SAN FRANCISCO (Reuters) - Venture firmsAndreessen Horowitz, Google Ventures, and Kleiner Perkins Caufield & Byers are teaming up to provide funding for startups working with Google Glass, the hybrid eyeglasses and smartphone developed by Google.
The firms aim to provide funding to startups working on applications and hardware designed to work with the glasses, they said on Wednesday.
"There's a potential for a paradigm shift here, like there was with browsers, PCs," said Bill Maris, partner at Google Ventures, referring to personal computers.
The firms will evaluate opportunities concurrently, and may invest collectively or individually. Funding for glass-related ventures will be carved out of the firms' existing funds.
Having three firms involved will increase the chance of success, the venture firms said, because the entrepreneurs they fund will benefit from three points of view. Google Ventures regularly co-invests with Andreessen and Kleiner, Maris said.
Kleiner was an early backer of Google.
There should be no shortage of developers willing to experiment with the technology.
"The tool set and the feature set that developers have to work with is very attractive," said Ben Arnold, director of industry analysis for consumer technology at the NPD Group, citing Google Glass features such as voice activation and augmented reality.
There is no dedicated sum set aside for Google Glass, making the project different to Kleiner's $200 million iFund, which Kleiner started five years ago to back entrepreneurs building applications and services for iPhones, iPods, and iPads. But the timing of the initiative-- coming before it is obvious that a big ecosystem will grow around Google Glass-- is similar, said John Doerr, a partner at Kleiner.
Google Glass can live-stream images and audio and perform computing tasks through a stamp-sized electronic screen mounted on the side of a pair of eyeglass frames. It can also record video, access email, and retrieve information from the Internet.
Chinese search engine Baidu said earlier this month that it was working on its own prototype of digital eye wear that is similar to Google Glass.
The technology started getting noticed around a year ago, when Google co-founder Sergey Brin began wearing Google Glass out and about. In February, Google invited members of the public to apply to test a version of the glasses in its Glass Explorer Program. Successful applicants must pay $1,500 for the glasses.
Google Glass will become more widely available later this year, Google has said, including a version that will work with eye wear prescriptions.
That is the version glasses-wearer Doerr said he is waiting for. In meantime, he has tried on another earlier style of Google Glass.
"My daughter thinks I look really weird," he said.
(Reporting By Sarah McBride; Editing by Chris Reese)
Research enables fishermen to harvest lucrative shellfish on Georges BankPublic release date: 10-Apr-2013 [ | E-mail | Share ]
Contact: WHOI Media Relations media@whoi.edu 508-289-3340 Woods Hole Oceanographic Institution
Combined research efforts by scientists involved in the Gulf of Maine Toxicity (GOMTOX) project, funded by NOAA's Ecology and Oceanography of Harmful Algal Blooms (ECOHAB) program, and administered by the National Centers for Coastal Ocean Science (NCCOS), have led to enhanced understanding of toxic algal blooms on Georges Bank. This new information, coupled with an at-sea and dockside testing protocol developed through collaboration between GOMTOX and U.S. Food and Drug Administration (FDA) investigators, has allowed fishermen to harvest ocean quahogs and surf clams in these offshore waters for the first time in more than two decades.
The shellfish industry estimates the Georges Bank fishery can produce up to 1 million bushels of surf clams and ocean quahogs a year, valued $10 15 million annually. "There is a billion dollars' worth of shellfish product on Georges Bank that is property of the United States but that can't be harvested because of the threat of toxicity, and 99.9% of the time, it is good wholesome product," says Dave Wallace of North Atlantic Clam Association and a GOMTOX participant. "In an unusual and unique partnership, we worked with GOMTOX scientists, the FDA, and the states of Massachusetts, Rhode Island, New Jersey and Delaware and now that huge resource can go into commerce, which helps the entire country."
"We are extremely pleased that research funded by NOAA can provide such an economic boost to New England shellfisheries," says Robert Magnien, Director of NCCOS' Center for Sponsored Coastal Ocean Research. "It is a clear example of how research authorized by the Harmful Algal Bloom and Hypoxia Research and Control Act can protect both public health and local economies through collaborations between academic scientists, state and federal regulatory agencies, and the shellfish industry."
An elevated area of the sea floor between Cape Cod and Nova Scotia, Georges Bank is one of the best fishing grounds on Earth. But since 1990, it has been closed to harvesting of surf clams and ocean quahogs after harmful algal blooms (also referred to as "red tides") caused paralytic shellfish poisoning (PSP) that sickened fishermen. For decades scientists speculated the blooms on Georges Bank were fueled by coastal blooms in the Gulf of Maine.
More recent research by GOMTOX investigators, however, has shown that Georges Bank is home to a separate and distinct population of the toxic algae, which is described in a recently published paper by Woods Hole Oceanographic Institution (WHOI) scientist Dennis McGillicuddy and other members of the GOMTOX team.
It has been known for many years that the phytoplankton Alexandrium fundyense is the cause of the harmful algal blooms that occur to varying severity each spring and summer along the coastal Gulf of Maine, sometimes extending as far south as Cape Cod and the adjacent islands. The algae's seed populations or "cysts" germinate from seabeds starting in early spring and bloom at the sea surface, until all of the necessary nutrients in the water are consumed. As the nutrients run out, the cells form cysts and fall to the seafloor, as seed for the following spring. High concentrations of the toxic algae can cause closure of shellfish beds and cost the region many millions of dollars.
Precisely why the blooms vary in severity has been much more difficult to determine, and has involved extensive seasonal sampling of water and sediments, study of coastal currents, environmental and oceanographic conditions, availability of nutrients, and the development of a computer program to model all of the variables.
Researchers got the first signal that something very different was happening on Georges Bank during a research cruise to count Alexandrium cells in sea water samples in spring/summer 2007. "We devised our sampling strategy to look at the cells' transport pathways from coastal waters onto the Bank," says McGillicuddy. Throughout the coastal Gulf of Maine, the numbers were very low. But when the research team started sampling at Georges Bank, they found very high concentrations of Alexandrium in the water, despite the fact that the bloom had not really begun along the coast of Maine.
"I'll never forget the moment we hit a big patch of cells on Georges Bank," says Dave Townsend, a GOMTOX scientist from the University of Maine and co-author of the paper. "We extended our sampling to go all the way across Georges Bank and we were still hitting them. We had to turn around and completely reorganize our sampling strategy based on what we were seeing in the microscope."
For such a large bloom to occur, the researchers reasoned the number of cysts on Georges Bank must be similar to the quantities needed to initiate a bloom along the coast. Yet, their fall 2007 survey to map the cyst distribution in the seabed on the Bank found very few cysts quantities not likely to cause a large bloom along the coast.
In the three-year course of intensive study on Georges Bank since then, blooms have occurred every year, in concentrations that would typically lead to toxicities in coastal shellfish beds. Yet, a parallel effort by the fishing industry and federal testing labs to analyze shellfish samples from Georges Bank found the bivalves to be clean of toxins. So while toxins were produced at and near the surface, they were not delivered to the surf clams and ocean quahogs in the seabed in quantities sufficient to threaten human health.
The system on Georges Bank was indeed a riddle: Few cysts, yet large blooms; a large bloom, yet little to no toxicity in the shellfish. Applying the same detailed analyses to the offshore population of Alexandrium that they applied to coastal populations, the scientists discovered the optimum growing conditions for Alexandrium on Georges Bank were colder and saltier than those of their coastal relatives. Their analysis uncovered how the currents in the region can isolate Georges Bank to create colder and saltier conditions. If the conditions are favorable, the researchers say, Alexandrium populations can double every three days, and in a month's time, grow from concentrations of 10 cells per liter to 10,000.
Further setting the Georges Bank population apart was the finding by GOMTOX colleagues at University of Massachusetts, Dartmouth's School for Marine Science and Technology (SMAST), working in collaboration with the FDA, who determined that the toxin content of algae on Georges Bank was different than the coastal Gulf of Maine populations. "The toxins present in Alexandrium cells from Georges Bank were, on average, two times lower than those in the coastal Gulf of Maine," said Chrissy Petitpas, a doctoral student working in Professor Jefferson Turner's lab at SMAST.
Despite this new information and the knowledge that the clams have been shown to be safe for humans to eat at the present time, the fact remains that concentrations of the toxins in the clams on Georges Bank in 1989 and 1990 did reach dangerous levels. Scientists know that coastal shellfish populations are directly exposed to the toxins when the blooms make landfall, but they remain uncertain about the conduit for toxicity from the surface ocean to the deep shellfish beds on Georges Bank, located at about 50m depth.
But, thanks to an innovative screening protocol and regulatory structure developed collaboratively by the FDA, NOAA's National Marine Fisheries Service, the fishing industry, and testing labs approved by the National Shellfish Sanitation Program, a system is now in place to monitor, test, and verify that clams harvested from Georges Bank are safe. The clams are checked by fishermen at sea using the newly available test kit, and re-checked by regulators when the fishing vessels reach the dock. Combined with the weekly monitoring of shellfish beds along the coast during the bloom season to protect human health, these monitoring systems are extremely effective at keeping toxic shellfish off the market.
"Toxin levels in shellfish on Georges Bank have been very low over the last few years. We are confident that this new testing protocol will serve to protect public health should toxin levels rise again in the future," said Stacey DeGrasse, seafood research coordinator in the FDA's Office of Regulatory Science and a major participant in the development of the new offshore testing protocol. "We intend to continue to work closely with NOAA to ensure that the shellfish from this region are harvested safely."
"I've run over 2,500 samples from Georges Bank since mid-March, and all of them have been clean of toxin," says Darcie Couture, a former manager of the marine biotoxins program at the Maine Department of Marine Resources, who now operates the federally permitted testing lab. "We've been fortunate in finding a way that we can safely harvest that product out there."
"Although we can't predict when conditions on Georges Bank will favor a large bloom, our knowledge of the bloom dynamics was used in establishing a suitable management approach," says Don Anderson, a senior scientist at WHOI and the lead investigator on the GOMTOX project.
For the scientists, the work to understand the dynamics of the Georges Bank population continues. New DNA evidence uncovered by Woods Hole Center for Oceans and Human Health researchers Deana Erdner (University of Texas) and Mindy Richlen from Don Anderson's laboratory at WHOI, suggests the Georges Bank Alexandrium population is genetically distinct.
"We thought the Georges Bank population was just the little toe at the end of the coastal population, but it's not. It is separate, and it occupies a distinct niche from the rest of the Alexandrium in this region," says McGillicuddy. "This was a big surprise to us."
###
The research was funded, in part, by NOAA's NCCOS, with additional support provided by NSF and NIEHS through the Woods Hole Center for Oceans and Human Health.
The Woods Hole Oceanographic Institution is a private, non-profit organization on Cape Cod, Mass., dedicated to marine research, engineering, and higher education. Established in 1930 on a recommendation from the National Academy of Sciences, its primary mission is to understand the oceans and their interaction with the Earth as a whole, and to communicate a basic understanding of the oceans' role in the changing global environment.
[ | E-mail | Share ]
?
AAAS and EurekAlert! are not responsible for the accuracy of news releases posted to EurekAlert! by contributing institutions or for the use of any information through the EurekAlert! system.
Research enables fishermen to harvest lucrative shellfish on Georges BankPublic release date: 10-Apr-2013 [ | E-mail | Share ]
Contact: WHOI Media Relations media@whoi.edu 508-289-3340 Woods Hole Oceanographic Institution
Combined research efforts by scientists involved in the Gulf of Maine Toxicity (GOMTOX) project, funded by NOAA's Ecology and Oceanography of Harmful Algal Blooms (ECOHAB) program, and administered by the National Centers for Coastal Ocean Science (NCCOS), have led to enhanced understanding of toxic algal blooms on Georges Bank. This new information, coupled with an at-sea and dockside testing protocol developed through collaboration between GOMTOX and U.S. Food and Drug Administration (FDA) investigators, has allowed fishermen to harvest ocean quahogs and surf clams in these offshore waters for the first time in more than two decades.
The shellfish industry estimates the Georges Bank fishery can produce up to 1 million bushels of surf clams and ocean quahogs a year, valued $10 15 million annually. "There is a billion dollars' worth of shellfish product on Georges Bank that is property of the United States but that can't be harvested because of the threat of toxicity, and 99.9% of the time, it is good wholesome product," says Dave Wallace of North Atlantic Clam Association and a GOMTOX participant. "In an unusual and unique partnership, we worked with GOMTOX scientists, the FDA, and the states of Massachusetts, Rhode Island, New Jersey and Delaware and now that huge resource can go into commerce, which helps the entire country."
"We are extremely pleased that research funded by NOAA can provide such an economic boost to New England shellfisheries," says Robert Magnien, Director of NCCOS' Center for Sponsored Coastal Ocean Research. "It is a clear example of how research authorized by the Harmful Algal Bloom and Hypoxia Research and Control Act can protect both public health and local economies through collaborations between academic scientists, state and federal regulatory agencies, and the shellfish industry."
An elevated area of the sea floor between Cape Cod and Nova Scotia, Georges Bank is one of the best fishing grounds on Earth. But since 1990, it has been closed to harvesting of surf clams and ocean quahogs after harmful algal blooms (also referred to as "red tides") caused paralytic shellfish poisoning (PSP) that sickened fishermen. For decades scientists speculated the blooms on Georges Bank were fueled by coastal blooms in the Gulf of Maine.
More recent research by GOMTOX investigators, however, has shown that Georges Bank is home to a separate and distinct population of the toxic algae, which is described in a recently published paper by Woods Hole Oceanographic Institution (WHOI) scientist Dennis McGillicuddy and other members of the GOMTOX team.
It has been known for many years that the phytoplankton Alexandrium fundyense is the cause of the harmful algal blooms that occur to varying severity each spring and summer along the coastal Gulf of Maine, sometimes extending as far south as Cape Cod and the adjacent islands. The algae's seed populations or "cysts" germinate from seabeds starting in early spring and bloom at the sea surface, until all of the necessary nutrients in the water are consumed. As the nutrients run out, the cells form cysts and fall to the seafloor, as seed for the following spring. High concentrations of the toxic algae can cause closure of shellfish beds and cost the region many millions of dollars.
Precisely why the blooms vary in severity has been much more difficult to determine, and has involved extensive seasonal sampling of water and sediments, study of coastal currents, environmental and oceanographic conditions, availability of nutrients, and the development of a computer program to model all of the variables.
Researchers got the first signal that something very different was happening on Georges Bank during a research cruise to count Alexandrium cells in sea water samples in spring/summer 2007. "We devised our sampling strategy to look at the cells' transport pathways from coastal waters onto the Bank," says McGillicuddy. Throughout the coastal Gulf of Maine, the numbers were very low. But when the research team started sampling at Georges Bank, they found very high concentrations of Alexandrium in the water, despite the fact that the bloom had not really begun along the coast of Maine.
"I'll never forget the moment we hit a big patch of cells on Georges Bank," says Dave Townsend, a GOMTOX scientist from the University of Maine and co-author of the paper. "We extended our sampling to go all the way across Georges Bank and we were still hitting them. We had to turn around and completely reorganize our sampling strategy based on what we were seeing in the microscope."
For such a large bloom to occur, the researchers reasoned the number of cysts on Georges Bank must be similar to the quantities needed to initiate a bloom along the coast. Yet, their fall 2007 survey to map the cyst distribution in the seabed on the Bank found very few cysts quantities not likely to cause a large bloom along the coast.
In the three-year course of intensive study on Georges Bank since then, blooms have occurred every year, in concentrations that would typically lead to toxicities in coastal shellfish beds. Yet, a parallel effort by the fishing industry and federal testing labs to analyze shellfish samples from Georges Bank found the bivalves to be clean of toxins. So while toxins were produced at and near the surface, they were not delivered to the surf clams and ocean quahogs in the seabed in quantities sufficient to threaten human health.
The system on Georges Bank was indeed a riddle: Few cysts, yet large blooms; a large bloom, yet little to no toxicity in the shellfish. Applying the same detailed analyses to the offshore population of Alexandrium that they applied to coastal populations, the scientists discovered the optimum growing conditions for Alexandrium on Georges Bank were colder and saltier than those of their coastal relatives. Their analysis uncovered how the currents in the region can isolate Georges Bank to create colder and saltier conditions. If the conditions are favorable, the researchers say, Alexandrium populations can double every three days, and in a month's time, grow from concentrations of 10 cells per liter to 10,000.
Further setting the Georges Bank population apart was the finding by GOMTOX colleagues at University of Massachusetts, Dartmouth's School for Marine Science and Technology (SMAST), working in collaboration with the FDA, who determined that the toxin content of algae on Georges Bank was different than the coastal Gulf of Maine populations. "The toxins present in Alexandrium cells from Georges Bank were, on average, two times lower than those in the coastal Gulf of Maine," said Chrissy Petitpas, a doctoral student working in Professor Jefferson Turner's lab at SMAST.
Despite this new information and the knowledge that the clams have been shown to be safe for humans to eat at the present time, the fact remains that concentrations of the toxins in the clams on Georges Bank in 1989 and 1990 did reach dangerous levels. Scientists know that coastal shellfish populations are directly exposed to the toxins when the blooms make landfall, but they remain uncertain about the conduit for toxicity from the surface ocean to the deep shellfish beds on Georges Bank, located at about 50m depth.
But, thanks to an innovative screening protocol and regulatory structure developed collaboratively by the FDA, NOAA's National Marine Fisheries Service, the fishing industry, and testing labs approved by the National Shellfish Sanitation Program, a system is now in place to monitor, test, and verify that clams harvested from Georges Bank are safe. The clams are checked by fishermen at sea using the newly available test kit, and re-checked by regulators when the fishing vessels reach the dock. Combined with the weekly monitoring of shellfish beds along the coast during the bloom season to protect human health, these monitoring systems are extremely effective at keeping toxic shellfish off the market.
"Toxin levels in shellfish on Georges Bank have been very low over the last few years. We are confident that this new testing protocol will serve to protect public health should toxin levels rise again in the future," said Stacey DeGrasse, seafood research coordinator in the FDA's Office of Regulatory Science and a major participant in the development of the new offshore testing protocol. "We intend to continue to work closely with NOAA to ensure that the shellfish from this region are harvested safely."
"I've run over 2,500 samples from Georges Bank since mid-March, and all of them have been clean of toxin," says Darcie Couture, a former manager of the marine biotoxins program at the Maine Department of Marine Resources, who now operates the federally permitted testing lab. "We've been fortunate in finding a way that we can safely harvest that product out there."
"Although we can't predict when conditions on Georges Bank will favor a large bloom, our knowledge of the bloom dynamics was used in establishing a suitable management approach," says Don Anderson, a senior scientist at WHOI and the lead investigator on the GOMTOX project.
For the scientists, the work to understand the dynamics of the Georges Bank population continues. New DNA evidence uncovered by Woods Hole Center for Oceans and Human Health researchers Deana Erdner (University of Texas) and Mindy Richlen from Don Anderson's laboratory at WHOI, suggests the Georges Bank Alexandrium population is genetically distinct.
"We thought the Georges Bank population was just the little toe at the end of the coastal population, but it's not. It is separate, and it occupies a distinct niche from the rest of the Alexandrium in this region," says McGillicuddy. "This was a big surprise to us."
###
The research was funded, in part, by NOAA's NCCOS, with additional support provided by NSF and NIEHS through the Woods Hole Center for Oceans and Human Health.
The Woods Hole Oceanographic Institution is a private, non-profit organization on Cape Cod, Mass., dedicated to marine research, engineering, and higher education. Established in 1930 on a recommendation from the National Academy of Sciences, its primary mission is to understand the oceans and their interaction with the Earth as a whole, and to communicate a basic understanding of the oceans' role in the changing global environment.
[ | E-mail | Share ]
?
AAAS and EurekAlert! are not responsible for the accuracy of news releases posted to EurekAlert! by contributing institutions or for the use of any information through the EurekAlert! system.
BLOOMINGTON, Ind. (AP) ? Indiana junior Victor Oladipo is heading to the NBA. Cody Zeller could be next.
Oladipo made his announcement official Tuesday at a news conference inside Assembly Hall. He is the Hoosiers' first underclassmen to leave school early since Eric Gordon and D.J. White departed after the 2007-08 season. Zeller's announcement is expected later this week, possibly Wednesday.
Losing Oladipo was no surprise to those inside the Indiana program who watched the 6-foot-5 guard mature from talented freshmen into a refined star. NBA scouts have been so impressed with Oladipo's progression that many mock drafts now project him to be taken among the top six picks.
With Oladipo expected to graduate May 4, his 21st birthday, and coach Tom Crean collecting information that Oladipo would be a certain lottery pick, it was too much too turn down. Crean said the two would start looking into potential agents soon.
"I swayed back and forth especially throughout the season, but I felt this was best for my family," Oladipo said softly, explaining how difficult the choice was. "Coming here and graduating in three years, I feel like I'm prepared for it. So I feel like it's the best thing for me."
What the NBA will get in Oladipo is a workaholic.
The once overlooked recruit has improved each season in Bloomington, dazzling the nation this season with his athleticism and defense. He was a first-team All-American after finishing second on the Hoosiers in scoring (13.6), tying for second on the team in rebounds (6.3) and earning Big Ten defensive player of the honors. He can play above the rim, too, as evidenced when Oladipo delivered a spectacular game-sealing 360-degree dunk against Illinois in the Big Ten tournament. This past season, he shot 59.9 percent from the field, 44.1 percent on 3-pointers -- both up from his sophomore numbers of 47.1 and 20.8.
But that's only part of Oladipo's game.
"He's still not satisfied being an NBA player or a draft pick, so he's going to continue to work hard," said Mike Jones, Oladipo's high school coach at national power Hyattsville (Md.) DeMatha. "He's the same person today that I coached in high school."
If scouts had any doubts regarding Oladipo's plans, all they had to do was walk into Assembly Hall before the news conference.
There, a sweaty Oladipo was dressed in his crimson practice jersey for yet another individual workout with some of his soon-to-be ex-teammates at Indiana. The group included forwards Will Sheehey and Hanner Mosquera-Perea and point guard Kevin "Yogi" Ferrell, three players who will try to fill the void left by Oladipo's absence.
It won't be easy.
Oladipo's infectious personality and relentless drive were two big reasons the Hoosiers went from 12 wins in Oladipo's freshman season, 2010-11, to making back-to-back appearances in the regional semifinals. Indiana came into the 2012-13 season ranked No. 1 for the first time since 1979 and stayed there longer than any other team this season.
But he just couldn't pass up the opportunity to become one of the highest-drafted players to ever come out of DeMatha. Other alums include Danny Ferry, the No. 2 pick in the 1989 draft; Adrian Dantley, who went sixth overall in 1976; and Kenny Carr, who went No. 6 in 1977.
"If you take me back to when I was playing for DeMatha and you asked who would have been in the position I am today, I guarantee you I would have been the last one picked," Oladipo said. "Whenever I say he (Crean) believed in me when nobody else did, I really mean it. Coach Crean was the most consistent and most persistent (recruiter), and I just saw it as a sign from God that I needed to be wearing the candy stripes. I've become a great man because of it and I'm becoming a great basketball player because of it."
Oladipo may not be the only underclassmen Indiana has to replace next season.
Zeller, the 7-foot sophomore center, led Indiana in scoring (16.3) and rebounding (8.1) and was considered a top-three pick for most of the season. Many believe that Zeller, Indiana's 2011 Mr. Basketball and a three-time state champ, will try to join his older brothers, Tyler and Luke, in the NBA next season.
Crean didn't discuss Zeller's decision Tuesday. Oladipo and Zeller did talk about it over the last week, though.
"We talked about it a little bit, I have no idea what he decided because Cody, as you know, is pretty quiet anyway," Oladipo said. "I just wished the best for him and wished him the best of luck."
If Zeller also leaves, Crean would be replacing four starters -- Jordan Hulls, Christian Watford, Oladipo and Zeller -- next season.
Crean signed six players during the fall despite having only three graduating seniors. Oladipo's decision will clear another spot and if Zeller leaves early, that would create a fifth opening.
For the first time publicly, Crean acknowledged Tuesday that they were preparing all along for the likelihood of more than one player leaving early for the NBA this spring.
"That's one of the reasons we oversigned. There's no question," he said. "Was that a given? Absolutely not."
Google has spent the past couple years facing down antitrust accusations in Europe for pushing its web services over those of competitors. But, just as that case is coming to a close, the New York Times now reports that new anti-competitive allegations have been levied against Android. This new complaint was filed by a group called Fairsearch -- whose members include old EU foes Microsoft and Nokia, plus Oracle and a host of travel booking websites -- and claims that Google's using Android as a way to deceive consumers into using Google apps instead of competitors' software. The problem, as Fairsearch sees it, is that Google forces OEMs who use Android to unfairly place apps like YouTube and Gmail in prominent places on the desktop. Of course, this new complaint is just the beginning, so we'll have to wait and see what the European Commission's investigation into the matter uncovers, and how the folks in Mountain View respond.
NEW YORK (AP) ? Stocks opened slightly lower on Wall Street Monday as major U.S. companies prepare to start reporting their first-quarter earnings results.
Alcoa, the first company in the Dow Jones industrial average to report earnings, will release its results after the markets close Monday. Alcoa was unchanged in early trading at $8.24.
Currently, analysts expect earnings for companies in the S&P 500 to rise by 0.6 percent, with the telecommunications and so-called consumer discretionary stocks forecast to lead the growth in profits, according to data from S&P Capital IQ. Consumer discretionary stocks include department store chains such as Macy's.
The Dow fell 50 points, or 0.4 percent, to 14,515 in the first half-hour of trading. The Standard & Poor's 500 index declined three points, or 0.2 percent, to 1,550.
Telecommunications and health care stocks had the biggest declines in early trading, falling 1 percent and 0.7 percent respectively. Seven of the 10 industry groups in the Standard & Poor's 500 index were lower.
Lufkin Industries, an oilfield equipment maker, surged $24.22 to $88.15 after General Electric Co. agreed to buy the company for $3 billion in an effort to bolster its oil and gas operations. GE said Monday it would pay Lufkin shareholders $88.50 per share in the all-cash deal, a 38 percent premium over Lufkin's closing price of $63.93 Friday. GE edged 8 cents lower to $22.87.
Stocks fell Friday after the government reported a sharp slowdown in hiring last month that was far worse than economists had expected. The report capped a bad week for stocks, with the S&P 500 logging its biggest weekly decline of the year, as signs emerged that U.S. economic growth is starting to cool.
In other trading, the Nasdaq composite index dropped two points, or 0.1 percent, to 3,201.
The yield on the 10-year Treasury note rose from 1.71 percent to 1.72 percent, after falling as low as 1.69 percent Friday, the lowest level of the year so far.
The benchmark rate has fallen in the past month as demand for low-risk assets increased amid mounting evidence that growth in the U.S. economy is slowing.
TechCrunch founder Michael Arringtonhas responded to the allegations of battery and rape?lobbed at him on social media and blogs last week, calling the claims "completely untrue" and confirming that he will take legal action against the accusers, including getting the police involved.
"There have been some extremely serious and criminal allegations against me over the last week. All of the allegations are completely untrue, and I?ve hired a law firm to represent me in the legal actions against the offending parties.
The Union flag flies at half mast at the Houses of Parliament in London, Monday, April 8, 2013, in honour of former British Prime Minister Margaret Thatcher. Thatcher's spokesman, Tim Bell, said the former prime minister died Monday morning of a stroke. Flags were flown at half-staff at Buckingham Palace, Parliament and Downing Street for the 87 year old. Queen Elizabeth II authorized Thatcher to have a ceremonial funeral ? a step short of a state funeral ? to be held at St. Paul's Cathedral in London with military honors. (AP Photo/Sang Tan)
The Union flag flies at half mast at the Houses of Parliament in London, Monday, April 8, 2013, in honour of former British Prime Minister Margaret Thatcher. Thatcher's spokesman, Tim Bell, said the former prime minister died Monday morning of a stroke. Flags were flown at half-staff at Buckingham Palace, Parliament and Downing Street for the 87 year old. Queen Elizabeth II authorized Thatcher to have a ceremonial funeral ? a step short of a state funeral ? to be held at St. Paul's Cathedral in London with military honors. (AP Photo/Sang Tan)
FILE - This is a 1980 file photo showing British Prime Minister Margaret Thatcher. Ex-spokesman Tim Bell says that Thatcher has died. She was 87. Bell said the woman known to friends and foes as "the Iron Lady" passed away Monday morning, April 8, 2013. (AP Photo/File)
British Prime Minister David Cameron steps out from 10 Downing Street, in London, Monday, April 8, 2013, to pay tribute to former British Prime Minister Margaret Thatcher who died from a stroke, at the age of 87. Thatcher's spokesman, Tim Bell, said the former prime minister died from a stroke Monday morning at the Ritz hotel in London. (AP Photo/Sang Tan)
A floral tribute is seen after being laid outside the home of the late former British Prime Minister Margaret Thatcher in London, Monday, April 8, 2013. Margaret Thatcher, the combative "Iron Lady" who infuriated European allies, found a fellow believer in Ronald Reagan and transformed her country by a ruthless dedication to free markets in 11 bruising years as prime minister, has died. She was 87 years old. (AP Photo/Matt Dunham)
FILE - In a Feb. 20, 1985 file photo, British Prime Minister Margaret Thatcher is applauded by Vice President George Bush, left, as House Speaker Thomas P. O'Neill, Jr. looks on just before she addressed a joint meeting of the U.S. Congress, in Washington. Thatchers former spokesman, Tim Bell, said that the former British Prime Minister Margaret Thatcher had died Monday morning, April 8, 2013, of a stroke. She was 87. (AP Photo/Bob Daugherty, File)
Combative and determined to get her way, Margaret Thatcher divided opinion down the middle in life ? and in death.
Many leaders lauded Thatcher for her steely determination to modernize Britain's industrial landscape, even at the cost of strikes and riots, and to stand beside the United States as the west triumphed in the Cold War versus the Soviet Union. Others saw a pitiless tyrant who preferred conflict to compromise.
British Prime Minister David Cameron lauded his 1980s predecessor as "a great Briton," but others ? particularly Europe's socialists who often clashed with her ? were less enamored in their reactions to the death Monday of the conservative icon.
Flags at Buckingham Palace, Parliament and across the United Kingdom were lowered to half-staff. Buckingham Palace said Queen Elizabeth II would send a private message of sympathy to the Thatcher family. Government officials began preparations for a London funeral with military honors at St. Paul's Cathedral next week, followed by a private cremation.
"As our first woman prime minister, Margaret Thatcher succeeded against all the odds," Cameron said in Madrid. He cut short his trip to Spain and canceled a visit to France to return to London for the funeral preparations.
"The real thing about Margaret Thatcher is that she didn't just lead our country. She saved our country," Cameron said, "and I believe she'll go down as the greatest British peacetime prime minister."
In Washington, President Barack Obama said many Americans "will never forget her standing shoulder to shoulder with President (Ronald) Reagan, reminding the world that we are not simply carried along by the currents of history. We can shape them with moral conviction, unyielding courage and iron will."
And former first lady Nancy Reagan said her husband and Thatcher "enjoyed a very special relationship" driven by a common hatred of Communism. "Ronnie and Margaret were political soul mates," she said in a statement that lauded Thatcher's "clear vision and strong determination to stand up for her beliefs at a time when so many were afraid to rock the boat."
In Poland, Foreign Minister Radoslaw Sikorski said his country should erect a statue of the British leader. In a tweet he praised Thatcher as "a fearless champion of liberty, stood up for captive nations, helped free world win the Cold War."
Former Prime Minister Tony Blair, who ousted the Conservative Party from power seven years after Thatcher's resignation, conceded that Thatcher had been right to challenge labor union power ? the traditional bedrock for Blair's own Labour Party.
"Very few leaders get to change not only the political landscape of their country but of the world. Margaret was such a leader. Her global impact was vast," said Blair, who credited Thatcher with being "immensely supportive" despite their opposing views on many issues.
"You could not disrespect her character or her contribution to Britain's national life," Blair said.
Not all Britons agreed. Several hundred people gathered in Glasgow and in London's Brixton neighborhood for impromptu celebrations, complete with party hats and streamers.
The National Union of Miners ? which tussled with Thatcher in a long 1984-85 strike, and lost ? expressed condolences to Thatcher's family, but said: "The damage caused by her fatally flawed politics sadly lingers on. Good Riddance."
A cooler breeze also blew from across the English Channel, where many of the men who ran European governments in the 1980s expressed admiration for Thatcher's toughness mixed with femininity ? but not her European Union-bashing politics.
European Commission President Jose Manuel Barroso of Portugal called Thatcher "a circumspect yet engaged player in the European Union."
Former French President Valerie Giscard d'Estaing called her "a woman unique in history" with "an unwavering strength."
D'Estaing recalled her impressive entrance to one meeting of EU premiers in France, where all the men were in black tie. "She went out of her car and she wore a long dress, a gown for a sort of ball, and everybody was sort of surprised and impressed. All the other members were flattered to speak with her," he recalled.
Harsh criticism came from Northern Ireland and Argentina, where Thatcher's reputation for unbending determination received early tests ? when breaking an Irish Republican Army prison hunger strike in 1981 that left 10 inmates dead, then leading Britain into a 1982 war to reclaim the Falkland Islands from Argentine invaders.
Gerry Adams, leader of the Irish nationalist Sinn Fein party that gained strength from Thatcher's confrontation with IRA prison demands, denounced her as a hypocrite who sanctioned secret talks with senior IRA figures yet refused any concessions in public.
"Here in Ireland her espousal of old draconian, militaristic policies prolonged the war and caused great suffering. She embraced censorship, collusion and the killing of citizens by covert operations," said Adams, whose party ultimately gained a share of power in Northern Ireland after the IRA ceased fire and Blair invited Sinn Fein to the negotiating table.
Many other Irish politicians countered that Thatcher talked tough, but was more pragmatic in private ? and dramatically demonstrated this by signing the Anglo-Irish Agreement of 1985 giving the Republic of Ireland a role in Northern Ireland for the first time. She struck the deal, infuriating the north's Protestant majority, barely a year after the IRA tried to assassinate her in a hotel bombing.
"She was presented as the Iron Lady, but she was open to change and she did change," said Noel Dorr, one of Ireland's senior diplomats in the 1980s who had close personal dealings with Thatcher.
Argentina's government offered no official reaction, but many Argentines blamed Thatcher for the deaths of 649 Argentine troops during the South Atlantic conflict. Some 255 British military personnel and three Falkland Islanders also died.
"Thatcher ? it's more or less a bad word here in Argentina," said Buenos Aires resident Ruben Chaves. "Nobody here has good feelings towards that name."
Falklands lawmaker Mike Summers said Thatcher was "one of very few political leaders who could have mounted the expedition she mounted in 1982 to restore our freedom, and from a Falkland Islands perspective she will be forever remembered for that."
Pop culture figures past and present sounded off, too.
Arnold Schwarzenegger, the actor and former Republican governor of California, offered a Twitter tribute to Thatcher as "a visionary, a warrior and a once-in-a-lifetime leader who left the world better than she found it."
Others noted her inspirational role to women, even though Thatcher famously eschewed feminism and rarely promoted women herself.
"Thinking of our 1st Lady of girl power, Margaret Thatcher, a green grocer's daughter who taught me anything is possible," tweeted a former member of the Spice Girls band, Geri Halliwell.
Now, this is news: A bunch of big and powerful companies may have something in their common interest that also benefits their customers.
The Linux Foundation, which has managed the creation of that popular computer operating system, is working with a number of large technology companies to develop an open source project around software-defined networking.
S.D.N., as it is called, is important both in lowering costs and increasing the capabilities of the globe-spanning data center networks that have come to dominate the computer industry. These networks, which carry Internet traffic, hold personal and corporate data and manage cellphones, among other things, have largely been cobbled together from older equipment and use traditional practices.
S.D.N., which involves putting more complex software atop standardized components, would make it easier to improve network performance and create new applications.
Members of the group include Cisco Systems, Juniper Networks, I.B.M. and VMware, along with Big Switch Networks, Brocade, Citrix, Microsoft, Arista Networks, NEC and Red Hat. Each company will contribute some of its technology to the open source effort, called the OpenDaylight Project. As with many other open source projects, the final specifications of the product will be determined by a steering committee elected by members.
In some ways, OpenDaylight looks like a more efficient version of the kind of industrial standards body that governs the creation of radio systems for cellphones. While ostensibly impartial, these bodies have often been highly political and could delay technology deployment for years while companies fought to have their technology incorporated into common use.
The companies in the project have spent billions of dollars already on S.D.N. VMware, for example, paid $1.23 billion for an S.D.N. company called Nicira, while Cisco has financed its own S.D.N. company.
The OpenDaylight participants may have decided it?s just more efficient to get to work, and work on the parts of their technologies that mean something to customers, than to fight each other over details. OpenDaylight could also lower customer resistance to adopting S.D.N., as there will be fewer concerns about incompatible technologies.
?We were contacted, based on our ability to structure the project,? said Jim Zemlin, the executive director of the Linux Foundation. ?These folks are pooling their research and development costs. The value is at the higher levels (of software), rather than who has the best file format.?
The first code for the project is supposed to be released in the third quarter this year. This will include basics like a controller, a virtual overlay network, and switch device enhancements. These are far from trivial creations: One contribution from Big Switch alone has over 200,000 lines of software code.
The real test of whether this works like an open source project will come over a longer time. It will depend on how well it attracts new members and independent developers and how fast it creates new products.
If you zoom in on the surface of a vinyl record using a microscope, to the untrained eye it kind of looks like a series of mountains and valleys. It's actually the waveform representation of a song or other sounds, but what would happen if you took a map of the Earth's mountains and valleys and turned that into a record? The results, of course, sound terrible. More »
Nobel laureates and their research teams at American Chemical Society meetingPublic release date: 7-Apr-2013 [ | E-mail | Share ]
Contact: Michael Bernstein
m_bernstein@acs.org
504-670-4707 (New Orleans Press Center, April 5-10)
202-872-6042
Michael Woods
m_woods@acs.org
504-670-4707 (New Orleans Press Center, April 5-10)
202-872-6293
American Chemical Society
NEW ORLEANS, April 7, 2013 At least nine Nobel laureates have research that will be presented here this week during the 245th National Meeting & Exposition of the American Chemical Society, the world's largest scientific society. Research from the laureates' teams will be among almost 12,000 presentations during the event, expected to attract more than 14,000 scientists and others.
They are Robert H. Grubbs, Ph.D.; Richard R Schrock, Ph.D.; Brian K. Kobilka, Ph.D.; Robert J. Lefkowitz, Ph.D.; Ei-ichi Negishi, Ph.D.; George A. Olah, Ph.D.; Karl Barry Sharpless, Ph.D.; Ada Yonath, Ph.D.; and Ahmed Zewail, Ph.D.
Grubbs, who is with the California Institute of Technology, and Schrock, who is with the Massachusetts Institute of Technology, shared the 2005 Nobel Prize in Chemistry with Yves Chauvin for the development of the "metathesis method." That new way to make plastics, medicines and other products was an advance in "green chemistry," because it reduces the production of potentially hazardous waste compared with other approaches.
Kobilka, who is with the Stanford University School of Medicine, and Lefkowitz, who is with the Howard Hughes Medical Institute and the Duke University Medical Center, shared the 2012 Nobel Prize in Chemistry "for studies of G-protein-coupled receptors." Their research showed how these receptors work to sense the environment of the cell.
Negishi, the Herbert C. Brown Distinguished Professor of Organic Chemistry at Purdue University, shared the 2010 Nobel Prize in Chemistry "for palladium-catalyzed cross couplings in organic synthesis." This helped develop techniques to synthesize complex carbon molecules that have had an enormous impact on the manufacture of medicines and other products.
Olah, who is with the University of Southern California, won the 1994 Nobel Prize in Chemistry for work on "carbocations," charged molecules that were considered too unstable to study. Olah developed a way to isolate these molecules, which was useful in the oil and coal industries.
Sharpless, who is with The Scripps Research Institute, won the 2001 Nobel Prize in Chemistry "for his work on chirally catalysed oxidation reactions." Sharpless worked on ways to synthesize just one of a set of "mirror" image molecules. This work led to advances in drug development.
Yonath, who is with the Weizmann Institute of Science, shared the 2009 Nobel Prize in Chemistry with Venkatraman Ramakrishnan and Thomas A. Steitz "for studies of the structure and function of the ribosome." They showed how the ribosome works at an atomic level to translate the information in DNA into proteins for life.
Zewail, who is with the California Institute of Technology, won the 1999 Nobel Prize in Chemistry "for his studies of the transition states of chemical reactions using femtosecond spectroscopy." Zewail showed that it was possible to watch chemical reactions in "slow-motion" using lasers to see how the molecules move.
Further information on the presentations follows.
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Abstracts
Robert H. Grubbs, Ph.D.
Milder routes to chelated ruthenium complexes for Z-selective metathesis
Lauren E. Rosebrugh, Myles B. Herbert, Vanessa M. Marx, Benjamin K. Keitz, Robert H. Grubbs
A novel method to effect the salt metathesis and C-H activation of ruthenium-based, Z-selective metathesis catalysts containing a chelated N-heterocyclic carbene (NHC) ligand using sodium carboxylates is reported. This method allows for the successful formation of stable chelated species containing a variety of alterations to the NHC ligand that had decomposed under the previous approach. As such, several new, chelated metathesis-active ruthenium complexes are described, including a catalyst system exhibiting >95% Z-selectivity and record TONs (up to 8100) in homodimerization reactions of terminal olefins. Moreover, a catalyst has been synthesized that gives highly cis, highly tactic polymers via ring opening metathesis polymerization of strained, cyclic olefins, marking the first time tactic polymers have been made using a ruthenium-based metathesis catalysts.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 06:00 PM
Organometallic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Methods for the cleavage of C-O bonds
Robert H Grubbs
The conversion of biorenewable resources into chemical will require the efficient removal of excess functionality. The C-O bonds in a variety of highly oxidized biomaterials can be difficult to convert into compounds of lower oxidation state. While screening a variety of catalysts, new methods for the efficient cleavage of aromatic and aliphatic C-O linkages have been developed.
Tuesday, April 9, 2013 11:25 AM
ACS Award in Pure Chemistry: Symposium in Honor of Theodor Agapie (08:30 AM - 12:30 PM)
Location: Morial Convention Center
Room: 345
Design of selective catalysts for olefin metathesis
Robert H Grubbs
Olefin metathesis has become a tool for the synthesis of a variety of molecules and materials. In the past several years the efficiency and selectivity of the catalysts have greatly improved. Catalysts are now available that allow the precise control of the double bond geometrh of the product double bond. Organometallic synthesis and computational results have resulted in new levels of selectivity and efficiency.
Tuesday, April 9, 2013 08:30 AM
Gabor A. Somorjai Award for Creative Research in Catalysis: Symposium in Honor of Tobin J. Marks (08:25 AM - 11:45 AM)
Location: Morial Convention Center
Room: 346
Design and synthesis of new ruthenium-based catalysts for improved activity in challenging Z-selective metathesis reactions
Brendan L. Quigley, Vanessa M. Marx, Robert H. Grubbs
Our group has recently reported a series of ruthenium-based metathesis catalysts that contain a chelating NHC. These catalysts demonstrate high Z-selectivity in a variety of metathesis reactions including cross metathesis, ring-closing metathesis and ring-opening metathesis polymerization. However, the substrate scope has so far been limited to relatively unhindered olefins. In order to probe the origin of this selectivity, a series of catalysts with N-heterocyclic carbene (NHC) substituents of varying steric bulk were prepared. These catalysts were subsequently examined for improved reactivity in a range of olefins that contain bulky substituents. In addition, the mechanism of the C-H-activation step in the synthesis of such catalysts was probed through variation of the sterics and electronics of both the adamantyl and aryl NHC substituents.
Tuesday, April 9, 2013 08:00 PM
Graphene Chemistry, Metal-Mediated Reactions and Syntheses, Molecular Recognition and Self-Assembly, Physical Organic Chemistry, Materials Devices and Switches (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Transition-metal-free reductive cleavage of lignin-related C-O bonds by an activated silane
Anton A Toutov, Alexey Fedorov, Nicholas Swisher, Robert H. Grubbs
Reported herein is a transition-metal-free protocol for the efficient reductive cleavage of diaryl and aryl alkyl ethers. The combination of triethylsilane with simple bases forms an unusually powerful reductive couple that affords regioselective rupture of lignin- and coal-related C-O bonds in aromatic ethers. Interestingly, this is accompanied by ortho-directed C-H silylation that be-comes preferred with certain bases and temperature re-gimes. However, the tuning of selectivity proved possible thus enabling the development of a practical method for the title transformation, as illustrated by the reduction of lignin model compounds to their corresponding phenolic and aromatic constituents.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 02:00 PM
Advances in Energy and Fuels Processes, Systems, Materials and Utilization (02:00 PM - 04:00 PM)
Location: Morial Convention Center
Room: Hall D
Preparation of rapidly initiating ruthenium based olefin metathesis catalysts
Alexandra H. Sullivan, Benjamin K. Keitz, Robert H. Grubbs
Z-selective olefin metathesis ruthenium catalysts are highly sought after, due to their wide applications in both pharmaceuticals and materials science. A crucial step towards the preparation of rapidly initiating, Z-selective, olefin metathesis catalysts was found to be the addition of sodium pivalate to phosphonium alkyidene catalyst 1, resulting in the formation of the C-H activated complex 2 after two days of heating. Preparation of 2, a close analog to the target catalyst 4, promises that future synthesis of 4 should be facile.
Sunday, April 7, 2013 06:00 PM
Undergraduate Research at the Frontiers of Inorganic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Catalyst-controlled anti-Markovnikov palladium-catalyzed oxidation of aliphatic olefins
Zachary K Wickens, Bill Morandi, Robert H Grubbs
The Wacker oxidation, or the palladium-catalyzed oxidation of olefins to carbonyls, is one of the most well-known palladium-catalyzed reactions and has extensive synthetic applications. Traditional Wacker oxidation conditions obey Markonikov's rule and thus yield methyl ketones with high selectivity from the majority of terminal olefins. A Wacker oxidation capable of producing aldehydes from unbiased terminal olefins would be synthetically useful and is a long-standing challenge in palladium oxidation chemistry. A palladium-catalyzed oxidation system capable of providing synthetic access to aldehydes from unbiased terminal olefins will be discussed.
Tuesday, April 9, 2013 08:20 AM
Metal Mediated Reactions (08:00 AM - 12:00 PM)
Location: Morial Convention Center
Room: 256/257
Synthetic applications of Z-selective ruthenium-based olefin metathesis catalysts
Vanessa M Marx, Myles B Herbert, Benjamin K Keitz, Robert H Grubbs
The first report of Z-selective macrocyclizations using a ruthenium-based metathesis catalyst is described. Selectivity for Z-macrocycles is consistently high for a diverse set of substrates bearing different functional groups and comprised of various ring sizes. The same catalyst was employed for the Z-selective ethenolysis of a mixture of E and Z macrocycles, providing the pure E-isomers. These methodologies were successfully applied to the construction of several olfactory macrocycles, as well as the backbone of cytotoxic alkaloid natural products. Conditions were also optimized for a series of challenging cross metathesis reactions using the same catalyst system, and subsequently exploited in the synthesis of a family of lepidopteran insect pheromones. A detailed mechanistic study probing the origin of the stereoselectivity in these challenging transformations is currently underway, and will also be discussed in detail.
Monday, April 8, 2013 01:00 PM
Metal Mediated Reactions (01:00 PM - 05:00 PM)
Location: Morial Convention Center
Room: 256/257
Functionalized corroles as diatherapeutic, multi-modal imaging agents
Melanie A Pribisko, Punnajit Lim, John Termini, Robert H Grubbs, Joshua H Palmer, Harry B Gray
Recent synthetic advancements have made it possible to produce substituted derivatives of meso-5,10,15-(tris)pentafluorophenylcorrole (H3tpfc) in reasonable yields. We present the scalable syntheses of new H3tpfc derivatives, and a few of their metal complexes, through nucleophilic aromatic substitution on the pentafluorophenyl substituents. These complexes have potential applications both as imaging agents and chemotherapeutic drugs.
Sunday, April 7, 2013 06:00 PM
Metals in Medicine: Diagnostic and Therapeutic Applications (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
ROMP with stable initiators
Robert Howard Grubbs
Tim Swager introduced the name ROMP for ring opening metathesis polymerization when he was a a graduate student. Since that time, many new initiators for the ROMP of strained olefins have been developed. Recent advances now allow polymers with precise chain length and composition to be prepared. The synthesis of brush polymers demonstrates the control of polymeric structures that are now possible with modern initiators.
Tuesday, April 9, 2013 02:50 PM
ACS Award for Creative Invention: Symposium in Honor of Timothy M. Swager (01:15 PM - 05:30 PM)
Location: Hilton Riverside
Room: HEC C
Z-selective ethenolysis using a ruthenium catalyst: Applications and mechanistic implications
Myles B Herbert, Hiroshi Miyazaki, Peng Liu, Vanessa M Marx, Benjamin K. Keitz, Robert H Grubbs
Unique ethenolysis reactivity has been uncovered with a new family of chelated ruthenium alkylidene catalysts that have exhibited high Z-selectivity in cross metathesis, ring opening metathesis polymerization, and macrocyclic ring closure reactions. Exposure of a mixture of cis- and trans-internal olefins to ethylene and a chelated ruthenium catalyst results in the selective ethenolysis of only the cis-isomer; this phenomenon was first reported for a Z-selective molybdenum metathesis catalyst. Applications for the resolution of trans-internal olefins have been explored particularly in the isolation of purely trans-olefin containing macrocyclic rings. Additionally, Z-selective ethenolysis is being explored as an important process in the mechanism and behavior of this family of chelated Z-selective catalysts.
Thursday, April 11, 2013 12:20 PM
Organometallic Chemistry (08:30 AM - 12:40 PM)
Location: Morial Convention Center
Room: 335/336
Asymmetric cyclic alkyl amino carbene (CAAC) ruthenium complexes as improved catalysts for ethenolysis
Vanessa M Marx, Mohand Melaimi, Robert H Grubbs, Guy Bertrand
Ethenolysis, the cross metathesis reaction of an internal olefin with ethylene to generate two terminal olefin products, has long been proposed as a method for the rapid production of commodity, value-added products from inexpensive, readily-available seed oil derivatives. For application to commodity chemicals, the TON should be at least 50,000. Prior to this report, such a catalyst system had yet to be developed. Herein, we disclose ruthenium complexes of cyclic alkyl amino carbene (CAAC) ligands bearing asymmetric ortho substitution on the N-aryl ring, as potentially viable catalyst systems for ethenolysis reactions on an industrial scale. In the ethenolysis of methyl oleate, these catalyst systems exhibit TONs > 100,000 and >90% selectivity for terminal olefins, at a loading of 3 ppm. Mechanistic investigations probing this remarkable activity are ongoing, and will also be presented in detail.
Wednesday, April 10, 2013 02:10 PM
Organometallic Chemistry (01:30 PM - 05:40 PM)
Location: Morial Convention Center
Room: 342
Initiator control of the tacticity of ROMP polymers
Robert Howard Grubbs
A variety of metal based ROMP initiators have been developed over the past several years that allow precise control of polymer structure. Recently initiators based on molybdenum and ruthenium that provide control of the double bond geometry of the resulting polymers. Many of these also provide precise control of the tacticity of the backbone. Metallocene catalysts provide good models for this control
Monday, April 8, 2013 10:00 AM
ACS Award in Applied Polymer Science: Symposium in Honor of Mitchell A. Winnik (08:55 AM - 12:00 PM)
Location: Hilton Riverside
Room: Grand Ballroom B
Milder routes to chelated ruthenium complexes for Z-selective metathesis
Lauren E. Rosebrugh, Myles B. Herbert, Vanessa M. Marx, Benjamin K. Keitz, Robert H. Grubbs
A novel method to effect the salt metathesis and C-H activation of ruthenium-based, Z-selective metathesis catalysts containing a chelated N-heterocyclic carbene (NHC) ligand using sodium carboxylates is reported. This method allows for the successful formation of stable chelated species containing a variety of alterations to the NHC ligand that had decomposed under the previous approach. As such, several new, chelated metathesis-active ruthenium complexes are described, including a catalyst system exhibiting >95% Z-selectivity and record TONs (up to 8100) in homodimerization reactions of terminal olefins. Moreover, a catalyst has been synthesized that gives highly cis, highly tactic polymers via ring opening metathesis polymerization of strained, cyclic olefins, marking the first time tactic polymers have been made using a ruthenium-based metathesis catalysts.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 06:00 PM
Organometallic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Richard R Schrock, Ph.D.
Highly Z-selective and chemoselective olefin metathesis of 1,3-dienes: Catalytic studies and exploration of unusual intermediates
Erik M Townsend, Amir H Hoveyda, Richard R Schrock
Molybdenum and tungsten monoaryloxide pyrrolide (MAP) alkylidene complexes catalyze the Z-selective metathesis homocoupling of (E)-1,3-diene substrates to give (E,Z,E) conjugated trienes in high yield. The most effective catalysts highly prefer reaction with the terminal alkene functionality of the dienes, limiting the formation of unwanted side products. Cross metathesis of (E)-1,3-dienes with various olefinic substrates (including vinyl ethers) using the same catalyst systems selectively furnishes products containing the (E,Z) conjugated diene motif. These reactions proceed through unusual alkylidene intermediates, such as vinylalkylidenes and alkoxyalkylidenes. Isolation and characterization of vinylalkylidene and alkoxyalkylidene MAP species are reported along with investigations of their stability and reactivity.
Wednesday, April 10, 2013 12:20 PM
Organometallic Chemistry (08:30 AM - 12:40 PM)
Location: Morial Convention Center
Room: 344
Energetics and dynamics of the low-lying electronic states of constrained polyenes: Implications for infinite polyenes
Ronald L Christensen, Miriam M Enriquez, Nicole L Wagner, Alexandra Y Peacock-Villada, Corina Scriban, Richard R Schrock, Tom Polvka, Harry A Frank, Robert R Birge
Steady-state and ultrafast transient absorption spectra have been recorded for a series of conformationally-constrained, isomerically pure polyenes with 5?23 conjugated double bonds (N). These data and fluorescence spectra of the shorter polyenes reveal the N dependence of the energies of several 1Bu+ and 1Ag? excited states. The 1Bu+ states converge to a common long polyene asymptotic limit of 15,900 100 cm-1. On the other hand, the excited 1Ag? states exhibit a large (~9000 cm-1) energy difference in their long polyene limits, in contrast to the common value previously predicted by theory. EOM-CCSD ab-initio and MNDO-PSDCI semi-empirical MO theories account for the experimental transition energies and intensities. The complex, multistep dynamics of the 11Bu+ ? 21Ag? ? 11Ag? excited state decay pathways as a function of N have been compared with kinetic data from several natural and synthetic carotenoids. Analysis of the lifetimes of the 21Ag? states, using the energy gap law for nonradiative decay, reveals remarkable similarities in the N dependence of the 21Ag? decay kinetics of carotenoid and polyene systems. These data are important for understanding the mechanisms by which carotenoids carry out their roles as light-harvesting molecules and photoprotective agents in biological systems.
Wednesday, April 10, 2013 06:00 PM
PHYS Poster Session (06:00 PM - 09:00 PM)
Location: Morial Convention Center
Room: Hall D
Dehydrogenation and metathesis of alkanes catalyzed by pincer-iridium complexes: Mechanistic studies and catalyst design
Soumik Biswas, Tian Zhou, David Y. Wang, Jason Hackenberg, Agnieszka Nawara-Hultzsch, Richard R. Schrock, Maurice Brookhart, Karsten Krogh-Jespersen, Alan S. Goldman
Pincer-iridium complexes have been reported to catalyze the dehydrogenation of alkanes and these catalyst have been combined with olefin metathesis catalysts to give a tandem catalytic system for alkane metathesis. A major challenge in dehydrogenation, and in alkane metathesis in particular, is to achieve regioselectivity for the terminal position of n-alkane substrates. We report combined computational and experimental studies which have elucidated the factors that determine the regioselectivity of dehydrogenation. In particular, we find that various pincer-iridium complexes will react with n-alkanes to initially give the 1-alkene dihydride. However, in some cases, e.g. (tBuPOCOP)Ir, the barrier to loss of olefin is high and the coordinated 1-alkene re-inserts into an Ir-H bond and ultimately gives internal olefin as a major kinetic product. We also report the rational development of pincer-iridium complexes that are more effective for alkane metathesis than the parent complexes (tBuPOCOP)Ir and (tBuPCP)Ir.
Tuesday, April 9, 2013 04:35 PM
Organometallic Developments in C-H Bond Activation (01:30 PM - 05:00 PM)
Location: Morial Convention Center
Room: 343
Brian K. Kobilka, Ph.D. and Robert J Lefkowitz, Ph.D.
G-protein coupled receptors in virtual screening: Functional fidelity and selectivity
Dahlia R Weiss, SeungKirl Ahn, Maria F Sassano, Andrew C Kruse, Joel Karpiak, Bryan L Roth, Brian K Kobilka, Brian K Shoichet, Robert J Lefkowitz
A prospective, large library virtual screen against an activated 2-adrenergic receptor structure returned potent agonists, essentially to the exclusion of antagonists. In addition, two hits recapitulated the arrestin signaling bias of the co-crystal ligand. This functional fidelity has important implications in drug-design, as the ability to predict ligands with predefined signaling properties is highly desirable. Furthermore, we use virtual screening to predict ligands of pre-defined selectivity. We are searching for ligands with high affinity for dopamine and serotonin receptors, which mediate the therapeutic effects of anti-psychotic medications, and poor affinity for histamine receptor, which mediates serious metabolic side effects. This has led to selective molecules, but also to molecules with high affinity for the "anti-target" histamine receptor, raising important questions about false negatives in docking. Finally, using docking against structures of the M2 and M3 muscarinic receptor subtypes, we have identified novel binding chemotypes, some which show a functional selectivity.
Wednesday, April 10, 2013 02:00 PM
Protein-Ligand Interactions: Insights, New Tools and Applications in Drug Design (01:30 PM - 05:15 PM)
Location: Morial Convention Center
Room: 355
Ei-ichi Negishi, Ph.D.
Widely applicable, catalytic, and asymmetric method for the synthesis of enantiomerically pure (99%) tertiary alkyl-containing 1-alkanols via ZACA-Pd- or Cu-catalyzed cross-coupling
Despite recent major advances in the synthesis of chiral tertiary alkyl-containing compounds including a large number of those with biologically and medicinally important properties, e.g., isoprenoids, deoxypolypropionates, and others, through the development of catalytic asymmetric alkene hydrogenation, epoxidation, carboalumination, and so on, it still remains very challenging to prepare these classes of compounds, especially of feeble chirality, as isomerically pure (>99%) substances. To overcome these problems, a widely applicable, catalytic, and asymmetric method for the synthesis of enantiomerically pure (>99%) various tertiary alkyl-containing 1-alkanols, especially of feeble chirality, via ziconium-catalyzed asymmetric carboalumination of alkenes (ZACA)-Pd- or Cu-catalyzed cross-coupling tandem processes has been developed. The utility of this new synthetic method for the total synthesis of natural productsof biological and medicinal importance will also be discussed.
Sunday, April 7, 2013 08:00 PM
Chemistry of Energy and Food, Asymmetric Reactions and Syntheses, Total Synthesis of Complex Molecules, Biologically-Related Molecules and Processes (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
George A. Olah, Ph.D.
N-difluoromethylation of heterocyclic aromatic compounds using Ruppert-Prakash reagent
G. K. Surya Prakash, Sankarganesh Krishnamoorthy, Aditya Kulkarni, Somesh Kumar Ganesh, George A Olah
Organofluorine compounds possess interesting biological properties such as enhanced metabolic stability, lipophilicity and bioavailability as compared to the nonfluorinated analogs. Difluoromethylated organofluorine compounds are of particular interest since the CF2H group is known to be isosteric and isopolar with the hydroxyl group. N-heterocycles containing CF2H group at the N atom are important drug candidates and agrochemicals. Herein, we report direct difluoromethylation of heterocycles such as imidiazoles, benzimidazoles and indoles using the Ruppert-Prakash reagent (Scheme 1). The reactions were initiated under neutral conditions in presence of catalytic amount of fluoride initiators. The difluoromethylated products were formed in moderate to good yields through CF2carbene insertion in the N-H bond. Inexpensive and commercially available starting materials and ambient reaction conditions are the highlights of this methodology.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Wednesday, April 10, 2013 07:00 PM
New Reactions and Methodology, Heterocycles and Aromatics (07:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall A
Regenerable polyamine bbased solid adsorbents for CO2 capture from the air
Hang Zhang, Alain Goeppert, Miklos Czaun, Robert B May, G. K. Surya Prakash, George A. Olah, S R Narayanan
Fumed silica supported PEI adsorbents are promising candidates for capturing CO2 directly from air. They have high CO2 adsorption capacity and can be regenerated under mild conditions over repeated adsorption/desorption cycles. They are easy to prepare from readily available and inexpensive materials. Being solids these adsorbents avoid many of the problems associated with existing CO2 separation technologies based on liquid amine based scrubbers. Once capture, the CO2 could be recycled to fuels and materials representing essentially a first step in an anthropogenic carbon cycle. More immediate applications include the scrubbing of CO2 from closed environments such as space stations and submarines. Supplying of CO2 free air is also important for the operation of inexpensive and robust iron-air batteries using alkaline electrolytes for large scale energy storage in grid applications.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 02:00 PM
Advances in Energy and Fuels Processes, Systems, Materials and Utilization (02:00 PM - 04:00 PM)
Location: Morial Convention Center
Room: Hall D
Ruthenium-catalyzed hydrogen generation from formic acid
Miklos Czaun, Alain Goeppert, Jenny Yun Yue Zhang, Robert B. May, Michael Sax, G. K. Surya Prakash, George A. Olah
As our rising energy demand is met with limited fossil fuel resources, energy contribution from renewables has to be increased. Due to the intermittent and fluctuating nature of renewable energy and the variations in energy consumption, energy storage has gained increasing attention. Hydrogen can be generated from water, converted to formic acid (FA) using renewable electricity and then used as a fuel in hydrogen-air fuel cells to produce electricity on demand. A carbon neutral energy storage cycle using FA as a storage medium is depicted in Figure 1.
Decomposition of FA to H2 and CO2 in the presence of RuCl3 resulted in the formation of [H4Ru4(CO)12] in situ in high yield indicating that this cluster complex is an active catalyst or its direct precursor. X-ray diffraction, FTIR, 1H, and 13C NMR measurements confirmed the presence of a tetrahedral Ru core with terminal carbonyl and bridging hydride ligands.
On the basis of kinetic and spectroscopic measurements, we suggest a reaction mechanism for the decomposition of FA involving a dissociative rate limiting step.
Tuesday, April 9, 2013 06:00 PM
Organometallic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Development of safe and efficient catalysts for organic transformations
G. K. Surya Prakash, Thomas Mathew, George A. Olah
Development of efficient and recyclable catalysts and their use in various organic transformations with emphasizing the need for reducing the toxic wastes and solvents, thereby conducting the reactions under green conditions become the main focus of recent research in sustainable development. Lewis and metal based catalysts such as gallium tetraflate and related systems were prepared and used for a series of organic reactions in our laboratories. They are found to be stable, often recyclable and require very low catalyst loadings.
Monday, April 8, 2013 02:20 PM
New Reactions and Methodology (01:00 PM - 05:00 PM)
Location: Morial Convention Center
Room: 245
Hydrogen generation by selective decomposition of formic acid in the presence of ruthenium pincer ligand complexes
Jotheeswari Kothandaraman, Miklos Czaun, Alain Goeppert, Robert B. May, G. K. Surya Prakash, George A. Olah
Selective decomposition of formic acid (FA) to H2 and CO2 mixture with no trace of CO has gained increasing attention as the gas stream can be directly used in a H2/air fuel cell without poisoning of the anode catalyst. The commercially available pincer ligand complex, carbonylchlorohydrido[bis(2-(diphenylphosphinoethyl)amino]ruthenium(II)(Ru-MACHOTM) was investigated as a potential catalyst for the decarboxylation of FA.. The in situ formed new hydrido carbonyl species were explored by the spectroscopic methods, such as, FTIR, 1H NMR, 13C NMR, COSY, HMBC, HSQC, 2D NOESY and 31P NMR. In addition, the gas evolved in the course of the reaction was studied by GC and FTIR in order to determine the selectivity of the catalyst. Based on the spectroscopic studies, a plausible mechanism was suggested for the catalytic decomposition of FA to H2 and CO2. The isolation and structural characterization of the intermediate complexes by single crystal X-ray diffraction further supports the mechanism.
Tuesday, April 9, 2013 06:00 PM
Organometallic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Regenerable polyamine bbased solid adsorbents for CO2 capture from the air
Hang Zhang, Alain Goeppert, Miklos Czaun, Robert B May, G. K. Surya Prakash, George A. Olah, S R Narayanan
Fumed silica supported PEI adsorbents are promising candidates for capturing CO2 directly from air. They have high CO2 adsorption capacity and can be regenerated under mild conditions over repeated adsorption/desorption cycles. They are easy to prepare from readily available and inexpensive materials. Being solids these adsorbents avoid many of the problems associated with existing CO2 separation technologies based on liquid amine based scrubbers. Once capture, the CO2 could be recycled to fuels and materials representing essentially a first step in an anthropogenic carbon cycle. More immediate applications include the scrubbing of CO2 from closed environments such as space stations and submarines. Supplying of CO2 free air is also important for the operation of inexpensive and robust iron-air batteries using alkaline electrolytes for large scale energy storage in grid applications.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 02:00 PM
Advances in Energy and Fuels Processes, Systems, Materials and Utilization (02:00 PM - 04:00 PM)
Location: Morial Convention Center
Room: Hall D
Karl Barry Sharpless, Ph.D.
Click chemistry today
Karl Barry Sharpless
The rapid discovery of new and/or desirable function, and that function's equally rapid development into superior chemical products--that's what click chemistry was created to do.
Click chemistry's method is linking up super-smart modules via a few near-quantitative steps; click chemistry's reach and power are a factor of how nearly those linking reactions approach perfection. In 2001 this radical strategy was proposed to the world's chemists on the strength of a few good reactions--and it was not well received! However, click chemistry took off after the discovery (and rediscovery) of two or three near-perfect click reactions. These best reactions' best applications will be presented. The fact of their overnight adoption in nearly all fields of chemistry surprised us along with everyone. In hindsight, until witnessing at least one perfect linkage process in action, unstoppable under terrestrial conditions, how could anyone imagine what it would do for chemical technology.
Sunday, April 7, 2013 03:05 PM
Isbell Award and Gin New Investigator Award Symposium (01:00 PM - 04:50 PM)
Location: New Orleans Downtown Marriott at the Convention Center
Room: Blaine Kern A
Ada Yonath, Ph.D.
From basic science to advanced medicine
Ada Yonath
Ribosomes, the universal cellular machines that translate the genetic code into proteins, are targeted by many antibiotics that paralyze them by binding to their functional sites. Antibiotics binding modes, inhibitory action and synergism pathways have been determined for almost all ribosomal antibiotics. These show the principles of differentiate between patients and pathogens, suggest mechanisms leading to bacterial resistance and paved ways to design advanced therapeutics capable of minimizing antibiotics resistance.
Sunday, April 7, 2013 01:30 PM
Global Health Challenges: The Need for New Anti-Infectives and Antivirals (01:30 PM - 05:10 PM)
Location: Morial Convention Center
Room: R08/R09
Ahmed Zewail, Ph.D.
Single-nanoparticle switching dynamics visualized by 4D electron microscopy
Renske M van der Veen, Sang Tae Park, Oh-Hoon Kwon, Antoine Tissot, Andreas Hauser, Ahmed Zewail
4D electron microscopy enables simultaneous real- and reciprocal-space imaging of nanostructured materials with unprecedented spatio-temporal resolutions. Here we apply it to visualize the photoswitching dynamics of single spin-crossover nanocrystals. The nanoparticles are largely influenced by the frictional and thermal characteristics of the interface, which are unique on the level of a single nanoparticle, while averaged out in conventional studies on nanoparticles ensembles. Theoretical modeling reveals the non-equilibrium thermoswitching pathways in the phase diagram of the spin transition.
Tuesday, April 9, 2013 02:30 PM
Ultrafast Excited-State Dynamics in Transition Metal-Containing Systems (01:30 PM - 04:30 PM)
Location: Morial Convention Center
Room: 346
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Nobel laureates and their research teams at American Chemical Society meetingPublic release date: 7-Apr-2013 [ | E-mail | Share ]
Contact: Michael Bernstein
m_bernstein@acs.org
504-670-4707 (New Orleans Press Center, April 5-10)
202-872-6042
Michael Woods
m_woods@acs.org
504-670-4707 (New Orleans Press Center, April 5-10)
202-872-6293
American Chemical Society
NEW ORLEANS, April 7, 2013 At least nine Nobel laureates have research that will be presented here this week during the 245th National Meeting & Exposition of the American Chemical Society, the world's largest scientific society. Research from the laureates' teams will be among almost 12,000 presentations during the event, expected to attract more than 14,000 scientists and others.
They are Robert H. Grubbs, Ph.D.; Richard R Schrock, Ph.D.; Brian K. Kobilka, Ph.D.; Robert J. Lefkowitz, Ph.D.; Ei-ichi Negishi, Ph.D.; George A. Olah, Ph.D.; Karl Barry Sharpless, Ph.D.; Ada Yonath, Ph.D.; and Ahmed Zewail, Ph.D.
Grubbs, who is with the California Institute of Technology, and Schrock, who is with the Massachusetts Institute of Technology, shared the 2005 Nobel Prize in Chemistry with Yves Chauvin for the development of the "metathesis method." That new way to make plastics, medicines and other products was an advance in "green chemistry," because it reduces the production of potentially hazardous waste compared with other approaches.
Kobilka, who is with the Stanford University School of Medicine, and Lefkowitz, who is with the Howard Hughes Medical Institute and the Duke University Medical Center, shared the 2012 Nobel Prize in Chemistry "for studies of G-protein-coupled receptors." Their research showed how these receptors work to sense the environment of the cell.
Negishi, the Herbert C. Brown Distinguished Professor of Organic Chemistry at Purdue University, shared the 2010 Nobel Prize in Chemistry "for palladium-catalyzed cross couplings in organic synthesis." This helped develop techniques to synthesize complex carbon molecules that have had an enormous impact on the manufacture of medicines and other products.
Olah, who is with the University of Southern California, won the 1994 Nobel Prize in Chemistry for work on "carbocations," charged molecules that were considered too unstable to study. Olah developed a way to isolate these molecules, which was useful in the oil and coal industries.
Sharpless, who is with The Scripps Research Institute, won the 2001 Nobel Prize in Chemistry "for his work on chirally catalysed oxidation reactions." Sharpless worked on ways to synthesize just one of a set of "mirror" image molecules. This work led to advances in drug development.
Yonath, who is with the Weizmann Institute of Science, shared the 2009 Nobel Prize in Chemistry with Venkatraman Ramakrishnan and Thomas A. Steitz "for studies of the structure and function of the ribosome." They showed how the ribosome works at an atomic level to translate the information in DNA into proteins for life.
Zewail, who is with the California Institute of Technology, won the 1999 Nobel Prize in Chemistry "for his studies of the transition states of chemical reactions using femtosecond spectroscopy." Zewail showed that it was possible to watch chemical reactions in "slow-motion" using lasers to see how the molecules move.
Further information on the presentations follows.
###
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To automatically receive news releases from the American Chemical Society, contact newsroom@acs.org.
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Abstracts
Robert H. Grubbs, Ph.D.
Milder routes to chelated ruthenium complexes for Z-selective metathesis
Lauren E. Rosebrugh, Myles B. Herbert, Vanessa M. Marx, Benjamin K. Keitz, Robert H. Grubbs
A novel method to effect the salt metathesis and C-H activation of ruthenium-based, Z-selective metathesis catalysts containing a chelated N-heterocyclic carbene (NHC) ligand using sodium carboxylates is reported. This method allows for the successful formation of stable chelated species containing a variety of alterations to the NHC ligand that had decomposed under the previous approach. As such, several new, chelated metathesis-active ruthenium complexes are described, including a catalyst system exhibiting >95% Z-selectivity and record TONs (up to 8100) in homodimerization reactions of terminal olefins. Moreover, a catalyst has been synthesized that gives highly cis, highly tactic polymers via ring opening metathesis polymerization of strained, cyclic olefins, marking the first time tactic polymers have been made using a ruthenium-based metathesis catalysts.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 06:00 PM
Organometallic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Methods for the cleavage of C-O bonds
Robert H Grubbs
The conversion of biorenewable resources into chemical will require the efficient removal of excess functionality. The C-O bonds in a variety of highly oxidized biomaterials can be difficult to convert into compounds of lower oxidation state. While screening a variety of catalysts, new methods for the efficient cleavage of aromatic and aliphatic C-O linkages have been developed.
Tuesday, April 9, 2013 11:25 AM
ACS Award in Pure Chemistry: Symposium in Honor of Theodor Agapie (08:30 AM - 12:30 PM)
Location: Morial Convention Center
Room: 345
Design of selective catalysts for olefin metathesis
Robert H Grubbs
Olefin metathesis has become a tool for the synthesis of a variety of molecules and materials. In the past several years the efficiency and selectivity of the catalysts have greatly improved. Catalysts are now available that allow the precise control of the double bond geometrh of the product double bond. Organometallic synthesis and computational results have resulted in new levels of selectivity and efficiency.
Tuesday, April 9, 2013 08:30 AM
Gabor A. Somorjai Award for Creative Research in Catalysis: Symposium in Honor of Tobin J. Marks (08:25 AM - 11:45 AM)
Location: Morial Convention Center
Room: 346
Design and synthesis of new ruthenium-based catalysts for improved activity in challenging Z-selective metathesis reactions
Brendan L. Quigley, Vanessa M. Marx, Robert H. Grubbs
Our group has recently reported a series of ruthenium-based metathesis catalysts that contain a chelating NHC. These catalysts demonstrate high Z-selectivity in a variety of metathesis reactions including cross metathesis, ring-closing metathesis and ring-opening metathesis polymerization. However, the substrate scope has so far been limited to relatively unhindered olefins. In order to probe the origin of this selectivity, a series of catalysts with N-heterocyclic carbene (NHC) substituents of varying steric bulk were prepared. These catalysts were subsequently examined for improved reactivity in a range of olefins that contain bulky substituents. In addition, the mechanism of the C-H-activation step in the synthesis of such catalysts was probed through variation of the sterics and electronics of both the adamantyl and aryl NHC substituents.
Tuesday, April 9, 2013 08:00 PM
Graphene Chemistry, Metal-Mediated Reactions and Syntheses, Molecular Recognition and Self-Assembly, Physical Organic Chemistry, Materials Devices and Switches (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Transition-metal-free reductive cleavage of lignin-related C-O bonds by an activated silane
Anton A Toutov, Alexey Fedorov, Nicholas Swisher, Robert H. Grubbs
Reported herein is a transition-metal-free protocol for the efficient reductive cleavage of diaryl and aryl alkyl ethers. The combination of triethylsilane with simple bases forms an unusually powerful reductive couple that affords regioselective rupture of lignin- and coal-related C-O bonds in aromatic ethers. Interestingly, this is accompanied by ortho-directed C-H silylation that be-comes preferred with certain bases and temperature re-gimes. However, the tuning of selectivity proved possible thus enabling the development of a practical method for the title transformation, as illustrated by the reduction of lignin model compounds to their corresponding phenolic and aromatic constituents.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 02:00 PM
Advances in Energy and Fuels Processes, Systems, Materials and Utilization (02:00 PM - 04:00 PM)
Location: Morial Convention Center
Room: Hall D
Preparation of rapidly initiating ruthenium based olefin metathesis catalysts
Alexandra H. Sullivan, Benjamin K. Keitz, Robert H. Grubbs
Z-selective olefin metathesis ruthenium catalysts are highly sought after, due to their wide applications in both pharmaceuticals and materials science. A crucial step towards the preparation of rapidly initiating, Z-selective, olefin metathesis catalysts was found to be the addition of sodium pivalate to phosphonium alkyidene catalyst 1, resulting in the formation of the C-H activated complex 2 after two days of heating. Preparation of 2, a close analog to the target catalyst 4, promises that future synthesis of 4 should be facile.
Sunday, April 7, 2013 06:00 PM
Undergraduate Research at the Frontiers of Inorganic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Catalyst-controlled anti-Markovnikov palladium-catalyzed oxidation of aliphatic olefins
Zachary K Wickens, Bill Morandi, Robert H Grubbs
The Wacker oxidation, or the palladium-catalyzed oxidation of olefins to carbonyls, is one of the most well-known palladium-catalyzed reactions and has extensive synthetic applications. Traditional Wacker oxidation conditions obey Markonikov's rule and thus yield methyl ketones with high selectivity from the majority of terminal olefins. A Wacker oxidation capable of producing aldehydes from unbiased terminal olefins would be synthetically useful and is a long-standing challenge in palladium oxidation chemistry. A palladium-catalyzed oxidation system capable of providing synthetic access to aldehydes from unbiased terminal olefins will be discussed.
Tuesday, April 9, 2013 08:20 AM
Metal Mediated Reactions (08:00 AM - 12:00 PM)
Location: Morial Convention Center
Room: 256/257
Synthetic applications of Z-selective ruthenium-based olefin metathesis catalysts
Vanessa M Marx, Myles B Herbert, Benjamin K Keitz, Robert H Grubbs
The first report of Z-selective macrocyclizations using a ruthenium-based metathesis catalyst is described. Selectivity for Z-macrocycles is consistently high for a diverse set of substrates bearing different functional groups and comprised of various ring sizes. The same catalyst was employed for the Z-selective ethenolysis of a mixture of E and Z macrocycles, providing the pure E-isomers. These methodologies were successfully applied to the construction of several olfactory macrocycles, as well as the backbone of cytotoxic alkaloid natural products. Conditions were also optimized for a series of challenging cross metathesis reactions using the same catalyst system, and subsequently exploited in the synthesis of a family of lepidopteran insect pheromones. A detailed mechanistic study probing the origin of the stereoselectivity in these challenging transformations is currently underway, and will also be discussed in detail.
Monday, April 8, 2013 01:00 PM
Metal Mediated Reactions (01:00 PM - 05:00 PM)
Location: Morial Convention Center
Room: 256/257
Functionalized corroles as diatherapeutic, multi-modal imaging agents
Melanie A Pribisko, Punnajit Lim, John Termini, Robert H Grubbs, Joshua H Palmer, Harry B Gray
Recent synthetic advancements have made it possible to produce substituted derivatives of meso-5,10,15-(tris)pentafluorophenylcorrole (H3tpfc) in reasonable yields. We present the scalable syntheses of new H3tpfc derivatives, and a few of their metal complexes, through nucleophilic aromatic substitution on the pentafluorophenyl substituents. These complexes have potential applications both as imaging agents and chemotherapeutic drugs.
Sunday, April 7, 2013 06:00 PM
Metals in Medicine: Diagnostic and Therapeutic Applications (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
ROMP with stable initiators
Robert Howard Grubbs
Tim Swager introduced the name ROMP for ring opening metathesis polymerization when he was a a graduate student. Since that time, many new initiators for the ROMP of strained olefins have been developed. Recent advances now allow polymers with precise chain length and composition to be prepared. The synthesis of brush polymers demonstrates the control of polymeric structures that are now possible with modern initiators.
Tuesday, April 9, 2013 02:50 PM
ACS Award for Creative Invention: Symposium in Honor of Timothy M. Swager (01:15 PM - 05:30 PM)
Location: Hilton Riverside
Room: HEC C
Z-selective ethenolysis using a ruthenium catalyst: Applications and mechanistic implications
Myles B Herbert, Hiroshi Miyazaki, Peng Liu, Vanessa M Marx, Benjamin K. Keitz, Robert H Grubbs
Unique ethenolysis reactivity has been uncovered with a new family of chelated ruthenium alkylidene catalysts that have exhibited high Z-selectivity in cross metathesis, ring opening metathesis polymerization, and macrocyclic ring closure reactions. Exposure of a mixture of cis- and trans-internal olefins to ethylene and a chelated ruthenium catalyst results in the selective ethenolysis of only the cis-isomer; this phenomenon was first reported for a Z-selective molybdenum metathesis catalyst. Applications for the resolution of trans-internal olefins have been explored particularly in the isolation of purely trans-olefin containing macrocyclic rings. Additionally, Z-selective ethenolysis is being explored as an important process in the mechanism and behavior of this family of chelated Z-selective catalysts.
Thursday, April 11, 2013 12:20 PM
Organometallic Chemistry (08:30 AM - 12:40 PM)
Location: Morial Convention Center
Room: 335/336
Asymmetric cyclic alkyl amino carbene (CAAC) ruthenium complexes as improved catalysts for ethenolysis
Vanessa M Marx, Mohand Melaimi, Robert H Grubbs, Guy Bertrand
Ethenolysis, the cross metathesis reaction of an internal olefin with ethylene to generate two terminal olefin products, has long been proposed as a method for the rapid production of commodity, value-added products from inexpensive, readily-available seed oil derivatives. For application to commodity chemicals, the TON should be at least 50,000. Prior to this report, such a catalyst system had yet to be developed. Herein, we disclose ruthenium complexes of cyclic alkyl amino carbene (CAAC) ligands bearing asymmetric ortho substitution on the N-aryl ring, as potentially viable catalyst systems for ethenolysis reactions on an industrial scale. In the ethenolysis of methyl oleate, these catalyst systems exhibit TONs > 100,000 and >90% selectivity for terminal olefins, at a loading of 3 ppm. Mechanistic investigations probing this remarkable activity are ongoing, and will also be presented in detail.
Wednesday, April 10, 2013 02:10 PM
Organometallic Chemistry (01:30 PM - 05:40 PM)
Location: Morial Convention Center
Room: 342
Initiator control of the tacticity of ROMP polymers
Robert Howard Grubbs
A variety of metal based ROMP initiators have been developed over the past several years that allow precise control of polymer structure. Recently initiators based on molybdenum and ruthenium that provide control of the double bond geometry of the resulting polymers. Many of these also provide precise control of the tacticity of the backbone. Metallocene catalysts provide good models for this control
Monday, April 8, 2013 10:00 AM
ACS Award in Applied Polymer Science: Symposium in Honor of Mitchell A. Winnik (08:55 AM - 12:00 PM)
Location: Hilton Riverside
Room: Grand Ballroom B
Milder routes to chelated ruthenium complexes for Z-selective metathesis
Lauren E. Rosebrugh, Myles B. Herbert, Vanessa M. Marx, Benjamin K. Keitz, Robert H. Grubbs
A novel method to effect the salt metathesis and C-H activation of ruthenium-based, Z-selective metathesis catalysts containing a chelated N-heterocyclic carbene (NHC) ligand using sodium carboxylates is reported. This method allows for the successful formation of stable chelated species containing a variety of alterations to the NHC ligand that had decomposed under the previous approach. As such, several new, chelated metathesis-active ruthenium complexes are described, including a catalyst system exhibiting >95% Z-selectivity and record TONs (up to 8100) in homodimerization reactions of terminal olefins. Moreover, a catalyst has been synthesized that gives highly cis, highly tactic polymers via ring opening metathesis polymerization of strained, cyclic olefins, marking the first time tactic polymers have been made using a ruthenium-based metathesis catalysts.
Monday, April 8, 2013 08:00 PM
Sci-Mix (08:00 PM - 10:00 PM)
Location: Morial Convention Center
Room: Hall D
Tuesday, April 9, 2013 06:00 PM
Organometallic Chemistry (06:00 PM - 08:00 PM)
Location: Morial Convention Center
Room: Hall D
Richard R Schrock, Ph.D.
Highly Z-selective and chemoselective olefin metathesis of 1,3-dienes: Catalytic studies and exploration of unusual intermediates
Erik M Townsend, Amir H Hoveyda, Richard R Schrock
Molybdenum and tungsten monoaryloxide pyrrolide (MAP) alkylidene complexes catalyze the Z-selective metathesis homocoupling of (E)-1,3-diene substrates to give (E,Z,E) conjugated trienes in high yield. The most effective catalysts highly prefer reaction with the terminal alkene functionality of the dienes, limiting the formation of unwanted side products. Cross metathesis of (E)-1,3-dienes with various olefinic substrates (including vinyl ethers) using the same catalyst systems selectively furnishes products containing the (E,Z) conjugated diene motif. These reactions proceed through unusual alkylidene intermediates, such as vinylalkylidenes and alkoxyalkylidenes. Isolation and characterization of vinylalkylidene and alkoxyalkylidene MAP species are reported along with investigations of their stability and reactivity.
Wednesday, April 10, 2013 12:20 PM
Organometallic Chemistry (08:30 AM - 12:40 PM)
Location: Morial Convention Center
Room: 344
Energetics and dynamics of the low-lying electronic states of constrained polyenes: Implications for infinite polyenes
Ronald L Christensen, Miriam M Enriquez, Nicole L Wagner, Alexandra Y Peacock-Villada, Corina Scriban, Richard R Schrock, Tom Polvka, Harry A F
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Public release date: 10-Apr-2013
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