Giant flakes make graphene oxide gel: Discovery could boost metamaterials, high-strength fibers

ScienceDaily (Oct. 20, 2011) — Giant flakes of graphene oxide in water aggregate like a stack of pancakes, but infinitely thinner, and in the process gain characteristics that materials scientists may find delicious.

A new paper by scientists at Rice University and the University of Colorado details how slices of graphene, the single-atom form of carbon, in a solution arrange themselves to form a nematic liquid crystal in which particles are free-floating but aligned.

That much was already known. The new twist is that if the flakes -- in this case, graphene oxide -- are big enough and concentrated enough, they retain their alignment as they form a gel. That gel is a handy precursor for manufacturing metamaterials or fibers with unique mechanical and electronic properties.

The team reported its discovery online this week in the Royal Society of Chemistry journal Soft Matter. Rice authors include Matteo Pasquali, a professor of chemical and biomolecular engineering and of chemistry; James Tour, the T.T. and W.F. Chao Chair in Chemistry as well as a professor of mechanical engineering and materials science and of computer science; postdoctoral research associate Dmitry Kosynkin; and graduate students Budhadipta Dan and Natnael Behabtu. Ivan Smalyukh, an assistant professor of physics at the University of Colorado at Boulder, led research for his group, in which Dan served as a visiting scientist.

"Graphene materials and fluid phases are a great research area," Pasquali said. "From the fundamental point of view, fluid phases comprising flakes are relatively unexplored, and certainly so when the flakes have important electronic properties.

"From the application standpoint, graphene and graphene oxide can be important building blocks in such areas as flexible electronics and conductive and high-strength materials, and can serve as templates for ordering plasmonic structures," he said.

By "giant," the researchers referred to irregular flakes of graphene oxide up to 10,000 times as wide as they are high. (That's still impossibly small: on average, roughly 12 microns wide and less than a nanometer high.) Previous studies showed smaller bits of pristine graphene suspended in acid would form a liquid crystal and that graphene oxide would do likewise in other solutions, including water.

This time the team discovered that if the flakes are big enough and concentrated enough, the solution becomes semisolid. When they constrained the gel to a thin pipette and evaporated some of the water, the graphene oxide flakes got closer to each other and stacked up spontaneously, although imperfectly.

"The exciting part for me is the spontaneous ordering of graphene oxide into a liquid crystal, which nobody had observed before," said Behabtu, a member of Pasquali's lab. "It's still a liquid, but it's ordered. That's useful to make fibers, but it could also induce order on other particles like nanorods."

He said it would be a simple matter to heat the concentrated gel and extrude it into something like carbon fiber, with enhanced properties provided by "mix-ins."

Testing the possibilities, the researchers mixed gold microtriangles and glass microrods into the solution, and found both were effectively forced to line up with the pancaking flakes. Their inclusion also helped the team get visual confirmation of the flakes' orientation.

The process offers the possibility of the large-scale ordering and alignment of such plasmonic particles as gold, silver and palladium nanorods, important components in optoelectronic devices and metamaterials, they reported.

Behabtu added that heating the gel "crosslinks the flakes, and that's good for mechanical strength. You can even heat graphene oxide enough to reduce it, stripping out the oxygen and turning it back into graphite."

Co-authors of the paper are Angel Martinez and Julian Evans, graduate students of Smalyukh at the University of Colorado at Boulder.

The Institute for Complex Adaptive Matter, the Colorado Renewable and Sustainable Energy Initiative, the National Science Foundation, the Air Force Research Lab, the Air Force Office of Scientific Research, the Welch Foundation, the U.S. Army Corps of Engineers Environmental Quality and Installation Program and M-I Swaco supported the research.

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Journal Reference:

Budhadipta Dan, Natnael Behabtu, Angel Martinez, Julian S. Evans, Dmitry V. Kosynkin, James M. Tour, Matteo Pasquali, Ivan I. Smalyukh. Liquid crystals of aqueous, giant graphene oxide flakes. Soft Matter, 2011; DOI: 10.1039/C1SM06418E

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Giant flakes make graphene oxide gel: Discovery could boost metamaterials, high-strength fibers

ScienceDaily (Oct. 20, 2011) — Giant flakes of graphene oxide in water aggregate like a stack of pancakes, but infinitely thinner, and in the process gain characteristics that materials scientists may find delicious.

A new paper by scientists at Rice University and the University of Colorado details how slices of graphene, the single-atom form of carbon, in a solution arrange themselves to form a nematic liquid crystal in which particles are free-floating but aligned.

That much was already known. The new twist is that if the flakes -- in this case, graphene oxide -- are big enough and concentrated enough, they retain their alignment as they form a gel. That gel is a handy precursor for manufacturing metamaterials or fibers with unique mechanical and electronic properties.

The team reported its discovery online this week in the Royal Society of Chemistry journal Soft Matter. Rice authors include Matteo Pasquali, a professor of chemical and biomolecular engineering and of chemistry; James Tour, the T.T. and W.F. Chao Chair in Chemistry as well as a professor of mechanical engineering and materials science and of computer science; postdoctoral research associate Dmitry Kosynkin; and graduate students Budhadipta Dan and Natnael Behabtu. Ivan Smalyukh, an assistant professor of physics at the University of Colorado at Boulder, led research for his group, in which Dan served as a visiting scientist.

"Graphene materials and fluid phases are a great research area," Pasquali said. "From the fundamental point of view, fluid phases comprising flakes are relatively unexplored, and certainly so when the flakes have important electronic properties.

"From the application standpoint, graphene and graphene oxide can be important building blocks in such areas as flexible electronics and conductive and high-strength materials, and can serve as templates for ordering plasmonic structures," he said.

By "giant," the researchers referred to irregular flakes of graphene oxide up to 10,000 times as wide as they are high. (That's still impossibly small: on average, roughly 12 microns wide and less than a nanometer high.) Previous studies showed smaller bits of pristine graphene suspended in acid would form a liquid crystal and that graphene oxide would do likewise in other solutions, including water.

This time the team discovered that if the flakes are big enough and concentrated enough, the solution becomes semisolid. When they constrained the gel to a thin pipette and evaporated some of the water, the graphene oxide flakes got closer to each other and stacked up spontaneously, although imperfectly.

"The exciting part for me is the spontaneous ordering of graphene oxide into a liquid crystal, which nobody had observed before," said Behabtu, a member of Pasquali's lab. "It's still a liquid, but it's ordered. That's useful to make fibers, but it could also induce order on other particles like nanorods."

He said it would be a simple matter to heat the concentrated gel and extrude it into something like carbon fiber, with enhanced properties provided by "mix-ins."

Testing the possibilities, the researchers mixed gold microtriangles and glass microrods into the solution, and found both were effectively forced to line up with the pancaking flakes. Their inclusion also helped the team get visual confirmation of the flakes' orientation.

The process offers the possibility of the large-scale ordering and alignment of such plasmonic particles as gold, silver and palladium nanorods, important components in optoelectronic devices and metamaterials, they reported.

Behabtu added that heating the gel "crosslinks the flakes, and that's good for mechanical strength. You can even heat graphene oxide enough to reduce it, stripping out the oxygen and turning it back into graphite."

Co-authors of the paper are Angel Martinez and Julian Evans, graduate students of Smalyukh at the University of Colorado at Boulder.

The Institute for Complex Adaptive Matter, the Colorado Renewable and Sustainable Energy Initiative, the National Science Foundation, the Air Force Research Lab, the Air Force Office of Scientific Research, the Welch Foundation, the U.S. Army Corps of Engineers Environmental Quality and Installation Program and M-I Swaco supported the research.

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Story Source:

The above story is reprinted from materials provided by Rice University.

Note: ScienceDaily reserves the right to edit materials for content and length. For further information, please contact the source cited above.

Journal Reference:

Budhadipta Dan, Natnael Behabtu, Angel Martinez, Julian S. Evans, Dmitry V. Kosynkin, James M. Tour, Matteo Pasquali, Ivan I. Smalyukh. Liquid crystals of aqueous, giant graphene oxide flakes. Soft Matter, 2011; DOI: 10.1039/C1SM06418E

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

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Exercise protects the heart via nitric oxide, researchers discover

ScienceDaily (May 4, 2011) — Exercise both reduces the risk of a heart attack and protects the heart from injury if a heart attack does occur. For years, doctors have been trying to dissect how this second benefit of exercise works, with the aim of finding ways to protect the heart after a heart attack.

Researchers at Emory University School of Medicine have identified the ability of the heart to produce and store nitric oxide as an important way exercise protects the heart from injury.

Nitric oxide, a short-lived gas generated within the body, turns on chemical pathways that relax blood vessels to increase blood flow and activate survival pathways. Both the chemical nitrite and nitrosothiols, where nitric oxide is attached to proteins via sulfur, appear to act as convertible reservoirs for nitric oxide in situations where the body needs it, such as a lack of blood flow or oxygen.

The Emory team's results, published online in the journal Circulation Research, strengthen the case for nitrite and nitrosothiols as possible protectants from the damage of a heart attack.

The first author is John Calvert, PhD, assistant professor of surgery at Emory University School of Medicine. The senior author is David Lefer, PhD, professor of surgery at Emory University School of Medicine and director of the Cardiothoracic Research Laboratory at Emory University Hospital Midtown. Collaborators included scientists at University of Colorado, Boulder, and Johns Hopkins University.

"Our study provides new evidence that nitric oxide generated during physical exercise is actually stored in the bloodstream and heart in the form of nitrite and nitrosothiols. These more stable nitric oxide intermediates appear to be critical for the cardioprotection against a subsequent heart attack," Lefer says.

Timing is key -- the benefits of exercise don't last In experiments with mice, the researchers showed that four weeks of being able to run on a wheel protected them from having a coronary artery was blocked; the amount of heart muscle damaged by the blockage was less after the exercise period. Importantly, the mice are still protected a week after the wheel is taken away.

The researchers found that voluntary exercise boosted levels of an enzyme that produces nitric oxide (eNOS, endothelial nitric oxide synthase). Moreover, the levels of eNOS in heart tissue, and nitrite and nitrosothiols in the blood as well as heart tissue, stayed high for a week after exercise ceased, unlike other heart enzymes stimulated by exercise. The protective effects of exercise did not extend beyond four weeks after the exercise period was over, when nitrite and nitrosothiols in the heart returned to baseline.

In mice that lack the eNOS enzyme, exercise did not protect the heart from a coronary blockage, although these mice appeared to lack the ability to exercise as much as normal mice.

Another molecule that appears to be important for the benefits of exercise is the beta-3-adrenergic receptor, which allows cells to respond to the hormones epinephrine and norepinephrine. All of the beneficial effects of voluntary exercise are lost in mice that are deficient in this receptor. One of the effects of stimulating the receptor appears to be activating eNOS. Additional animal studies are currently underway in Lefer's lab to determine the potential benefit of beta-3-adrenergic receptor activating drugs following a heart attack.

The research was supported by the American Diabetes Association, the National Institutes of Health and the Carlyle Fraser Heart Center of Emory University Hospital Midtown.

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by Emory University.

Journal Reference:

J. W. Calvert, M. Elston, J. Pablo Aragon, C. K. Nicholson, B. F. Moody, R. L. Hood, A. Sindler, S. Gundewar, D. R. Seals, L. A. Barouch, D. J. Lefer. Exercise Protects Against Myocardial Ischemia-Reperfusion Injury via Stimulation of ß3-Adrenergic Receptors and Increased Nitric Oxide Signaling: Role of Nitrite and Nitrosothiols. Circulation Research, 2011; DOI: 10.1161/CIRCRESAHA.111.241117

Note: If no author is given, the source is cited instead.

Disclaimer: This article is not intended to provide medical advice, diagnosis or treatment. Views expressed here do not necessarily reflect those of ScienceDaily or its staff.

View the original article here