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Dec. 22, 2007
LOGAN, Utah - Lindsey Shipley scored a career-high 19 points to lead a quartet of double-figure scorers for Utah State in an easy 81-60 non-conference win against Saint Mary's here at the Dee Glen Smith Spectrum Saturday afternoon, giving the Aggies its first home win of the season.
The win snapped a two-game losing skid for USU and improved its record to 3-7, while Saint Mary's has lost six of its last seven games in falling to 6-8.
Taylor Richards added 17 points, five rebounds, four assists and three steals for Utah State, while Danyelle Snelgro and Alice Coddington each added 11 points.
Louella Tomlinson had game-highs of 26 points and 13 rebounds to lead Saint Mary's, while Serena Benavente scored 11 points.
Saint Mary's scored the first points of the game on a jumper by Benavente, but the lead was short-lived as Coddington hit a three-pointer on Utah State's next possession and the Aggies never trailed again. USU increased its margin to 21-9 on a free throw by Ana Pares and went into the half with a 38-27 advantage.
In the opening period, Utah State shot 45.5 percent from the field (15-33) and 60.0 percent from behind the arc (3-5), while Saint Mary's made just 35.5 percent of its field goals (11-31), including 3-of-8 (.375) from three-point range. Shipley led the Aggies with nine points at the break, while Richards and Snelgro each had eight.
Utah State scored the first four points of the second-half to increase its lead to 15, before Saint Mary's scored the next six points to get within nine. USU then went on an 11-2 run over the next three-plus minutes to push its margin to 18 at 53-35. The Gaels got back within nine points on a jumper by Tomlinson at the 12:18 mark to make the score 55-46, but the Aggies regained control of the game with a 15-2 run en route to the 21-point win.
Utah State finished the game by shooting 44.9 percent from the field (31-69), 45.5 percent from three-point range (5-11) and 66.7 percent from the free throw line (14-21), while Saint Mary's shot just 37.5 percent (24-64), including 30.8 percent from behind the three-point arc (4-13). The Gaels did out-rebound USU, 47-40, but the Aggies did a much better job controlling the ball as it recorded a season-high 19 assists to go along with a season-low nine turnovers.
Utah State will return to action on Saturday, Dec. 29 when it hosts in-state rival BYU (5-6) at 5 p.m. in the Dee Glen Smith Spectrum prior to USU's men's team hosting Oral Roberts at 7 p.m.
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WASHINGTON – More than 300 Navajo Nation jobs are at stake because of "excessively stringent and expensive" regulations the Environmental Protection Agency has proposed for the San Juan power plant, a tribal official testified Wednesday.Read More »
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BLM to hold meetings on NM-Ariz. power line
The public will have a chance to chime in on a proposed high-voltage power line that would run through New Mexico and Arizona. The Bureau of Land Management has scheduled a series of open house meetings in both states on an electrical transmission line that could provide up to 2,500 megawatts of electricity.Read More »
Phoenix Mayor Stanton sees empty lots full of opportunities
Recently elected Phoenix Mayor Greg Stanton and architectural sustainability consultant Bill McDonough held a conversation with the downtown Phoenix community last month to figure out ways to put the empty lots that dot the city to work.Read More »
Milking the Sun: Zimmerman Dairy goes 100% solar – first in Arizona
Zimmerman Diary has been operating in Arizona for nearly 90 years, but its long-lasting success doesn't mean its third-generation owners haven't had to innovate to survive along the way. Facing rising costs, in March 2011 the Zimmermans installed a shiny new fixture they say will enable them to continue to stay in business regardless of electricity rates.Read More »
Corp. Comm. attorney: Measure to restrict renewable standards is power grab
Legislation aimed at barring the Arizona Corporation Commission from adopting renewable energy standards that are more stringent than what is currently in place is an unconstitutional power grab by lawmakers, the Commission's lead attorney says.Read More »
BLM to hold meetings on renewable energy proposals
The U.S. Bureau of Land Management is holding a series of public meetings across Arizona on proposals for renewable energy development. Three meetings are scheduled next week in Phoenix, Flagstaff and Kingman. Two others are scheduled in Yuma and Tucson next month.Read More »
Corp. Comm. barred from adopting more stringent renewable energy standards
A panel of senators today approved legislation to bar the Arizona Corporation Commission from adopting renewable energy standards that are more stringent than what is currently in place. Many consider the bill an attempt by lawmakers to assert control over the state's energy policy, but critics said it infringes on the commission's constitutional authority to set rates for public utility companies.Read More »
New proposal would limit AZ renewable energy rule
A bill that would give the Legislature a say over energy rules adopted by the Arizona Corporation Commission is being scaled back. An amendment proposed for consideration by a Senate committee Wednesday would rewrite the bill approved by the House.Read More »
Environmentalists fear utility will be exempt from efficiency requirement
Environmentalists fear that the Arizona Corporation Commission may waive its stringent energy efficiency standards rather than approve a power-cutting plan submitted by Tucson Electric Power and scheduled for a vote Friday.Read More »
Energy and Irony: HB2789 will cost Arizona dearly
The Arizona Legislature is considering HB2789, which significantly increases government regulation by requiring every rule the Arizona Corporation Commission (ACC) makes that affects "public service corporations" (a.k.a. utilities) go before the full House, the Senate and the governor for approval ...Read More »

subset: commoncrawl


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This is the home page for a variety of services provided by Hamilton Utilities Corporation. As your source for rental hot water heaters, we offer a 30-year trMore
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(905) 522-6611(905) 317-4703Fax
Pro2015_Iteration9_NoTests.148[03] SEIDXWK-41


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"This is an absolute must for every physician who performs perioperative consultation services. It is an excellent compendium in a very easy to use format." - DOODY'S BOOK REVIEW, 5 Stars *****
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Champions League: Bayern Munich advances
Manchester City reaches second round, Man United ties Real Sociedad.
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FRANKFURT—Titleholder Bayern Munich won 1-0 at Viktoria Plzen on Tuesday to advance to the knockout stage of the Champions League, while group rival Manchester City reached the second round for the first time by outclassing CSKA Moscow 5-2.
Paris Saint-Germain and Real Madrid missed early opportunities to qualify by being held to draws — PSG 1-1 at home to Anderlecht, Real 2-2 at Juventus — and both had to come from behind.
Later, Robin van Persie missed a penalty as Manchester United was held to a 0-0 draw at Real Sociedad in Group A. United can clinch a place in the knockout stage with a victory at Leverkusen next time out.
In a match with few thrills, substitute Mario Mandzukic scored with a second-half header to put Bayern through, while a hat trick from Alvaro Negredo and a brace from Sergio Aguero propelled City into the next stage.
Bayern has four wins from four games and tops Group D with 12 points, while second-place City has nine following its victory over CSKA.
It was Bayern's ninth consecutive win in the Champions League over two seasons, equalling Barcelona's record from the 2002-03 campaign. Bayern and City advanced with two matches to spare.
"We would have wished for a better performance," Bayern goalkeeper Manuel Neuer said.
Captain Philipp Lahm said his team had "slept through the early stage of the match. Perhaps we think it's going to be easy."
Midfielder Toni Kroos said Bayern lost possession too often, "but we have 12 points from four games and we can be proud of that."
Plzen slipped to a fourth straight loss and is out of contention.
The in-form Aguero converted a penalty in the third minute, added a sumptuous second in the 20th and then fed Negredo for a tap-in as City raced into a 3-0 lead after half an hour in Manchester. CSKA striker Seydou Doumbia also scored twice — either side of Negredo's second goal in the 51st — before the Spanish striker completed his hat trick with the last touch of the game from a header.
Top News
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7 Free Tutorials on How to Cook Practically Anything
These seven free cooking lessons will finally teach you how to cook — from mastering knife skills to perfecting that chicken dish.
These seven free cooking lessons will finally teach you how to cook — from mastering knife skills to perfecting that chicken dish.
Coffee just got even better. It turns out you can repurpose old coffee grounds to de-stink your stuff, fertilize your garden, or exfoliate your skin. We'll raise our mug to that.
Hate cooking but trying to clean up your diet? These new kitchen gadgets can help you create satisfying homemade meals.
Breathlessness results from hard workouts, but what about when it's due to harmful toxins? Learn how air pollution affects outdoor exercise and tips to minimize damage.
Some spas are now offering energy-boosting injections of nutrients like vitamin B. Here's why it might be risky to get a shot outside your doctor's office.
Want an easier way to maintain those healthy eating habits? From smart meal prep tips to kitchen organization hacks, these organizing ideas will help set you up for success.
Spring's here and we all want to get outside. But for those with an allergy, it could mean misery. Read on for tips to keep allergies from ruining your workout.
New season, new start on your nutrition plan! Learn how to stock up on healthy foods with these easy "spring cleaning" for your kitchen tips.
Do you know what vaccines you should be getting as a grown-up? Here's what you need to know about immunizations for measles, Tdap, HPV and more.
Why buy new kitchen gadgets when you can do more with what you have? From blender tricks to waffle iron techniques, these kitchen hacks will step up your healthy cooking game.
Gluten-free may be all the rage, but new research shows that another molecule could be wreaking havoc on your digestion. Is the low-FODMAP diet is right for you?
Don't be yellow about eating egg yolks; science shows there's nothing to fear. Read on for the skinny on which are healthier, egg whites versus whole eggs.
In honor of American Heart Month, get the scoop on four causes of chest pain you've never heard of before — and learn why you should get them checked out.
Spirulina has been called one of the most potent superfoods. Before adding it to your diet, check out these spirulina benefits (and drawbacks).


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TULSA — After Oklahoma State clinched the outright Big 12 baseball title Friday night with a 2-1 walk-off win over Oklahoma, Cowboys coach Josh Holliday looked down the table at Saulyer Saxon, his senior centerfielder, and shook his head.
College baseball: Cowboys trim Sooners, clinch Big 12 regular-season title
"Man, how many moments can one guy have in one night?" Holliday said.
Saxon came up with several big catches in the outfield before his infield single in the ninth set off a celebration that left Saxon covered in shaving cream as the Cowboys celebrated their first regular-season title in Big 12 history in front of a sold-out crowd of 8,391 at ONEOK Field.
Oklahoma State won this one much like it had done all year, with timely hitting, solid defense, strong arms and a consistent sense of composure.
Even after normally unshakeable reliever Vince Wheeland gave up the tying run in the eighth, Holliday never wavered on OSU finding a way.
"Our team owed it to him to score that run," Holliday said. "That kid has pitched so good, so good that I just knew those kids would find a way to score because that's what teammates do."
Continue reading this story on the...


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Full name Sundaram Ravi
Born April 22, 1966, Bangalore, Karnataka
Current age 49 years 165 days
Other Umpire
|Test debut
|Bangladesh v New Zealand at Chittagong, Oct 9-13, 2013 scorecard
|Last Test
|England v Australia at Nottingham, Aug 6-8, 2015 scorecard
|Test matches
|Test statistics
|ODI debut
|India v West Indies at Visakhapatnam, Dec 2, 2011 scorecard
|Last ODI
|Afghanistan v England at Sydney, Mar 13, 2015 scorecard
|ODI matches
|ODI statistics
|T20I debut
|India v England at Kolkata, Oct 29, 2011 scorecard
|Last T20I
|New Zealand v South Africa at Chittagong, Mar 24, 2014 scorecard
|T20I matches
|T20I statistics
The makeshift opener who batted and batted
Thrust into the job in Kanpur in 2004, Andrew Hall gave an underachieving South Africa side belief that they could wear India down at home
West Indies still reeling from India pullout
The controversy over selection for the Sri Lanka ODIs shows that the board hasn't moved on from the tumultuous events of last year
The Azhar Ali answer to Pakistan's top-order woes
In Pakistan's Test history, no player batting in the top three positions has scored 4500 runs; Azhar Ali is well on course to becoming the first
Obstructing winners, and in-law captains
Also: slowest to 100 Test wickets, run out in both innings, and the oldest surviving Test captain
Most sixes hit in India, and Duminy's fastest fifty
Stats highlights from the first T20I between India and South Africa in Dharamsala
He's delightful to watch because he makes batting look easy, but there are some gaps in his technique in the long form
West Indies still reeling from India pullout (38)
The controversy over selection for the Sri Lanka ODIs shows that the board hasn't moved on from the tumultuous events of last year
Ditch the toss? Hold fire (27)
In a new series, we look at what the numbers reveal about the toss in Test matches, and the emergence of No. 5 as the most pivotal batting position
Ranji Trophy's familiar tale of indifference (22)
The Ranji Trophy is a logistical wonder, yet it exists in a vacuum at the heart of the Indian cricket season
Mishra benched in depth and dew dilemma (20)
With India wanting a bowler who can bat at No. 7, the defensive left-arm spinner Axar Patel was preferred over the legspinner Amit Mishra in Dharamsala


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Im working on a project that has a main swf file associated with the document class. It loads XML that provides the text content for the project, then it loads a swf that contains a font in its library, then it loads the first of several content module swfs. When the font swf has inited, I'm registering its library font with Font.registerFont(), and using it in a TextFormat object. After everything is done, I can add code to the document class to create a text field on the stage of the main swf and format it successfully with the TextFormat object, but when I try to do the same thing inside the loaded content module swf, the text doesn't show up there at all. Any help would be appreciated.
I love the difficulty of the question.
Never faced the problem, but first you may verify :
Or can't you simply embed the font with :
(in this order, setting the text before the textformat doesn't worked for me)
Be sure you're using the embedded font's fontName for define your textFormat's font.


text:
Inject some glamour into your resort look with these jewel embellished sandals, they're the perfect style to wear with a maxi dress for evening. Shown here with an Elizabeth and James dress, a Christian Louboutin bag and a DAY Birger et Mikkelsen bangle set.
Blush satin leather thong sandals with a jeweled front. Giuseppe Zanotti sandals have strap across arch, a small heel and a side fastening ankle strap.
Product code: 37587 - Need help? Contact us


text:
Our holdings include hundreds of glass and film negatives/transparencies that we've scanned ourselves; in addition, many other photos on this site were extracted from reference images (high-resolution tiffs) in the Library of Congress research archive. (To query the database click here.) They are adjusted, restored and reworked by your webmaster in accordance with his aesthetic sensibilities before being downsized and turned into the jpegs you see here. All of these images (including "derivative works") are protected by copyright laws of the United States and other jurisdictions and may not be sold, reproduced or otherwise used for commercial purposes without permission.
Vintage photos of:
January 1911. "First Aid to the Injured" man with Draeger Oxygen Helmet. Avondale Shaft, D.L. & W. [Delaware, Lackawanna & Western Railroad] Colliery near Nanticoke, Pennsylvania. View full size. Photo by Lewis Wickes Hine.
January 1911. Shaft #6, Pennsylvania Coal Co. mine at South Pittston. "At the close of the day. Waiting for the cage to go up. Small boy in front is Joe Pume, a Nipper, 163 Pine St." View full size. Photo and caption by Lewis Wickes Hine.
October 1908. Digging coal by machinery at the Brown Mine in West Virginia. Note open-flame headlamps. View full size. Photograph by Lewis Wickes Hine.
September 1908. Young mule drivers and trapper boy at the Brown Mine near Brown, West Virginia. Underground from 7 a.m. to 5:30 p.m. View full size.
January 1911. "Serafino driving Chub, his mule. Shaft #7, Pennsylvania Coal Company mine at South Pittston." Bright spots are open flames of lamps on the boys' hats. Photograph by Lewis Wickes Hine. View full size.
A young leader and a driver, Shaft #6, Pennsylvania Coal Company mine at Pittston. Pasquale Salvo and Sandy Castina. January 1911. View full size. Photograph by Lewis Wickes Hine.
January 1911. A lonely job. Waiting all alone in the dark for a trip to come through. Willie Bryden, a nipper, lives at 164 Center St. in South Pittston. It was so damp that Willie said he had to be doctoring all the time for his cough. A short distance from here, the gas was pouring into the mine so rapidly that it made a great torch when the foreman lit it. Willie had been working here for four months, 500 feet down the shaft, and a quarter mile from there. (Shaft #6, Pennsylvania Coal Co.) Walls have been whitewashed to make it lighter. January 16, I found Willie at home sick. His mother admitted that he is only 13; will be 14 next July. Said that 4 months ago the mine boss told the father to take Willie to work, and that they obtained the certificate from Squire Barrett. (The only thing the Squire could do was to make Willie out to be 16 yrs old.) Willie's father and brother are miners and the home is that of a frugal German family. View full size. Photograph (5x7 glass negative) and caption by Lewis Wickes Hine.


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Your first look at what's happening around Milwaukee. All of the latest events you can't miss in the city.
On Tap for Today: Music, bikes and hissing cockroaches
We're not going to sugar-coat things. If you're a glass half-full kind of person, you're that much closer to the weekend. If you're not, well, these activities might help make the time pass more quickly.
It's International Walk or Ride Your Bike to School Day. Students, parents and staff at Fairview School in are meeting at 7:15 a.m. at 60th and Oklahoma to join in. Look out for them.
Since you're on the lookout, check this out. Buyseasons.com will try to break the Guinness World Record for the most people dressed in costumes of video game characters today. They plan to have 450 people dressed as Angry Birds, Mortal Kombat, well, you get the idea. It happens from 1 to 2:30 p.m. at 5915 S. Moorland Road. It should be obvious.
And this isn't for everyone but just in case -- Batzner Pest Management in New Berlin hosts its annual Madagascar Hissing Cockroach Race today. Teams of employees will race the roaches on a specially-built 8-foot track. Here's a blog post from last year's race.
The race starts at 1:30 p.m. is open to the public.
Keb Mo is at the Pabst Theater tonight. That should help with any mid-week moodiness. Bobby Long plays at Turner Hall Ballroom.
A new exhibit opens today at the Museum of Wisconsin Art in West Bend. You can get more details here.
On television you'll find "Penn & Teller Tell a Lie;" "Mad Scientists" and "American Horror Stories." Times and stations are listed here.
Comments »
Read and share your thoughts on this story.


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Diwali with Television and Bollywood Stars
Added on 11/5/2010
By : bollycurry
Overall Rating :
Rate Me... Rating Saved!
View : 113018 Comments : 6 Video Courtesy : www.india-forums.com
|Total Votes : 7
|Sunni.L.Arman, sashishezi, Bollywood, .-BalleBalle-., .Senorita., lonelyshadow
really happy to see all of them cheerfully wishing us happy diwali...thanx india forms loved yashashsri/kt happily smiling and wishing us happy diwali in the very beginning.
good 4 see bips after long time
luv u sachi n shravaan
:) Happy Diwali. Great vid.
wow thats a really wonderful collage...
Wow.. thats quite a wholesome lot of celebs wishing Happy Diwali.
Global Indian film and Television Awards
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Winners of Star Parivaar Award on Star Plus
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Star Cintaa Superstar Ka Jalwa Ep#5 - ...
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Latest News
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Win10 new build integrates Skype, shows off UI tweaks
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David Quainton
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Recent articles by David Quainton
Briefing: Israel - Focus on the future
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Cisco and Oracle panned, shaken, stirred
Cisco and Oracle have been panned by a security expert for dealing with software vulnerabilities and putting users at risk.
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Sep 23 2005 11:41AM
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- jarradSeptember 30, 2011TelemarketerPerth, Australia
I keep getting calls from these guys to. I used to be a DODO customer but never again. This should be illegal, why would anyone want to pay their hard earned money to sly companies that engage in these types of practices. We should all work together to stamp these companies out, BOYCOTT THEM ALL I SAY!
- chimoSeptember 5, 2011TelemarketerNewcastle, Australia
i've never been w/ dodo, they called and i answered... could've been a client... they were trying to sell me some sily usa holiday for "discounted price" w/ the only catch being having to go to some timeshare seminar or something similar! I like the suggestion of programming a "special" ringtone just for these numbers that are annoying solicitations who don't know how to STOP calling! Great tip!
- PBJanuary 13, 2012UnknownSydney, Australia
Yes, it's DODO Sales. Regular callers. I ignore their constant calls. On occasions when I have inadvertently answered it has been a real battle to end the call politely. "Hi **** how are you? We'd like to thank you for being such a great customer by giving you, free, this ...." When I say no they don't accept it. "Why would you say no? We're offering...." After one such intrusive call at work one of my colleagues, who had listened to my end of the call, marvelled at my patience, such was the time & polite argument required for them to leave me alone on that occasion. I would advise you to add the number into your contact list so you know who it is and don't answer. Also don't check any messages they leave - the message will be nothing but call centre background noise but it will cost you to check. If you find a way to stop them calling you ever again that is even better.
- FionaOctober 13, 2011UnknownCaroline Springs, Australia
They call me every day... first the home phone, and when I don't answer, my mobile. YES I am with DODO but I am SICK of them calling me to try to upsell me! I have internet and two mobile phones, and I also agreed to get a netbook with a wirless internet on a 2 year contract... you would THINK that'd be enough... but no they keep trying to sell me more mobiles...wtf
Can't wait till my contract is over...
- George.September 17, 2012UnknownRichmond, Australia
They keep calling me and I don't even know how they get my number. I have never been with dodo before.
- JamieMarch 1, 2013TelemarketerAdelaide, Australia
Very annoying telemarking callers :(
I handle it by putting them on mute, then just putting the phone in a drawer while I keep working.
I figure if they are going to annoy me on my mobile phone, at least it is going to cost them to do it! :P
- Saxon HallApril 5, 2012TelemarketerNew South Wales, Australia
Dodo are f*****g c***s, never sign with them.
Thanks you
- JosephMarch 15, 2013UnknownSurry Hills, Australia
I kept receiving their calls without leaving any messages in my answering machine. It is annoying and they should stop bothering us
- DagsMarch 1, 2013TelemarketerVictoria, Australia
Play dumb! Let them spend their time talking and explaining everything over and over again. Then when they have finished their sales pitch for the 10th time, say "so what are you offering?" And let them get tiered of calling you. You don't have to actually listen to their garble. Put the phone down and every minute or so, say "ok" or "I see" the marketer will think he has a sale and will get more annoyed than you when he realizes he has been wasting his own time. Do this with all telemarketers and they will never call twice.
- angryClissMay 8, 2012TelemarketerRedland Bay, Australia
they call me EVERY *%@ DAY 3 OR MORE TIMES!!! on both my home phone numbers & if I ever broadcast my mobile they would call me there too no doubt!
I was thinking of going with them for mobile broadband & maybe even power but thanks to this forum I am now much wiser! cheers & thanks to the people here. I know your frustration. I have thrown my phone across the room in the early days of their calling which is 2yrs ago now. FOR 2YRS I HAVEN'T BEEN ABLE TO ANSWER MY HOME PHONE WITHOUT CHECKING TO SEE THE CALLER. IT IS HARASSMENT IN THE EXTREME. I'M ON THE DO NOT CALL REGISTER. IT MAKES NO DIFFERENCE. GRRRRRRRRRRRR
the only way to stop them & others is to change my numbers & that is to happen soon. I will tell NO-ONE my new numbers.
- KarinAugust 24, 2011UnknownSydney, Australia
I have received calls from this number several times. I save all the telemarketer numbers I get, then customize their ringtones to "telemarketer calling, don't pick up!".
- nomadApril 10, 2015TelemarketerFootscray, Australia
its dodo
just block them
- LynsMay 24, 2013UnknownSydney, Australia
I've started answering the phone and leaving it so at least they have to pay for the call. Annoying bastards.
- RGCDecember 19, 2012UnknownMelbourne, Australia
I am fairly sure that this number is not the real DODO. In the past they have asked me to supply personal details that I know that the real DODO has on their computer records. I then told them to check their records, which usually caused them to hang up on me immediately. I have been a customer of DODO for years and I am sure that the callers from this particular number are not who they say they are.
- JessicaSeptember 21, 2012TelemarketerMelbourne, Australia
My work used to get calls from this number every now and then, but it's been at least twice a day everyday this week. As soon as you pick up, the other end hangs up. This is extremely annoying when I'm trying to answer the phone to help clients - I don't have time to waste with these stupid hang ups!
- AnonymousJuly 15, 2015UnknownMelbourne, Australia
- RayJuly 3, 2015UnknownMelbourne, Australia
Pests, gonna cancel dodo power now ha
- KauchyJune 26, 2015UnknownNew South Wales, Australia
Its DODO, annoying calls, l answered the phone call one day and the guys keep going telling me irrelevant stories, and l just cut the phone.
Don't they have anything better to do?
- MartinMay 6, 2015UnknownSydney, Australia
I got a call today (6/5/15) abut it wasn't from dodo: it was from Commander technical support regarding an open ticket I had with them. They informed me that my problem should be solved. No problem with such a call
- jimmyApril 13, 2015UnknownVictoria, Australia
DODO is a mther fker dpr bldy stpd excrmnt crp sht ever ever company cnt
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getting calls from this number. says disconnected. both 0411 923 000 and 0411 932 000. noticed...
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This number calls my phone at least twice a day every day, if I answer it the calls disconnects....
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At Rice -- 2013: Conference USA Academic Honor Roll; Appeared in four games with three starts as the designated hitter, all against left-handed pitchers... Made Division I debut in the second game of the season against national power Stanford... Collected first hit in the series-opener against eventual Conference USA opponent FIU.
Grayson College - Two-year starter at Grayson Community College in Sherman, Tex.... Helped lead team to the 2011 Junior College World Series in Grand Junction, Col.... Batted .370 with 35 RBI, five home runs and ten doubles for the 45-16 Vikings in 2012... Was selected to play in the junior college regional all-star game... Finished two-years with a .350 career average... Coached by Dusty Hart... Played in the Northwoods League over the summer, where he helped lead the Wisconsin Woodchucks to a 26-9 record and South Division title.
High School - A 2010 graduate of Cypress Woods High School in Cypress, Tex.... Batted .388 with 30 RBI, four home runs and ten doubles for the 24-10 Wildcats... Earned second team all-District 15-5A honors as an outfielder... Varsity letterman under head coach Thomas Loria... Outstanding student who graduated Summa cum Laude and maintained a 6.54 grade point average on a 7.0 scale.
Personal - Full name: Brian Scott Smith. Born: July 2, 1991, in Akron, Ohio. Parents: Scott and Susan Smith. Father and an uncle, Fred Smith, were both four-year football lettermen at Northern Michigan University. A cousin, Frederick Smith, played lacrosse for two years at Wheeling Jesuit University in West Virginia. College: Jones
|Jones College
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07/20/2015 - Players on the Rice baseball team are staying busy this summer competing in a host of collegiate leagues across the nation.
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07/13/2015 - Rice baseball players are staying busy this summer playing in a host of collegiate leagues across the country. Here's a weekly look at the Owls'...
Holt Named A Major League All-Star
07/07/2015 - Former Rice Owl Brock Holt, currently of the Boston Red Sox, was named to the American League All Star team for next week's mid-summer classic in...
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06/30/2015 - Richard and William Barker, Bubba Crosby, Jarett Dillard, Funmilayo Jimoh, Holly Jones-Wright, Lauren Shockley and Brent Scott will be inducted as ...
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06/30/2015 - Rice great Lance Berkman was part of a star-studded group inducted into the College Baseball Hall of Fame on its "Night of Champions" in Lubbock,...
Reeves Named ABCA Third Team All-America
06/14/2015 - John Clay Reeves was named a third-team All-America selection by the American Baseball Coaches Association (ABCA), the organization announced from ...
A Very Cool Draft
06/10/2015 - Rice's Kevin McCanna, Austin Orewiler, Matt Ditman, John Clay Reeves and John Williamson were all selected on the final day of the of the 2015...
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06/09/2015 - Rice's Leon Byrd and Jordan Stephens were both selected on Tuesday's second day of the 2015 Major League Baseball amateur draft.
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Join relationship and dating expert, Damien Diecke in this exclusive evening...
What Women Wish You Knew About Dating
(Limit 150 spots)
Did you know the fastest way to become more attractive to women is by following some simple rules on self confidence, speaking well, body language and motivation?
Dating and Relationship Expert Damien Diecke will help you do just that.
What he teaches is amazing – he demystifies dating and shows you exactly how to get women interested in you. He's been featured heavily in the media as the #1 Dating Coach in Australia.
Best of all Damien has agreed to share his insider dating & attraction secrets in an exclusive upcoming seminar. You probably haven't tried dating properly because you just don't know where to start
The good news is you can learn how to date and only spend an hour or two each week doing it to get big results. Damien has created a simple step by step system that any single man can use, regardless of age, skill level, looks or money.
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This teaching is not only good for meeting hot girls, but improving relationships with male and female friends and work colleagues. Everyone should do a course
Life will never be the same. I have received more joy during this course than I have in my whole life!
To sum up the last four wks in one word, emancipating!
Not only with women, but the work we have done has opened my eyes about how I can better myself in other areas of my life from work, to lifestyle and dealing more confidently with all the people I meet. I even feel like my relationship with my family has improved and I'm starting to surround myself with better quality friends.
4 Topics Damien Will Cover In This Event
- You see a girl you really like, what's the best way to approach her?
- How do you create massive attraction when you're talking to her?
- How do you get a rock solid phone number so she always texts back quickly?
- How do you create a first date so awesome, she texts you back to organise the next one?
You see, Damien spent 5 years trying all dating advice out there. He knows the secret and proven formula to getting dates and he's helped thousands of men (who thought they had nothing of interest to offer women) generate hundreds of dates for themselves.
What you need to know about Damien is he's all about Science – all of his advice is based on scientific data used in other industries successfully. He applies strategies you'll find in business text-books, psychology papers and sales events to get you more dates. Best of all, everything you learn can be applied to your everyday to make your life awesome. Isn't what this is ultimately about?
I know you're busy, but if there is one thing you do this year to step up to getting what you want – make it dating – and take the first step by enrolling now. Every man, including you, has plenty of women out there looking to date them - and Damien can prove it to you.
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The Media Love Us
My tuition from Damien has given me newfound confidence. I'm now making a more conscious effort to go out and meet new people. I'm also more aware of what I want.
Very Interesting. I think that you're doing a great job. I was slightly apprehensive [about the interview] but I have to say I like the ethos that you're coaching to these blokes.
The industry is maturing. [Diecke] teaches guys to be a confident, suave version of themselves, not to be sleazy. When you meet the guys doing it you see they're just trying to become better human beings. By 11pm at the Ivy, his students certainly feel like better human beings. They're confident, chatty and vulpine without having a drop of drink.
Men are calling in professional help and paying for tips on how to pick up. Damien...helps blokes work up the courage to talk to potential partners by taking them out to clubs and pubs for practical lessons.


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Cell Culture and Tissue Engineering
Dynamics of diffusivity and pressure drop in flow-through and parallel-flow bioreactors during tissue regeneration
Article first published online: 21 MAY 2012
DOI: 10.1002/btpr.1547
Copyright © 2012 American Institute of Chemical Engineers (AIChE)
Biotechnology Progress
Volume 28, Issue 4, pages 1045–1054, July/August 2012
Additional Information
How to Cite
Podichetty, J. T., Dhane, D. V. and Madihally, S. V. (2012), Dynamics of diffusivity and pressure drop in flow-through and parallel-flow bioreactors during tissue regeneration. Biotechnol Progress, 28: 1045–1054. doi: 10.1002/btpr.1547
Publication History
- Issue published online: 7 AUG 2012
- Article first published online: 21 MAY 2012
- Accepted manuscript online: 2 APR 2012 01:43AM EST
- Manuscript Revised: 27 MAR 2012
- Manuscript Received: 23 DEC 2011
- Abstract
- Article
- References
- Cited By
- 3D scaffold;
- diffusivity;
- chitosan;
- gelatin;
- porosity;
- bioreactor design
In this study, transport characteristics in flow-through and parallel-flow bioreactors used in tissue engineering were simulated using computational fluid dynamics. To study nutrient distribution and consumption by smooth muscle cells colonizing the 100 mm diameter and 2-mm thick scaffold, effective diffusivity of glucose was experimentally determined using a two-chambered setup. Three different concentrations of chitosan–gelatin scaffolds were prepared by freezing at −80°C followed by lyophilization. Experiments were performed in both bioreactors to measure pressure drop at different flow rates. At low flow rates, experimental results were in agreement with the simulation results for both bioreactors. However, increase in flow rate beyond 5 mL/min in flow-through bioreactor showed channeling at the circumference resulting in lower pressure drop relative to simulation results. The Peclet number inside the scaffold indicated nutrient distribution within the flow-through bioreactor to be convection-dependent, whereas the parallel-flow bioreactor was diffusion-dependent. Three alternative design modifications to the parallel-flow were made by (i) introducing an additional inlet and an outlet, (ii) changing channel position, and (iii) changing the hold-up volume. Simulation studies were performed to assess the effect of scaffold thickness, cell densities, and permeability. These new designs improved nutrient distribution for 2 mm scaffolds; however, parallel-flow configuration was found to be unsuitable for scaffolds more than 4-mm thick, especially at low porosities as tissues regenerate. Furthermore, operable flow rate in flow-through bioreactors is constrained by the mechanical strength of the scaffold. In summary, this study showed limitations and differences between flow-through and parallel-flow bioreactors used in tissue engineering. © 2012 American Institute of Chemical Engineers Biotechnol. Prog., 28: 1045–1054, 2012


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//cellBYTES : V.02 Call For Entries
Call for Artworks
Sun May 01, 2005 00:00
//cellBYTES was the first exhibition of mobile motion capture + camera snaps by inter/national practitioners exploring the potential of creative digital media content for the next generation of mobile technology. //cellBYTES is a project created by Once Bitten - an intranational collective of digital practitioners + writers. Once Bitten launched cellBYTES in 2004 with the intention to investigate, exhibit + promote the first creative byte sized steps being taken by creative practitioners with mobile phone ...
art writers wanted
Mon Mar 07, 2005 04:09
Antipoda is looking for insightful writers to conduct interviews to selected emerging international artists. for more information email us email@example.com or visit www.antipoda.org
New Media in South Africa
Hey there, this is my first posting on rhizome... I'm an American expat artist/teacher in Cape Town. i arrived a few months ago (i lived in this amazing city before, couldnt stay away...), and just started work at city varsity, a local media arts college. its very exciting...there place is just buzzing, everyone running around in every direction, all sorts of changes and new ideas... I've been assigned the task of creating the school's foundatioins ...
Maya Animators Needed for Planetarium Artwork
Sun Mar 06, 2005 15:51
As a project in the UCLA Design/Media Arts department, we are creating an experimental artwork that will use planetariums as a new form of media experience. We're producing a 'night sky' program that, instead of showing stars and planets, will show the various strata of man-made technologies in the sky above us. At any moment, there are 9000 planes, 6000 satellites, thousands of weather technologies, helicopters, and more. We hope to find the patterns in ...
Sun Mar 06, 2005 00:00
INVITATION TO WWW.DIESEL-NEW-ART.COM Do you have works ready, half-finished or just an idea. Get going! We are open to anything! You can use the DNA web site to publish your works and update the world about your progress. You can in a simple way upload images, texts and edit your portfolio when necessary by logging in to the web site. All your contributions will be displayed on the DNA site and judged by an independent ...
Artist Studios Applications - Temple Bar Gallery & Studios, Dublin, Ireland
Sun Mar 06, 2005 02:57
Temple Bar Gallery & Studios is one of Ireland's leading contemporary art venues. Centrally located in Temple Bar, Dublin's designated Cultural Quarter, TBG&S is a publicly funded, not-for-profit organisation which hosts a high profile programme of Irish and international art. This programme includes the work of both established and emerging artists working in a wide range of media and has in recent years featured such artists as Katie Holten, Caroline McCarthy, Shirana Shahbazi, Walker and ...
New York Underground Film Festival - Friday Lineup
Fri Mar 11, 2005 00:00 - Sat Mar 05, 2005
For complete descriptions, check out www.nyuff.com For (more) free beer and cheer, as well as info about the evening's afterparty, check in at the theatre--Anthology Film Archives, 32 Second Ave @ 2nd Street 6:15pm THE FOREST FOR THE TREES: JUDI BARI V. THE FBI by Bernadine Mellis, Documentary. http://www.nyuff.com/2005/index2.php?p=arc&s=res&fid 7:30pm WHAT IT WAS LIKE Documentaries by Takeshi Inamura, Christine Khalafian, and Joel Schlemowitz http://www.nyuff.com/2005/index2.php?p=arc&s=res&fid,20,21&program=What+It+Was+Like&switch=1 8:00pm IN THE STARS Experimental Shorts by Kate McCabe, Elizabeth Henry, ...
New York Underground Film Festival - Thursday Line-up
Thu Mar 10, 2005 00:00 - Sat Mar 05, 2005
For complete descriptions, check out www.nyuff.com For free beer and cheer, as well as info about the evening's afterparty, check in at the theatre--Anthology Film Archives, 32 Second Ave @ 2nd Street 6:15pm - -+-+FREE+-+- dvd release screening GETTING NOWHERE FASTER by Tiffany Morgan, Nicole Morgan, Lori Damiano & Lisa Whitaker, Skateboard Video, 2005 http://www.nyuff.com/2005/index2.php?p=arc&s=res&fid=2 7:30pm EXIST MERCENARIES by Robert Banks, 35mm, 3min, Experimental EXIST: NOT A PROTEST FILM by Esther Bell, Video, 80min, Feature ...
New York Underground Film Festival - The Heart is Deceitful Above All Things
Wed Mar 09, 2005 00:00 - Sat Mar 05, 2005
8pm, Anthology Film Archives, 32 Second Ave @ 2nd Street www.nyuff.com "Asia Argento, woman director and star in her own new movie, The Heart is Deceitful Above All Things, does something remarkable— she doesn't try to look good. In fact, she looks like hell, and I know few directors, and fewer stars who are brave enough to show their unmitigated dark side, with all its swollen reddish green blemishes, splotchy skin, inability to love, desire ...
seismic memory
Sat Mar 05, 2005 00:00 - Sat Mar 05, 2005
Carrizo-Parkfield Diaries, an intensive exploration of seismic memory, based on locative data, digital audio remix and documentary photography and video on location at Carrizo Plains, California and Parkfield, active sites on the San Andreas Fault, opens tonight, Saturday, March 5, 2005 at Transport Gallery Los Angeles through April 16, 2005 1308 Factory Place, near 6th and Alameda, downtown Christina McPhee, with Jeremy Hight, Sindee Nakatani, Terry Hargrave and Glorious Ninth
Center for Tactical Magic presents UPRISING! sUnDaY, MaRcH 6!!
Sun Mar 06, 2005 00:00 - Sat Mar 05, 2005
Rise up with the Center for Tactical Magic this Sunday, March 6 in Huntington Beach from noon onwards!!! UPRISING! is a community kite-making project that invites participants to design and build their own kites with a message they wish to communicate from up high. This contemporary twist on the ancient practice of aeromancy (divining messages from the sky) encourages people to rise above the dark clouds hovering overhead by unleashing their own messages upon the ...
HARVESTWORKS Alternate Controller Series - First Performance March 14 7PM
Mon Mar 14, 2005 00:00 - Fri Mar 04, 2005
HARVESTWORKS Digital Media Arts Center Presents The Alternate Controllers Series Inaugural Concert: Andrea Polli Harvestworks, a non-profit arts organization that provides opportunities for the public to see and hear innovative artists, presents "Alternate Controllers," a concert series focusing on the modern intersections of art and technology. Central to this series is the exciting way that musicians and composers assimilate various machines into their creative processes. From Bruce Gremo and Jeff Fedderson's compositions for shakuhachi and ...
Prix Ars Electronica: Entry Deadline Extended
Fri Mar 18, 2005 00:00
Contestants worldwide still have until March 18th to submit their entries to the world's premiere cyberarts competition. This extended deadline also applies to the u19 - freestyle computing category for young people as well as art and technology grant. The Ars Electronica Center and the ORF Upper Austria are pleased to invite artists, scientists, researchers and developers throughout the world to take part in the Prix Ars Electronica, the international competition for cyberarts being held ...
animated and graphic score: call for works
Call for Artworks
Sun Mar 06, 2005 00:00
Dear Rhizomits, on behalf of the Rattling Wall Collective in Dutch, i would like to put a call to all artists interested in submitting material for our next project. for the past few years our collective has been performing animated scores that i have written, using a variety of techniques, software, etc. examples can be found here http://smallbrainrecords.com/text/animatedscore.html For this next project we'd like to perform works by other artists. these pieces would be rehersed, ...
March 10-13 Home/Away From Home Festival
Thu Mar 10, 2005 00:00 - Thu Mar 03, 2005
The Compound Eye and Strange Candy presentHome/Away From Home Festival March 10-13 8pm at The Connolly Theater 220 East 4th St. between A/B $10 tickets @ Door Featuring The Queen Says Good-bye to her Favorite by Merrianne Moore How 2 Men Got On in the World by Emily Mendelsohn Wilderness by Jesse Phillips-Fein Home/Away Art Exhibit by Flux Factory artists The Compound Eye and Strange Candy are pleased to present Home/Away From Home Festival: 4 ...


text:
Amazon SQS New Features: Delay Queues, Message Timers and Batch APIs
We are excited to announce three new Amazon SQS features today: delay queues, message timers, and the ability to send or delete multiple messages in a single API call (batch operations). Delay can be used to apply a uniform delay to all messages. Alternatively message timers can be used to apply delay to specific messages that can be sent individually, or in a batch.
New support for batch send and delete operations complements the existing batch receive functionality. With batch operations many workloads will benefit from improved single thread message throughput, reduced connection overhead and lower API call latencies.
As distributed applications become larger and more complex, greater scalability and control of message-based systems becomes increasingly important. With support for both queue delays and message timers, a wider array of real world distributed application scenarios can be addressed. With batch APIs, developing Internet-scale distributed applications is easier and more cost effective than ever.
These new features can be easily accessed from the AWS Management Console.
Source: AWS
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text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 10, 1985
|Filing date
|Oct 19, 1984
|Priority date
|Oct 19, 1984
|Fee status
|Also published as
|Publication number
|Robert C. Fay, David A. Thompson
|Original Assignee
|Corning Glass Works
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (3), Non-Patent Citations (7), Referenced by (23), Classifications (11), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention relates to organometallic compounds, and particularly relates to β-diketonate complexes of magnesium and zinc which exhibit a combination of high volatility and good thermal stability.
Volatile metal complexes are of interest for a variety of applications including fuel additives, metal vapor sources, and gas transport reagents. A useful discussion of β-diketonate complexes and their uses is provided by R. E. Sievers et al. in Science, 201 [4352], pages 217-223 (July 1978), wherein numerous references to these complexes and methods for their preparation are cited.
The metal complexes or chelates of the anion of hexafluoroacetylacetone(1,1,1,5,5,5,-hexafluoro-2,4-pentanedione), the anion having the formula [CF3 --CO--CH--CO--CF3 ]- and hereinafter abbreviated (hfa)-, have been the objects of specific study. For example, the complexes Cd(hfa)2, Mg(hfa)2 and Zn(hfa)2 are known, although these complexes are most frequently isolated as adducts with Lewis bases that are dissolved in the solvents used in their preparation, such as H2 O and NH3. Thus the adducts Cd(hfa)2.NH3.H2 O, Cd(hfa)2.2H2 O and Zn(hfa)2.2H2 O, the latter being characterized as hydrates, have been reported by S. C. Chattoraj et al. in J. Inorg. Nucl. Chem., 28, pages 1937-1943 (1966).
European patent application EP No. 0103446 describes metal diketonate adducts of the formula M(hfa)2.nTHF, wherein M is Mg or Zn and n is 1-4, which exhibit good thermal stability and volatility. As reported in that application, the magnesium complex Mg(hfa)2.2THF can be volatilized without decomposition at 200� C. However, complexes of even higher volatility and thermal stability are still being sought.
The present invention provides novel complexes of magnesium or zinc which exhibit improved thermal stability and volatility. The complexes of the invention are adducts with 1,2-dimethoxyethane(1,2-DME) of magnesium or zinc hexafluoroacetylacetonates.
Complexes provided in accordance with the invention have the molecular formula: M(hfa)2.1,2-DME wherein M is Zn or Mg, and wherein 1,2-DME represents a single 1,2-dimethoxyethane ligand forming a 1:1 adduct with the M(hfa)2 molecule. These adducts exhibit not only higher thermal stability than many of the known adducts, but also a high volatility and lower melting temperature. Such characteristics significantly increase the utility of these complexes as source materials for chemical vapor deposition reactions.
The invention may be further understood by reference to the drawings, wherein:
FIGS. 1 and 2 contain thermogravimetric curves for complexes provided according to the invention;
FIGS. 3 and 4 contain infrared transmittance spectra for complexes provided in accordance with the invention; and
FIGS. 5 and 6 are proton nuclear magnetic resonance spectra for complexes provided in accordance with the invention.
As is known, the volatility of metal β-diketonate complexes depends not only upon the selection of the diketone used to form the complex but also, for each possible diketone, upon the presence or absence and nature of the additional ligands (e.g., Lewis bases) present within the molecule. β-Diketonate complexes are known to form adducts with solvents used in their preparation, particularly when the complex is not coordinatively saturated and the solvent is a good Lewis base. These adducts can be relatively stable, and can be more volatile than the β-diketonate itself. Examples of molecules which can form adducts with metal β-diketonates are ammonia, water, ether, pyridine, bipyridine, phenanthroline, tetrahydrofuran and dimethylformamide. These molecules, termed neutral ligands, attach to the complex giving a metal atom with six-fold or higher coordination.
The stability of the metal β-diketonate adducts appears to depend on both the acidity of the β-diketonate and the base strength of the added molecule. The central metal atom of divalent metal β-diketonates such as Zn(hfa)2 are known to exhibit significant electron affinity (Lewis acidity) due to the size of the metal atom and to the presence of the fluorine-containing β-diketonate ligands. Thus very stable adducts can be formed with some of the stronger Lewis bases. Particularly stable are adducts with certain of the nitrogenous bases.
Unfortunately stability alone is insufficient for qualification as a useful source material. As reported by Izumi et al., Bull. Chem. Soc. Jap., 48(11), 3188 (1975), nitrogen-containing Lewis bases such as pyridine, 1,10-phenanthroline, and 2,2'-bipyridine form highly stable adducts with M(hfa)2 β-diketonates, but these adducts can exhibit melting points significantly higher than some of the known adducts. A high melting point is undesirable in a metal source material. A low melting point and high volatility are greatly to be preferred, particularly where high mass transfer rates are needed.
The present invention is founded on the discovery that the 1,2-dimethoxyethane adducts of Mg(hfa)2 and Zn(hfa)2 exhibit improved stability and lower melting temperatures than previously known adducts of these complexes, but without sacrifice of volatility. Thus these 1,2-DME adducts, M(hfa)2.1,2-DME can be volatilized rapidly and completely with lower risk of decomposition than can the parent complexes or other M(hfa)2 adducts of the same diketonates, rendering them particularly useful, for example, as sources of metal vapors for vapor phase reactions.
The compound 1,2-dimethoxyethane(CH3 --O--CH2 --CH2 --O--CH3) is characterized as a bidentate ether with a boiling point of about 82� C. Adducts of this compound with the β-diketonates Mg(hfa)2 and Zn(hfa)2 can be prepared by synthesizing the β-diketonates as hydrates and then reacting the hydrates with the chelating bidentate ether. The resulting ether adduct can then be sublimed in vacuo without loss of the 1,2-DME ligand.
The following example describes a procedure useful for the synthesis of the Mg(hfa)2.1,2-DME adduct.
To 1.6 liters of freshly distilled ether (Et2 O) in a three-necked flask is added 164 g of pure basic magnesium carbonate. The magnesium carbonate is commercially available as F.O. Optipur grade from E.M. Chemicals, Inc., Hawthorne, N.Y. The three-necked flask is equipped with a mechanical stirrer and provisions are made for maintaining an argon atmosphere over the reactants in the flask.
Hexafluoroacetylacetone(CF3 --CO--CH2 --CO--CF3) is distilled over P2 O5 and 480 ml of the distilled β-diketone is added dropwise to the magnesium carbonate solution in the flask, with continuous stirring of the mixture. After completion of this addition and after the evolution of CO2 from the reaction mixture ceases, the mixture is refluxed for 18 hours, cooled, and filtered. The ether is then removed by rotary evaporation to isolate the Mg(hfa)2.2H2 O intermediate hydrate.
This intermediate hydrate is next dissolved in excess 1,2-dimethoxyethane, and the resulting solution is gently refluxed for 16 hours to effect a replacement of the water of hydration by 1,2-DME. At the conclusion of this treatment, the excess 1,2-DME is removed by evaporation and the Mg(hfa)2.1,2-DME product is sublimed in vacuo using a water-cooled sublimator. 740 g of Mg(hfa)2.1,2-DME is recovered, for a yield of approximately 77%. The product has a melting point of 70� C., and has a vapor pressure of 10 mm (Hg) at about 120� C.
Mg(hfa)2.1,2-DME produced by the above procedure has been characterized by chemical analysis, thermogravimetric analysis, Fourier transform infrared (FT-IR) analysis, and 1 H nuclear magnetic resonance (nmr) examination. Chemical analysis of the product for Mg, C, and H provided the results reported in Table I below. Included in the Table are experimental (analyzed) and calculated (theoretical) concentrations for these elements, reported in weight percent.
TABLE I______________________________________Analysis of Mg(hfa)2.1,2-DMEElement Theoretical (%) Analyzed (%)______________________________________Mg 4.6 4.82C 31.8 31.1,31.3H 2.3 2.3,2.3______________________________________
A thermogravimetric analysis (TGA) of the product was carried out on a 20 mg sample of the material, heated at a rate of 10� C./min under an argon atmosphere. A thermogravimetric curve resulting from such a study, identified as "TGA-Mg(hfa)2.1,2-DME", is reproduced in FIG. 1 of the drawing. The TGA curve shows rapid and complete volatilization of the complex over a narrow temperature range, indicating the absence of detectable decomposition under the vaporization conditions employed. The temperature at which one-half of the sample has been evaporated (T1/2), which temperature is a good relative indicator of the volatility of the compound, is estimated from the TGA curve to be about 170� C. This compares favorably with a T1/2 temperature of 180� C. for Mg(hfa)2.2THF.
FIG. 3 of the drawing consists of an FT-IR spectrum of a Mg(hfa)2.1,2-DME sample in potassium bromide. The spectrum is similar to that obtained at higher temperatures for the pure compound in the vapor phase.
FIG. 5 of the drawing consists of a 1 H nmr spectrum of an Mg(hfa)2.1,2-DME sample in a CD2 Cl2 solvent containing a tetramethylsilane (TMS) standard. The spectrum was generated on Varian model EM360L equipment. The resonance peaks at chemical shifts of 3.4 (intensity 6) and 3.7 ppm (intensity 4) are assigned to the 1,2-DME ligand, while the peak at 6.05 ppm (intensity 2) is assigned to the --CH group of the β-diketonate ligand. Electronic integration of the areas under the peaks support the proposed chemical formulation of one DME ligand per magnesium atom.
The thermal stability of Mg(hfa)2.1,2-DME is evidenced not only by the TGA data set forth in FIG. 1, but also by investigations as to the extent and nature of the decomposition of Mg(hfa)2.1,2-DME after prolonged heating at temperatures in the 100�-200� C. range. The superior thermal stability of the DME adduct was demonstrated by heating samples of the DME adduct and the THF adduct in individual evacuated ampoules at 200� C. for 24 hours and observing residual pressure in the ampoules after cooling to room temperature, and any sample discoloration which occurred. The DME adduct exhibits lower residual pressure after such a treatment than the corresponding bis-THF adduct, and also less discoloration.
The corresponding zinc adduct with the bidentate ether, Zn(hfa)2.1,2-DME, can be prepared in a manner similar to that used for the preparation of the magnesium adduct according to Example I. The following Example describes such a procedure.
To a twelve-liter reaction vessel equipped with a stirrer, condenser, heating mantel, and a provision for argon purging are added 233 grams of pure (99.999%) zinc oxide and 800 ml of double-distilled water. Under an atmosphere of argon, 760 ml of 1,1,1,5,5,5-hexafluoracetylacetone, distilled as in Example 1, is slowly added with constant stirring. This addition is completed within about thirty minutes.
Two liters of diethyl ether is next added to the vessel, and the resulting mixture is gently heated for 80 hours. Thereafter the vessel and contents are allowed to cool, excess ZnO is removed by filtration, and the ether layer containing a dissolved Zn(hfa)2 2H2 O intermediate is separated from the water layer in a separatory funnel. Evaporation of this ether solution gives the hydrated zinc β-diketonate intermediate, Zn(hfa)2.2H2 O.
The intermediate hydrate is next dissolved in excess hot 1,2-dimethoxyethane, and the resulting solution is refluxed for 16 hours at 68� C. to effect a replacement of the water of hydration with 1,2-DME. At the conclusion of this treatment, remaining excess 1,2-DME is removed by rotary evaporation and some of the Zn(hfa)2.1,2-DME product is sublimed in a water-cooled sublimator to remove a small residual fraction of uncombined DME prior to product characterization.
The above process yields approximately 763 g of Zn(hfa)2.1,2-DME, a yield of approximately 56%. The melting point of the sublimed Zn(hfa)2.1,2-DME product is about 125� C., and this complex has a vapor pressure of about 16 mm (Hg) at 125� C.
Zn(hfa)2.1,2-DME produced in accordance with the above-described procedure was analyzed for zinc, carbon, and hydrogen content with the results reported in Table II. Included in Table II are experimental (analyzed) and calculated (theoretical) concentrations for these elements, reported in weight percent.
TABLE II______________________________________Analysis of Zn(hfa)2.1,2-DMEElement Theoretical (%) Analyzed (%)______________________________________Zn 11.5 11.1C 29.5 29.3H 2.1 2.0______________________________________
Thermogravimetric analysis of a sublimed 20 mg sample of the Zn(hfa)2.1,2-DME product, heated at 10� C./min. under argon, resulted in the TGA curve shown in FIG. 2 of the drawing. As in the case of the magnesium complex, the zinc complex exhibits rapid and complete vaporization over a narrow range of temperatures, indicating no detectable thermal decomposition in the course of vaporization. The estimated T1/2 temperature for the zinc complex under these conditions is 162� C., which is only slightly higher than the T1/2 temperature of Zn(hfa)2.2THF determined under the same conditions.
FIG. 4 of the drawing consists of an FT-IR spectrum exhibited by a sample of Zn(hfa)2.1,2-DME between salt plates. That spectrum is similar to spectra obtained from vaporized Zn(hfa).1,2-DME at higher temperatures.
FIG. 6 of the drawing consists of an 1 H nmr spectrum of a Zn(hfa)2.1,2-DME sample, dissolved in a CDCl3 solvent which contained a TMS standard. The resonance peaks at chemical shifts of 3.43 and 3.65 ppm from the standard are assigned to the 1,2-DME ligand, while the peak at the 5.95 ppm chemical shift is assigned to the --CH group in the β-diketonate ligand. The small signal at 7.12 ppm is CHCl3 impurity in the deuterated chloroform. Again, electronic integration of the areas under the peaks indicate one DME ligand per zinc atom.
As in the case of the magnesium complex, the thermal stability of Zn(hfa)2.1,2-DME is evidenced not only by the observed rapid and complete TGA volatilization behavior shown in FIG. 2, but also by measuring residual gas pressure after heating a sample of the material in a sealed ampoule at 200� C. for 24 hours. Again the 1,2-DME adduct exhibits lower residual pressure and less discoloration after this test than the analogous THF adduct.
The combination of volatility and thermal stability exhibited by the M(hfa)2.1,2-DME complexes of the invention appears to be unique. Attempts to produce stable complexes with other bidentate ethers such as 1,1-dimethoxyethane and 2,2-dimethoxypropane did not produce stable products. Further, addition complexes with the strongly coordinating nitrogen bases 1,10-phenanthroline and 2,2'-bipyridine, which are readily formed, failed to exhibit better properties than the 1,2-DME adduct.
Table III below sets forth comparative melting point and T1/2 volatility data for 1,2-DME and nitrogen base adducts.
TABLE III______________________________________Adduct Melting Point - �C.�C. T1/2______________________________________Mg(hfa)2.1,10-phenanthroline 246 295Zn(hfa)2.1,10-phenanthroline 272 310Zn(hfa)2.2,2'-bipyridine 266 295Mg(hfa)2.1,2-DME 70 170Zn(hfa)2.1,2-DME 125 162______________________________________
These data show a dramatic difference in volatility between the DME adducts and the adducts with strongly coordinating nitrogen bases of magnesium and zinc hexafluoroacetylacetonates, and demonstrate why the nitrogen adducts, although stable, are not good candidates for use as metal vapor source materials.
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|METAL β-DIKETONATES
|U.S. Classification
|556/40, 427/252, 568/412
|International Classification
|Cooperative Classification
|European Classification
|Aug 6, 1985
Owner name: CORNING GLASS WORKS, CORNING, NY A CORP OF NY
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