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Gov. Mark Dayton is blasting legislative Republicans for refusing to pay for additional construction projects that could bring new economic development to the state.
"They are just dead wrong," Dayton said Tuesday. "The Republicans have been wrong on this since I arrived. They are short-changing projects all around the state that are job-creating projects."
Democratic and Republican legislative leaders cut a deal last year to limit new construction spending to about $850 million this session. They made the agreement before a strong economic turnout left the state with a surplus of more than $1.2 billion.
Dayton says the strengthening economy and strong budget outlook give the state more cushion to increase statewide borrowing to pay for roughly $400 million in additional projects.
Since state borrowing requires a two-thirds vote, the measure gives Republicans a rare moment of leverage as Democrats control both the House and the Senate.
Republicans say that the state should not run up taxpayer debt, and leaders have publicly not budged from the $850 million target. They say that the agreed upon number fits with historical averages and see no reason to break from it now.
The statewide construction measure stands as one of the last major initiatives to get completed in the final weeks of the legislative session.
Dayton said a recent Star Tribune story about an unfinished water project in southwestern Minnesota "is a prime example of where the lack of a public investment has crippled that area for economic growth."
The governor said he is willing to fully fund the water project if it would persuade some GOP legislators to support a higher borrowing measure.
"I don't think they have a toenail to stand on to justify this rigid ideology," Dayton said. Holding to that number "would deny a whole range of projects around the state because of their fiscal ideology."
DFL Gov. Mark Dayton signed into law a dramatic increase in the state's minimum wage Monday, giving raises to more than 325,000 Minnesotans.
The new $9.50 base hourly wage takes the state from having one of the lowest minimum wages to one of the highest when it fully kicks in by 2016.
"Minnesotans who work full-time should be able to earn enough money to lift their families out of poverty, and through hard work and additional training, achieve the middle-class American Dream," said Dayton, surrounded by legislators, labor and labor leaders at a ceremonial bill signing in the State Capitol rotunda. "Raising the minimum wage to $9.50, and indexing it to inflation, will improve the lives of over 325,000 hard-working Minnesotans. I thank the Legislature for recognizing the need to make work pay in Minnesota."
Minnesota's dramatic wage increase puts the state at the forefront of a major initiative of President Obama, who has failed to persuade Congress to raise the federal minimum wage to $10.10 and instead focused on pressing his case state by state.
The state's higher minimum wage has angered Republicans and business leaders, who say the higher wage will force them to lay off workers and become a drag on the fragile economic recovery.
"We believe that all Minnesotans deserve the dignity of supporting themselves and their families through hard work," said state Rep. Ryan Winkler, a Golden Valley DFLer who was a chief negotiator of the minimum wage effort. "Raising the minimum wage and indexing it to inflation is an important step to create a rising floor for all wages that will benefit hundreds of thousands of Minnesotans who work hard and deserve to get ahead."
At $6.15 per hour, Minnesota has one of the lowest minimum wages in the nation, lower than neighboring Wisconsin, Iowa, North Dakota and South Dakota. Minnesota is one of only four states with a minimum wage below the national rate of $7.25 per hour.
State officials estimate that the $9.50 base wage will put an additional $472 million in the pockets of Minnesota's lowest-wage workers each year. Supporters say the increase in consumer spending is expected to help local businesses in communities across our state, and provide another boost to Minnesota's growing economy.
"Today represents a big step forward for low-wage workers in our community," said Sen. Jeff Hayden, a Minneapolis DFLer who was a chief supporter of the wage-hike measure. "We rely on these workers every day, yet many of them cannot support their own families. Raising the minimum wage is part of a larger effort to lift up the working poor and ensure all Minnesotans have the opportunity to earn enough to get by."
A Minnesotan who earns $6.15 per hour work full-time earns an annual salary of just $12,792, about $7,000 below the poverty line. Raising the minimum wage to $9.50 per hour comes within $30 of closing that gap for the year.
To help small businesses, the bill also establishes lower minimum wage requirements for small employers and young workers once the new law takes effect Aug. 1.
Minnesota would spend an addition $209 million for education, prisons and raises for state-paid home health workers, under a proposal that passed through the state Senate on Tuesday.
"There are many things in here that are desirous," said Senate Finance Committee Chairman Dick Cohen, DFL-St. Paul.
The 37-27 vote came after a prolonged floor debate in which Republicans repeatedly failed to amend the measure. Republicans have pushed for deeper tax cuts instead of more spending.
"Minnesotans have once again been denied additional tax relief," said Sen. Michelle Benson, R-Ham Lake. She called the measure "a disappointing display of misplaced priorities."
DFL legislators who control both the House and Senate are trying to finish up the spending measures that they are paying for out of the state's $1.2 billion projected budget surplus for he remainder of the budget cycle. Already, legislators have earmarked about $550 million for business and consumer tax relief and another $150 million for the state's rainy-day fund.
The Senate proposal includes several provisions with strong bipartisan support, including 5 percent raises for home health workers, which will cost about $80 million.
"We support this," said Senate Minority Leader David Hann, R-Eden Prairie. "This is something that was neglected in the budget last year."
The proposal also includes a $2 million-a-year boost to state nursing homes to offset a measure to raise the state's minimum wage to $9.50 an hour.
An unexpected increase in criminal convictions prompted Democratic legislators to set aside an additional $11 million to pay for the growth in the state prison population and the cost of renting beds from county jails.
The Minnesota Department of Corrections reported that incarcerations were up 8 percent over earlier estimates, which is an average of 513 extra offenders each year.
Law enforcement officials say the increased incarcerations come from a wide range of crimes, including a 23 percent jump in methamphetamine convictions, a 15 percent increase in DWI offenders, a 5 percent increase in criminal sexual conduct convictions. Corrections officials logged a decrease in prisoners for non-methamphetamine drug offenses.
The proposal adds millions in new spending on elementary education, including $8.8 million in early learning scholarships. The proposal sets aside money to bridge the disparity gap for minority students and for teacher evaluations.
Senators also included $3.5 million to ensure that all low-income students have a hot school lunch.
The measure also includes a one-time appropriation of $2.5 million to deal with financial challenges at the University of Minnesota Duluth.
The Senate measure differs from the House, so a special conference committee will try to resolve differences between the two. The measure increases spending by more than $741 million in the next budget cycle, ending in 2017.
On Tuesday the U.S. Supreme Court struck down federal limits on how much an individual can give to campaigns in aggregate, which could allow high dollar donors to spread their largess to a wider swath of political hopefuls and parties.
Unlike the federal system, which essentially limited how many donations in total a donor could give, Minnesota law does not place restrictions on the number of campaigns to which a high-dollar donor can contribute.
Current state law allows donors to give massive amounts to parties or PACs and allows donors to spread their donations to as many candidates or party committees as they wish.
"We've never limited the amount that an individual donor can give to a whole group of candidates," said Gary Goldsmith, executive director of the Minnesota campaign finance board. "We don't limit at all the amount of money that an individual can give to a party."
Minnesota does place limits on how much candidates can accept from certain types of donors but Goldsmith said those restrictions were not considered by the court.
Other states, including Wisconsin, do have laws to limit the aggregate donations a contributor can spend in an election cycle, according to the National Institute of Money in State Politics. Those nine states' laws may be directly impacted by the federal decision.
The Supreme Court did not overturn the concept of limiting what a campaign can accept from a donor. Currently, donors are limited to giving $5,200 per candidate per election cycle to federal candidates. Minnesota law puts similar restrictions on what an individual can give to a single candidate.
The court's decision will have a much more far reaching impact on federal campaigns and parties, including those from Minnesota.
DFL chair Ken Martin said the ruling allows parties to tap donors for funds, even if those donors had already given to multiple other parties or candidates.
"It has a big impact on state parties," said Martin.
Currently, donors are limited to giving $123,200 for 2013 and 2014 in total to all federal campaigns. That limit made federal cash difficult to raise, Martin said. The Minnesota parties were not limited to what they could raise from individuals in their state committees.
After the decision, Minnesota parties will be able to raise more federal money -- up to $10,000 per individual -- from donors whether or not those individuals had already given to many other federal committees.
"That is hugely helpful to state parties," Martin said. He said the lifting of the overall cap will mean that parties can be more involved in helping federal candidates "up and down the ballot here in Minnesota."
Minnesota Republican Party chair Keith Downey said the decision may mean candidates and parties will be able to raise more.
"It will serve to direct campaign spending toward those who are closest to the public and most publicly accountable for their campaign activities. It also underscores the importance of both transparency and the protection of political speech, which are so important in our political process," Downey said.
Several donors with Minnesota ties have contributed enough in 2013 that they could have bumped up against the limit the court struck down.
According to a Star Tribune analysis of data from the Center for Responsive Politics, John Grundhofer, former chairman of U.S. Bancorps, donated $142,200 through the end of last year and Patricia Grundhofer, whose is listed on federal documents as the director of the John F. Grundhofer Charitable Foundation, donated $125,600. They gave primarily to non-Minnesota Republican committees.
Stanley Hubbard, head of Hubbard Broadcasting and a a frequent donor to state as well as federal causes, gave nearly $100,000 to federal committees last year alone. He said that every election cycle he gets many calls soliciting donations and he has to refuse them because he is maxed out.
Hubbard has a simple prediction for what will happen now that the court rejected the overall limits: "They are going to start calling."
Star Tribune data editor Glenn Howatt contributed to this report.
A new report finds that both the successful campaign to legalize gay marriage and the unsuccessful campaign to stop cigarette and tobacco tax increases spent more than $1 million on lobbying in Minnesota last year.
The report, released Tuesday by the Minnesota Campaign Finance and Public Disclosure Board, shows that the pro-gay marriage Minnesotans United and the Altria Client Services, the parent company for Philip Morris, joined the million dollar spenders for the first time in 2013.
Also appearing on the big spender list -- business groups and the teachers union. With spending of more than $2 million, the Minnesota Chamber of Commerce was the single biggest spender on lobbying, as it often is.
Reports to the campaign watchdog agency found that both the Chamber and the Minnesota Business Partnership increased their spending last year. The chamber spent $100,000 more than it had in 2012 and the Business Partnership spent $600,000 more. The Business Partnership spent a total of nearly $1.5 million in 2013.
The two business groups successfully batted back massive proposed business-to-business tax increases in 2013. Some smaller tax increases on businesses transactions with other businesses did pass, however, This year's Legislature is looking at repealing those.
Education Minnesota's lobbying spending came in just behind the business groups, with $1.2 million in spending on lobbying. That, too, constitutes an increase from the year before but is still slightly less than the massive teacher's union spent in 2009.
See all the big spenders in the list below:
|Vikings (7)
|Health care (1)
|1st District (163)
|2nd District (160)
|3rd District (124)
|4th District (99)
|5th District (178)
|6th District (561)
|Funding (672)
|Health care (255)
|Minnesota U.S. senators (640)
|Minnesota campaigns (1625)
|Minnesota congressional (874)
|Minnesota governor (1795)
|Minnesota legislature (2161)
|Minnesota state senators (890)
|National campaigns (510)
|President Obama (431)
|State budgets (877)
|Celebrities (1)
|Anoka (1)
|Fridley (1)
|2012 Presidential election (325)
|7th District (123)
|8th District (242)
|NHL news (1)
|Gov. Tim Pawlenty (456)
|Political ads (126)
|Recount (98)
|Gov. Mark Dayton (1388)
|Democrats (1293)
|Republicans (1482)
|Morning Hot Dish newsletter (178)
|Sept11 (1)
|Public safety (2)
|Marriage Amendment News (1)
|Voter ID News (2)
|Budget news (4)


text:
I have a file download script that I have written, which reads files from below public_html and allows the user to download them after checking to see if the user is logged in and that the file is a valid file for them to download.
An issue I've recently come across is that on an iPad it just fails to do anything when the link is clicked.
Example download file code after all the checks have been done:
header("Pragma: public");
header("Expires: 0");
header("Cache-Control: must-revalidate, post-check=0, pre-check=0");
header("Cache-Control: private",false);
header("Content-Type: application/msword");
header("Content-Disposition: attachment; filename=\"file.doc\";" );
header("Content-Length: 50688");
readfile(SITE_PATH .'/files/file.doc');
This script has been tested and checked on PC, Mac and Linux machines in multiple browsers (FF, Opera, IE6-9, Chrome, Safari) and all seem to work fine, so it must be something that the iPad does differently.
I'd imagine it's something to do with the iPad not actually having a file structure as such to download files to, but I'm not certain.
Has anyone come across this problem before? If so, is there a fix?

subset: commoncrawl


text:
28 Mar 2015 Last updated at 18:59 ET
|All market data carried by BBC News is provided by DigitalLook.com. The data is for your general information and enjoys indicative status only. Neither the BBC nor Digital Look accept any responsibility for its accuracy or for any use to which it may be put. All share prices and market indexes delayed at least 15 minutes. 52 week high and low values are calculated from close price data. Click here for terms and conditions
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Book your room at Americinn Greenville
Please enter your travel dates.
Collect 200 points
Simply enter your Nectar card number when prompted. Your points will be credited 30 days after you return from your trip.*Offers may apply
This Greenville, Michigan hotel is located off M57 conveniently located near Rockford, Michigan. The hotel offers a variety of room types including suites with whirlpools and fireplaces. In addition, enjoy our inviting indoor pool, hot tub, and sauna. For people who like to stay fit on the road we offer free access to a local gym. Stay connected on the road with free, hotel-wide, high-speed internet. Wake up each morning to our free, hot, home-style AmericInn Perk breakfast with fresh waffles, fresh fruit, eggs, sausage, pastries, coffee, juice, and more. You are sure to enjoy this clean, quiet, comfortable hotel that offers all the amenities, and friendly staff, you expect most.Information missing or incorrect? Tell us!
Hotel Amenities
Hotel Amenities
- Business center
- Free breakfast
- Dry cleaning/laundry service
- Free WiFi
- Laundry facilities
- One meeting room
- Free self parking
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Available in some public areas: Free WiFi
Free self parking
Room Amenities
- Air conditioning
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Because of each country's product availability, the selection on this site may not be the same as the one you were previously on.Confirm Cancel
Put classic chic front and center with this freshwater cultured pearl necklace, featuring a 14k white gold cable chain and shimmering diamond centerpiece.
View our education section to learn more about our gold jewelry.
second positive buying experience from BN - fast, good quality, good prices
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Highlight: Allora & Calzadilla
Spotlight: Phillips New York
Featured: Ronald Feldman Fine Arts
Now On: Jack Spencer
Top Lot: Kim Keever
View Catalogue: Almut Heise
Over 9 MillionAuction Results
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Sample Report
Stone and Wind is an exhibition pairing the sculptures of Yongjin Han with the photographs of Jungjin Lee.
Yongjin Han (b. 1934, Seoul) is a seminal figure in Korean contemporary sculpture. Following the Korean War (1950-53), he has been the leader in bringing Korea's tradition of direct stone carving out of figuration and into a refined abstraction. Like the great Romanian sculptor Constantin Brancusi, Yongjin Han pursues truth to materials, seeking authentic engagement with stone as a substance that is both ancient and alive. The spirit of his practice is simultaneously light and profound: "The stone asks me to scratch its itch here, or there, so that's what I do!" His works are in museums and private collections worldwide. Major commissions include the National Museum of Contemporary Art, Korea; the city of Redding, California; and the Olympic Sculpture Park, Seoul.
Jungjin Lee (b. 1961, Korea) is one of Korea's most celebrated photographers. For her "Wind" series, she visited the American southwest and photographed the landscape; her discerning eye can somehow capture unseen energies. She brushes photographic emulsion on traditional Korean mulberry bark paper, and then prints upon this paper through a darkroom process. The resulting works have a textural interplay of paper, brushwork and image that powerfully evokes invisible forces. Jungjin Lee's photographs are in collections including the Metropolitan Museum of Art in New York and the National Museum of Contemporary Art, Korea; she is currently planning a new body of work in Israel.
- David Parker


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Study: Russia's Tricolor to Overtake BSkyB, Become No. 2 Euro Pay TV Company
LONDON – John Malone's Liberty Global will remain the largest European pay TV operator in terms of subscribers in the coming years, but Britain's BSkyB will have to give up the second spot to a Russian company, according to a new report.
Research firm Digital TV Research said Liberty Global "extended its lead as Europe's largest pay TV operation with the recent acquisition of the U.K.'s Virgin Media," coming in with 20.97 million TV subscribers as of the end of 2012. "The group had twice as many subscribers as second-placed BSkyB," which ended 2012 with 10.33 million, the firm highlighted.
It forecast that by 2018, Liberty Global would see slight growth to 21.25 million pay TV subscribers.
BSkyB, in which Rupert Murdoch's 21st Century Fox owns a 39 percent stake, will then have 10.84 million subscribers, according to the Digital TV Research projection. Russia's Tricolor will overtake its user count, growing from 9.20 million TV subscribers last year to 15.75 million in 2018, it predicted.
Low-cost provider Tricolor has many non-paying users, which the research firm said it did not include in its user count.
Rounding out the top 5 European pay TV firms are Kabel Deutschland with 8.14 million subscribers as of the end of 2012, which could edge up to 8.16 million in 2018, and Russia's Rostelecom (6.60 million, 7.13 million).
Pay TV subscriptions for 102 operators across 26 countries covered in the report will increase from 105.8 million in 2008 and 131.9 million in 2012 to 147.1 million in 2018, according to from Digital TV Research.
"However, not all of these operators will increase their subscriber bases, with 36 percent expected to decline between 2012 and 2018," Digital TV Research predicted. "Traditional pay TV operators now face greater rivalry than ever before – either from other pay TV platforms such as IPTV or satellite or from "free" multi-channel TV services, such as DTT and online TV and video."
Total subscriber and VOD revenue for the operators covered increased from $26.8 billion in 2008 to $34.5 billion in 2012. That will only grow to $35.1 billion by 2018 though, Digital TV Research predicted.
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Two people were taken to a hospital after a Monday afternoon collision in Lancaster.
2 injured when cars collide in LancasterPublished 1:16 PM EDT Aug 06, 2012
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Get free worksheets plus activities, articles and science projects.
The United States is made up of many different people, from many different countries, who wear many different kinds of clothing. Color in this picture of an Indian girl in a traditional dress. Do you know where India is?
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Dublin Liffey River Cruise
- Liffey River cruise through Dublin
- 45-minute scenic cruise past Dublin's city-center sights
- Custom House, docklands, bridges and 18th-century buildings
- Professional commentary from your local guide
Recent Photos of This Tour
Custom House Building, River ...Photo by: Anonymous
06 2011
Liffey River cruisePhoto by: Anonymous
06 2011
from the boatPhoto by: STEPHEN Y
09 2013
Liffey River Cruise Captain ...Photo by: MommaK
09 2013
Liffey River Cruise Tour GuidePhoto by: MommaK
09 2013
Liffey River CruisePhoto by: MommaK
09 2013
Dublin 2011 (80)Photo by: michael n
07 2011
What You Can Expect
You will learn the story behind the iconic Ha'penny bridge as well as Gandon's masterpiece, the majestic Custom House. You will follow the story of Dublin's Royal and Grand Canals and see where Oliver Cromwell landed in 1649. You'll also hear how Captain William Bligh surveyed Dublin Bay in 1800. Learn of how much of present day Dublin now sits on reclaimed land, including Trinity College and the Spire in O'Connell Street.
Customer Reviews
October 2014
loved this...learned all sorts of hidden info about Dublin and the waterway
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This tour was amazing!


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best suppliers
After many years of apathy, I've recently become wise to the beauty of begonias. Do you have any suggestions about good (mail order) suppliers, particularly of the rex begonia type? I know Logees carries; any others?
My favorite begonia supplier is Lauray of Salisbury. She also sells cuttings at half the catalog price, which I like a lot because I get more plants. Rob's Violets also sells begonias and is very reliable. Mostly theirs are smaller-growing ones. Of course, the absolute best source is begonia conventions! There are other sources, but they seem to have mixed reviews or I haven't ordered from them and don't know.
Palm Hammock, Kartuz, Glasshouse Works all have a good selection but not of rexes. I've ordered from all of them plus the two greenelbows mentioned and Logee's as well. They all have their good and bad points (price, substitution policy, delivery speed, selection, etc.)
Lyndon Lyon has an array of rexes (I have not ordered from them). eBay is hit and miss and is best to buy more than one from the same seller to minimize shipping. There are several nice ones being offered now but shipping can be higher in the winter (I think they make more money this way).
Speaking of begonia conventions, the national one is in Miami first week of March this year. Check Palm Hammock Orchid Estate's web site for some details.


text:
Grown-Up Christmas List
|This article needs additional citations for verification. (March 2007)
|"Grown-Up Christmas List"
|Single by Amy Grant
|from the album Home for Christmas
|Promo CD single
|Christmas, pop
|A&M, Word Records
|David Foster, Linda Thompson-Jenner, Amy Grant
|Amy Grant singles chronology
"Grown-Up Christmas List" (sometimes titled "My Grown-Up Christmas List") is a Christmas song composed by David Foster (music) and Linda Thompson-Jenner (lyrics),[1] and originally recorded by Foster (with singer Natalie Cole on vocals) for his 1990 non-holiday album River of Love. Though it was also released as a single, the song was not a hit upon its first appearance. In 1992, however, Amy Grant recorded a version for her second holiday album, Home for Christmas. Grant's version featured altered lyrics and an additional verse that Grant penned herself. Her record label at the time, A&M Records, promoted the song as the second single from the album, and it received substantially more radio airplay than the original version by Foster.
The song is about a visit with Santa Claus by an adult who does not ask Santa for anything material for Christmas, but rather nothing but good things for all humanity.
The original version by David Foster with Natalie Cole also appeared on Foster's 1993 holiday set, The Christmas Album.[2]
In 2003, former American Idol winner Kelly Clarkson performed "Grown-Up Christmas List" on the show's Christmas special, which resulted in renewed airplay of the song during the holiday season that year.
Music video[edit]
A&M Records released a music video for Amy Grant's recording of the song, featuring an appearance by Grant's son, Matthew Chapman. Grant's version is the one most people associate with the song.
List of notable recordings[edit]
The song has been frequently covered by other artists, including:
- Bryan Duncan (1995)
- Stephanie Beaumont (1995)
- Chuck Negron (1996)[3]
- B.J. Thomas (1997)[4]
- Donny Osmond (1998)
- David Pomeranz (2000)
- Monica (2000)[5]
- Barbra Streisand (2001)[6]
- Ginette Reno (2002)[7]
- Michael Bublé (2003)
- Kelly Clarkson (2003)
- Lea Salonga (2004)
- The Manhattan Transfer (2005)
- Jane Monheit (2005)
- Regine Velasquez (2005)
- Clay Aiken (2006)
- Ayaka Hirahara (2006)
- Ali Lohan (from the holiday album Lohan Holiday) (2006)
- Luis Miguel (2006)
- Boney James (2007)
- Ayla Brown (2007)
- Jed Madela (2007)
- Aretha Franklin (from her holiday album This Christmas, Aretha) (2008)
- Kyla (2008)
- Kanami Ayano (2008)
- Martin Nievera (2008)
- Rissi Palmer (2008)
- Twin Cities Gay Men's Chorus (2008)
- Rodney Carrington (2009)
- Joe (2009)
- Charice (2010)
- The Veronicas (2010)
- Richard Poon (2011)
- Elena Nordé & Syllabus the Don (2012)[8][9]
- Ailee (2012)
- Lauren Alaina (2013)
- Liz Callaway (2013)
- Linda Eder (2013)
- Tae Yeon (2013)
The 2000 version by Monica also contains a second verse penned by Thompson-Jenner. Kelly Clarkson's 2003 version was the first version to make any of Billboard's singles chart; her rendition peaked at no. 17 on the Hot Adult Contemporary chart during the Christmas holiday season of 2003-2004. Miguel's cover was recorded in Spanish as "Mi Humilde Oración" for his album Navidades and it peaked at No. 37 on the Billboard Latin Pop Songs chart.[10]
Track listing (Amy Grant single)[edit]
- "Grown Up Christmas List – Edit 3:44"
- "Grown Up Christmas List – LP Version 5:00"
The original version of Grant's single failed to enter any of the Billboard charts. Clarkson's version entered the Adult Contemporary chart in 2003 where it spent five weeks on the chart.[11]
|Chart (2003-2004)
|US Adult Contemporary (Billboard)[12]
- ^ Holden, Stephen (December 10, 1993). "Holiday Noises, Joyful and Otherwise, on Disk", The New York Times, p. C33.
- ^ Takiff, Jonathan (November 26, 1993). "Spicing up the season: Holiday albums abound", Philadelphia Daily News, p. 72.
- ^ Gundersen, Edna (December 16, 1996). "Getting in tune with the holiday season", USA Today, p. D4.
- ^ Galante Block, Debbie (August 23, 1997). "Holi-discs for '97 marry Christmas to every conceivable musical genre", Billboard 109 (34): 64–5.
- ^ Harrington, Richard (December 10, 2000). "Musicmakers, Taking Up the Santa Cause: From Christina Aguilera to – Yikes! – Rosie O'Donnell, the Sounds of the Season Packaged Just for You", The Washington Post, p. G5.
- ^ Mervis, Scott (November 23, 2001). "Holiday gems & lumps of coal: Santa's got a mixed bag of new Christmas music", Pittsburgh Post-Gazette, p. W1.
- ^ Blakey, Bob (December 8, 2002). "Sounds of the season: Ginette Reno: The First Noel", Calgary Herald, p. D5.
- ^ https://www.youtube.com/watch?v=lUIrcddAdhY
- ^ http://www.cdbaby.com/cd/elenanordesyllabusthedon
- ^ "Navidades - Luis Miguel: Awards". Allmusic. Rovi. Retrieved 2013-05-14.
- ^ http://www.allmusic.com/artist/kelly-clarkson-p542180/charts-awards/billboard-singles/chart_name-asc
- ^ "Kelly Clarkson Album & Song Chart History" Billboard Adult Contemporary for Kelly Clarkson.


text:
Town Square
Monterey vegetable processor makes record-setting donation to county food bank
Original post made on Jun 17, 2008
Read the full story here Web Link posted Monday, June 16, 2008, 4:08 PM
Comments (2)
a resident of Highland Oaks
on Jun 17, 2008 at 2:45 pm
Good on you, SK!
a resident of Livermore
on Jun 17, 2008 at 5:26 pm
SALMONELLA FREE? Hmmmmmmmmmmmmmmmmmmmmmmmmmmm...
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Another bad idea from the air board
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3 reasons to be excited about Dream Candidate 2
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According to an aspect of the present invention, various medical devices, including implantable or insertable medical devices, are provided, which comprise at least one particle-containing region whose surface is at least partially coated with a diamond-like coating.
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This patent application relates to medical devices, including implantable or insertable medical devices, having particle-containing regions with diamond-like coatings.
Implantable and insertable medical devices are well known in the medical community. Many of these devices are configured to expand upon implantation or insertion into the body. For instance, angioplasty procedures are well known, in which a catheter is navigated through a lumen of a vertebrate subject to a site needing expansion. For example, a distal portion of a catheter containing a deflated balloon may be directed to an area of an artery that is substantially blocked, and that may be enlarged upon expansion of the balloon, typically by a hydraulic or pneumatic mechanism.
U.S. Patent Appln. Pub. No. 2004/0138733, the entire disclosure of which is hereby incorporated by reference, describes medical devices, which include the use of nanopaper for mechanical actuation. The medical devices may be provided, for example, in the form of a balloon catheter, in which the nanopaper is mounted about an electrode and into which an electrically conductive solution is dispersed. Actuation of the electrode causes generation of bubbles, which in turn causes the nanopaper, and thus the medical device to which it is applied, to expand. Whereas inner bubbles are generally trapped and act to expand the nanopaper, an issue encountered with devices of this type is that bubbles created at the outer surfaces may escape into the surrounding media. Without wishing to be bound by theory, it is believed that, due to the very high surface area of the carbon nanotubes, bubbles can arise at many locations throughout the nanopaper. Small bubbles have tremendous inner pressure. Normally when they contact one another, smaller bubbles merge to form larger ones as the pressure is decreased inside the larger bubbles. However in the case of nanopaper, bubbles cannot merge together due to the network of carbon nanotubes. They can only merge if they crack open the carbon nantube paper. The bubbles on the surface of the paper, however, don't have the restriction of being surrounded by carbon nanotubes and can readily merge together to become larger. If they get large enough, their upward force (due to gravity) eventually becomes larger then the adhesion force which keeps them sticking to the paper surface, and the bubbles depart from the surface.
Even if the actuator is sheathed, it is desirable to prevent bubbles from escaping from the surface as they and expand the sheath. For example, if the sheath happened to burst, this would allow the gas between the sheath and the nanopaper to escape into the body. If this occurs at high pressure, the gas bubbles will expand due to a drop in pressure and may cause a blockage in the arteries.
Other implantable and insertable medical devices are adapted to achieve enhanced or suppressed interactions with surrounding cells and tissue. For example, carbon nanotube materials have been shown to be an ideal matrix for endothelial cell growth. See, e.g., �Carbon Nanotube Bucky Paper Scaffold for Retinal Cell Transplantation,� NASA Ames Research Center, including spatial organization. This is likely due, at least in part, to the nanostructure and porosity of such materials. For example, it is known that nanostructured surfaces may directly interact with cell receptors, thereby controlling the adhesion or non-adhesion of cells to the surface. It is also noted that carbon nanotube materials are porous and therefore may allow for the flow of therapeutic agents, including growth factors and nutrients.
However, the mechanical robustness of many particle-based materials, including paper formed from carbon nanotubes, is in need of enhancement.
The invention is directed to medical devices which include a diamond-like coating over at least a portion of their surfaces. According to an aspect of the present invention, various medical devices, including various implantable or insertable medical devices, are provided, which comprise at least one particle-containing region whose surface is at least partially coated with a diamond-like coating. In some embodiments, the particle-containing region is conductive. In some embodiments, the particle-containing region contains a therapeutic agent.
An advantage of this invention is that medical devices having particle-containing regions may be provided, in which the robustness of the particle-containing region is improved.
Another advantage of this invention is that medical devices having expandable particle-containing regions, for example, carbon-particle-containing regions, may be provided in which bubble formation at (and hence bubble loss from) the outer surfaces of the particle-containing regions is reduced or prevented.
These and other embodiments and advantages of the present invention will become readily apparent to those of ordinary skill in the art upon review of the Detailed Description and Claims to follow.
A more complete understanding of the present invention is available by reference to the following detailed description of various aspects and embodiments of the invention. The detailed description of the invention which follows is intended to illustrate but not limit the invention.
According to an aspect of the present invention, medical devices, including various implantable or insertable medical devices, are provided, which comprise at least one particle-containing region whose surface is at least partially coated with a diamond-like coating.
Medical devices which may be provided with such diamond-coated particle-containing regions include implantable or insertable medical devices, which can be selected, for example, from the following: catheters (e.g., renal or vascular catheters such as balloon catheters), guide wires, balloons, filters (e.g., vena cava filters), filter wires, stents (e.g., coronary vascular stents, peripheral vascular stents, cerebral, urethral, urethral, biliary, tracheal, gastrointestinal and esophageal stents), bifurcation stents, stent grafts, stent delivery catheters, vascular grafts, vascular access ports, embolization devices including cerebral aneurysm filler coils (including Guglilmi detachable coils and metal coils), intravascular occlusion devices, septal defect devices, myocardial plugs, Y-adapters, patches, pacemakers and pacemaker leads, left ventricular assist hearts and pumps, total artificial hearts, heart valves, vascular valves, shunts, drain tubes, urinary sphincters, urinary dilators, penile prosthesis, distal protection devices, biopsy devices, and any coated substrate (which may comprise, for example, glass, metal, polymer, ceramic and combinations thereof) that is implanted or inserted into the body. Further examples of medical devices include sutures, suture anchors, anastomosis clips and rings, tissue staples and ligating clips at surgical sites; cannulae, metal wire ligatures, orthopedic prosthesis such as bone grafts, bone plates, joint prostheses, orthopedic fixation devices such as interference screws in the ankle, knee, and hand areas, tacks for ligament attachment and meniscal repair, rods and pins for fracture fixation, screws and plates for craniomaxillofacial repair; dental devices such as void fillers following tooth extraction and guided-tissue-regeneration membrane films following periodontal surgery, tissue bulking devices, and tissue engineering scaffolds for cartilage, bone, skin and other in vivo tissue regeneration.
The diamond-coated particle-containing regions may, for example, be disposed over all or a portion of a substrate (e.g., a metallic substrate or a non-metallic substrate, such as a polymeric or ceramic substrate) that corresponds to a medical device or a portion of a medical device, or they may constitute the bulk of the medical device (e.g., in the case of a tissue engineering scaffold).
The diamond-coated particle-containing regions may be provided, for example, within the medical device (e.g., beneath a hydrogel coating, a balloon, a polymeric sheath, etc.) or at the medical device surface (e.g., on a balloon surface, a stent surface, a sheath surface, etc.).
Particle-containing regions may be employed in medical devices for a variety of reasons. One specific example of a particle-containing region is a conductive nanopaper region, which, as noted above, may be used for mechanical actuation. One specific example of a medical device that employs such an actuator is shown in longitudinal and lateral cross-sections, respectively, in
Although the actuators 130, 150 may appear superfluous in light of the balloon 120, this is not the case. In particular, balloon catheters can be described as having a hydraulic actuating mechanism. Because hydraulic systems are more efficient at larger dimensions, the present trend to downscale device sizes has created the need for actuators that efficiently function at very small diameters. Conductive nanopaper actuators meet this criterion.
Embodiments comprising more than one actuator may be configured so that the individual actuators may be activated collectively or independently. In some embodiments, multiple groups of actuators may each be activated collectively, with each group being capable of being activated independently of the other groups.
While an electrically actuated medical device for use in enlarging lumens is shown (e.g., an angioplasty balloon catheter system), it is to be understood that electromechanical actuation may be used in conjunction with essentially any type of medical device, including those described herein, for which expansion is useful, such as, for example, expandable stents, aneurysm filler coils, guidewires, and septal closure devices, expandable devices for deploying other medical devices, devices for taking biopsy samples, among many others.
The particular device illustrated comprises a balloon 120 having an outer perimeter 113. Either pneumatic or hydraulic balloons may be used, or both. The balloon 120 may comprise an exterior surface 122 and an interior 124. The device may comprise an interior tube 126 in the interior 124. The interior tube 126 may provide one or more apertures 128 that allow inflation media to enter the balloon 120 from the interior tube 126, i.e., in its role as an inflation lumen. (Note that, unlike the remainder of the figure, the interior tube 126 of
The actuator 130 may comprise a first electrode 132 and a second electrode 136. Suitable conductive materials for the first electrode 132 are described below. In some embodiments, the function of the first electrode 132 may by be performed by a conductive balloon wall 121. The second electrode 136 may comprise, for example, a particle-containing conductive region with a diamond-like coating provided at its outer surface 140, as described in more detail below. A separator 134, such as one of those described in more detail below, is provided between the first 132 and second 136 electrodes.
An electrolyte 138 is provided in the actuator 130 so as to allow for a completed electrical circuit between the first and second electrodes 132, 136. The electrolyte 138 may be supported by a suitable fluid 139 as described below. The electrolyte 138 and fluid 139 are operatively associated with the separator 134 and first and second electrodes 132, 136. In the embodiment shown, the electrolyte 138 provides an ion that allows for formation of a gas upon activation of the actuator 130, e.g., formation of oxygen, chlorine, or other gas, causing expansion of the second electrode 136. Being an electrochemical process, gas bubble formation does not occur at non-conductive surfaces. Consequently, gas bubble formation is impeded or eliminated at the outer surface, where the particle-containing conductive region is provided with the diamond-like coating, which is non-conductive. As noted above, bubbles created at the outer surfaces are likely to escape into the surrounding media.
The first and second electrodes 132, 136 may be operatively associated with a power source 146 by means of the first and second electrical conductors 142, 144, respectively. The power source 146 may be immediately adjacent to the actuator 130 or may be present in a proximal region 115 or distal region 117 of the medical device. The power source 146 may also be external to the subject during the medical procedure. The conductors 142, 144 may be formed of any suitable conductive material, such as those as described below.
During operation, the power source 146 may be actuated so as to apply, via conductors 142 and 144, a voltage that is sufficient to form bubbles at the second electrode 136, for example, a voltage on the order of about 1.0 to 1.2 Volts.
In operation, the medical device of FIGS. 1A-D may be employed for medical procedures such as, for example, an angioplasty procedure wherein the assembly 118 is navigated through a body lumen (not shown) of a vertebrate subject until it is appropriately positioned, such as within a blocked area of an artery. Once positioned, the power source 146 directs a voltage (and passes a current), via conductors 142 and 144, that is sufficient to form bubbles within the second electrode 136, causing it to expand. The procedure may also comprise the step of deactivating the actuators 130, 150 by reversing the voltage sufficiently such that the electrochemical reactions are reversed and the bubbles are removed, thereby reversing the expansion of the actuators 130, 150. On the other hand, actuator may be left in an activated state indefinitely, although over time the actuator may return to a deactivated state without reversing potential.
In some embodiments, the device may be provided with an elastic sheath 160, as illustrated in
In some embodiments, the expansion of the balloon may be made permanent by means including settable gels and mechanical mechanisms, such as those described, for example, in U.S. Patent Appln. Pub. No. 2004/0138733. For example, the balloon may be a detachable balloon that is used to plug various body lumens, for example, blood vessels.
In some embodiments, one or more actuators are disposed not around an outer perimeter of the balloon 120, but rather within the interior 124 of the balloon 120, for example, either being disposed on an inner surface of the balloon wall 121 or disposed around the interior tube 126 in the interior 124. In either latter case, the actuator 130 may be deployed when the balloon 120 is in a collapsed state, in which case the actuator 130 will expand the balloon 120 outward from a fully crimped state to a second partially expanded state. As its diameter is increased, the balloon 120 enters into a more efficient operating range, where less pressure is required to generate the large strains that are afforded by hydraulic/pneumatic actuation. Hence, in this embodiment, the actuator 130 may improve the efficiency of the balloon 120. A similar effect may be achieved where the actuator 130 is provided at an outer surface of the balloon 120, in which case the actuator 130 may be expanded while the balloon is in its fully crimped position, then contracted, followed by expansion of the balloon 120.
As discussed below, greater dimensional changes may be achieved in various ways, including using thicker electrodes (i.e., thicker particle-containing conductive regions) or by stacking multiple electrodes (e.g., by using multiple actuators). For example,
More specifically, theses drawings show an embodiment similar to that illustrated in
In the embodiment shown in FIGS. 2A-D, the first and second actuators 130, 150 have the same orientation (i.e., the first electrode 132 is beneath the second electrode 136). In other embodiments, at least one orientation is reversed. Where the orientation of the inner actuator 130 is reversed, a single first electrode 132 may be employed between two second electrodes 136.
In embodiments such as that shown in FIGS. 2A-D, the actuators 130, 150 may be operatively associated with a power source so that the actuators may be activated independently or collectively.
Any number of actuators may be stacked on one another, with FIGS. 2A-D depicting two stacked actuators for illustrative purposes only. Stacked actuator arrangements such as those shown in respect to the balloon catheter shown may also be employed in other medical devices for which actuation expansion is desired.
Actuators in accordance with the present invention, including those illustrated in
As another specific example, the components of the actuator 130, including first electrode 132, separator 134, and second electrode 136 may be pressed together at elevated temperature (e.g., between 130� C. and 150� C.) to create a robust structure. The diamond-like coating may be provided on the second electrode 136 either before or after pressing. The layers of the actuator may be hot-pressed together before or after applying the actuator to a surface 122 of the balloon 120. In some embodiments, during assembly, polymer components of the actuator 130 (e.g., the separator material) may be compressed near the melting temperatures of the polymer components to create a more robust interface.
Methods for connecting a preformed actuator 130 to the device (e.g., to balloon 120) include used of adhesives and outer elastic sheaths. Examples of adhesives include, for example, cyanoacrylic adhesives, polyurethane adhesives, and UV curable adhesives, among many others. The actuator may also be sewn to the balloon 120, attached with clamps, and so forth. The actuator 130 or components thereof may be molded in the shape of a particular medical device in some embodiments.
An actuator (with diamond-like coating) for use in the present invention, as well as in various other applications requiring an electrochemical actuator, including a method of forming the same, will now be discussed in conjunction with
In a subsequent step, top and bottom surfaces of the conductive region 336 are provided with a diamond-like coating 336 d, for example, using techniques such as those described below. The resulting structure is illustrated in
Note that the conductive region 336 may be treated to improve conductivity, for example, using the techniques described below, either before or after application of the diamond-like coating 336 d.
The structure of
At this point, construction of the electrochemical actuator is essentially complete. Being porous, the upper and lower conductive regions, 336 u and 336 l, may function as electrodes during various electrochemical reactions. Moreover, because they are provided with non-conductive surface, the porous central and outer diamond-like coated regions 336 dc and 336 do will not participate in these electrochemical reactions. Consequently, gas bubble formation will not occur and loss of gas at the outer surfaces may be reduced or eliminated as described above. Also, because the central diamond-like coated region 336 dc (which is actually two adjacent diamond-like coated regions) is porous and has a non-conductive surface, it may function as a separator. The conductors 344 facilitate electrical contact between a source of electrical potential and the upper and lower conductive regions 336 u and 336 l, respectively.
Referring now to
Particles for use in particle-containing regions in accordance with the present invention may be comprised of a variety of materials, including organic and inorganic materials. In certain embodiments, inorganic materials may be preferred as they are frequently stable under the conditions associated with the application of a diamond-like coating. Inorganic materials include metallic materials (e.g., metals and metal alloys) and non-metallic materials (e.g., carbon and semiconductors, glasses, ceramics and various other materials, including a variety of metal- and non-metal-oxides, various metal- and non-metal-nitrides, carbides, borides, phosphates, silicates, and sulfides, among others).
Specific examples of metallic inorganic materials may be selected, for example, from metals (e.g., biostable metals such as gold, platinum, palladium, iridium, osmium, rhodium, titanium, tantalum, tungsten, and ruthenium, and bioresorbable metals such as magnesium), metal alloys comprising iron and chromium (e.g., stainless steels, including platinum-enriched radiopaque stainless steel), alloys comprising nickel and titanium (e.g., Nitinol), alloys comprising cobalt and chromium, including alloys that comprise cobalt, chromium and iron (e.g., elgiloy alloys), alloys comprising nickel, cobalt and chromium (e.g., MP 35N), and alloys comprising cobalt, chromium, tungsten and nickel (e.g., L605), and alloys comprising nickel and chromium (e.g., inconel alloys).
Specific examples of non-metallic inorganic materials may be selected, for example, from materials containing one or more of the following: metal oxides, including aluminum oxides and transition metal oxides (e.g., oxides of titanium, zirconium, hafnium, tantalum, molybdenum, tungsten, rhenium, and iridium); silicon; silicon-based ceramics, such as those containing silicon nitrides, silicon carbides and silicon oxides (sometimes referred to as glass ceramics); calcium phosphate ceramics (e.g., hydroxyapatite); carbon; carbon-based, ceramic-like carbon materials such as carbon nitrides, and silicate particles including monomeric silicates, polyhedral oligomeric silsesquioxanes (POSS), and clays. Carbon particles are particularly beneficial for certain embodiments of the invention. However, it should be kept in mind that other particulate materials and regions may be used as well.
By �carbon particles� is meant particles that contain carbon, typically containing 50 mol % to 75 mol % to 90 mol % to 95 mol % to 99 mol % or more carbon atoms. Carbon particles for use in the carbon-particle-containing regions of the present invention may take on a variety of shapes, including spheres, polyhedral (e.g., fullerenes), solid cylinders (e.g., carbon fibers), tubes (e.g., carbon nanotubes), plates (e.g., graphite sheets) as well as other regular and irregular shapes.
Carbon particles for use in the invention may vary widely in size. In many embodiments, their smallest dimensions (e.g., the thickness for plates, the diameter for spheres, regular polyhedrons, fibers and tubes, etc.) are less than 10 micrometers (e.g., ranging from 0.5 nm to 1 nm to 10 nm to 100 nm to 1 micrometer to 10 micrometers), whereas additional dimensions (e.g., the width for plates, and the length for fibers and tubes) may be of the same order of magnitude or much larger (e.g., ranging from 0.5 nm to 1 nm to 10 nm to 100 nm to 1 micrometer to 10 micrometers to 100 micrometers to 1000 micrometers or even more).
Particularly beneficial carbon particles are those that comprise molecular carbon that is predominantly in sp2 hybridized form (i.e., structures in which the carbon atoms are predominantly connected to three other carbon atoms within a lattice structure, sometimes referred to as a �grapheme carbon lattice�). Examples of carbon particles that predominantly comprise carbon in sp2 hybridized form include graphite, fullerenes (also called �buckyballs�) and carbon nanotubes. Graphite molecules contain planar sheets of sp2 hybridized carbon, whereas fullerenes and carbon nanotubes contain curved sheets of sp2 hybridized carbon in the form of hollow polyhedral (e.g., �Bucky balls�) and tubes, respectively. Fullerenes and carbon nanotubes may be thought of as sheets of graphite that are shaped into polyhedral and tubes and, in fact, may be made, among other techniques, by directing a laser at a graphite surface, causing some of the sheets to be displaced from the graphite, which subsequently react to form fullerenes and/or nanotubes.
In certain embodiments of the invention, the carbon-particle-containing regions contain carbon nanotubes, typically 50 wt % to 75 wt % to 90 wt % to 95 wt % to 99 wt % or more carbon nanotubes. Examples of carbon nanotubes include single-wall carbon nanotubes and multi-wall carbon nanotubes (which term embraces so-called �few-wall� carbon nanotubes). Specific examples of nanotubes include single wall carbon nanotubes (SWNTs), which have inner diameters typically ranging from 0.25 nanometer to 0.5 nanometer to 1 nanometer to 2.5 nanometers to 5 nanometers, and lengths up to 100 micrometers, for example, lengths ranging from 10 nanometers to 100 nanometers to 1 micron (μm) to 10 microns to 100 microns, and multi-wall carbon nanotubes, which have inner diameters typically ranging from 2.5 nanometers to 5 nanometers to 10 nanometers, outer diameters of 5 nanometers to 10 nanometers to 25 nanometers to 50 nanometers, and lengths up to 100 micrometers, for example, lengths ranging from 10 nanometers to 100 nanometers to 1 micron (μm) to 10 microns to 100 microns.
SWNTs are particularly preferred for many embodiments of the present invention, including those where a conductive particle-containing region is desired. At present, the purest SWNTs are produced by pulsed laser vaporization of carbon that contains metal catalysts such as nickel and cobalt. Fullerenes are known to form when the carbon is vaporized, mixes with an inert gas, and then slowly condenses. The presence of a metal catalyst, however, is known to form SWNTs. SWNTs are generally considered to be individual molecules, yet as noted above, they may grow to be microns in length. SWNTs may also be produced by other processes such as arc discharge processes.
Regardless of the production technique, after formation, SWNTs are typically purified to remove impurities such as amorphous carbon and residual metal catalysts, for example, by exposure to NHO3 or HNO3/H2SO4, followed by rinsing, drying, and subsequent oxidation at high temperatures. A specific technique for providing SWNTs with >99.98 wt % purity (as measured by ICP analysis) is described in the Oak Ridge National Laboratory, Laboratory Directed Research and Development Program, Fy 2003, Annual Report. SWNTs are also commercially available as aqueous suspensions.
Regardless of the specific carbon particles selected, the carbon-particle-containing regions for use in the present invention will typically comprise 50 wt % to 75 wt % to 90 wt % to 95 wt % to 99 wt % or more carbon particles.
Carbon-particle-containing regions for use in the present invention may have various desirable traits, including nonplanar surface topography, porosity, and conductivity. For example, as noted above carbon nanotube materials have been shown to be an ideal matrix for endothelial cell growth, which is likely due, at least in part, to the nanostructure and porosity of such materials. Porosity allows for free flow of therapeutic agents, including growth factors and nutrients, and waste products.
Where the particle-containing regions are conductive they may also have the ability to expand substantially under certain conditions, as discussed further below. Macroscopic electrical conductivities typically employed for this and other purposes are generally greater than about 1�103 Siemens/meter (S/m), more generally ranging from 1�104 S/m to 5�106 S/m. Conductivities may be measured, for example, using a four probe measurement.
Particle-containing regions for use in conjunction with the present invention may be formed using any suitable method for forming such regions. For example, carbon-particle-containing regions may be formed by suspending carbon particles (e.g., SWNTs) in an appropriate fluid (e.g., water, one or more organic solvents such as toluene or chloroform, or a mixture of water and organic solvent), which may contain further optional agents as desired such as surfactants (e.g., Triton X-100, an alkylaryl polyether alcohol or octyl phenol ethoxylate). SWNT suspensions are commercially available, for example, from Zyvex, Richardson, Tex., USA and Rice University, Houston, Tex., USA. The suspension is then brought into contact with a substrate of choice to form a carbon-particle-containing region.
In some embodiments, a particle-containing region is formed on an underlying substrate, which is (or becomes) part of the medical device (i.e., a permanent substrate). In other embodiments, the particle-containing region is formed on a temporary substrate, from which it is subsequently removed (e.g., by separating the particle-containing region from the substrate or by sacrificing the substrate by a process such as dissolution, melting, etc.).
As a specific example, SWNT suspensions may be sprayed onto desired substrates (e.g., using single or multi-orifice spray heads, ink jet, etc.) and the liquid allowed to evaporate (e.g., at elevated temperatures), thereby forming SWNT layers. The density of the SWNT layers may be varied, for example, by adjusting the spray duration, the SWNT concentration, the nozzle pressure, and so forth, which may cause a variation, for example, in the diameter of bundles (or so-called �ropes�) of SWNTs that are formed. Alternatively, substrates may be dipped into suspensions of SWNTs to form SWNT layers. For high density packing of the SWNTs, an additional step may be taken by compressing the SWNTs.
As another specific example, carbon particle suspensions (e.g., SWNT suspensions) may be vacuum-filtered to produce freestanding carbon-particle-containing sheets, for instance, so-called �carbon nanotube paper� or �bucky paper,� which contains highly entangled nanotube ropes, as described, for example, in U.S. Patent Appln. Pub. No. 2004/0138733 and in G. M. Spinks, et al., �Pneumatic Actuator Response from Carbon Nanotube Sheets,� Materials Research Society Symposium Proceedings, Vol. 706, Making Functional Materials and Nanotubes (Materials Research Society, Pittsburgh, 2002) pp. Z9.22.1-6, the disclosures of each of which are hereby incorporated by reference. A typical nanotube paper produced by such a process is between 15 and 35 microns thick, has a bulk density of 0.3 to 0.4 grams per cubic centimeter, and has a four point conductivity on the order of 5,000 S/cm (e.g., 1,000 to 10,000 S/cm). The nanotubes commonly aggregate spontaneously into bundles or �ropes� of approximately 10 nanometers in diameter and many microns in length. The nanotube paper may then be peeled from the filter to produce a freestanding film. Alternatively, a filter material may be employed that is subsequently sacrificed (e.g., by dissolution, evaporation, combustion, etc.).
Other processes for producing carbon nanotube paper are described, for example, in A. G. Rinzler, J. Liu, et al., �Large scale purification of single-wall carbon nanotubes: process, product and characterization,� Applied Physics A, A67, 29-37 (1998), K. D. Ausman, et al., �Organic Solvent Dispersions of Single-Walled Carbon Nanotubes: Towards Solutions of Pristine Nanotubes,� J Physical Chem., 104(38):8911-8915 (2000), and T. V. Sreekumar, et al., �Single-Wall Carbon Nanotube Films,� Chem. Mater., 15:175-178 (2003), each of which are also expressly incorporated herein by reference. Commercially available carbon nanotube layers may also be employed. Once formed or obtained, such carbon-particle-containing regions may be adhered to a permanent substrate of choice.
Alternatively, a permanent substrate (e.g., a medical device or medical device component, a conductive or non-conductive mesh, etc.) may be positioned on top of a filter whereby at least part of the substrate is embedded within the particle-containing region at the same time as the region is formed. For instance, a tubular filter may be used in which one initially produces a first particle-containing layer on the inside of the tubular filter (e.g., using centrifugal force), after which one positions a tubular medical device (a stent, for example) within this ensemble, with close contact being established between the device and the particle-containing layer. One then repeats the process of making the particle-containing layer to create a second layer, such that the device becomes encapsulated between the first and second layers. In case of a stent having multiple struts or wires, the struts or wires are surrounded in whole or part by the particle-containing material. Many stent designs may also be readily expanded in the tubular filter and thus brought into close contact with the first layer.
In certain embodiments of the invention, multiple particle-containing layers are laminated to form a single particle-containing region. For example, as schematically illustrated in
Where conductive carbon-particle-containing regions are employed, various measures may be employed to increase the conductivity of the same. For example, the carbon-particle-containing regions may be irradiated with a dose of radiation (e.g., gamma irradiation) that is sufficient to increase the conductivity. This may be done either before or after providing the carbon-particle-containing region with a diamond-like coating (discussed below in more detail). As another example, the carbon-particle-containing region may be chemically treated under conditions sufficient to increase conductivity, likewise either before or after providing the region with a diamond-like coating.
In a specific example, a carbon-nanotube-containing region is irradiated with approximately 170 kGy of gamma radiation as described in Skakalova, V., et al. �Gamma-irradiated and functionalized single wall nanotubes.� Diamond Relat. Mater. 13(2): 296-8 (2004). A diamond-like coating is then applied, for example, as described below. This structure may then be treated with thionyl chloride, SOCl2, as described in Urszula Dettlaff-Weglikowska et al., Abstract HH 13.36 �Enhancement of Conductivity of Bucky Paper by Chemical Modification� Symposium HH, Functional Carbon Nanotubes, 2004 MRS Fall Meeting, Boston Mass., USA. As noted above, diamond-like coatings are typically very thin. Consequently, the texture and porosity of the underlying carbon-nanotube-containing region is typically at least partially preserved, allowing the SOCl2 to react with the defects on the carbon nanotubes in the interior of the structure. In addition to improving conductivity, functionalization with SOCl2 is also believed to improve bubble retention within the carbon-particle-containing region�a desirable trait where the carbon-particle-containing region is used as an actuator.
As used herein a �diamond-like coating� is one that, like diamond, is both hard and non-conductive. As used herein a �non-conductive� material is one that has a volume resistivity in excess of 1 ohm-cm. Examples of diamond-like coatings include boron nitride coatings, boron carbide coatings, and diamond-like carbon coatings, among others.
Analogous to carbon, boron nitride forms both hard, diamond-like sp3-bonded phases and softer, graphite-like sp2-bonded phases. The cubic phase of boron nitride, or cBN, is reported to be second in hardness only to diamond, with a Vickers hardness of about 5000 kg mm−2. Resistivities are on the order of 109 and higher have been reported to for predominantly cBN films. BN films with a high (>85%) percentage of the cubic phase may be deposited by a variety of deposition techniques (e.g., vapor deposition, pulsed laser deposition, etc.), which may employ energetic particle bombardment. For further information, see, e.g., P. B. Mirkarimi et al., �Review of advances in cubic boron nitride film synthesis,� Materials Science and Engineering, R21 (1997) 47-100.
Boron carbide (B4C) is the third hardest material after diamond and cBN, with a highest Vickers hardness (VH) similar to that of cBN at around 5000 kg mm−2. Volume resistivity is on the order of 102 Ohm-cm or less. Techniques for forming boron carbide layers include pulsed laser deposition, chemical vapor deposition (CVD), magnetron sputtering, and plasma spraying, among others. For further information, see, e.g., S. Aoqui et al., �Preparation of boron carbide thin film by pulsed KrF excimer laser deposition process,� Thin Solid Films 407 (2002) 126-131.
�Diamond-like carbon coating� is a generic term for a mixture of sp2 (as in graphite) and sp3 (as in diamond) bonded carbon. It is generally described as hard, amorphous, and chemically inert. Diamond-like carbon coatings are known to be biocompatible and they are relatively non-conductive, with electrical resistivities of 109 Ohm-cm and higher being typical. Typical diamond-like carbon coatings contain 80 mol % to 90 mol % to 95 mol % or more carbon atoms. Consequently, these coatings may contain other elements, introduced either unintentionally (e.g., as impurities) or intentionally (e.g., as dopants).
Properties of diamond-like carbon coatings generally vary with the ratio of sp3 to sp2 bonding. For example, a variation in the sp3 fraction (i.e., the number of sp3 carbons�(the number of sp carbons+sp2 carbons)) from 10% to 80% has been reported to correspond to a change in hardness from about 10 GPa to about 90 GPa. Preferably, the diamond-like carbon coatings comprise an sp3 fraction of 50% to 60% to 70% to 80% or more. In this regard, the term �tetrahedral amorphous carbon� (ta-C) is sometimes used to refer to diamond-like carbon materials with a high degree of sp3 bonding (e.g., greater than or equal 80%, typically 80-90%).
The diamond-like coating renders the underlying particle-containing region highly wear resistant. Furthermore, diamond-like coatings may be quite thin, ranging, for example, from 5 nm up to several micrometers, more typically from 10 nm to 100 nm. Thus, these coatings generally at least partially preserve the topography of the underlying particle-containing region.
Diamond-like coatings may be formed using a number of deposition techniques, including laser plasma deposition (e.g., pulsed laser deposition), ion beam deposition, magnetron sputtering, ion sputtering, plasma activated chemical vapor deposition, and ion plating. These processes may involve, for example, deposition from a beam/plume of energized (e.g., 10-500 eV) ions.
For instance, the deposition of amorphous diamond coatings on SWNTs is described in A. A. Puretzky et al., �Synthesis and characterization of single-wall carbon nanotube-amorphous diamond thin-film composites,� Applied Physics Letters, Vol. 81, No. 11, 9 Sep. 2002. Specifically, pulsed laser deposition (PLD) of tetragonally-coordinated amorphous carbon is performed in vacuum (�10−5 Torr) using a pyrolytic graphite target irradiated at 193-nm with an ArF-excimer laser (energy density F�1.8 J/cm2), which generates a plume that contains carbon ions having kinetic energies up to 100 eV.
Diamond-like coatings have also been applied to polymers. In this regard, Mark S. Hammond and A. Wesley Moorehead of SI Diamond Technology, Inc. have reported the use of a diamond like carbon coating material, Amorphic Diamond�, which comprises nodules of carbon that have the molecular/crystalline structure of diamond, with sizes of 100 to 200 nm, densely and uniformly packed in a net of amorphous carbon polytypes. This material is reported to be able to withstand flexure and shock without cracking, and it can be applied to plastic, polymer, metal, and ceramic substrates.
One could introduce a polymer inside of a carbon paper structure after a diamond like coating has been applied, for example, by dip coating or spraying a dissolved polymer, polymerizing a monomer in a plasma process, by applying a thin polymer film onto the carbon paper structure and melting the polymer into the top layer of the paper.
The unique properties of carbon-particle-containing regions with diamond-like coatings (also referred to herein as a �diamond-coated carbon-particle-containing regions�), including their flexibility, wear resistance, surface texture and porosity, as well as their conductivity characteristics, render them useful for a broad range of medical device applications.
Specific embodiments of medical devices in accordance with the present invention will now be described in conjunction with
In one embodiment, illustrated in
Although the substrate in this particular embodiment is a stent wire core 410, clearly the diamond-coated layer 436,436 d may be applied to practically any suitable medical device substrate, including substrates corresponding to all or a portion of the various medical devices described above.
As indicated above, diamond-coated particle-containing regions are desirable for a wide range of medical devices because, among other things, they may be biocompatible, wear resistant, flexible, porous, and have a surface topography that may influence cell growth.
Where porous, the diamond-coated particle-containing regions are capable of acting as reservoirs or metering membranes for therapeutic agents. For example, the therapeutic agent may be provided beneath the diamond-coated particle-containing regions, within the non-diamond-coated portions of the particle-containing regions, and/or within the diamond-coated portions of the particle-containing regions.
Numerous therapeutic agents which may be disposed beneath or within the diamond-coated particle-containing layers of present invention are described in paragraphs [0040] to [0046] of commonly assigned U.S. Patent Application Pub. No. 2003/0236514, the entire disclosure of which is hereby incorporated by reference. A few specific examples of therapeutic agents for use in conjunction with medical devices in accordance with the present invention, including drug eluting catheters and stents, include paclitaxel, sirolimus, everolimus, tacrolimus, Epo D, dexamethasone, estradiol, halofuginone, cilostazole, geldanamycin, ABT-578 (Abbott Laboratories), trapidil, liprostin, Actinomcin D, Resten-NG, Ap-17, abciximab, clopidogrel, Ridogrel, beta-blockers, bARKct inhibitors, phospholamban inhibitors, and Serca 2 gene/protein among others.
Hence, one or more therapeutic agents may be provided within (or beneath) the diamond-coated particle-containing layers of the present invention, including within the diamond-coated particle-containing layer 436, 436 d of
The embodiment illustrated in cross-section in
In certain embodiments, the following materials may be utilized for the device illustrated in
In accordance with other embodiments, the core 410 illustrated in
In still other embodiments of the invention, diamond-coated particle-containing regions in accordance with the invention are used to encapsulate pockets of therapeutic agents within one or more apertures (e.g., mechanically or laser cut apertures), which apertures may extend partially or completely through a medical device surface.
For example,
Numerous techniques are available for forming the structure of
Once the removable material 514 is in place, a particle-containing layer 536 is applied over the structure of
The removable material 514 is then removed from the structure of
Regardless of how the voids are filled, an additional particle-containing layer 536 is then applied opposite the previously established layer 536, for example, using techniques such as those described above. Finally, the top and bottom particle-containing layers 536 are provided with a diamond-like coating 536 d, again using techniques such as those described above, thereby producing a structure in accordance with
In other embodiments, for example, where a therapeutic agent is employed that cannot survive the diamond-like coating process conditions, the removable material may be removed and replaced with the therapeutic agent after the formation of the top and bottom particle-containing layers and diamond-like coating.
In other embodiments, a medical device is provided which has apertures that do not extend completely through the same. For example,
Such a device may be made in a fashion similar to that described in
In other embodiments, diamond-coated particle-containing regions are used as outer coatings for bioerodible stents made, for example, from a bioerodible polymer or a bioerodible metal, such as magnesium, iron, or their alloys. In this way, a coating is provided which surrounds the bioerodible material while at the same time allowing erosion to proceed. Any particles escaping from the main stent structure during degradation are captured within the coating. As indicated elsewhere herein, therapeutic agents may be provided within the coating, where desired. Where the coating is diamond-coated, carbon-nanotube-containing region, after the stent has completely degraded, one is left with a structure consisting of the carbon nanotubes, some of which are diamond-coated.
As indicated above, certain embodiments of the invention make use of the fact that particle-containing conductive regions like those described herein are known to be useful for purposes of electromechanical actuation, for example, where carbon-particle-containing conductive regions are employed. See, e.g., Spinks et al. above and U.S. Patent Appln. Pub. No. 2004/0138733.
In these embodiments, a power source is used to provide a voltage across at least first and second electrodes, which are in electrically bridged to one another by an electrolyte and supporting medium. In order to prevent shorting, a separator may be provided between the electrodes. For example, with reference to
More particularly, the first electrode may comprise any conductive material suitable for functioning as an anode and/or cathode in the electrochemical reactions that take place during the course of activation or de-activation. Examples of conductive materials include suitable members of the following: metals and metal alloys (e.g., gold or platinum, due to their high conductivity, oxidation resistance, and radiopacity, which facilitates visibility of the device during fluoroscopy or the like), carbon-particle-containing conductive materials and conductive polymers, and among many other materials.
The second electrode may comprise a particle-containing conductive region with a diamond-like coating as described herein. For actuators, the thickness of the particle-containing conductive region may vary widely, for example, ranging from 1 to 100 μm. Single or multiple particle-containing conductive regions may be employed in a given electrode, for example, arranged laterally or stacked in order to achieve greater dimensional changes. Greater dimensional changes may also be achieved by stacking multiple actuators.
The separator, where employed, may be selected from various separators known in the electrochemical arts, and is typically formed from a material that serves to prevent the first and second electrodes from shorting, while at the same time allowing transport of charged species between the same, thereby closing the electrical circuit between the electrodes. Examples of separator materials include proton exchange membranes (PEMs). PEMs that may be utilized include, for example, Nafion (which, for example, may comprise a perfluorinated ion-exchange solution), and ionomers such as sulfonated poly(styrene-isobutylene-styrene) (S-SIBS). Nafion products, including membranes and ion-exchange solutions are available from ElectroChem, Inc., Woburn, Mass., USA. Details and use of S-SIBS is provided in �Transport Properties of Triblock Copolymer Ionomer Membranes For Fuels Cells,� Y. A. Elabd, et al., 23rd Annual Army Science Conference Oral Paper AO-02 (2002), the disclosure of which is expressly incorporated herein by reference. Other examples of separators include electrical insulators, such as various ceramic materials and polymers (e.g. polyolefin, polyamide, silicone, polyurethane, polyester and poly(vinyl aromatic) homopolymers and copolymers, among many others, for example, TECOTHANE), which provide a way for ions to move through the separator, for example, due to the presence of pores, holes or other openings.
The electrolyte provides mobile charged species (e.g., ions) which move between the first and second electrodes and which may participate in the chemical reactions that occur at the electrodes. Examples of suitable electrolytes include organic and inorganic salts and acids, such as alkali metal halides and alkaline earth metal halides, more preferably alkali metal chlorides, such as potassium chloride or sodium chloride, and acid chlorides such as HCl. The electrolyte may be supported in ionized form within any suitable ion supporting medium, including solids, gels and liquids. Liquids are preferred as supporting media in various embodiments of the invention. Specific examples of liquids suitable for this purpose include, for example, polar organic liquids, water, and mixtures of water and organic liquids.
For mechanical actuation, the electrolyte may provide ions (e.g., chloride ions) that participate in electrochemical reactions that result in bubble formation (e.g., bubbles of oxygen, chlorine, etc.) upon application of a suitable electric potential across the first and second electrodes. These bubbles, in turn, cause expansion of the second electrode.
One will appreciate that the choice of electrolyte and supporting medium will be influenced by whether the actuator is to be open to body fluids or not. For example, diamond-coated particle-containing regions are frequently porous and may therefore allow use of blood plasma or other body fluids to supply both the desired electrolyte (e.g., ions within the blood) and supporting medium (e.g., water).
In other embodiments, the actuator components are not open to the surrounding environment and are therefore provided with an appropriate electrolyte and supporting medium prior to deployment of the device. For example, a sheath may be provided which isolates the actuator components from the outer environment. See, e.g.,
The power source employed should be capable of applying a first voltage sufficient for the electrochemical formation of gas bubbles within the particle-containing conductive region(s), and may also be capable of applying a second voltage of opposite polarity from the first voltage that is sufficient to reverse the electrochemical reactions leading to bubble formation. The power source may supply, for example, a constant (direct) or variable (e.g., pulsed) current/voltage. Examples of power sources for supplying direct current include batteries and rectified alternating current sources. Voltages on the order of one volt are sufficient to generate gas within the diamond-coated particle-containing conductive regions.
Without wishing to be bound by theory, it is believed that one or both of the following reactions typically occur during gas bubble formation:
Gas bubbles are generally observed at the surfaces of the carbon particles within carbon-particle-containing conductive regions. Gas bubble formation causes the carbon particles, or aggregates of the carbon particles (e.g., nanotube �ropes�) to move apart, which in turn causes the volume of the conductive region to expand. As a specific example, carbon nanotube layers have been observed to increase in thickness by around 300% (although lesser and greater percentages are also possible), with the length of the layer remaining substantially the same. By reversing the polarity, the reactions may likewise be reversed, causing the carbon-particle-containing layer to shrink. Kinetically, the reactions leading to bubble formation and expansion may occur over a period that is on the order of tens of seconds, whereas the reactions leading to collapse may occur over a period that is on the order of a second.
In general, gas bubbles generated in the interior of the particle-containing regions are trapped within the region and do not escape to any significant degree. However, gas bubbles created at the surface of the conductive region can have a tendency to escape into the surrounding environment, unless preventative steps are taken. In the present invention, formation of gas bubbles at the surface of the particle-containing region is prevented by providing this region with a diamond-like coating. Unlike the underlying conductive region, the diamond-like coating is sufficiently non-conductive to prevent the surface region from functioning as an active electrode region during the electrochemical reactions that result in bubble formation. Consequently, bubbles do not form at the diamond-like coating surface.
Although various embodiments are specifically illustrated and described herein, it will be appreciated that modifications and variations of the present invention are covered by the above teachings and are within the purview of the appended claims without departing from the spirit and intended scope of the invention.
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Neuroendocrine Tumor - Additional Resources
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