Oil and water: An icy interaction when oil chains are short, but steamy when chains are long

[ Back to EurekAlert! ] Public release date: 3-Dec-2012
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Contact: Elizabeth K. Gardner
ekgardner@purdue.edu
765-494-2081
Purdue University

WEST LAFAYETTE, Ind. Water transforms into a previously unknown structure in between a liquid and a vapor when in contact with alcohol molecules containing long oily chains, according to Purdue University researchers. However, around short oily chains water is more icelike.

Water plays a huge role in biological processes, from protein folding to membrane formation, and it could be that this transformation is useful in a way not yet understood, said Dor Ben-Amotz, the professor of chemistry who led the research.

Ben-Amotz's research team found that as they examined alcohols with increasingly long carbon chains, the transformation occurred at lower and lower temperatures.

When in contact with a chain seven carbon atoms long, the water molecules became much looser and more vaporlike at a temperature of 140 degrees Fahrenheit, which is about halfway between the melting and boiling points.

"For oils with chains longer than four carbons, or about one nanometer in length, we saw the water transform into a completely new structure as the temperature rose," Ben-Amotz said. "If the trend we saw holds true, then this transformation could be happening at body temperature around important physiological molecules like proteins and phospholipids.Water responds very sensitively in its structure to small changes, he said.

"Water's versatility is what makes it so special," he said. "For instance, the surfaces of proteins have both oily and charged regions; and water changes itself to accommodate these very different components and everything in between. We are learning more about exactly how it does this."

The researchers found that water molecules interacting with the oil always formed a more ordered, icelike structure at lower temperatures, while the bulk of the water remained liquid. This ice-like structure would melt away as the temperatures increased and in longer molecules a new structure would appear, he said.

A paper detailing the National Science Foundation-funded work is published in the current issue of Nature and is also highlighted in a news and views article in the same issue. In addition to Ben-Amotz, co-authors include Purdue graduate student Joel Davis and postdoctoral fellows Kamil Gierszal and Ping Wang.

The team's observations add to a more than 70-year debate over the interaction of oil and water, with some studies suggesting that water forms little icebergs around the oil molecules, while others point to a more disordered, vaporlike water structure.

"This question was really up for grabs until we introduced an experimental method that could see these subtle changes in water structure," Ben-Amotz said. "Surprisingly, we found that both sides are right, and it depends on the size of the oil."

The challenge of the experiment was that the team needed to see the very small number of water molecules that are in contact with the oil chains in the presence of a very large number of other water molecules.

The team combined Raman scattering and multivariate curve resolution to create an analysis method capable of managing an unprecedented signal-to-noise ratio of 10,000-to-1.

"Most people never take a spectrum with a signal-to-noise ratio greater than 100-to-1, but if we performed this experiment that way we wouldn't see anything," Ben-Amotz said. "We needed to have a higher signal-to-noise ratio because we were looking for a needle in a mountain-sized haystack."

Raman scattering involves shooting a beam of light containing photons into a sample. As the photons hit molecules within the sample, they lose or gain energy. Such measurements create a spectrum of peaks that reveal the vibrational motions of the molecules present in the sample. Shifts in the peaks' shapes can show changes in the strength of bonds between water molecules and whether the molecules are becoming more or less ordered.

"With Raman scattering the bulk of the water creates a mountainous peak in the spectrum that buries everything else," Ben-Amotz said. "Multivariate curve resolution lets us see small changes in water structure under that mountain. As is often the case in science, the key was combining two already established techniques in a new way."

Davis said the team next plans to explore the effects of changes in pH and ionic charges on this transformation with the goal of making the experiments more relevant to proteins and biological systems.

"We are trying to better understand the driving f orces of the behavior of proteins and cell membranes that are critical to our health," he said. "The role of water is an important piece of the puzzle."

###

Writer: Elizabeth K. Gardner, 765-494-2081, ekgardner@purdue.edu

Sources: Dor Ben-Amotz, 765-494-5256, bendor@purdue.edu

Joel Davis, jgdavis@purdue.edu

Related website: Be-Amotz research group


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?


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.


[ Back to EurekAlert! ] Public release date: 3-Dec-2012
[ | E-mail | Share Share ]

Contact: Elizabeth K. Gardner
ekgardner@purdue.edu
765-494-2081
Purdue University

WEST LAFAYETTE, Ind. Water transforms into a previously unknown structure in between a liquid and a vapor when in contact with alcohol molecules containing long oily chains, according to Purdue University researchers. However, around short oily chains water is more icelike.

Water plays a huge role in biological processes, from protein folding to membrane formation, and it could be that this transformation is useful in a way not yet understood, said Dor Ben-Amotz, the professor of chemistry who led the research.

Ben-Amotz's research team found that as they examined alcohols with increasingly long carbon chains, the transformation occurred at lower and lower temperatures.

When in contact with a chain seven carbon atoms long, the water molecules became much looser and more vaporlike at a temperature of 140 degrees Fahrenheit, which is about halfway between the melting and boiling points.

"For oils with chains longer than four carbons, or about one nanometer in length, we saw the water transform into a completely new structure as the temperature rose," Ben-Amotz said. "If the trend we saw holds true, then this transformation could be happening at body temperature around important physiological molecules like proteins and phospholipids.Water responds very sensitively in its structure to small changes, he said.

"Water's versatility is what makes it so special," he said. "For instance, the surfaces of proteins have both oily and charged regions; and water changes itself to accommodate these very different components and everything in between. We are learning more about exactly how it does this."

The researchers found that water molecules interacting with the oil always formed a more ordered, icelike structure at lower temperatures, while the bulk of the water remained liquid. This ice-like structure would melt away as the temperatures increased and in longer molecules a new structure would appear, he said.

A paper detailing the National Science Foundation-funded work is published in the current issue of Nature and is also highlighted in a news and views article in the same issue. In addition to Ben-Amotz, co-authors include Purdue graduate student Joel Davis and postdoctoral fellows Kamil Gierszal and Ping Wang.

The team's observations add to a more than 70-year debate over the interaction of oil and water, with some studies suggesting that water forms little icebergs around the oil molecules, while others point to a more disordered, vaporlike water structure.

"This question was really up for grabs until we introduced an experimental method that could see these subtle changes in water structure," Ben-Amotz said. "Surprisingly, we found that both sides are right, and it depends on the size of the oil."

The challenge of the experiment was that the team needed to see the very small number of water molecules that are in contact with the oil chains in the presence of a very large number of other water molecules.

The team combined Raman scattering and multivariate curve resolution to create an analysis method capable of managing an unprecedented signal-to-noise ratio of 10,000-to-1.

"Most people never take a spectrum with a signal-to-noise ratio greater than 100-to-1, but if we performed this experiment that way we wouldn't see anything," Ben-Amotz said. "We needed to have a higher signal-to-noise ratio because we were looking for a needle in a mountain-sized haystack."

Raman scattering involves shooting a beam of light containing photons into a sample. As the photons hit molecules within the sample, they lose or gain energy. Such measurements create a spectrum of peaks that reveal the vibrational motions of the molecules present in the sample. Shifts in the peaks' shapes can show changes in the strength of bonds between water molecules and whether the molecules are becoming more or less ordered.

"With Raman scattering the bulk of the water creates a mountainous peak in the spectrum that buries everything else," Ben-Amotz said. "Multivariate curve resolution lets us see small changes in water structure under that mountain. As is often the case in science, the key was combining two already established techniques in a new way."

Davis said the team next plans to explore the effects of changes in pH and ionic charges on this transformation with the goal of making the experiments more relevant to proteins and biological systems.

"We are trying to better understand the driving f orces of the behavior of proteins and cell membranes that are critical to our health," he said. "The role of water is an important piece of the puzzle."

###

Writer: Elizabeth K. Gardner, 765-494-2081, ekgardner@purdue.edu

Sources: Dor Ben-Amotz, 765-494-5256, bendor@purdue.edu

Joel Davis, jgdavis@purdue.edu

Related website: Be-Amotz research group


[ Back to EurekAlert! ] [ | E-mail | Share 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.


Source: http://www.eurekalert.org/pub_releases/2012-12/pu-oaw120312.php

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Cold, mold loom as hazards in Sandy disaster zones

NEW YORK (AP) ? A month after Sandy's floodwaters swept up his block, punched a hole in his foundation and drowned his furnace, John Frawley still has no electricity or heat in his dilapidated home on the Rockaway seashore.

The 57-year-old, who also lost his car and all his winter clothes in the flood, now spends his nights shivering in a pair of donated snow pants, worrying whether the cold might make his chronic heart condition worse.

"I've been coughing like crazy," said Frawley, a former commercial fisherman disabled by a spine injury. He said his family doesn't have the money to pay for even basic repairs. So far, he has avoided going to a shelter, saying he'd rather sleep in his own home.

"But I'm telling you, I can't stay here much longer," he said.

City officials estimate at least 12,000 New Yorkers are trying to survive in unheated, flood-damaged homes, despite warnings that dropping temperatures could pose a health risk.

The chill is only one of the potential environmental hazards that experts say might endanger people trying to resume their lives in the vast New York and New Jersey disaster zone.

Uncounted numbers of families have returned to coastal homes that are contaminated with mold, which can aggravate allergies and leave people perpetually wheezing. Others have been sleeping in houses filled with construction dust, as workers have ripped out walls and flooring. That dust can sometimes trigger asthma.

But it is the approaching winter that has some public health officials worried most. Nighttime temperatures have been around freezing and stand to drop in the coming weeks.

New York City's health department said the number of people visiting hospital emergency rooms for cold-related problems has already doubled this November, compared with previous years. Those statistics are likely only the proverbial tip of the iceberg.

Mortality rates for the elderly and chronically ill rise when people live for extended periods in unheated apartments, even when the temperature is still above freezing, said the city's health commissioner, Dr. Thomas Farley.

"As the temperatures get colder, the risk increases," he said. "It is especially risky for the elderly. I really want to encourage people, if they don't have heat in their apartment, to look elsewhere."

Since the storm, the health department has been sending National Guard troops door to door, trying to persuade people to leave cold homes until their heating systems are fixed. The city is also carrying out a plan to spend hundreds of millions of dollars helping residents make emergency repairs needed to restore their heat and hot water.

Convincing people that they could be endangering themselves by staying until that work is complete, though, isn't always easy.

For weeks, Eddie Saman, 57, slept on sheets of plywood in the frigid, ruined shell of his flooded Staten Island bungalow. He stayed even as the house filled up with a disgusting mold that agitated his asthma so much that it sent him to the emergency room.

Volunteers eventually helped clean the place up somewhat and got Saman a mattress. But on Sunday the wood-burning stove he had been using for heat caught fire.

Melting materials in the ceiling burned his cheek. A neighbor who dashed into the house to look for Saman also suffered burns. The interior of the house ? what was left of it after the flood ? was destroyed.

Two days later, another fire broke out in a flood-damaged house across the street, also occupied by a resident trying to keep warm without a working furnace.

Asked why he hadn't sought lodging elsewhere, Saman said he didn't have family in the region and was rattled by the one night he spent in an emergency shelter. He said it seemed more populated by homeless drug addicts than displaced families.

"That place was not for me," he said.

The Federal Emergency Management Agency offered to pay for a hotel, but Saman said he stopped looking because every inn within 100 miles of the city seemed to be booked solid through December.

Saman's case may be extreme, but experts said it isn't unusual for people to hurry back to homes not ready for habitation.

After Hurricane Katrina, medical researchers in New Orleans documented a rise in respiratory ailments among people living in neighborhoods where buildings were being repaired.

The issue wasn't just mold, which can cause problems for years if it isn't mediated properly, said Felicia Rabito, an epidemiologist at Tulane University's School of Public Health and Tropical Medicine. There was simply so much work being done, families spent their days breathing the fine particles of sanded wood and drywall.

People complained of something that became known as the "Katrina cough," and while it subsided once the dust settled, researchers later found high lead levels in some neighborhoods due to work crews ignoring standards for lead paint removal.

A group of occupational health experts in New York City, including doctors who run programs for people sickened by World Trade Center dust after 9/11, warned last week that workers cleaning up Sandy's wreckage need to protect themselves by suppressing dust with water, wearing masks and being aware of potential asbestos exposure.

"There are clearly sites that you don't want children at ... and it is very challenging for homeowners to know whether it is safe to go home," said Dr. Maida Galvez, a pediatrician and environmental health expert at The Mount Sinai Hospital who is part of a team evaluating hazards in the disaster zone.

U.S. Rep. Jerrold Nadler has urged FEMA and the Environmental Protection Agency to develop a testing program that could give residents an indication of whether their homes were free of mold, sewage and other hazardous substances.

Farley, New York City's health commissioner, said people entering rooms contaminated by floodwater should wear rubber boots and gloves, and exercise care in cleanup. The hazard posed by spilled sewage is a short-term one and experts say the disease-causing bacteria found in it can be wiped out with a good cleaning. But they say anything absorbent that touched tainted water, like curtains or rugs, should be thrown out.

As for the bitter cold, there was no test needed to tell John Frawley that his home is no place to be spending frigid autumn nights.

"A couple of days ago, I was shivering so badly, I just couldn't stop," he said.

Yet with winter nearly here, he still had no plan for getting his heat working again or his ruined electrical system restored, although he also has passed up some of the programs designed to help people like him.

And he has no intention of heading to a shelter.

Source: http://news.yahoo.com/cold-mold-loom-hazards-sandy-disaster-zones-164536193.html

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Fed trio spars on low-rate policy ahead of December meeting

CHICAGO (Reuters) - Three top Federal Reserve officials on Saturday offered sharply different takes on the U.S. central bank's unprecedented efforts to push down long-term borrowing costs, highlighting what may be some key themes at the Fed's upcoming policy-setting meeting.

Charles Evans, the dovish president of the Chicago Fed, made no bones about his view that more policy accommodation is needed, repeating his call for keeping rates low until unemployment falls to at least 6.5 percent, as long as inflation does not threaten to rise above 2.5 percent.

"We are in a period where having low policy rates for a very long time would be helpful," he said at panel at the University of Chicago sponsored by the university's Becker Friedman Institute for Research

Also on the panel, which was held ahead of the Fed's December 11-12 closed-door policy meeting, were Charles Plosser, the hawkish president of the Philadelphia Fed, and Minneapolis Fed President Narayana Kocherlakota -- a former advocate of policy tightening who in September began calling for further easing.

Showing a series of slides to a mostly student audience, Evans argued that high joblessness now means that even with interest rates kept low for years, inflation is unlikely to rise above 2.3 percent.

But Plosser, seated between Evans and Kocherlakota on the panel, said he is worried that the continuing high unemployment rate may mean the Fed's policies are not working as expected.

With unemployment at historically high levels - it ticked up to 7.9 percent in October -- and inflation low, policymakers could "walk away from that evidence and say, either we haven't done enough, or we haven't got the right model of how the transmission mechanism is working," Plosser said.

He also expressed concern about reversing the Fed's longstanding low-rate policy. Although the Fed has the tools to raise rates, he said, "History suggests that it's always been easier for the Fed to lower rates than to raise them."

The Fed has kept short-term rates almost at zero percent since December 2008 and has bought some $2.5 trillion in bonds to drive down longer-term borrowing costs and boost the recovery from recession.

It has also said it expects to keep rates low until at least mid-2015, as it works to bring down too-high unemployment.

Since September the Fed has been buying a total of $85 billion in long-term securities each month to help push down borrowing costs. Part of that is the program known as Operation Twist, in which the Fed buys $45 billion in longer-term Treasuries and sells the same amount of shorter-term ones.

Twist expires at year end, and officials will need to decide at their December meeting whether to ramp up the quantitative easing program, dubbed QE3, to make up for the shortfall.

Under QE3, the Fed has said it would buy $40 billion in mortgage-backed securities per month until the outlook for the labor market improves substantially.

THE MERITS OF THRESHOLDS

The three policymakers on Saturday gave no hint as to their views on what the Fed should do, although Evans has previously advocated for keeping asset purchases at a monthly rate of $85 billion, while Plosser has said he does not view Twist's expiration necessarily as tightening.

Instead, the three debated the merits of adopting thresholds for inflation and unemployment as guideposts for policy. Fed officials have been discussing such plans for months, although few economists believe they will come to a decision in December.

"I'm terribly worried that we are asking too much of policy here," Plosser said, of the value of setting thresholds. "I'm worried that the strategies are going to sow more confusion than clarity."

Kocherlakota, like Evans, reiterated his support for a threshold-based policy. The Minneapolis Fed chief -- who, like Plosser, did his graduate training in economics at the University of Chicago -- repeated his call for the Fed to keep rates low until the jobless rate reaches 5.5 percent or even below, as long as inflation does not threaten to rise above 2.25 percent.

Such a promise is "credible," he said, because it shows investors the Fed will not sacrifice price stability in order to reduce unemployment. The Fed in January set an inflation target for the first time, aiming at 2 percent inflation.

"I think we are falling short on both metrics, more so on employment than inflation," he said, referring to the Fed's mandates to keep prices stable and to maximize employment.

Evans also emphasized his "inflation safeguard" of 2.5 percent, saying that if he is wrong and easier monetary policy is not the answer to unemployment, inflation will rise, and the Fed can then take its foot off the gas pedal.

Plosser said he was "dubious." The public could easily misinterpret an inflation "threshold" as a target that conflicts with the Fed's newly adopted 2 percent inflation goal, he said.

"I am worried that the commitment we have is not credible, or is not well understood, and we won't get the effects that these models tell us," Plosser said.

(Reporting by Ann Saphir; Editing by Leslie Adler)

Source: http://news.yahoo.com/fed-trio-spars-low-rate-policy-ahead-december-005635069--business.html

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Recreation-and-Sports:Swimming Articles from EzineArticles.com ...

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Source: http://pruitt5370.typepad.com/blog/2012/12/recreation-and-sportsswimming-articles-from-ezinearticlescom.html

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North Korea Rocket Launch: Pyongyang Vows To Test Long-Range Rocket Soon

SEOUL, South Korea -- North Korea announced Saturday that it would attempt to launch a long-range rocket in mid-December, a defiant move just eight months after a failed April bid was widely condemned as a violation of a U.N. ban against developing its nuclear and missile programs.

The launch, set for Dec. 10 to 22, is likely to heighten already strained tensions with Washington and Seoul as the United States prepares for Barack Obama's second term as U.S. president and South Korea holds its own presidential election on Dec. 19.

This would be North Korea's second launch attempt under leader Kim Jong Un, who took power following his father Kim Jong Il's death nearly a year ago. The announcement by North Korea's space agency followed speculation overseas about stepped-up activity at North Korea's west coast launch pad captured in satellite imagery.

A spokesman for North Korea's Korean Committee for Space Technology said scientists have "analyzed the mistakes" made in the failed April launch and improved the precision of its Unha rocket and Kwangmyongsong satellite, according to the official Korean Central News Agency.

KCNA said the launch was a request of late leader Kim Jong Il, whose Dec. 17, 2011, death North Koreans are expected to mark with some fanfare. The space agency said the rocket would be mounted with a polar-orbiting Earth observation satellite, and maintained its right to develop a peaceful space program.

Washington considers North Korea's rocket launches to be veiled covers for tests of technology for long-range missiles designed to strike the United States, and such tests are banned by the United Nations.

North Korea has capable short- and medium-range missiles, but long-range launches in 1998, 2006, 2009 and in April of this year ended in failure. North Korea is not known to have succeeded in mounting an atomic bomb on a missile but is believed to have enough weaponized plutonium for at least half a dozen bombs, according to U.S. experts, and in 2010 revealed a uranium enrichment program that could provide a second source of material for nuclear weapons.

Six-nation negotiations on dismantling North Korea's nuclear program in exchange for aid fell apart in early 2009.

In Seoul, South Korean officials have accused North Korea of trying to influence its presidential election with what they consider provocations meant to put pressure on voters and on the United States as the North seeks concessions. Conservative Park Geun-hye, the daughter of late President Park Chung-hee, is facing liberal Moon Jae-in in the South Korean presidential vote. Polls show the candidates in a close race.

Some analysts, however, question whether North Korean scientists have corrected whatever caused the misfire of its last rocket.

"Preparing for a launch less than a year after a failure calls into question whether the North could have analyzed and fixed whatever went wrong," David Wright, a physicist with the Union of Concerned Scientists, wrote on the organization's website this week.

The United States has criticized North Korea's pursuit of nuclear weapons and ballistic missiles as a threat to Asian and world security. In 2009, North Korea conducted rocket and nuclear tests within months of Obama taking office.

"A North Korean `satellite' launch would be a highly provocative act," State Department spokeswoman Victoria Nuland said in Washington, D.C. "Any North Korean launch using ballistic missile technology is in direct violation of U.N. Security Council resolutions."

North Korea under its young leader has pledged to bolster its nuclear arsenal unless Washington scraps what the North calls a "hostile" policy. North Korea maintains that it is building bombs to defend itself against what it sees as a U.S. nuclear threat in the region.

This year is the centennial of the birth of national founder Kim Il Sung, the grandfather of Kim Jong Un. According to North Korean propaganda, 2012 is meant to put the North on a path toward a "strong, prosperous and great nation."

"North Korea appears to be under pressure to redeem its April launch failure before the year of the `strong, prosperous and great nation' ends," said Koh Yu-hwan, a North Korea expert at Dongguk University in Seoul.

He added that a successful rocket launch would raise North Korea's bargaining power with South Korea and the United States "because it means the country is closer to developing missiles capable of carrying nuclear warheads."

Before its last two rocket launches, North Korea notified the International Civil Aviation Organization and the International Maritime Organization about its intentions to launch. IMO spokeswoman Natasha Brown said that as of Friday the organization had not been notified by North Korea.

The North's announcement comes two days after South Korea canceled what would have been the launch of its first satellite from its own territory. Scientists in Seoul cited technical difficulties. South Korea's Foreign Ministry said in a statement that the North's planned launch is "a grave provocation and a head-on challenge to the international community."

North Korea's missile and nuclear programs will be a challenge for Obama in his second term and for the incoming South Korean leader. Washington's most recent attempt to negotiate a freeze of the North's nuclear program and a test moratorium in exchange for food aid collapsed with the April launch.

In Japan, Prime Minister Yoshihiko Noda said he would coordinate with the U.S., South Korea, China and Russia in strongly urging the North to refrain from the rocket launch. Kyodo News agency said Japan also postponed high-level talks with North Korea scheduled for Wednesday and Thursday.

The Korean Peninsula remains in a state of war because the 1950-53 Korean conflict ended in a truce, not a peace treaty. Washington stations nearly 30,000 troops in South Korea as a buttress against any North Korean aggression. Tens of thousands more are in nearby Japan.

___

Associated Press writers Jean H. Lee and Sam Kim in Seoul, Jill Lawless in London, Thomas Strong in Washington, D.C., and Elaine Kurtenbach in Tokyo contributed to this report.

Earlier on HuffPost:

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Source: http://www.huffingtonpost.com/2012/12/01/nkorea-says-it-will-launc_0_n_2223847.html

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'Twilight,' 'Skyfall' remain top picks for fans

FILE - This Oct. 22, 2012 file photo shows British actor Robert Pattinson, right, having his photo taken with fans upon arrival for an exclusive fan event for the final chapter of the Twilight Saga "Breaking Dawn Part 2" in Sydney, Australia. Thanksgiving newcomers have been unable to knock off the big three at the box office: Bella, Bond and Abe Lincoln. Kristen Stewart's finale as Bella Swan led the holiday weekend ticket sales. (AP Photo/Rob Griffith, File)

FILE - This Oct. 22, 2012 file photo shows British actor Robert Pattinson, right, having his photo taken with fans upon arrival for an exclusive fan event for the final chapter of the Twilight Saga "Breaking Dawn Part 2" in Sydney, Australia. Thanksgiving newcomers have been unable to knock off the big three at the box office: Bella, Bond and Abe Lincoln. Kristen Stewart's finale as Bella Swan led the holiday weekend ticket sales. (AP Photo/Rob Griffith, File)

(AP) ? The "Twilight" finale and "Skyfall continued to dominate the box office on a typically slow post-Thanksgiving weekend that brought big business for holdover films but a poor start for Brad Pitt's new crime story.

Sunday studio estimates put "The Twilight Saga: Breaking Dawn ? Part 2" out front for the third-straight weekend with $17.4 million domestically.

That raised the domestic total to $254.6 million for the vampire tale released by Lionsgate banner Summit Entertainment. The movie added $48.4 million overseas for an international haul of $447.8 million and a worldwide sum of $702.4 million, approaching the franchise record of $710 million for last year's "Breaking Dawn ? Part 2."

Sony's James Bond adventure "Skyfall" was a fraction behind with $17 million domestically, raising revenue to $246 million after four weekends.

Adding in about $600 million overseas, "Skyfall" already is the top-grossing Bond flick ever, approaching $900 million worldwide.

Pitt's "Killing Them Softly," the weekend's top new release, tanked with just $7 million domestically, coming in at No. 7 behind a big batch of holdovers.

The "Twilight" finale and "Skyfall" were close enough that domestic rankings could flip-flop when final numbers are released Monday. Either way, the two movies have led a brisk start to the holiday season that could lift Hollywood to record domestic revenues for the year.

"I keep upping my revenue estimates for the full end-of-year box office because it's just been a lot stronger than anticipated lately," said Paul Dergarabedian, analyst for box-office tracker Hollywood.com.

With domestic business totaling $9.9 billion so far in 2012, receipts are running 6 percent ahead of last year's and are on track to top the record of $10.6 billion set in 2009, according to Hollywood.com.

After record revenue over Thanksgiving, business eased off, though it still was a stronger-than-usual post-holiday weekend. Domestic revenues totaled $115 million, up 42 percent from the same weekend last year, when "Breaking Dawn ? Part 1" led with $16.5 million.

A Weinstein Co. release, "Killing Them Softly" averaged just $2,888 in 2,424 theaters, meager results compared to the "Twilight" finale's average of $4,344 in 4,008 cinemas over its third weekend.

Adapted from George V. Higgins' novel "Cogan's Trade," ''Killing Them Softly" stars Pitt as a gang enforcer on the trail of two small-time crooks who held up a mob-protected card game.

The weekend's other new wide release, LD Entertainment's horror tale "The Collection," also flopped at No. 10 with $3.4 million, averaging $2,430 in 1,403 theaters.

Estimated ticket sales for Friday through Sunday at U.S. and Canadian theaters, according to Hollywood.com. Where available, latest international numbers are also included. Final domestic figures will be released Monday.

1. "The Twilight Saga: Breaking Dawn ? Part 2," $17.4 million ($48.4 million international)

2. "Skyfall," $17 million.

3. "Lincoln," $13.51 million.

4. "Rise of the Guardians," $13.5 million ($40 million international).

5. "Life of Pi," $12 million ($21.5 million international).

6. "Wreck-It Ralph," $7.02 million ($1.5 million international).

7. "Killing Them Softly," $7 million.

8. "Red Dawn," $6.6 million.

9. "Flight," $4.5 million.

10. "The Collection," $3.4 million.

___

Online:

http://www.hollywood.com

http://www.rentrak.com

___

Universal and Focus are owned by NBC Universal, a unit of Comcast Corp.; Sony, Columbia, Sony Screen Gems and Sony Pictures Classics are units of Sony Corp.; Paramount is owned by Viacom Inc.; Disney, Pixar and Marvel are owned by The Walt Disney Co.; Miramax is owned by Filmyard Holdings LLC; 20th Century Fox and Fox Searchlight are owned by News Corp.; Warner Bros. and New Line are units of Time Warner Inc.; MGM is owned by a group of former creditors including Highland Capital, Anchorage Advisors and Carl Icahn; Lionsgate is owned by Lions Gate Entertainment Corp.; IFC is owned by AMC Networks Inc.; Rogue is owned by Relativity Media LLC.

Associated Press

Source: http://hosted2.ap.org/APDEFAULT/4e67281c3f754d0696fbfdee0f3f1469/Article_2012-12-02-Box%20Office/id-e7fb5c74fad2421294b2adcdde80e634

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Kansas City Chiefs' Belcher in fatal double shooting

KANSAS CITY, Missouri (Reuters) - Kansas City Chiefs starting linebacker Jovan Belcher shot his girlfriend to death, then drove to the team training facility and killed himself in front of the coach and general manager in a burst of violence on Saturday that stunned the NFL and its fans.

There was no immediate indication from police or others what prompted the 25-year-old Belcher to shoot Kasandra Perkins, 22 with whom he had a 3-month-old child, in the house they shared in Kansas City about 2 miles from the Chiefs' home field at Arrowhead Stadium.

Police spokesman Darin Snapp said Perkins' mother witnessed the killing and called police. Perkins had suffered multiple gunshot wounds and was pronounced dead at a hospital.

The mother told investigators that Perkins and Belcher had quarreled just before the shooting but that Belcher had never before been physically abusive with her daughter, Snapp added.

Belcher then drove his car to the team's training facility near the stadium, where he encountered head coach Romeo Crennel and general manager Scott Pioli, then shot himself in the head just as police arrived.

"As officers pulled up and were getting ready to get out of their car, they heard a gunshot," Snapp said. "The individual, it appears, took his own life."

Snapp said Belcher had made no threats to Crennel, Pioli or other employees when he arrived. "He was just talking to them and thanking them for everything they had done for him," the police spokesman said.

The suicide of Belcher followed a recent string of former National Football League players who have taken their own lives, including Junior Seau in May, Ray Easterling in April and Dave Duerson last year.

Those deaths heightened growing concerns about the risk of brain injury from repeated concussions suffered by veteran NFL players in a game that some critics say has grown too aggressive and brutal.

At a news conference later in the day, Kansas City Mayor Sly James decried the violence as "part of the tragedy of urban living in this country."

"Handguns all over the place, people blowing themselves away, and others. At some point, we have to get a handle on this kind of stuff. We are not doing a good job of it," he said.

'GREAT GREAT GREAT TEAM MATE'

He also expressed bewilderment at what drove Belcher to such violent behavior.

"A young man in a high-profile position, for whatever reason, felt the end of the world had come, and he had to act in the way he did," James said. "What kind of burden was he under to do that?"

Although news of the murder-suicide stunned the tight-knit NFL community, the Chiefs announced later their game against the Carolina Panthers at Arrowhead would be played on Sunday as scheduled.

The Chiefs have won just one of 11 games this season, the worst record in the NFL.

In a message on the social media network Twitter, Chiefs' tight end Tony Moeaki wrote: "Devastated. One of everyone's favorite team mates including one of mine. Great great great team mate. We will miss him forever."

Belcher was signed by the team in 2009 after he was overlooked in the NFL draft and established himself as a regular starter in his second season. Earlier this year, he signed a one-year deal worth just under $2 million. This season, Belcher started 10 of 11 games, making 38 tackles.

"Our thoughts and prayers are with the Chiefs and the families and friends of those who lost their lives in this terrible tragedy," NFL spokesman Greg Aiello said, adding that professional counselors were being made available to team members and their families.

The Chiefs' chairman, Clark Hunt, issued a statement offering sympathy and condolences to "the families and friends affected by this unthinkable tragedy."

"We will continue to fully cooperate with the authorities and work to ensure that the appropriate counseling resources are available to all members of the organization," he wrote.

Condolences from others throughout the NFL sprang up on Twitter, where NFL Players Association assistant executive George Atallah wrote, "There is nothing profound or comforting to say that can help us understand or explain a situation like this."

Defensive end Justin Tuck, a two-time Super Bowl winner with the New York Giants, tweeted, "Man prayers go out to the KC Chiefs community and families after this mornings tragic incident."

(Writing by Steve Gorman; Editing by Julian Linden and Peter Cooney)

Source: http://news.yahoo.com/kansas-citys-belcher-fatal-double-shooting-005235424--nfl.html

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Lindsey Vonn wins 2nd Lake Louise downhill

Lindsey Vonn of the United States, speeds down the course in the women's World Cup downhill ski race in Lake Louise, Alberta, on Saturday, Dec. 1, 2012. (AP Photo/The Canadian Press, Jonathan Hayward)

Lindsey Vonn of the United States, speeds down the course in the women's World Cup downhill ski race in Lake Louise, Alberta, on Saturday, Dec. 1, 2012. (AP Photo/The Canadian Press, Jonathan Hayward)

Lindsey Vonn of the United States, speeds down the course in the women's World Cup downhill ski race in Lake Louise, Alberta, on Saturday, Dec. 1, 2012. (AP Photo/The Canadian Press, Jonathan Hayward)

Lindsey Vonn, of the United States, reacts in the finish area following her run in the women's World Cup downhill ski race in Lake Louise, Alberta, on Saturday, Dec. 1, 2012. (AP Photo/The Canadian Press, Jeff McIntosh)

Stacey Cook of the United States, speeds down the course in the women's World Cup downhill ski race in Lake Louise, Alberta, on Saturday, Dec. 1, 2012. (AP Photo/The Canadian Press, Jonathan Hayward)

Stacey Cook, from the United States, speeds down the course in the women's World Cup downhill ski race in Lake Louise, Alberta, on Saturday, Dec. 1, 2012. (AP Photo/The Canadian Press, Jonathan Hayward)

LAKE LOUISE, Alberta (AP) ? Lindsey Vonn raced to her 13th World Cup victory at Lake Louise on Saturday, leading another 1-2 U.S. sweep in the second downhill at the Canadian resort.

Vonn finished in 1 minute, 52.9 seconds to edge teammate Stacey Cook by 0.52 seconds. On Friday in the season-opening downhill, Vonn beat Cook by 1.73 seconds.

Vonn nearly skidded into safety nets rounding a corner halfway down the course.

"A lot of people make mistakes in a lot of races, but if you don't think you're going to win after a mistake then you're not," Vonn said. "I kept charging. I knew I could make up some time if I skied well on the bottom and thankfully my skis were fast and I had a good line and I was able to make it up."

Switzerland's Marianne Kaufmann-Abderhalden was third in 1:53.52.

The 28-year-old Vonn, from Burnsville, Minn., will race in the super-G on Sunday in a bid to sweep the three-race event for the second straight year.

"I did it last year and I'm going to do my best but super-G is a whole other ball game," Vonn said. "I really hope I can get another sweep, but I would be extremely happy to be on the podium."

Vonn tied Switzerland's Vreni Schneider for second place on the World Cup victory list with 55. Austria's Annamarie Moser-Proell is the leader with 62.

Vonn raced for the third time since returning from a stomach bug that landed her in the hospital. Last week in Aspen, Colo., she was 21st in the giant slalom, then skipped the slalom.

"I'm a little bit more tired today for sure, especially with that mistake," Vonn said. "It was definitely interesting today and an adventure. I've made mistakes here before. I haven't won with that big of a mistake before."

She said she pressure to win the women's races because she asked the world governing body of skiing to race the men's World Cup at Lake Louise. Vonn was denied by FIS, but hasn't given up on that dream. Her best argument to race the men at Lake Louise is to continue winning by large margins.

"I've been racing here for so many years that there's definitely been a lot of interesting things that have gone in the races, but this weekend was very important for me to make sure I won at least one race and to come away with two wins is more than I hoped for being sick," she said.

"I felt like I had a lot of pressure coming into these races because I, of course, wanted to race the men. You make that kind of statement, you kind of have to back it up. I'm confident in the way I ski here. I know what to do and I think I proved that this weekend."

Cook watched Vonn's run on television at the bottom of the course.

"I was like 'I don't have a chance' and then I saw her make a mistake. My heart stopped beating for a second," Cook said. "But she's so good. She's the only person who can stop and still win."

The 28-year-old Cook, from Mammoth Mountain, Calif., celebrated her first two podium finishes.

"I really kind of lifted a monkey off my back yesterday getting that first podium out of the way," she said. "I know I can compete with these girls. It's just been a long time coming to actually believe it and I think I'm starting to."

Associated Press

Source: http://hosted2.ap.org/APDEFAULT/347875155d53465d95cec892aeb06419/Article_2012-12-01-Women's%20World%20Cup/id-1da71f2608d34a2ba3c117ce9e80cc8c

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