The Dallas Innovates article “SMU Chemists Find New Way to Break Carbon, Hydrogen Bond” notes that the new catalyst for breaking the tough molecular bond between carbon and hydrogen holds the promise of a cleaner, easier and cheaper way to derive products from petroleum.
An assistant professor, Garcia-Bosch is Harold A. Jeskey Endowed Chair in Chemistry.
Chemists at Southern Methodist University in Dallas have found a cheaper, cleaner method to break the stubborn molecular bond between carbon and hydrogen, a development that could lead to better ways to derive products from petroleum.
“Some of the most useful building blocks we have in the world are simple, plentiful hydrocarbons like methane, which we extract from the ground. They can be used as starting materials for complex chemical products such as plastics and pharmaceuticals,” Isaac Garcia-Bosch, Harold A. Jeskey Endowed Chair and assistant professor in the Department of Chemistry at SMU, told Eurekalert.org. “But the first step of the process is very, very difficult — breaking that carbon-hydrogen bond. The stronger the bond, the more difficult it is to oxidize.”
Oxidizing causes the molecule to undergo a reaction that combines with oxygen and breaks the carbon-hydrogen bonds, according to Eurekalert.
SMU chemists have been working on the project in collaboration with a team from the Johns Hopkins University.
According to the report, Garcia-Bosch and chemist Maxime A. Siegler, director of the X-Ray Crystallography facility at the Johns Hopkins University, used copper catalysts in conjunction with hydrogen peroxide to create the carbon-oxygen bonds.
Upon mixing the reactants (copper + ligand + hydrogen peroxide + carbon-hydrogen substrate) the starting colorless solution turns green-blue, indicating that an oxidative process is occurring. (Credit: SMU)
Chemists discover new way to crack the stubborn carbon-hydrogen bond that could allow industry to make petroleum-derived commercial products easier, cheaper and cleaner
A new catalyst for breaking the tough molecular bond between carbon and hydrogen holds the promise of a cleaner, easier and cheaper way to derive products from petroleum, says a researcher at Southern Methodist University, Dallas.
“Some of the most useful building blocks we have in the world are simple, plentiful hydrocarbons like methane, which we extract from the ground. They can be used as starting materials for complex chemical products such as plastics and pharmaceuticals,” said Isaac Garcia-Bosch, Harold A. Jeskey Endowed Chair assistant professor in the Department of Chemistry at SMU. “But the first step of the process is very, very difficult — breaking that carbon-hydrogen bond. The stronger the bond, the more difficult it is to oxidize.”
The chemical industry must break the tenacious bond between carbon and hydrogen molecules to synthesize oxidative products such as methanol and phenols. It’s called oxidizing because it causes the molecule to undergo a reaction in which it combines with oxygen, breaking C-H bonds and forming new carbon-oxygen bonds.
The conventional chemical recipe calls for inefficient and expensive oxidants to break the C-H bond. That process is costly, difficult and leaves behind dirty waste products.
Chemists at SMU, in collaboration with The Johns Hopkins University, have found a cheaper, cleaner way to crack the stubborn C-H bond.
Garcia-Bosch and chemist Maxime A. Siegler, director of the X-ray Crystallography Facility at The Johns Hopkins University, used copper catalysts that in combination with hydrogen peroxide (oxygen source) can convert C-H bonds to C-O bonds.
“This is a very important discovery because it’s the first time it’s been proven that copper can carry out this kind of oxidation outside of nature in an efficient way,” Garcia-Bosch said. “The prep is very simple, so labs anywhere can do it. Copper is relatively cheap compared to other metals such as palladium, gold or silver, and hydrogen peroxide is readily available, relatively cheap and very clean. One of the byproducts of oxidations with hydrogen peroxide (H2O2) is water (H2O), which is the cleanest waste product you could have.”
Additionally, the researchers found the right ligand — a nitrogen-based material that binds to the copper so that the oxidation process can occur with close to perfect efficiency.
It’s important to have the right ligand, the right amount of hydrogen peroxide, and the right metal in order to oxidize these challenging C-H bonds.
“We found that combination,” Garcia-Bosch said.
Chemistry is like a puzzle, where you build new molecules out of other molecules, he said.
In any one molecule there are many C-H bonds. For example in octanes, such as the ones found in gasoline, there’s a carbon chain of eight carbons with multiple C-H bonds with different chemical properties, Garcia-Bosch said, and from the oxidation of each of the C-H bonds, a different product results.
Chemists design catalysts that are capable of breaking and forming bonds in order to build complex chemical structures.
“Catalysts have to be able to select between different C-H bonds and form new carbon-oxygen, carbon-nitrogen or carbon-fluoride bonds, for example,” Garcia-Bosch said. “Biological processes use metals to do this all the time, for example in our bodies when our liver processes a pharmaceutical that we ingest using iron. Minerals such as iron, copper, manganese, calcium and potassium are critical for the natural catalytic process. For example, trees use manganese (photosynthesis) to transform water into the oxygen that we breathe”
First time for using copper for C-H oxidation
In organic chemistry, there aren’t many examples of copper as a catalyst for carbon-hydrogen oxidation. Most examples are based on iron.
“This is the first time in our field that we’ve used copper to do this C-H oxidation in a very efficient way,” Garcia-Bosch said.
“Copper is very versatile in nature,” he said. “With small changes in the environment of copper, you can do very diverse chemistry. That’s why we picked it.”
That environment is the ligand, which gives properties to the copper to spark the chemical reaction when the chemical ingredients are combined in a vial or round bottom flask.
The researchers discovered that these catalysts — copper in the form of a white salt and the ligand as an oil — can oxidize C-H bonds in a very efficient way in combination with hydrogen peroxide, a reduced form of oxygen that nature uses.
“You can find hydrogen peroxide anywhere, even at home in your medicine cabinet. So it’s a mild oxidant,” Garcia-Bosch said. “It’s convenient also, because it’s a liquid, rather than, say, a gas, which might require special storage. You mix everything together in a solvent and it reacts. It’s like making a soup, a recipe, then you analyze the result to see what you get.”
Using a gas chromatography instrument, the Garcia-Bosch and Siegler analyzed the final solution to observe the results of the reaction. That allowed them to quantify the amount of oxidation product that was formed during the reaction.
Next step — targeting a specific C-H bond
“We tested this catalytic system for different substrates and we saw that it’s not very selective,” Garcia-Bosch said. “That’s a problem. So if we have molecules that have many different C-H bonds, then it’s going to oxidize all of them in a non-selective manner. In our lab, we would like to find selective catalysts. That’s the next project.”
Garcia-Bosch holds the Harold A. Jeskey Endowed Chair in Chemistry. The research was funded through The Robert A. Welch Foundation (Grant N-1900).
SMU scientists and their research have a global reach that is frequently noted, beyond peer publications and media mentions.
By Margaret Allen
SMU News & Communications
It was a good year for SMU faculty and student research efforts. Here is a small sampling of public and published acknowledgements during 2015:
Hot topic merits open access
Taylor & Francis, publisher of the online journal Environmental Education Research, lifted its subscription-only requirement to meet demand for an article on how climate change is taught to middle-schoolers in California.
Co-author of the research was Diego Román, assistant professor in the Department of Teaching and Learning, Annette Caldwell Simmons School of Education and Human Development.
Román’s research revealed that California textbooks are teaching sixth graders that climate change is a controversial debate stemming from differing opinions, rather than a scientific conclusion based on rigorous scientific evidence.
Research makes the cover of Biochemistry
Drugs important in the battle against cancer were tested in a virtual lab by SMU biology professors to see how they would behave in the human cell.
A computer-generated composite image of the simulation made the Dec. 15 cover of the journal Biochemistry.
Scientific articles about discoveries from the simulation were also published in the peer review journals Biochemistry and in Pharmacology Research & Perspectives.
The researchers tested the drugs by simulating their interaction in a computer-generated model of one of the cell’s key molecular pumps — the protein P-glycoprotein, or P-gp. Outcomes of interest were then tested in the Wise-Vogel wet lab.
The ongoing research is the work of biochemists John Wise, associate professor, and Pia Vogel, professor and director of the SMU Center for Drug Discovery, Design and Delivery in Dedman College. Assisting them were a team of SMU graduate and undergraduate students.
The researchers developed the model to overcome the problem of relying on traditional static images for the structure of P-gp. The simulation makes it possible for researchers to dock nearly any drug in the protein and see how it behaves, then test those of interest in an actual lab.
To date, the researchers have run millions of compounds through the pump and have discovered some that are promising for development into pharmaceutical drugs to battle cancer.
Strong interest in research on sexual victimization
Teen girls were less likely to report being sexually victimized after learning to assertively resist unwanted sexual overtures and after practicing resistance in a realistic virtual environment, according to three professors from the SMU Department of Psychology.
The finding was reported in Behavior Therapy. The article was one of the psychology journal’s most heavily shared and mentioned articles across social media, blogs and news outlets during 2015, the publisher announced.
The study was the work of Dedman College faculty Lorelei Simpson Rowe, associate professor and Psychology Department graduate program co-director; Ernest Jouriles, professor; and Renee McDonald, SMU associate dean for research and academic affairs.
Consumers assume bigger price equals better quality
Even when competing firms can credibly disclose the positive attributes of their products to buyers, they may not do so.
Instead, they find it more lucrative to “signal” quality through the prices they charge, typically working on the assumption that shoppers think a high price indicates high quality. The resulting high prices hurt buyers, and may create a case for mandatory disclosure of quality through public policy.
That was a finding of the research of Dedman College’s Santanu Roy, professor, Department of Economics. Roy’s article about the research was published in February in one of the blue-ribbon journals, and the oldest, in the field, The Economic Journal.
Published by the U.K.’s Royal Economic Society, The Economic Journal is one of the founding journals of modern economics. The journal issued a media briefing about the paper, “Competition, Disclosure and Signaling,” typically reserved for academic papers of broad public interest.
Chemistry research group edits special issue
Chemistry professors Dieter Cremer and Elfi Kraka, who lead SMU’s Computational and Theoretical Chemistry Group, were guest editors of a special issue of the prestigious Journal of Physical Chemistry. The issue published in March.
The Computational and Theoretical research group, called CATCO for short, is a union of computational and theoretical chemistry scientists at SMU. Their focus is research in computational chemistry, educating and training graduate and undergraduate students, disseminating and explaining results of their research to the broader public, and programming computers for the calculation of molecules and molecular aggregates.
The special issue of Physical Chemistry included 40 contributions from participants of a four-day conference in Dallas in March 2014 that was hosted by CATCO. The 25th Austin Symposium drew 108 participants from 22 different countries who, combined, presented eight plenary talks, 60 lectures and about 40 posters.
CATCO presented its research with contributions from Cremer and Kraka, as well as Marek Freindorf, research assistant professor; Wenli Zou, visiting professor; Robert Kalescky, post-doctoral fellow; and graduate students Alan Humason, Thomas Sexton, Dani Setlawan and Vytor Oliveira.
There have been more than 75 graduate students and research associates working in the CATCO group, which originally was formed at the University of Cologne, Germany, before moving to SMU in 2009.
Vertebrate paleontology recognized with proclamation
Dallas Mayor Mike Rawlings proclaimed Oct. 11-17, 2015 Vertebrate Paleontology week in Dallas on behalf of the Dallas City Council.
The proclamation honored the 75th Annual Meeting of the Society of Vertebrate Paleontology, which was jointly hosted by SMU’s Roy M. Huffington Department of Earth Sciences in Dedman College and the Perot Museum of Science and Nature. The conference drew to Dallas some 1,200 scientists from around the world.
Making research presentations or presenting research posters were: faculty members Bonnie Jacobs, Louis Jacobs, Michael Polcyn, Neil Tabor and Dale Winkler; adjunct research assistant professor Alisa Winkler; research staff member Kurt Ferguson; post-doctoral researchers T. Scott Myers and Lauren Michael; and graduate students Matthew Clemens, John Graf, Gary Johnson and Kate Andrzejewski.
The host committee co-chairs were Anthony Fiorillo, adjunct research professor; and Louis Jacobs, professor. Committee members included Polcyn; Christopher Strganac, graduate student; Diana Vineyard, research associate; and research professor Dale Winkler.
KERA radio reporter Kat Chow filed a report from the conference, explaining to listeners the science of vertebrate paleontology, which exposes the past, present and future of life on earth by studying fossils of animals that had backbones.
SMU earthquake scientists rock scientific journal
Modelled pressure changes caused by injection and production. (Nature Communications/SMU)
Findings by the SMU earthquake team reverberated across the nation with publication of their scientific article in the prestigious British interdisciplinary journal Nature, ranked as one of the world’s most cited scientific journals.
The article reported that the SMU-led seismology team found that high volumes of wastewater injection combined with saltwater extraction from natural gas wells is the most likely cause of unusually frequent earthquakes occurring in the Dallas-Fort Worth area near the small community of Azle.
The research was the work of Dedman College faculty Matthew Hornbach, associate professor of geophysics; Heather DeShon, associate professor of geophysics; Brian Stump, SMU Albritton Chair in Earth Sciences; Chris Hayward, research staff and director geophysics research program; and Beatrice Magnani, associate professor of geophysics.
The article, “Causal factors for seismicity near Azle, Texas,” published online in late April. Already the article has been downloaded nearly 6,000 times, and heavily shared on both social and conventional media. The article has achieved a ranking of 270, which puts it in the 99th percentile of 144,972 tracked articles of a similar age in all journals, and 98th percentile of 626 tracked articles of a similar age in Nature.
“It has a very high impact factor for an article of its age,” said Robert Gregory, professor and chair, SMU Earth Sciences Department.
The scientific article also was entered into the record for public hearings both at the Texas Railroad Commission and the Texas House Subcommittee on Seismic Activity.
Researchers settle long-debated heritage question of “The Ancient One”
The skull of Kennewick Man and a sculpted bust by StudioEIS based on forensic facial reconstruction by sculptor Amanda Danning. (Credit: Brittany Tatchell)
The research of Dedman College anthropologist and Henderson-Morrison Professor of Prehistory David Meltzer played a role in settling the long-debated and highly controversial heritage of “Kennewick Man.”
Also known as “The Ancient One,” the 8,400-year-old male skeleton discovered in Washington state has been the subject of debate for nearly two decades. Argument over his ancestry has gained him notoriety in high-profile newspaper and magazine articles, as well as making him the subject of intense scholarly study.
Officially the jurisdiction of the U.S. Army Corps of Engineers, Kennewick Man was discovered in 1996 and radiocarbon dated to 8500 years ago.
Because of his cranial shape and size he was declared not Native American but instead ‘Caucasoid,’ implying a very different population had once been in the Americas, one that was unrelated to contemporary Native Americans.
But Native Americans long have claimed Kennewick Man as theirs and had asked for repatriation of his remains for burial according to their customs.
Meltzer, collaborating with his geneticist colleague Eske Willerslev and his team at the Centre for GeoGenetics at the University of Copenhagen, in June reported the results of their analysis of the DNA of Kennewick in the prestigious British journal Nature in the scientific paper “The ancestry and affiliations of Kennewick Man.”
The results were announced at a news conference, settling the question based on first-ever DNA evidence: Kennewick Man is Native American.
The announcement garnered national and international media attention, and propelled a new push to return the skeleton to a coalition of Columbia Basin tribes. Sen. Patty Murray (D-WA) introduced the Bring the Ancient One Home Act of 2015 and Washington Gov. Jay Inslee has offered state assistance for returning the remains to Native Tribes.
Science named the Kennewick work one of its nine runners-up in the highly esteemed magazine’s annual “Breakthrough of the Year” competition.
The research article has been viewed more than 60,000 times. It has achieved a ranking of 665, which puts it in the 99th percentile of 169,466 tracked articles of a similar age in all journals, and in the 94th percentile of 958 tracked articles of a similar age in Nature.
In “Kennewick Man: coming to closure,” an article in the December issue of Antiquity, a journal of Cambridge University Press, Meltzer noted that the DNA merely confirmed what the tribes had known all along: “We are him, he is us,” said one tribal spokesman. Meltzer concludes: “We presented the DNA evidence. The tribal members gave it meaning.”
Prehistoric vacuum cleaner captures singular award
Paleontologists Louis L. Jacobs, SMU, and Anthony Fiorillo, Perot Museum, have identified a new species of marine mammal from bones recovered from Unalaska, an Aleutian island in the North Pacific. (Hillsman Jackson, SMU)
Science writer Laura Geggel with Live Science named a new species of extinct marine mammal identified by two SMU paleontologists among “The 10 Strangest Animal Discoveries of 2015.”
The new species, dubbed a prehistoric hoover by London’s Daily Mail online news site, was identified by SMU paleontologist Louis L. Jacobs, a professor in the Roy M. Huffington Department of Earth Sciences, Dedman College of Humanities and Sciences, and paleontologist and SMU adjunct research professor Anthony Fiorillo, vice president of research and collections and chief curator at the Perot Museum of Nature and Science.
Jacobs and Fiorillo co-authored a study about the identification of new fossils from the oddball creature Desmostylia, discovered in the same waters where the popular “Deadliest Catch” TV show is filmed. The hippo-like creature ate like a vacuum cleaner and is a new genus and species of the only order of marine mammals ever to go extinct — surviving a mere 23 million years.
Desmostylians, every single species combined, lived in an interval between 33 million and 10 million years ago. Their strange columnar teeth and odd style of eating don’t occur in any other animal, Jacobs said.
As noted by the CERN Courier — the news magazine of the CERN Laboratory in Geneva, which hosts the Large Hadron Collider, the world’s largest science experiment — more than 250 scientists from 30 countries presented more than 200 talks on a multitude of subjects relevant to experimental and theoretical research. SMU physicists presented at the conference.
The SMU organizing committee was led by Fred Olness, professor and chair of the SMU Department of Physics in Dedman College, who also gave opening and closing remarks at the conference. The committee consisted of other SMU faculty, including Jodi Cooley, associate professor; Simon Dalley, senior lecturer; Robert Kehoe, professor; Pavel Nadolsky, associate professor, who also presented progress on experiments at CERN’s Large Hadron Collider; Randy Scalise, senior lecturer; and Stephen Sekula, associate professor.
Sekula also organized a series of short talks for the public about physics and the big questions that face us as we try to understand our universe.
SMU chemist Nicolay (Nick) Tsarevsky has received a prestigious National Science Foundation CAREER Award, expected to total $650,000 over five years, to fund his research into new methods of creating polymers — whose uses range from fluorescent materials to drug carriers, to everyday technologies.
NSF CAREER Awards are given to tenure-track faculty members who exemplify the role of teacher-scholars through outstanding research, excellent education and the integration of education and research in American colleges and universities.
Tsarevsky, an assistant professor in the Department of Chemistry in SMU’s Dedman College of Humanities and Science, is a polymer chemist and the adviser to seven doctoral students who assist in his research. Polymers are molecules that can be found in just about anything and include both natural and synthetic materials. DNA and proteins are natural polymers, as is the cellulose found in wood and paper. Plastics are a group of synthetic polymers, as are many of the materials used in modern electronic technology. As the slogan for Tsarevsky’s lab group says, “It’s a polymer world…”
Prior to 20 years ago, the lab techniques used to make polymers with any precision approaching that of nature were very limited or didn’t exist. The Tsarevsky group specializes in developing methods to make large polymeric molecules in a lab with desired shapes, sizes and functionalities.
“We try to provide the tools, which can be used to prepare a vast number of complex functional materials,” says Tsarevsky, who, in a nod to history’s Stone, Bronze and Iron Ages, refers to our era as the ‘Polymer Age.’
“We make polymers that have the ability to kill bacteria on contact, and self-healing materials that you could break and that would heal by themselves,” Tsarevsky adds. “I like to think of our work as trying to design and control the architecture of very large molecules.”
Polymer research taps less toxic compounds and those with weaker bonds
To make complex macromolecules, Tsarevsky took advantage of the special behavior (reactivity) of a group of compounds that contain hypervalent chemical bonds. These bonds are weaker than other “classical” chemical bonds, and can be broken in two different ways as well as reconstructed. The atoms they connect can be “swapped” or exchanged — think building with Legos instead of permanent glue — enabling the construction of new materials that couldn’t be made otherwise. Several elements in the Periodic Table are able to form hypervalent bonds, but Tsarevsky feels iodine is one of the most attractive, in part because it’s less toxic than many alternatives.
Many of the current methods for making polymers use toxic heavy metals. The toxic impurities present in the final materials must be removed at potentially significant expense. The hypervalent iodine compounds Tsarevsky is employing aren’t just less toxic, they also allow for processes to be carried out using fewer steps than traditional methods to yield the final functional products. Another chemical element that also is promising for its diverse chemistry (including ability to form hypervalent bonds) and lack of toxicity is bismuth, which Tsarevsky would like to explore in his future research.
“The NSF CAREER funding is absolutely essential,” Tsarevsky says. “Some of the money will go to support doctoral students conducting the research, some will go to support supplies or equipment. Without this support, it would be extremely difficult or impossible to do these studies.”
Desire to show students that chemistry is beautiful, inspiring, allows creativity
Tsarevsky’s long-term educational goal is to increase interest in chemistry, a subject he says too many students are intimidated by.
“It’s only scary when you know nothing about it or when you had a bad teacher in school who made chemistry torture,” Tsarevsky says. “Without chemistry, we wouldn’t have pharmaceuticals or materials like plastics. We wouldn’t have many pigments or paints. Chemistry is not scary – it is beautiful and inspiring and allows you to be creative and make useful things nobody has seen before.”
Tsarevsky joined SMU in 2010. He was a chief science officer at ATRP Solutions, Inc., from 2007-10 and a visiting assistant professor at Carnegie Mellon University from 2005-07. Tsarevsky received a Ph.D. in chemistry from Carnegie Mellon University in 2005 and a Bachelor and Master of Science in theoretical chemistry and chemical physics from the University of Sofia, Bulgaria in 1999. — Kenneth Ryan
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“As a society, we are using more technology, and there’s increasing evidence that artificial light has had a negative consequence on our health,” says Zoltowski, who was awarded $320,500 from the National Institute of General Medical Sciences of the National Institutes of Health to continue its research on the impact of blue light.
“Our study uses physical techniques and chemical approaches to probe an inherently biological problem,” Zoltowski said. “We want to understand the chemical basis for how organisms use light as an environmental cue to regulate growth and development.”
By Doug Dunbar
CBS DFW 11
Can’t get a good night’s sleep. You might be getting a little too much blue light.
What’s that? It’s a big issue the Federal government is asking researchers at SMU to study.
There’s a reason why it’s dark in this lab. It’s because they’re studying light.
They have the lights off so they can purify the proteins in the dark.
So that we can study the activation process when we first expose them to light. But not just any light. Blue light. The stuff in fluorescents, and devices like laptops and phones. But also daylight.
One of the negative consequences of blue light is associated with our metabolic clock being offset from our brain clock. That can lead to problems for diabetes, cancer, mood disorders.
[ …] But Zoltowski and his crew could potentially tackle problems much bigger than sleeping.
“If we understand how these proteins that respond to light work we can create new biotechnology.”
Maybe new ways to deliver drugs, or even targeted cancer treatments.
“We can shine light on a very specific spot and that can allow us to activate any biological event we want at that very precise location and time.”
Fermilab experiment observes change in neutrinos from one type to another over 500 miles
Large genome-scale study finds Native American ancestors arrived in single migration wave
$3.78 million awarded by Department of Defense to SMU STEM project for minority students
Kennewick Man: genome sequence of 8,500-year-old skeleton solves scientific controversy
At peak fertility, women who desire to maintain body attractiveness report they eat less
SMU seismology team to cooperate with state, federal scientists in study of May 7 Venus, Texas earthquake
1st proton collisions at the world’s largest science experiment expected to start the first or second week of June
Most likely cause of 2013-14 earthquakes: Combination of gas field fluid injection, removal