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Hasbro trying to find footing posts weak 3Q

first_imgNEWARK, N.J. – Hasbro, wrestling with the demise of Toys R Us and elusive shoppers spending a lot more on high-tech gadgets, fell well short of third-quarter expectations Monday and said it will cut some jobs to save costs.The toy maker, whose brands include Monopoly and Play-Doh, did not specify the exact number of layoffs, but said it will affect a “mid-single digit” percentage of its worldwide workforce. Hasbro had about 5,400 employees at the end of last year; a 5 per cent cut would put the layoffs at about 270 jobs. Hasbro said it will absorb charges of as much as $60 million in the next quarter related to paying severance.Mattel, Hasbro’s rival, said in July that it would cut more than 2,200 jobs. Both toy makers have acknowledged they’ve been hurt this year by the shuttering of Toys R Us stores, the largest independent toy seller in the world.It is the first full quarter that the company has been without Toys R Us as a customer.“We continue to believe this is a near-term retail disruption that will last for the next few quarters,” Chairman and CEO Brian Goldner said during a conference call.Sales of games and toys at brick-and-mortar stores fell in the quarter, but Goldner said that online point-of-sale climbed by the high-single digits at the same time.The lost Toys R Us revenue hurt Hasbro most notably in the U.S., Europe, Australia and Asia, contributing to the company’s 12 per cent revenue decline overall for the quarter. Goldner said the company has recaptured about one third of the U.S. and Canada Toys R Us revenues heading into the holiday.“We are successfully managing retail inventory and it is down significantly in the U.S. and in Europe, where we are aggressively working to clear excess inventory by year end,” Goldner said.Hasbro Inc.’s third-quarter earnings slipped to $263.9 million, or $2.06 per share. Adjusted for pretax gains, per-share earnings were $1.93, far below Wall Street projections for per-share earnings of $2.24, according to a survey by Zacks Investment Research.Revenue of $1.57 billion also missed analyst expectations for $1.71 billion. Hasbro experienced a 24 per cent drop in international revenue, with Europe falling 29 per cent, Latin America slipping 16 per cent and the Asia Pacific region declining 14 per cent.Tablets and smartphones have become the most desired toys in many households, and that is taking a toll on the sale of more traditional playthings.Sales fell for Nerf, My Little Pony and Transformers products in the quarter, but the Pawtucket, Rhode Island-based company did put up some very strong numbers in the same period last year thanks to new My Little Pony and Transformers movies.Hasbro’s stock tumbled 5 per cent in morning trading Monday. Shares of Mattel Inc., which posts earnings Thursday, fell 2 per cent._____Portions of this story were generated by Automated Insights (http://automatedinsights.com/ap) using data from Zacks Investment Research. Access a Zacks stock report on HAS at https://www.zacks.com/ap/HASlast_img read more

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Kosovo plan is a practical and workable solution Ban tells Security Council

Addressing a Security Council debate on Kosovo, a week after unveiling plans to adjust the profile and structure of the UN Interim Administration Mission in Kosovo (UNMIK), Mr. Ban said he had rarely encountered such a delicate or divisive issue during his 40-year diplomatic career.“Legally, politically and morally, it is a landscape of enormous complexity and sensitivity that required the exercise of extraordinary objectivity and balance,” he said, adding that such developments this year as the declaration of independence in February and the Kosovo Serb community’s overwhelming rejection of a new constitution in Pristina have brought lasting changes to the situation.“It is my assessment that, taken together, these developments have created a profoundly new reality in which UNMIK is no longer able to perform as effectively as in the past the vast majority of its tasks as an interim administration. This needs to be acknowledged as a fact of life.”Under Mr. Ban’s plan, the UN is neutral on the question of Kosovo’s status. The European Union would also play an enhanced operational role in the area of rule of law under a UN “umbrella” headed by the Secretary-General’s Special Representative and in line with the 1999 Security Council resolution that established UNMIK.A reconfigured and restructured UNMIK would continue to carry out many functions, including those related to a dialogue with Serbia on provisions in six areas: police, courts, customs, transport and infrastructure, boundaries and Serbian patrimony.To lead this new phase, Mr. Ban said he intends to appoint Lamberto Zannier of Italy to be his new Special Representative, succeeding Joachim Rücker.“He will help to carry forward the vision I have presented in my report, and to lead a new phase of dialogue, and he will be scrupulously balanced in his approach.”Mr. Zannier is currently on secondment from the Italian Government to the Organization for Security and Co-operation in Europe (OSCE) as director of its conflict prevention centre, and has worked closely with the UN system since joining the Italian foreign ministry in 1978.The Secretary-General stressed to the Council that his package of changes is aimed at finding “an operational modus vivendi to help move Kosovo a few steps back from the brink of further conflict.”He said he now awaited the reaction of Council members and the other participants in today’s debate, saying that dialogue was critically important for all of Kosovo’s communities.“The package is a practical and workable solution – a concrete and sustainable response to a complex and difficult situation. It is founded on the imperative, overriding need, as I said, to maintain international peace and security and stability in Kosovo and the region, while responding and adapting to changing circumstances on the ground.”UNMIK has been in place since mid-1999 after NATO forces drove Yugoslav troops out of Kosovo, where ethnic Albanians outnumber Serbs and other minorities by nine to one, that year amid deadly inter-communal fighting. On 17 February this year, the Assembly of Kosovo’s Provisional Institutions of Self-Government adopted a resolution declaring independence from Serbia. 20 June 2008The proposal to reconfigure the United Nations’ presence in Kosovo is “a practical and workable solution” to one of the world’s most intractable issues, Secretary-General Ban Ki-moon said today, warning that reaching a mutually acceptable settlement will not be easy. read more

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Northern Gateway pipeline gets handed another setback from BC Supreme Court

VANCOUVER — An alliance of First Nations is celebrating a British Columbia Supreme Court ruling that it says could set back the Northern Gateway pipeline by years and throw a wrench into another high-profile project review.The case was brought forward by the Gitga’at First Nation and Coastal First Nations, which represents nine aboriginal communities along B.C.’s northern and central coast, including the Gitg’aat.At the centre of the challenge was an equivalency agreement in which British Columbia gave the National Energy Board the power to review the controversial pipeline proposal. The court found the province “breached the honour of the Crown” by failing to consult with the Gitga’at and Coastal First Nations.That means the equivalency agreement is invalid and the province must make its own decision on Northern Gateway — after consulting with and accommodating First Nations along the route.“We’re now at the point where if Northern Gateway as a company wanted to move ahead, it would almost have to start over,” said Art Sterritt, a member of the Gitga’at who’s been a staunch opponent of Northern Gateway.Northern Gateway has had a federal permit in hand — with 209 conditions attached — since mid-2014, but the company has not officially committed to building the project. Instead, it has been looking to garner support from First Nations along the route.The ruling is the latest setback for the project, which aims to ship 525,000 barrels of oilsands crude a day to the port of Kitimat, B.C., for export to Asia. The federal Liberal government has said it wants to formalize a tanker ban on B.C.’s north coast — a move many say would essentially kill the project.Northern Gateway spokesman Ivan Giesbrecht said Enbridge remains committed and that the NEB’s review was one of the “most exhaustive” in Canadian history.With B.C.’s rejection of Trans Mountain pipeline expansion, Canada’s diversification strategy is unravellingTrans Mountain review looks for closure as pipeline expansion becomes increasingly difficult in CanadaFirst Nations spar over pipelines“This decision from the British Columbia Supreme Court does not change that approval,” he said, adding the company welcomes the court’s direction for more aboriginal consultation and will continue to work with all levels of government.“This comes down to a jurisdictional matter between the federal and provincial governments.”Joseph Arvay, lead counsel for the petitioners, said it’s a “very significant” decision that goes beyond Northern Gateway.“The court said that the province abdicated, gave away its powers to the federal government over the Northern Gateway project when it entered into this so-called equivalency agreement with the NEB. But it entered into exactly the same equivalency agreement with the NEB on the Kinder Morgan project,” he said.The B.C. government said this week it could not support Kinder Morgan’s Trans Mountain expansion, which would triple the amount of crude shipped from Alberta to the Vancouver area, because it hasn’t met its five conditions.“As far as I’m concerned, the province should congratulate us on this win even though they opposed us in the court,” said Arvey. “The court essentially provided the province with the legal backbone that it didn’t have up until this point.”B.C. Justice Minister Suzanne Anton said the province is reviewing the decision, but the interpretation so far is that the province won’t have to duplicate the entire review process.“Our reading of it is not that the judge is requiring us to do everything all over again. But what we do have to do is assess our B.C. requirement as per our B.C. statute and make sure that we’re complying with those requirements,” she said.Tara O’Donovan, a spokeswoman for the National Energy Board, declined to comment on what the ruling would mean for other projects under review.Sterritt, with the Gitga’at. said he’s been pleased with the shift in tone at the federal level when it comes to aboriginal engagement, and he’s hoping Wednesday’s ruling spurs a similar change in B.C.“Maybe this will be that final straw that will make British Columbia realize that you don’t just agree with First Nations when they like your project,” he said. “You basically have to listen to them and work with them even when they don’t like your project.” read more

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BBS says it is being unfairly accused of links to violence

The monk had visited Kandy and there was a feeling that he instigated the violence but Gnanasara Thera insisted that he attempted to calm the people in the area. The Bodu Bala Sena (BBS) says it is being unfairly accused of links to violence targeting innocent Muslims.General Secretary of the BBS, the Venerable Galagodaatte Gnanasara Thera said that every-time an incident takes place the BBS is blamed. Gnanasara Thera said the BBS has concerns over some Muslim groups in Sri Lanka but is not taking a confrontational approach to address its concerns. (Colombo Gazette) He told reporters today that the BBS has changed its ways and is pushing for unity among all communities. read more

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Touring Wesleys Reception House

The United Nations refugee agency is pressuring our country to help resettle more of the 100,000 people displaced by the war in Syria. So far Canada has agreed to take in 1300 people by the end of this year. This comes as Hamilton’s Wesley Urban Ministries is well on its way to providing smooth transitions for the roughly 300 government-sponsored refugees that come to the city each year.“It’s war. There’s nothing there. There’s nothing there.”25 year old Farooq Kaml had been living in Egypt for the last nine years after his family fled Iraq due to war. While he says they had peace in Egypt, they had no rights.“I came to Canada because it’s a good country. I have rights here and it’s more secure and more quiet.”Along with his parents, brothers and sisters, Kaml has now been living at Wesley Urban Ministries’ new Reception House for the last month as a government-sponsored refugee. He hopes to one day study computer sciences — but first, the family is looking for a permanent home, and Wesley’s Reception House program is helping them prepare for life in Canada.Executive director Daljit Garry says up to 35 people can live at the reception house at a time.“It’s a home-like environment for them. There’s common lounge space, eating areas and then they have their rooms.”Before it opened in October, the program was run out of hotel rooms. This new site is making a difference by allowing the centre to help build relationships.“It also allows us to bring in those connections for them so settlement workers can come on site. We have a health clinic within the space.”Families typically stay at the centre for weeks, but Wesley’s services continue once they’ve found permanent homes. And after three years of living in Canada, refugees like Kaml can apply to become citizens.It’s important to note these are not refugees making claims; only government-sponsored refugees who were mostly living in camps can stay at the centre. About 300 are placed at Wesley each year. For more information just go to the Wesley Urban Ministries website. read more

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Czech Government requests UN help to battle deadly flooding

In its latest report on the floods, which have killed nine people so far, OCHA said that the Ministry of the Interior has requested portable dryers, floating pumps and electric submersible pumps.As of yesterday evening, the level of the Vlatva River was still rising in Prague, and on Monday, authorities in the capital ordered the evacuation of an estimated 50,000 people as the rising water approached the city after days of rainfall swelled rivers in the south, OCHA said.The Czech Prime Minister declared a state of emergency in Prague, Bohemia, Plzen and Karlovy Vary in the Zapadocesky region in the western of the country. read more

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How To Build A Bracket For This WideOpen NCAA Tournament

After a chaotic regular season in men’s college basketball — during which 18 separate teams ranked among the AP’s top 5 at various points — it’s finally time for the real Madness to begin. And that means we’re breaking out the FiveThirtyEight NCAA Tournament model to help you make all of your bracket picks, as always (you can read about how the system works here). Below I’m highlighting the key teams and matchups to watch in each region, including dark horses and cinderellas who could bust up the bracket. With overall favorite Virginia only boasting an 18 percent chance of winning it all, this year’s Big Dance should be as crazy as ever. Favorites: According to the FiveThirtyEight model, top seed Villanova has the best chance of advancing to the Final Four in the entire field, with a 50 percent probability of winning the East. The Wildcats are an exceptionally strong offensive team, with guard Jalen Brunson leading ‘Nova to the nation’s top efficiency mark in Ken Pomeroy’s ratings during the season. But their 22nd-ranked defense is no slouch either, spearheaded by do-everything wing Mikal Bridges. The only thing keeping Villanova from being our overall favorite is the way the bracket has situated the East region on the same side as the Midwest, which contains three of the top eight teams in the field according to our power ratings.No. 2 seed Purdue has the potential to make some noise, but a tough matchup with Texas Tech or Florida could loom in the Sweet 16 — if the Boilermakers make it past likely second-round opponent Butler first, that is. (More on the Bulldogs later.) Purdue’s difficult path is a big reason why it has only a 20 percent probability of making the Final Four, which ranks last among No. 2 seeds. Favorites: After a storybook 31-2 regular season, Virginia is a 47 percent favorite to make the Final Four out of the South — and an 18 percent favorite to win the whole tournament, tops among the entire field. You’ll hear a lot this month about how the Cavaliers play basketball: Yes, they’re painfully slow and they grind teams to a pulp with their defense. Yes, those kinds of teams have some history of coming up short in the postseason. These are questions Virginia must answer. But you have to give the Cavs credit: This is also a team whose only blemish in its last 24 games was a 1-point overtime loss. On paper at least, Tony Bennett’s team is set up well to silence its doubters this year.If that doesn’t happen, Cincinnati might very well be the reason. The second-seeded Bearcats are the fifth-best team in the country according to our power ratings, so they’re nearly top-seed-worthy in terms of quality. More importantly, they also play a similar style to Virginia — taking the air out of the ball and fighting every defensive possession to the bitter end — so a matchup between the two would be fascinating. We give Cincy a 53 percent chance of making the regional final and a 23 percent probability of pushing its way into the Final Four. Dark horse: Does Gonzaga count here? If not, and you’re looking for a sneaky Final Four bid out of the West, look no further than sixth-seeded Houston. The Cougars pushed Cincinnati to the brink in the American Athletic championship game Sunday, showing a national audience just how stifling this team’s defense can be. Houston is a solid favorite to beat San Diego State in round one; in Wichita, they’d also be playing comparably closer to home against Michigan in round two. From there, UNC likely awaits, but our model gives the Cougars a 33 percent chance of getting that far — and, as a result, a 7 percent chance of making the Final Four.Don’t bet on: No. 3 seed Michigan. It’s an unfortunate draw for a team heading into the tourney playing as well as just about anybody in the country (the Wolverines actually rank third in our pre-tournament Elo ratings, behind only Virginia and Villanova), but the selection committee did Michigan zero favors here. First-round opponent Montana is unusually strong for a No. 14 seed — check out the sea of 10, 11 and 12 seeds around them in Ken Pomeroy’s rankings — and likely second-round foe Houston was underseeded as a No. 6, too. Then, if the Wolverines survive opening weekend, they’ll probably be treated to a rematch of their 15-point loss to UNC from late November. Michigan has fought through similarly tough tourney paths before, but right now we give them only a 14 percent shot at a Final Four berth.Cinderella Watch: Sadly, this isn’t a very promising region for Cinderella bids. For instance, No. 11 seed San Diego State is the kind of good, solid team (it ranks 50th in Kenpom’s ratings) that you’d ordinarily pencil in for an upset or two, but Houston and Michigan are too difficult to realistically expect a Sweet 16 berth from the Aztecs. And the other teams in classic upset seeds — 10th-seeded Providence and 12th-seeded South Dakota State — are each the weakest at their seed-line in the whole field. Blah.Likeliest round-one upsets: Florida State over Missouri (61 percent); Providence over Texas A&M (42 percent) Midwest region Dark horse: Because of how strong its top-line teams are, the Midwest doesn’t really lend itself to dark-horse bids. But if you had to pick one, Auburn might be the one to emerge from the field. Led by the undersized trio of Mustapha Heron, Bryce Brown and Jared Harper, the fast-paced Tigers should be entertaining regardless. Auburn will probably have to tangle with a strong Clemson team in the round of 32, however, before potentially running through the gantlet of all those favorites listed above. Fun or not, that is why our model sets Auburn’s Final Four odds at a measly 3 percent.Don’t bet on: Sixth-seeded TCU. The Horned Frogs rank 22nd in Pomeroy’s ratings and enjoyed one of their best seasons in decades under coach Jamie Dixon. But no matter whether Syracuse or Arizona State wins their play-in game, they’ll give TCU a tough game in the first round — and it only gets harder from there, with Michigan State likely waiting in the wings. A deep run by the Frogs, playing in their first tournament since 1998, doesn’t appear to be in the cards this year.Cinderella Watch: Of all the Midwest’s double-digit seeds, No. 12 New Mexico State is most likely to find itself playing with the big-name programs on the tournament’s second weekend. The Aggies won 28 games this season and had the nation’s 14th-best defense according to Pomeroy. Our model thinks they have a fighting chance (38 percent) against Clemson and gives them an 18 percent chance of sneaking into the Sweet 16.Likeliest round-one upsets: Syracuse* over TCU (46 percent); Oklahoma over Rhode Island (42 percent); New Mexico State over Clemson (38 percent); NC State over Seton Hall (37 percent)(* – Must win play-in game first.)West region East region Favorites: The West is probably the weakest of all the regions in this year’s bracket. Its top seed, Xavier, ranks as only the 10th-best team in the country by the FiveThirtyEight power ratings — which would typically only fetch a No. 3 seed. The Musketeers are plenty good on offense, but a defense that ranked just 59th in Pomeroy’s ratings is among the reasons why our model assigns them only an 18 percent chance of making the Final Four, by far the worst of any No. 1 seed in the bracket.In fact, our projections say the West’s most likely Final Four team is the defending champion, North Carolina, which has a 25 percent probability of advancing to San Antonio despite getting a No. 2 seed from the committee. The Tar Heels had something of an up-and-down season, losing 10 games (including seven in conference play), but they looked solid in the ACC tourney and boast one of the country’s deadliest two-man scoring combos in Joel Berry and Luke Maye.Then there’s fourth-seeded Gonzaga, last year’s national runners-up, which also checks in with a better Final Four probability (24 percent) than Xavier. The Zags were badly underseeded here — we have them ranked ninth in the country by power rating — and their draw could have them set up for a very deep tourney run. According to Pomeroy, the Bulldogs were one of only three teams in the nation (alongside Duke and Michigan State) whose offense and defense each ranked among the top 20 in efficiency. Favorites: The Midwest is nothing if not top-heavy. While most regions have a clear favorite, this one has three that combine for an 85 percent total probability of making the Final Four. First among these near-equals is No. 1 seed Kansas, with a 31 percent chance of making it to the national semifinals. Like their top-seeded counterparts in the East, Villanova, the Jayhawks are an explosive offensive team led by a standout guard — in KU’s case, Devonte’ Graham. One big concern for Kansas is the availability of big man Udoka Azubuike, who led the team in Box Plus/Minus during the season but who hasn’t played since March 3 because of a knee injury. (He’s listed as questionable for the start of the NCAAs.) KU will also have to contend with a tough early draw that includes potential matchups with Seton Hall, Clemson or Auburn. (First-round opponent Penn is no pushover, either, at least as far as No. 16 seeds go.)The second co-favorite out of the Midwest is — sigh — Duke, at 29 percent. The Blue Devils lost some close games down the season’s final stretch. But none were by more than 5 points, and they were one of only two teams in the country to rank among Pomeroy’s top 10 in both offensive and defensive efficiency. (The other? No. 3 seed Michigan State. Again, the Midwest is stacked.) Rooting against Grayson Allen and Co. will once again be a top springtime ritual for most of America, but barring, say, something special from Oklahoma’s Trae Young,1Assuming the Sooners can pull out of their death spiral long enough to win their first game. Duke might not have much trouble until the Sweet 16.There, the Blue Devils might have to face Michigan State, our third co-favorite. Sparty is solidly No. 3 in the pecking order with 25 percent Final Four odds, but that’s also easily the highest of any team seeded lower than second in the entire bracket. This is your classic strong all-around Tom Izzo squad, with four players — Cassius Winston, Miles Bridges, Jaren Jackson Jr. and Nick Ward — who ranked among the Big Ten’s top 16 in Win Shares according to Sports-Reference.com. MSU and Duke’s potential Sweet 16 showdown is the game everyone is already circling in the second week. South region Dark horse: Underseeded at No. 5, West Virginia ranks 11th in our power ratings and could be a team to keep an eye on. The unfairly low seed means the Mountaineers will potentially have to unseat fourth-seeded Wichita State (always a tough out) and Villanova in back-to-back games, but West Virginia is a constant threat with its swarming, turnover-inducing defensive style. Even though WVU might have peaked too early with its terrific run around New Year’s — it has lost nine of its last 18 games — don’t count out Bob Huggins’s crew just yet.Don’t bet on: No. 3 seed Texas Tech. The Red Raiders are a fine team that plays some of the nation’s stingiest defense, but they’ll probably have to make it through an unusually strong No. 6 seed (Florida) in the round of 32 just for the right to face Purdue (or possibly Butler). Our model only sees a 6 percent Final Four chance for Texas Tech, easily the worst mark for any No. 3 seed.Cinderella Watch: Slotted in as the No. 10 seed by the committee, Butler probably deserved better. We have them ranked as the 23rd-best team in the field, thanks in large part to an offense that sits at No. 32 in the nation according to Pomeroy. The Bulldogs should be solidly favored (60 percent) over Arkansas in round one, and they could give Purdue trouble in the next round.Likeliest round-one upsets: Butler over Arkansas (60 percent); Alabama over Virginia Tech (41 percent); UCLA* over Florida (39 percent).(* – Must win play-in game first.) Dark horse: Laden as Kentucky perennially is with top recruits, we used to ask whether it was fair to slap the “dark horse” label on the Wildcats. But the SEC champs do seem to have perfected a certain formula under coach John Calipari: enter the season ranked highly, struggle around midseason, and then pour it on late in the schedule and slip into the NCAA tourney as a so-so seed before making a deep run through the bracket. This year’s squad has all the earmarks — from a No. 5 preseason ranking and a four-game February losing streak to an impressive run through the SEC tourney. Our model knows this kind of team, and it gives a little extra credit to highly touted preseason squads with inconsistent regular seasons. It’s no coincidence that we’re giving the Wildcats a solid 7 percent chance at making the Final Four.Don’t bet on: Fourth-seeded Arizona. Was the NCAA doling out early punishment for the Wildcats’ alleged recruiting scandal with this draw? The committee stuffed Arizona into a first-round matchup with Buffalo, which our power ratings easily consider the strongest 13-seed in the bracket. If they win, the Wildcats will then have to play either Kentucky (see above) or a dangerous Davidson team that easily rates as the strongest No. 12 seed in the bracket. And that’s just leading into a potential Sweet 16 matchup with No. 1 overall seed Virginia. Arizona big man DeAndre Ayton might be the best player in the country — he leads all major-conference players in Win Shares this season — but the odds of us seeing much of him in the tournament aren’t very high.Cinderella Watch: Keep an eye on No. 11 seed Loyola-Chicago in this region. We give it a 40 percent chance of knocking off an overseeded Miami squad in the opening round of the tourney, and it wouldn’t have terrible odds against Tennessee in round two, either. Of course, Loyola would have an even better Sweet 16 shot if there were any chance the No. 3 seed Volunteers would lose in round one, but Tennessee’s first-round opponent, Wright State, is worse than two No. 15 seeds and a No. 16 seed.Likeliest round-one upsets: Texas over Nevada (60 percent); Kansas State over Creighton (42 percent); Loyola-Chicago over Miami (40 percent)Check out our March Madness predictions. read more

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Family of Nazi criminal searches for missing body

first_imgIt’s unheard of that a casket can be made to disappear in this country, taken from those who had custody of it in a private place — a place of worship — and taking it by force without any order, any notification. We want clarity.Priebke died Friday at age 100 in Rome, where he was serving a life term for the 1944 massacre of 335 civilians at the Ardeatine Caves outside Rome. It was one of the worst atrocities in German-occupied Italy during World War II.His death sparked waves of outrage in Italy’s Jewish community because, in a final statement issued by his lawyer upon his death, Priebke denied that Jews were gassed in Nazi death camps.In a separate video statement released by Giachini today, Priebke also defended his actions at the Ardeatine Caves, saying the orders to shoot the civilians came from Adolf Hitler himself and that members of his SS unit were told they would be shot if they didn’t obey.Giachini said he had been in touch with the German embassy for possible burial in Priebke’s native land, once the body is located.Read: 30 Auschwitz guards to face criminal probes> THE CASE OF Nazi war criminal Erich Priebke took on another bizarre twist today as his family said it doesn’t know where his body is.Family lawyer Paolo Giachini said he and the former SS captain’s family lost track of Priebke’s casket on Tuesday night, when they tried to celebrate a funeral Mass for him in a church compound in Albano Laziale south of Rome.At a certain point, he told Sky TG24, a group of about 30 people entered the compound and took the casket out following protests pitting Priebke’s right-wing supporters against his detractors.Italian state radio said the casket was taken to a nearby military base. But Giachini said he hadn’t been able to establish who has the body or where it is, and Italian officials have refused to divulge information about it.Giachini said:last_img read more

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Motorola CEO Were Taking a Hit From Verizon iPhone

first_imgThe Verizon iPhone isn’t actually due out until February 10th, but Motorola is already feeling the burn. The company experienced a renaissance of sorts recently, thanks in no small part to a a number of Android-based handsets released for Verizon.And now the anticipation of the addition of Apple’s ultra popular handset to carrier has Motorola a bit freaked out.“Since the announcement of the iPhone, we have seen a little slow down in our sell through of devices at Verizon,” the company’s CEO Sanjay Jha, told investors during a call yesterday. The company shipped 4.9 million smartphones last quarter–down from the 5.2 million analysts were anticipating. Motorola added that it expects to lose $26 million to $62 million in the first quarter of this year. MThe company is offering smartphones on other US carriers, as well, of course, but many of its fights will continue to be fought on Verizon. “When customers go into the Verizon stores now, they’ll be offered choices,” Jha added. “And time will tell what percentage of sales goes to which brand.”Doesn’t sound particularly hopeful, does it? Perhaps the Xoom will turn things around a bit…AdChoices广告last_img read more

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VLC for Windows 8 beta coming soon no thanks to Microsoft

first_imgVideolan’s Jean-Baptiste Kempf says that Kickstarter supporters of the VLC for Windows 8 app should get their hands on a beta version before the end of the month. It has been a long road to the Windows Store already for the VLC crew, with Kempf and his cohorts having to re-license the entire project to ensure compliance.The Kickstarter campaign wrapped up at the end of last year, and Videolan finished well ahead of its goal of $40,000. Having funds available to pay your developers never hurts when porting an app, but sometimes outside assistance is required. VLC for Windows 8 presented some unique challenges, and things were looking good when Microsoft announced that it would be happy to offer technical and design help.Speaking with Neowin, Kempf said that compatibility with the Windows Store is still a problem. “We are still blocked by technical difficulties and we don’t know how to fix them,” stated Kempf, adding, “the lack of external help makes it quite difficult.”So wait just a second. The lack of external help? Isn’t external help exactly what Microsoft said that it was going to provide? If the Videolan developers are still struggling to make VLC for Windows 8 “Windows Store ready,” doesn’t that mean that Microsoft isn’t delivering on its promise?That would also contradict the company’s earlier comment that it was “thrilled” about Videolan’s decision to bring VLC to the Windows Store. How thrilled can you be if you’re not willing to help Videolan developers sort out the issues that are preventing them from getting their app into the store?Hopefully Kempf and his co-workers are able to get the help they need from somewhere. If Microsoft has dropped the ball, let’s hope that someone else who has experience with the Windows  Store is able to jump in and lend a hand.last_img read more

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Some livestreamers make 50000 per hour playing video games report says

first_img Ninja and more Twitch streamers get their own toys Video Games Tech Industry Tags Post a comment Share your voice 1:20 Playing video games could make you more money than you think. Getty Images Publishers are reportedly paying popular livestreamers upwards of $50,000 to play their latest games live in an attempt to dethrone games like Fortnite.Electronic Arts, Activision Blizzard, Ubisoft and Take-Two Interactive Software are some of the publishers shelling out serious cash to streamers, according to a report published Saturday by The Wall Street Journal. Publishers sometimes send the streamers a beta of their game ahead of the release date. The streamer will then play through the demo on Twitch, a livestreaming platform, or upload a video of the play-through onto their YouTube channel. For example, Take-Two will reportedly pay livestreamers to test Borderlands 3 and Ubisoft plans to give streamers access to Tom Clancy’s Ghost Recon Breakpoint.”Having celebrity streamers play games is an important part of the business,” Strauss Zelnick, Take-Two’s chief executive, said in an interview with the Journal. “It is relatively new, but it has to be organic. The streamers have to believe in it.”Publishers understand that “professional gamers” have massive followings and it’s one of the best ways to advertise their games. For example, streamers Tyler “Ninja” Blevins and Sean “Jacksepticeye” McLoughlin have more than 22 million subscribers (respectively) to date. McLoughlin earns about $300,000 per month and Blevins earns between $500,000 and $1 million per month, according to Celebrity Networth. Electronic Arts, Activision Blizzard, Ubisoft and Take-Two Interactive Software didn’t immediately respond to a request for comment. Now playing: Watch this: 0last_img read more

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Nevada man dies when commercial canoe flips in Alaska river

first_imgA Coast Guard Jayhawk rescue helicopter from Air Station Sitka participates in a training exercise. (Photo courtesy Petty Officer 3rd Class Wes Shinn/U.S. Coast Guard)The U.S. Coast Guard carried out a rescue on the Chilkat Inlet near Haines today after a canoe carrying 11 people capsized at Glacier Point, nine miles south of the Haines townsite.Listen nowThe canoe was being used for a guided tour for passengers from three different cruise ships, Coast Guard spokeswoman Meredith Manning said.A Jayhawk helicopter from Sitka responded.One of the passengers was unresponsive at the scene. First responders performed CPR, but the passenger remained unconscious.The Coast Guard transported the passenger to Juneau by helicopter.The Associated Press reported that Steven Tod Willis, 50, of North Las Vegas, Nevada, died.The remaining 10 passengers were transferred to a small boat operated by the company in charge of the guided canoe tour.last_img read more

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RVRJC Engineering College alumni meet held in Guntur

first_imgGuntur: RVR&JC Engineering College 1990-94 batch students on Saturday visited the college at Chowdavaram near Guntur city and met the principal Dr K Srinivasu. They recalled their memories in student days and association with the college. Dr K Srinivasu explained development in the college and plans for the development of the college. He sought the cooperation of the alumni for the development of the college. The old students met the lecturers. They visited college premises, ground and classrooms and recalled their memories.last_img read more

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Editors Guild of India concerned over shutdown in communication

first_imgNEW DELHI: The Editors Guild of India expressed deep concern on Saturday over the continued shutdown in communication links with the Kashmir Valley and the consequent “curtailment of the media’s freedom and ability” to report fairly on the developments there. The guild’s statement came days after the government revoked the provisions of Article 370 of the Constitution in Jammu and Kashmir to withdraw the special status given to the state and bifurcated it into two Union territories — Jammu and Kashmir and Ladakh. Also Read – Congress MLA Shivakumar moves High Court seeking protection from arrest Advertise With Us The guild said while some visiting journalists might be able to file their reports once they were out of the Valley, the lockdown was almost “total and draconian” for the vibrant local media organisations that were the first eyes and ears on the ground.The Editors Guild of India has issued a statement – https://t.co/xrPM0vb2jK pic.twitter.com/cBESCabl6Y— Editors Guild of India (@IndEditorsGuild) August 10, 2019 Also Read – Enforcement Directorate summons Karnataka Congress leader D.K. Shivakumar Advertise With Us The government knew very well that it was impossible to process and publish news now without the internet, it said. The government owed it to the people of the country, including those in Jammu and Kashmir, to allow the press, a vital institution of democracy, to function freely, the guild said. It added that it was deeply concerned over the continued shutdown in communication links with the Kashmir Valley and the consequent “curtailment of the media’s freedom and ability” to report fairly and accurately on current developments. Advertise With Us In a situation such as that prevailing in Jammu and Kashmir at present, the role of a free media, unhindered by such restrictions, becomes critically important in helping in dissemination of news and in its democratic duty of keeping a watch on institutions of the government and security, the guild said. “The Guild underlines the imprudence in creating an unfair distinction in the treatment: for access, curfew passes, communication between local journalists and those coming in to report from outside. All journalists and all Indian citizens are entitled to equal freedom,” the statement said. The guild urged the government to take immediate steps to restore normalcy for the media’s communication links. Media transparency had always been and should be India’s strength, not fear, it said. The guild also expressed its appreciation for and solidarity to all journalists reporting from the ground despite unprecedented challenges. “The Guild requests all, especially the government, to ensure their safety and freedom of movement,” the statement said.last_img read more

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Subuhi Joshi sent 500 messages to me after breakup threatened to commit

first_imgSidharth Sagar, Subuhi JoshiInstagramComedian Sidharth Sagar and fiancee Subuhi Joshi recently called off their engagement after their relationship reached an ugly stage. Subuhi even accused Sidharth of domestic violence, losing his cool over petty issues, and getting violent. Hearing about the allegations levelled against him, an upset Sidharth has shot back at Subuhi saying that if he was so much into domestic violence then why would she kept on messaging him repeatedly begging him to come back.Sidharth has revealed that he and Subuhi had been fighting with each other for a very long time and he had been telling her that he doesn’t want to stay in this relationship any longer. The two had started dating in 2014 but things had turned awry between them and they decided to split in 2016.After their bitter break-up, Subuhi had sent almost 500 messages and made repeated phone calls to Sidharth asking him to come back to her because she loved him so much. She even threatened him saying that she will commit suicide and hold him responsible for her death if he refused to come back. Sidharth somehow convinced Subuhi and the two then again got back together last year before getting engaged. “If I was into domestic violence, then why would she call me back again after the break-up,” Sidharth vented out his frustration over Subuhi’s allegations against him in an exclusive chat with International Business Times India. Sidharth also shared the screenshots of his WhatsApp chat with us when Subuhi had threatened to kill herself after Sidharth left her for her abusive behaviour. Sidharth Sagar shared the screenshot of his WhatsApp chat exclusively with IBTimes India Sidharth Sagar shared the screenshot of his WhatsApp chat exclusively with IBTimes India Sidharth Sagar shared the screenshot of his WhatsApp chat exclusively with IBTimes IndiaSidharth and Subhi had made their relationship official with an engagement in November last year. The two had mutually broke up with each other on April 1. Everything was fine until major fights started happening between them over participating in celebrity couple shows together.”We were offered a few celebrity couple reality shows like Nach Baliye 9 and Bigg Boss 13. I had clearly told her that ‘I can’t go do these shows with you because you will never know what you will say about us on the show. You play games but I don’t. For the unknowns, she has been the Splitsvilla queen (Splitsvilla 6 second runner-up). It’s a game show and I didn’t know that she will start playing games in real life as well,” Sidharth said. Sidharth Sagar shared the screenshot of his WhatsApp chat exclusively with IBTimes IndiaNarrating the domestic violence incident, Sidharth recalled, “And talking about the domestic violence incident, let me tell you that it had happened one month before we broke up. Now why did she talk about it in the media all of sudden. We had broke-up on good terms but she chose to use the incident for her own benefit. Let me tell you that she had been in relationships five or six times before ending this one, but for me, it was my first. And even on the fateful day, we had an argument on the same thing about doing celebrity couple shows together. I insisted her that we can’t go together as things may turn more ugly between us.He continued, “She then suddenly grabbed me by my neck and punched me hard on my nose. I had started bleeding profusely and I even had blood stains on my T-shirt and my shorts. I somehow tried to get out of the situation, I pushed her and I think she got hurt. I stepped out of the house and Subuhi, by then, had locked the door from inside. I asked her to give me my phone that I had left inside but she replied, ‘ab nahi dungi, jo karna hai kar.’ So when I bought a new T-shirt from outside and got back home, Subuhi had already called the police. I was shocked. I started wondering why would a person who claims to love you so much, would do such a thing.”Click here to continue reading…last_img read more

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Houston Company Takes Telecommuters Around The World For A Year

first_imgListen Share To embed this piece of audio in your site, please use this code: Andrew SchneiderMeredith Kalinov is one of the co-founders of Pangea196, along with Lawrence Kalinov, Stela Tomova and Bobby Mansour.If you work remotely from home or a coffee shop, why not just work from an exotic vacation spot?That’s the concept of Houston startup company Pangea196.For $27,000, they organize flights and accommodations for one year for people who want to combine work and travel.For this week’s Bauer Business Focus, News 88.7’s Florian Martin spoke with one of the co-founders, Meredith Kalinov.You can listen to the interview by clicking on the play button above. 00:00 /03:44 Xlast_img read more

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Louisville to Host Notre Dame on Feb 16 on ACC Network

first_imgStory Links LOUISVILLE, Ky. – University of Louisville women’s basketball will host Notre Dame on Sunday, Feb. 16. The game will be televised exclusively on the ACC Network.The Cardinals and Fighting Irish will square off two times this season with the Atlantic Coast Conference schedule expanded to 18 games. The date for the contest in South Bend, Ind., has yet to be announced.It marks the first time that Louisville will host Notre Dame since Jan. 11, 2018, when the Cardinals downed the Fighting Irish, 100-67.That season, Louisville won both encounters with Notre Dame, winning 74-72 in the ACC title game for its first ACC Tournament title. Last season, the Fighting Irish returned the favor, winning both games against the Cardinals.Louisville released its 2019-20 non-conference schedule earlier this week, while the full ACC schedule is expected to be released in September.Last season, the Cardinals produced a second consecutive 30-win season with a 32-4 record and won their second straight ACC regular season title. They entered the NCAA Tournament as a No. 1 seed for the second straight year and advanced to the Elite Eight for the fifth time in program history.Louisville returns six players that made starts last season, including seniors Yacine Diop, Bionca Dunham, Jazmine Jones and Kylee Shook, along with junior Dana Evans, the reigning ACC Sixth Player of the Year.Women’s basketball season tickets go on sale to the general public on Monday, Aug. 5. Additional information is available online at www.GoCards.com/wbbtickets.For the latest on Louisville women’s basketball, visit GoCards.com, or follow the team’s Twitter account at @UofLWBB or on Facebook at facebook.com/UofLWBB. Print Friendly Versionlast_img read more

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Vice Media Reveals 182 Gender Pay Gap in UK Operations

first_imgVice Media has revealed an average gender pay gap of 18.2% in favor of male employees across its U.K. companies. The youth-focused media company informed its British-based staff of the figures, which show that the average hourly wage for men across the organization is 18.2% higher than their female colleagues – above the national average of 17.4%.The company was not obligated to share its figures as part of the British government’s requirement that all U.K. firms with more than 250 employees share their pay gap data by the end of Wednesday. None of Vice’s individual British-based operations, which consist of Vice U.K., Level Print, i-D, Pulse, Vice U.K. TV and Starworks, have 250 employees, and Vice noted that the law does not look at the combined staffing of multiple entities. Together, Vice’s operations employ more than 400 people. Popular on Variety However, Vice management said they had compiled the figures and shared them with staff because the company was “committed to being open and transparent.” They said a global audit of pay across different roles and levels of the media company was also underway and would be completed before the end of the year.Amazon also reported its numbers to the government by the Wednesday deadline, with each of its six U.K. operations employing more than 250 staff reporting separately. Most of these showed a significant gender pay gap, most lopsidedly Amazon Video, which saw women earning 40.1% less on average.Amazon Online U.K. posted an average gap of 17.4% in favor of men, Amazon Web Services a gap of 15.8%, and Amazon EU s.a.r.l’s U.K. branch a gap of 18.2%.However, across all Amazon U.K. operations, including those with less than 250 employees, the average gender pay gap was just 6.1% in favor of men – significantly lower than the 17.4% national average.center_img ×Actors Reveal Their Favorite Disney PrincessesSeveral actors, like Daisy Ridley, Awkwafina, Jeff Goldblum and Gina Rodriguez, reveal their favorite Disney princesses. Rapunzel, Mulan, Ariel,Tiana, Sleeping Beauty and Jasmine all got some love from the Disney stars.More VideosVolume 0%Press shift question mark to access a list of keyboard shortcutsKeyboard Shortcutsplay/pauseincrease volumedecrease volumeseek forwardsseek backwardstoggle captionstoggle fullscreenmute/unmuteseek to %SPACE↑↓→←cfm0-9Next UpJennifer Lopez Shares How She Became a Mogul04:350.5x1x1.25×1.5x2xLive00:0002:1502:15last_img read more

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MovieBob Review Jack Reacher Never Go Back

first_imgLee Childs’ Jack Reacher books are about an ex-military crime-solving prodigy who’s built like brick shithouse, has a mind like a steel trap, and is basically good at fucking everything “because Army.” He travels the United States as a no-frills drifter using his exceptional skills to beat up bad guys and solve mysteries frequently relating to injustices perpetrated against his fellow servicemen. This  allows him to comfortably straddle a line between just patriotic enough to be righteous about the brotherhood of armed service while being rebellious and anti-establishment enough to defy cretinous superiors and brace at bureaucratic rigidity.And, for some reason, instead of becoming a syndicated TV vehicle for whoever the present-day equivalent of Kevin Sorbo or Lorenzo Llamas is, somebody decided that this needed to be a movie franchise for Tom Cruise whenever the 54 year-old action star needs to get some jogging in between increasingly-interchangeable Mission: Impossible sequels.The first movie was really nothing special – at all – but at least it had the temerity to lean into the ridiculousness of its own premise: It was essentially wall-to-wall scenes where characters talked up “JACK REACHER!” as this legendary mythic god among ass-kickers who beats up dozens of guys at a time like nothing, is so good at using every conceivable weapon that people recognize him by taking rifle shots that “only the famous Jack Reacher could make!,” turns every woman immediately wobbly and smitten at the first glance of him, and basically playing him off like a black velvet painting of John Cena in human form. But meanwhile up onscreen it was still just itty-bitty adorable lil’ Tommy Cruise. Oh and they also got Werner Herzog to be the bad guy, so… points for that.The new film doesn’t really have much of that or anything else going on – to be honest, the whole thing feels like a really obvious rush-job; right down to most of it relocating from Washington DC to New Orleans for no particular reason, aka current movie-location shorthand for “We’re doing this shit so cheaply we’re not only taking that sweet-ass Louisiana tax credit, we’re not even gonna bother dressing the city up like it’s supposed to be someplace else!”As far as the story is concerned, there really isn’t much of one. Jack Reacher (“What? Not the Jack Reacher!!?”) shows up in DC basically looking to make an impromptu booty-call on a female Army Major he’s been playing phone tag with and discovers that she’s been framed for murder as part of a conspiracy to cover up nefarious goings on involving Blackwater-style Private Military Contractors because that’s who you use for bad guys when you want to do a movie about shady shit going down in the military but don’t want the actual military to be at all cross with you – heaven forbid.They whole thing basically turns into an oddly slow-paced cross-country chase story that – for reasons I’m assuming made more thematic sense as part of a multi-volume book series than they do here – for some reason also needs to involve Reacher’s maybe-maybe-not previously unknown teenager daughter getting dragged along as Reacher and Cobie Smulders as The Major dodge a singularly uninteresting set of bad guys until the film has run approximately long enough to qualify as a feature and presumably give the film’s predominantly China-based production investors the ability to have Tom Cruise’s face on Chinese movie posters for the late-Fall moviegoing season.The sole noteworthy thing in the film is finding out just how much of action-hero asset the Marvel movies have been overlooking in Smulders. Sure, she gets to fire off some guns and look slick in a S.H.I.E.L.D. uniform as Maria Hill, but here she gets full-on knock-around drag-out beatdown scenes and she comes off like a legit beast!It’s a hell of a physical turn and provides the only remotely lively or refreshing moments the otherwise disposable feature can muster… even if at this point after Emily Blunt in Edge of Tomorrow and Rebecca Ferguson in the last Mission Impossible I imagine we’re all used to this exact character being a Tom Cruise movie mainstay – what better way to bank progressive-feminist goodwill while also helping the increasingly all-too-human seeming Mr. Cruise lighten his fight-scene load?This movie would probably be offensively terrible if it bothered to try hard enough, but we aren’t even that lucky – and I’m not sure whether or not that’s actually preferable. The only reason I can imagine to actually watch Jack Reacher: Never Go Back would be to see exactly how little impact a film can leave while still, technically, existing.last_img read more

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Red light goes green Metalfree organic sensitizers portend significant advance in artificial

first_img(Phys.org)—Photosynthesis – the ubiquitous yet remarkable process by which most plants, algae, and cyanobacteria convert light energy into chemical energy – provides the atmospheric oxygen and organic compounds fundamental to the evolution of life on Earth, and in so doing captures some six times more energy than humans consume while annually converting roughly 100 billion tons of carbon into biomass. In the effort to find alternatives to fossil fuels, the field of artificial photosynthesis – a chemical process that replicates natural photosynthesis – seeks to capture and store energy from visible light, including sunlight, in the chemical bonds of what is known as a solar fuel (for example, hydrogen, methane or methanol). Citation: Red light goes green: Metal-free organic sensitizers portend significant advance in artificial photosynthesis (2015, February 18) retrieved 18 August 2019 from https://phys.org/news/2015-02-red-green-metal-free-sensitizers-portend.html Explore further © 2015 Phys.org “There are not many molecules that combine all the right properties,” Mallouk notes, these being:strongly absorbing in the visible spectrumlong-lived excited state that is energetically capable of rapidly injecting an electron into the conduction band of titanium dioxide (TiO2)highly oxidizing in its oxidized formchemically stable over many cycles of photoredox reactions (those that harness visible light energy to accelerate a chemical reaction via a single-electron transfer) To be both effective and efficient, artificial photosynthesis requires tunable photosensitizers (light-absorbing molecules also referred to simply as sensitizers that mediate reactions to light) to capture, convert, and transfer visible light energy. To also be practical, these sensitizers must have a very specific absorption, excitation, oxidative, and stability profile; react strongly to red light; and use readily available materials. Recently, scientists at Pennsylvania State University, University Park and Arizona State University, Tempe designed and demonstrated metal-free organic photosensitizers that meet these criteria, thereby achieving photoelectrochemical water oxidation at a level comparable to sensitizers based on rare materials while being the first artificial molecules to oxidize water using only red light.Prof. Thomas E. Mallouk discussed the paper that he, Dr. John R. Swierk and their co-authors published in Proceedings of the National Academy of Sciences. Describing the challenges of showing that metal-free organic photosensitizers are capable of driving photoelectrochemical water oxidation, Mallouk points out that while water splitting to hydrogen and oxygen is a thermodynamically straightforward reaction – it can be driven by light anywhere in the visible spectrum – a detailed thermodynamic analysis published in 1985 showed that light of wavelength shorter than 775 nm can in principle drive efficient solar water splitting1. “However,” Mallouk tells Phys.org, “there are a number of practical constraints for a system in which light is absorbed by a molecule and the molecule then oxidizes water to make oxygen” Excited states do not last long, and there is a strong driving force for them to return to the ground state, usually by a series of thermodynamically downhill and rapid electron transfer steps.”In both natural and artificial photosynthetic systems, the light-absorbing molecule in its excited state transfers an electron to an acceptor, which in the research being discussed is an oxide semiconductor electrode. “The oxidized form of the molecule must then take an electron from water – usually via another molecule that catalyzes water oxidation – before the photoinjected electron comes back from the semiconductor and regenerates the ground state. The back electron transfer process is parasitic, in that it converts the energy of the excited state into heat.” Moreover, Mallouk says, back electron transfer is typically fast – occurring in 100 microseconds or less – and so to oxidize water the oxidized dye molecule needs to work quickly, meaning that it has to be a fairly powerful oxidizer – at least 300 mV more positive in the electrochemical series than the oxygen/water couple. The Z-scheme electron transport chain links the two photosystems found in plants, algae and cyanobacteria. Credit: Wikimedia Commons. Licensed under GFDL/CC BY-SA 3.0. , Journal of the American Chemical Society The paper also notes that while the open-circuit photovoltages and integrated photocurrents are quite similar for most of the free-base porphyrin sensitizers, the scientists’ deeper analysis of the spectral and electrochemical properties of the sensitizers reveals significant differences. “We found that changing the substituents on the porphyrin ring had a relatively small effect on the energy of the excited state, which correlates with the difference between the excited and ground state oxidation potentials,” Mallouk explains. “However, changing the substituents did significantly shift these potentials relative to the oxygen/water potential.” For example, with electron-withdrawing substituents the oxidized form of the molecule was a more powerful oxidant, but the excited state was a weaker reductant. “There’s a tradeoff between these properties since one would like both electron injection from the excited state and oxidation of water from the oxidized form of the dye to be fast processes – and the rates of these processes depend on and are sensitive to the electrochemical driving force for electron transfer.”In the paper, the scientists discuss their ideas on developing a kinetic picture to enable rational design strategies for improving the system. Previously, they had developed2 a model for dye-sensitized water splitting photoelectrochemical cells that incorporates the kinetics of all the electron transfer reactions in the system. “These processes,” Mallouk tells Phys.org, “include electron injection from the excited state molecule into the TiO2 semiconductor, electron transfer from the water oxidation catalyst to the oxidized dye, electron transport in the TiO2 electrode, electron hopping between sensitizer molecules, and two parasitic recombination processes – that is, back electron transfer from TiO2 to the oxidized dye, and electron scavenging by the water oxidation catalyst. While the recombination processes are winning the battle, so the overall quantum yield of water splitting is low, we know that all the electron transfer rates depend strongly on the distance between redox partners – so we hope to slow down the parasitic reactions using core-shell electrode structures, a strategy already demonstrated with ruthenium-containing sensitizers by our team and by Prof. Thomas J. Meyer’s group at the University of North Carolina at Chapel Hill. We’re also investigating molecular catalysts in order to shorten the electron hopping pathway from the dye to the catalyst.” What’s critical is that each of these design ideas can be tested by measuring the kinetic rate constants, which the scientists obtain from the time-dependent photocurrent and photovoltage in the cell.A central point made in the paper is that the utilization of red light to drive water splitting represents a significant step forward for molecular photoelectrochemical water-splitting systems. “Yes, it’s an important step,” Mallouk explains, “because red light accounts for most of the energy in the solar spectrum. In addition, there are other macrocyclic compounds that are structurally related to porphyrins that while being a bit more challenging to synthesize are much stronger red light absorbers. We hope to investigate those molecules in the future.”In addition to developing core-shell structures and molecular catalysts, as discussed above, the scientists are creating sensitizer molecules that should absorb more strongly in the red visible spectrum. Moreover, the Arizona State team has made linked sensitizer-mediator molecules that speed up electron transfer between the catalyst and the sensitizer molecule. “We’re also working on a molecular photocathode assembly that should develop sufficient photovoltage to generate hydrogen without applying a bias voltage to the cell,” Mallouk adds. “Together with the photoanode assembly, this will make a photoelectrochemical ‘Z-scheme’ in which two photons are absorbed – one at the anode, the other at the cathode – for each electron transferred in the cell.” The so-called Z‐scheme typically refers to oxidation/reduction processes in reactions to light during natural photosynthesis.”As part of this project,” Mallouk concludes, “we and other groups have begun to develop membranes for use in water splitting solar cells3,4,5. “We believe that the membrane results could be broadly applicable to electrolyzers and related technologies for solar fuels, including systems that reduce CO2 to carbon-containing fuels.” This document is subject to copyright. Apart from any fair dealing for the purpose of private study or research, no part may be reproduced without the written permission. The content is provided for information purposes only.center_img More information: Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells, Proceedings of the National Academy of Sciences Published online before print January 12, 2015, doi:10.1073/pnas.1414901112Related: 1Limiting and realizable efficiencies of solar photolysis of water, Nature (1985) 316: 495-500, doi:10.1038/316495a0 2Effects of electron trapping and protonation on the efficiency of water-splitting dye-sensitized solar cells, Journal of the American Chemical Society (2014) 136:10974-10982, doi:10.1021/ja5040705 3Resistance and polarization losses in aqueous buffer–membrane electrolytes for water-splitting photoelectrochemical cells, Energy & Environmental Science (2012) 5:7582-7589, doi:10.1039/C2EE03422K 4Assessing the utility of bipolar membranes for use in photoelectrochemical water-splitting cells, Chemistry & Sustainability, Energy & Materials, (2014) 7:3017–3020, doi:10.1002/cssc.201402535 5Use of bipolar membranes for maintaining steady-state pH gradients in membrane-supported, solar-driven water splitting, Chemistry & Sustainability, Energy & Materials, (2014) 7:3021-3027, DOI: 10.1002/cssc.201402288 Journal information: Proceedings of the National Academy of Sciences Selected electron transfer processes in WS-DSPEC: (i) injection, (ii) recombination, (iii) hole transfer, (iv) regeneration of oxidized sensitizer, and (v) transport to the fluorine-doped tin oxide anode. Credit: Swierk JR, et al. (2015) Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells. Proc Natl Acad Sci USA 112(6): 1681-1686. , Energy & Environmental Science , Nature “To date,” he adds, “the field has been dominated by studies of ruthenium- and iridium-containing coordination compounds that combine these properties – but our paper explores the idea of using porphyrins in place of ruthenium and iridium complexes in a water-splitting dye-sensitized photoelectrochemical cell.” Porphyrins (macrocyclic organic compounds (that is, those with a ring structure consisting of 12 or more atoms) structurally related to the pigments in chlorophyll and hemoglobin are strongly absorbing. Moreover, with the right substituents (atoms or group of atoms taking the place of another atom or group or occupying a specified position in a molecule), porphyrins have the photoredox properties needed to drive water oxidation in a dye-sensitized electrode – and unlike ruthenium and iridium, are neither rare nor expensive. To accomplish this, the scientists had to synthesize the dye molecules, incorporate them into the cell with appropriate catalyst particles, and quantify the oxygen generated at the illuminated photoelectrodes.The researchers also demonstrated that under broadband illumination, these metal-free organic photosensitizers exhibit activity comparable to that of ruthenium-containing photosensitizers. “The activity is assessed by measuring the photocurrent and oxygen evolution yield as a function of the applied bias potential,” Mallouk explains. “Earlier studies had already established the 2:1 H2/O2 stoichiometry of water splitting in this kind of cell, where hydrogen is made by reduction of water at a dark platinum counter electrode.” (Stoichiometry is the relationship between the relative quantities of substances taking part in a reaction or forming a compound, typically a ratio of whole integers.)Another important finding presented in the paper was that this is the first molecular photosensitizer, outside of natural photosynthesis, that can drive water oxidation utilizing only red light. (Previous research based on ruthenium split water – but only using blue light.) Mallouk emphasizes that since porphyrins absorb strongly between the Soret band and the Q-bands (400-450 nm and 500-670 nm, respectively), it was important to show that the system worked under red light (wavelengths longer than 590 nm) – that is, so that absorption was occurring only in the Q-band region – because most of the photon flux in sunlight is in the red and near-infrared part of the spectrum. “Previously” he points out, “only metal-containing sensitizers that absorb in the blue at wavelengths shorter than 500 nm had been used in this kind of water splitting cell.”A significant challenge the Arizona State part of the team faced was to design and synthesize porphyrin molecules that were sufficiently oxidizing to drive the rapid oxidation of water, as well as sufficiently reducing in their excited state to rapidly inject an electron into the titanium dioxide conduction band. “We tuned the oxidizing power of the porphyrins by placing appropriate substituents on the porphyrin ring,” Mallouk recounts. “In addition, the porphyrins needed to be designed with specific functional groups that would allow attachment to the oxide electrode surface.” To that end, the Penn State part of the team had to determine the right conditions for adsorbing these molecules on the electrode surface, which was made easier by their already having worked out the testing conditions and the methods for determining electron transfer rate constants from earlier studies with other dye molecules. Mimicking photosynthesis path to solar-derived hydrogen fuel Free-base porphyrin sensitizers used in this study. Compound acronyms are defined in SI Appendix. Credit: Swierk JR, et al. (2015) Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells. Proc Natl Acad Sci USA 112(6): 1681-1686.last_img read more

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