's a favorable relationship,"he said.

Marti also found the nanotubes' natural fluorescence unaffected by the ruthenium complexes."Even though they've been purified, which can introduce defects, they still exhibit very good fluorescence,"he said.

He said that certain ruthenium complexes have the ability to stay in an excited state for a long time -- about 600 nanoseconds, or 100 times longer than normal."It means the probability that it will transfer an electron is high. That's convenient for energy transfer applications, which are important for imaging,"he said.

Thatstay suspended for a long time should catch the eye of manufacturers who use them in bulk."They should stay separated for weeks without problems,"Marti said."We have solutions that have been sitting for months without any signs of crashing."


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воскресенье, 27 февраля 2011 г.

Simpler way of making proteins could lead to new nanomedicine agents

Simpler way of making proteins could lead to new nanomedicine agents

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Researchers have developed a simple method of making short protein chains with spiral structures that can also dissolve in water, two desirable traits not often found together. Such structures could have applications as building blocks for self-assembling nanostructures and as agents for drug and gene delivery.

Led by Jianjun Cheng, a professor of materials science and engineering at the University of Illinois, the research team will publish its findings in the Feb. 22 edition of the journalNature Communications.

Materials scientists have been interested in designing largethat could be used as building blocks for self-assembling structures. The challenge has been that the molecules generally adopt a globular, spherical shape, limiting their ability to form orderly aggregates. However, polypeptides– chains of amino acids such as proteins– can form helical structures. Short polypeptide chains that adopt a spiral shape act like cylindrical rods.

"If you have two rigid rods, one positive and one negative, right next to each other, they're going to stick to each other. If you have a way to put the charge on the surface then they can pack together in a close, compact way, so they form a three-dimensional structure,"Cheng said.

However, it is difficult to make helical polypeptides that are water-soluble so they can be used in solution. Polypeptides gain their solubility from side chains– molecular structures that stem from each amino acid link in the polypeptide chain. Amino acids with positive or negative charges in their side chains are needed to make a polypeptide disperse in water.

The problem arises when chains with charged side chains form helical structures. The charges cause a strong repulsion between the side chains, which destabilizes the helical conformation. This causes water-soluble polypeptides to form random coil structures instead of the desired helices.

In exploring solutions to the riddle of helical, water-soluble polypeptides, researchers have tried several complicated methods. For example, scientists have attempted grafting highly water-soluble chemicals to the side chains to increase the polypeptides' overall solubility, or creating helices with charges only on one side.

"You can achieve the helical structure and the solubility but you have to design the helical structure in a very special way. The peptide design needs a very specific sequence. Then you're very limited in the type of polypeptide you can build, and it's not easy to design or handle these polypeptides,"Cheng said.

In contrast, Cheng's group developed a very straightforward solution. Since the close proximity of the charges causes the repulsion that disrupts the helix, the researchers simply elongated the side chains, moving the charges farther from the backbone and giving them more freedom to keep their distance from one another.

The researchers observed that as they increased the length of the side chains with charges on the end, the polypeptides' propensity for forming helices also increased.

"It's such a simple idea– move the charge away from the backbone,"Cheng said."It's not difficult at all to make the longer side chains, and it has amazing properties for winding up helical structures simply by pushing the distance between the charge and the backbone."

The group found that not only do polypeptides with long side chains form helices, they display remarkable stability even when compared to non-charged helices. The helices seem immune to temperature, pH, and other denaturing agents that would unwind most polypeptides.

This may explain why amino acids with large hydrophobic side chains are not found in nature. Such immutability would preclude dynamic winding and unwinding of protein structures, which is essential to many biological processes. However, rigid stability is a desirable trait for the types of applications Cheng's group explores: nanostructures for drug and, particularly targeting cancerous tumors and stem cells.

"We want to test the correlation of the lengths of the helices and the circulation in the body to see what's the impact of the shape and the charge and the side chains for clearance in the body,"Cheng said."Recent studies show that the aspect ratio of the nanostructures– spherical structures versus tubes– has a huge impact on their penetration of tumor tissues and circulation half-lives in the body."

Cheng plans to create a library of short helical polypeptides of varying backbone lengths, side chain lengths and types of charge. He hopes to simplify the chemistry even further and make the materials widely accessible. His lab already has demonstrated that helical structures can be effective gene delivery and membrane transduction agents, and building the library of soluble helical molecules will allow further investigation of tailoring suchfor specific biomedical applications.


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пятница, 25 февраля 2011 г.

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четверг, 24 февраля 2011 г.

Taming carbon nanotubes

Carbon nanotubes have many attractive properties, and their structure and areas of application can be compared with those of graphene, the material for whose discovery the most recent Nobel Prize was awarded. In order to be able to exploit these properties, however, it is necessary to have full control of the manufacturing process. Scientists at the University of Gothenburg (Sweden) are closing in on the answer.

"Our results show that the metal particles that form the basis of the manufacture of carbon nanotubes must have a certain minimum size, in order for growth to start and to continue. It is also probable that the particles are in liquid form at a manufacturing temperature of around 800 C, even though the metals used may have much higher melting points", says Anders Börjesson from the Department of Physics at the University of Gothenburg.

The scientists have used various computer models to study in detail properties that are difficult or impossible to examine in experimental conditions. Only when we fully understand the manufacturing process will we be able to exploit this material fully.

The diameter of the nanotubes is of the order of one billionth of a metre, and they can be as thin as a single carbon layer. The length of the tubes, in contrast, can extend from the nanometre scale up to several decimetres. Carbon nanotubes can be regarded, quite simply, as thin threads of pure carbon, whose length can be a billion times greater than their thickness.

Interest for nanotubes is based on their outstanding properties: they are among the strongest materials known and have extremely high conductivity for both electric current and heat.

The strength can be used to reinforce other materials, just as the strength of glass and carbon fibres is used in plastics, and steel reinforcement is used in concrete. Carbon nanotubes, however, would enable plastics to be manufactured that are ten times stronger than the strongest materials available today. Suchcould be used not only in exclusive sports equipment but also in the construction of buildings that appear to come from science fiction: a lift between the Earth and space could be anchored using a material based on nanotubes.

The carbon nanotubes may also replace other material when it comes to conducting very high electrical currents, since they do not become hot, nor do they catch fire. Certain nanotubes have semiconducting properties and could be used to build nanoelectronic circuits, giving much smaller and faster processors to be used in computers.

One way of combining the strength and electrical properties of the carbon nanotubes would be to mix them with polymer material, and by weaving threads that also contain electronic circuits. It would be possible, for example, to weave instruments for monitoring heart function directly into clothes.


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среда, 23 февраля 2011 г.

Long and narrow, free of defects, and soluble: graphene nanoribbons by bottom-up synthesis

Long and narrow, free of defects, and soluble: graphene nanoribbons by bottom-up synthesis

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(PhysOrg.com) -- Electronic components based on graphene could render our current silicon-based electronics obsolete. Graphene, a more recently discovered form of carbon, consists of two-dimensional sheets of aromatic six-membered carbon rings in a honeycomb arrangement. In contrast to extended graphene layers, narrow graphene nanoribbons have semiconducting properties and could thus be candidates for electronic applications.

Klaus Müllen and a team from the Max Planck Institute for Polymer Research in Mainz have now introduced a new method for the synthesis of long, narrow graphene ribbons with defined dimensions in the journalAngewandte Chemie.

Previously, graphene ribbons were mainly cut out of larger graphene sheets or were obtained by slitting open carbon nanotubes lengthwise. However, with these methods it is impossible to produce ribbons that have a precisely established ratio of width to length as well as defined edges. These details are important because they determine the electronic properties of the ribbons. The search has thus been on for a method that allows controlled production of very narrow graphene ribbons—an extremely difficult challenge. The German researchers working with Müllen are now well on the way to overcome it. They are not starting with large structures to cut up (top-down); instead they are building their ribbons from smaller components (bottom-up).

The building blocks selected by Müllen and his team are long chains of aromatic six-membered carbon rings called polyphenlyenes. In contrast to previous approaches, they did not produce straight chains; instead they made them with a flexible, zigzagging, bent backbone. Furthermore, they attached hydrocarbon side-chains to the backbone to increase the solubility in organic solvents, which allows the compounds to be synthesized and processed in solution.

The next step is a reaction that splits off hydrogen (dehydrogenation). This causes a ring-closing reaction in each pointy tip of the zigzag, forming a new aromatic six-memberedring that shares a side with three neighboring rings—the chain transforms in to a narrow ribbon.

In this way, the team was able to produce a series of different nanoribbons with lengths reaching over 40 nm. The width of the ribbon was defined by the size of the“points” of the polyphenylene precursor. The resulting ribbons are free of defects and soluble in common organic solvents.

“We have been the first to demonstrate that structural perfection can be achieved by the classical bottom-up synthesis of defined,” says Müllen.“The solubility of theis an important requirement for the large-scale production of.”


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вторник, 22 февраля 2011 г.

Nanonets give rust a boost as agent in water splitting's hydrogen harvest

Nanonets give rust a boost as agent in water splitting's hydrogen harvest

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Coating a lattice of tiny wires called Nanonets with iron oxide– known more commonly as rust– creates an economical and efficient platform for the process of water splitting, an emerging clean fuel science that harvests hydrogen from water, Boston College researchers report in the online edition of the<i>Journal of the American Chemical Society</i>.

Assistant Professor of Chemistry Dunwei Wang and his clean energy lab pioneered the development of Nanonets in 2008 and have since shown them to be a viable new platform for a number of energy applications by virtue of the increased surface area and improved conductivity of the nano-scale netting made from titanium disilicide, a readily available semiconductor.

Wang and his team report that coating the Nanonets with hematite, the plentiful mineral form of, showed the mineral could absorb light efficiently and without the added expense of enhancing the material with an oxygen evolving catalyst.

The results flow directly from the introduction of the Nanonet platform, Wang said. While constructed of wires 1/400th the size of a human hair, Nanonets are highly conductive and offer significant surface area. They serve dual roles as a structural support and an efficient charge collector, allowing for maximum photon-to-charge conversion, Wang said.

"Recent research has shown that the use of a catalyst can boost the performance of hematite,"said Wang."What we have shown is the potential performance of hematite at its fundamental level, without a catalyst. By using this unique Nanonet structure, we have shed new light on the fundamental performance capabilities of hematite in water splitting."

On its own, hematite faces natural limits in its ability to transport a charge. A photon can be absorbed, but has no place to go. By giving it structure and added conductivity, the charge transport abilities of hematite increase, said Wang. Water splitting, a chemical reaction that separates water into oxygen andgas, can be initiated by passing an electric current through water. But that process is expensive, so gains in efficiency and conductivity are required to make large-scale water splitting an economically viable source for clean energy, Wang said.

"The result highlights the importance of charge transport in semiconductor-based
splitting, particularly for materials whose performance is limited by poor charge diffusion,"the researchers report in the journal."Our design introduces material components to provide a dedicated charge transport pathway, alleviates the reliance on the materials' intrinsic properties, and therefore has the potential to greatly broaden where and how various existing materials can be used in energy-related applications."


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