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Larkham 'fluke' downs World Cup holders
Richard Seeckts
October 30, 1999
Stephen Larkham's famous drop-goal against South Africa
© Getty Images
Rugby World Cup 1999 arrived at semi-finals weekend desperately needing a contest to grab the public's attention and show that results don't always follow the form. In the event, two great matches were served up at Twickenham on successive days. Sunday's dramatic turnaround that saw France dump New Zealand out of the cup sticks in the memories of aficionados, but for 24 hours this first semi-final was the match of the tournament, and it remains a classic regardless of the upset the next day.
Those present knew they were privileged to see 100 minutes of brilliant rugby, such that there was no shame in defeat. Coach Nick Mallett's pride in his Springbok team was evident in the aftermath: "There are two ways to be disappointed," he explained. "You can be disappointed because you didn't do yourself justice or you can be disappointed because the result went against you. Both teams played well and the result went against us."
World Cup holders South Africa reached the semi-final thanks to Jannie de Beer's five drop goals in Paris against England. de Beer's retention in the side in preference to the fit-again first choice fly-half Henry Honiball indicated that South Africa would employ similar tactics. They did, but this time four of de Beer's five drop goal attempts missed and South Africa lost after extra time, ironically to a drop goal.
Australia, 1991 winners, were marginal underdogs for this game but it was hard to find a weak link in the team. South Africa looked to exploit the relative inexperience of Stephen Larkham, de Beer's opposite number, whose early international career had been played at full back. Outside Larkham were experienced, creative backs, as strong in defence as in attack and evenly matched with their opponents.
No tries were scored in this edge-of-the-seat match. Australia created the better opportunities, mainly through Tim Horan, for whom this was a career defining performance. Matt Burke tore through a gap early on, fed the ball via Horan to Ben Tune who was held up short of the line and Australia had to settle for the resulting penalty. Time and again Horan slipped a couple of tackles, but the Boks always found another tackler from somewhere to stop him.
Springbok captain and scrum half Joost van der Westhuizen was at the peak of his powers but could not conjure a way past the Aussies. One outrageous dummy on the half hour almost led to a try but they didn't come close again.
So even was the battle in open play that the points had to come from the boots of Burke and de Beer, who finally landed a drop goal early in the second half to level the scores at 12-12.
South Africa's belief and sheer bloody-mindedness kept the Aussies from finding the try line. Robbie Fleck's desperate cover tackle saved a near certain try after Horan had broken through Andre Venter and wrong-footed Percy Montgomery. Australia had to settle for three points instead.
Australia's Tim Horan breaks away from the Springbok defence © PA Photos
As time began to run out, referee Derek Bevan made some questionable decisions. Most baffling, however, was where he found six minutes of added time after the stadium announcer had declared two minutes would be added. Australia, now 18-15 ahead, conceded a penalty and de Beer calmly took the game to extra time.
Level again at 21-21 in the second half of extra time, it would take something special to separate the teams. Larkham, not renowned for his kicking prowess and struggling with a badly injured left leg, found enough space to attempt an enormously ambitious drop goal from 48 metres out. It sailed between the posts as he and his team-mates danced an astonished jig. Burke added another penalty in the remaining four minutes but it was Larkham's audacious swing of the boot that dashed Springbok hopes of retaining the World Cup.
Jannie de Beer never played for South Africa again. Australia went on to beat France 35-12 in the final a week later and became the first team to win the Rugby World Cup twice. Tim Horan was Player of the Tournament. Stephen Larkham retired in 2007 with 102 Wallaby caps and only two international drop goals. He described this one, the pivotal moment of the 1999 World Cup, as "only a fluke".
© ESPN Sports Media Ltd.
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Boy Baby Names That End in S
Wolfgang Amadeus Mozart's middle name could make an interesting pick for music-loving parents--if only in middle place. Amadeus is the title of a Peter Shaffer play which became an award-winning fi... Read More
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Angus is rapidly moving from fuddy-duddy, kilt-wearing old Scotsman to hip young American; it's definitely a plausible choice, particularly for parents whose roots go back to Glasgow. The ancient ... Read More
Atticus, with its trendy Roman feel combined with the upstanding, noble image of Atticus Finch in To Kill a Mockingbird , is a real winner. In fact so many people have been inspired by the charact... Read More
Parents are beginning to look at imposing, somewhat fusty-sounding names like this one with fresh eyes: they definitely make a strong statement. Augustus originated as a title given by the Roman S... Read More
Since Aurelius was given the supermodel seal of approval by Elle Macpherson, this is one of the Roman emperor names, like Augustus, now in the realm of possibility. Like the female Aurelia and Auro... Read More
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Caius is classical and serious but also has a simple, joyful quality. There was a third century pope named Caius, as well as an early Christian writer, several Shakespearean characters, and a Twili... Read More
Cassius is a Shakespearean name with the feel of antiquity that is coming into fashion. Cassius Clay was an abolitionist and the birth name of Muhammad Ali. It was chosen for their sons by singer B... Read More
Charles is a longtime traditional favorite that was in the Top 10 until the 1960s. Lately Charles has been resuscitated by many celeb parents, from Jodie Foster to Russell Crowe, honoring a distin... Read More
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subset: commoncrawl


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Top Linksmain detailsbiographyby votesphoto galleryquotes
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Stephen (Character)
from The Edge (1997)
FilmographyEdit Credits
- The Edge (1997) Played by Harold Perrineau
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Charles Morse: You saved me.
Robert Green: Get over it, Charles - I just need you to navigate.
Charles Morse: You saved my life.
Robert Green: Well, I couldn't kill you with Stephen around. I'd have to kill him too, and he's the only one that knows how I like my coffee.
Charles Morse: Come on, you saved my life.
Robert Green: Buy me something nice when we get home.
Charles Morse: How'd you like your coffee?
Robert Green: Huh. I like my coffee like I like my women.
Stephen: Bitter and murky!
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The Coro Sessions
The Coronation Hotel Motel will play host to a number of bands' live recording sessions every Sunday throughout April.
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You'll feel isolated or even marginalized in your work. This is due to a sudden shift in work policy. Go with the flow. The Moon and...
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AHN Award
Every year the Arts & Healing Network honors healing artists who are truly making a difference in the world. Our hope is that these awards offer the recipients encouragement and support to continue and expand their outstanding work. We also hope that by highlighting these artists on our web site that their amazing work will inspire and light the way for other healing artists.
The 2015 AHN Awards are now open for nominations. This year's theme is art and social change. Arts & Healing Network will present 1-4 awards of $5000 (US) each to artists who are healing societal issues, empowering communities and making positive, tangible change happen in the world.
Please click here to learn more and/or nominate yourself or another artist by May 1st, 2015.
To stay informed about future AHN Award opportunities, please sign up for our e-newsletter. If you have any questions, please email Tristy Taylor at email@example.com.
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2009 Awards: Healing Artists Working with Water
In 2009, we presented four awards of $2500 each to artists who are addressing one of the most important & threatened resources on our planet – WATER. The awardees are Liza Behrendt, Joan Carne & Louise Towell, Judith Selby Lang & Richard Lang, and Aviva Rahmani.
Since 1985, Rachel Bagby has pioneered vibralingual practices that help people form vocal communities for ecological and social healing. A vocal artist, writer, composer, teacher and founder of Choral Earth, Rachel is internationally recognized for inspiring multiple generations to bring their voices to life.
Learn More About the AHN Award
In 2007, we celebrated the 10th Anniversary of the AHN Award by creating a special episode of the Arts & Healing Podcast that includes the voices of all 10 recipients from 1998-2007. To listen to this podcast online click here and hear these inspiring artists talk about their current work and how art heals.
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It seems like everyday here at Streetside classics we are seeing more and more Fox-body mustangs roll in and out of our showroom. The... More
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Sustainable Innovation through Green Chemistry Case Competition Promotes Cross-Faculty Collaboration
On January 16-17, 2015, the Marcel Desautels Institute for Integrated Management (MDIIM), CREATE in Green Chemistry, and the Trottier Institute for Sustainability in Engineering and Design (TISED), jointly a workshop and case competition on Sustainable Innovation through Green Chemistry.
Information Session: BCom Major and Concentration in Managing for Sustainability
Are you interested in combining your managerial and business knowledge with a deep understanding of the interlinked economic, social and ecological challenges of achieving sustainability? Did you know that you can graduate with a McGill Desautels BCom degree while also having a solid foundation in the fundamentals of ecological and social systems? If so, please join us to learn about Desautels' Managing for Sustainability programs, course offerings, and possible career paths in sustainability.
MDIIM SEI Impact Internship Program - Call for Applications
Looking to apply your budding management skills towards something meaningful this summer? The Social Economy Initiative (SEI) invites you to apply to be part of the 2015 cohort of the Impact Internship Program!
The SEI Impact Internship Program (SEI IIP) places exceptional students, primarily in local Montreal-based social enterprises, to take on special projects and contribute to social impact and positive social change within the non-profit sector.
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Health Management Seminar
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Event description:
Sustainable Innovation through Green Chemistry: An Afternoon with the Experts
Date: Friday, January 16, 2015
Time: 1:00 – 3:00 PM
Location: Bronfman Building, Room 422
Event description:
3rd Annual Sustainable Innovation through Green Chemistry Workshop and Case Competition
Dear MBA students,
We wish to bring your attention to an opportunity to participate in the 3rd Annual Sustainable Innovation through Green Chemistry Workshop and Case Competition, January 16-17, 2015. The event will bring masters-level students and practitioners from the areas of management, chemistry, and engineering, to learn about sustainable development and product design. Students will then apply their knowledge and compete as integrated teams.
MDIIM Student Associates Program – Call for 2014-15 Applications Now Open
The Marcel Desautels Institute for Integrated Management (MDIIM)'s mandate is to address complex, systemic challenges through an integrative approach to management. Such an approach breaks down disciplinary barriers, embraces multiple perspectives and encourages holistic, context-sensitive thinking about organizations. Integrated management constructively faces the tensions of different perspectives on value to enact strategies that transcend rather than accept trade-offs.
Can renewables become the dominant source of electricity in Canada and the USA?
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How to tell if a paint color can be mixed in quart?
Is there an easy way to tell if an Ace paint color can be mixed in a quart size? I haven't looked at other brands .. Ace is the most convenient for me (other than discount stores), and I have some colors picked out.
Well, I'm assuming it's a serious question...;-)
99.5% of them can...I do it everyday!
It also depends on a stores' tinting equipment.
An old "manual" style tinter can't do very small quantities.
Check with your store. You may have to get a gallon in some colors.
We've got 2 fancy COROB's that can shoot really minute "shots" reliably. Not cheap tho'....~ $30K for the both a few years ago.
Our store still has a manual tinter for the Ace paint. We have a fancy computer tinter for the BM, though. There are pros and cons to each, but you just ran into one of the biggest cons of the manual tinter.
Usually the colors we find that can't go into quart formulas are the pale, pale off-whites (ie: Casual White and Continental Cream). However, many or most pale colors will go into quarts - it just depends on the numbers in the formula and how they can be divided. Sometimes there's a slightly darker color with an odd formula that won't do it, too (like Hint of Gold, which I unfortunately wanted to do in a sample quart).
Are you needing the exact color, like to sample the paint before doing a whole room? Or is this for a smaller project where just a quart would do? We've used our color matching computer to create quart formulas for some of the off-whites (great for small projects, but not an accurate method for sampling colors unless you stick with the new formula rather than the official one...does that make sense?). Also, some formulas are *nearly* divisible by 4, but not quite, in which case manually dividing them may be more accurate than using the computer's color-match eye (if it calls for different colorants, for instance).
If you have a list of the colors you have in mind, there's a slight chance I may recognize whether it will go into a quart or have time to look it up...but the best way to know for sure is to ask your local Ace paint folks, who should be happy to help!
Since I have the luxury of the big tinters, I scan all matches I do into a gallon on purpose. When doing a light color, choosing "Gallon" permits the computer more leeway in devising a match.
THEN... I use a calculator to divide the formula into 1/4s.
I also usually back off on Black & Red-Oxide if present. I'm usually right too! It's MUCH easier to tweak a color by adding some colorants back in. It's a PITA fighting too much Black, etc.
Now I enter the divided-down formula into the tinter & shoot it. Sometimes it's numbers like B= .325, F=2.85, etc.


text: Jobs Companies & Reviews Companies Salaries Interviews Hiring? Post a Job Interactive Media Developer Salaries in Libertyville, IL 1 Salaries Change location: US - All Cities – Chicago, IL Area — Libertyville, IL Sort: Popular Most Reports Salary Salaries in $ (USD) Average Min Max Interactive Media Developer Skyscape (2 Skyscape Libertyville Salaries) $61,779 $59k $64k $61,779 $59k $64k Embed this report Anonymized Range [?] If we only have one or two salaries posted for at , showing that salary information may risk employee anonymity. So in that case we generate an anonymous salary range by adding and subtracting a small percentage from the posted salary. The small percentage difference offers additional anonymity while still minimizing the difference between the range and the employee's actual salary. Salaries > Interactive Media Developer > Libertyville


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Veterinary Students
I Love My Veterinarian Because...
Why do you love your vet?
Tour: UC Davis' Veterinary Medical Teaching Hospital
Here's a look into the equine health and research programs at the University of California, Davis.
Photo by Courtesy University of California Davis
Protecting Vet Students from Horse-Related Injuries
What is the price of learning and love for animals?
Annual Career Fair Unites College Students, Equine Industry
March 23, 2015
The event allowed nearly 250 college students to meet prospective equine industry employers.... Read More
Embedding Equitation Science in Vet Student Cirriculum
September 28, 2014
One university integrated equitation science into their program to teach behavior and learning theory.... Read More
UK Graduate Student Spotlight: Ashish Tiwari
September 27, 2014
Viruses have always intrigued Ashish Tiwari and inspired him to pursue a career researching influenza virus.... Read More
Zoetis Provides $1.3 Million to AAEP, FFA, AABP Programs
September 24, 2014
The company's Industry Support Program has donated more than $7.3 million since 2008.... Read More
Byron Joins Virginia Tech as Large Animal Surgeon
August 18, 2014
Chris Byron, DVM, MS, Dipl. ACVS, will serve as an associate professor of large animal surgery. ... Read More
Nunnery Joins Penn Vet as Large Animal Ophthalmologist
August 12, 2014
Catherine Nunnery, DVM, will begin seeing cases at the New Bolton Center on Sept. 3.... Read More
UK Graduate Student Spotlight: Jennifer Janes
July 26, 2014
Janes' research has focused on the roles of orthopedic pathology and genetic determinants in wobbler syndrome.... Read More
AAEP Foundation, Zoetis Award Scholarships to New Vets
July 21, 2014
Nine veterinary graduates of 2014 committed to careers in equine health care received $4,000 scholarships.... Read More
Program Helps UF Students Get Set for Equine Industry Work
July 05, 2014
Learn how students help care for stallions, mares, and foals as they prepare for work in the equine industry.... Read More
UK Graduate Student Spotlight: Anthony Claes
June 28, 2014
Claes' research is focused on anti-Mullerian hormone, which plays an important role in equine reproduction.... Read More
UC Davis Adds Equine Surgeon
June 16, 2014
Scott Katzman, DVM, Dipl. ACVS, will serve as an assistant clinical professor of equine surgery.... Read More
34 Vet Students Rewarded for Commitment to Equine Medicine
June 01, 2014
Since its establishment in 2008, the scholarship program has provided $905,500 to 228 veterinary students.... Read More
MU Receives $2.5 Million for Vet Medicine Scholarships
March 05, 2014
The gift will support scholarships for veterinary students and will encourage volunteer work among recipients.... Read More
Zoetis to Support AAEP, FFA, AABP Programs in 2014
February 26, 2014
Since its inception, this program has donated more than $5.9 million to veterinary students and FFA chapters.... Read More
UK Forage Bowl Team Wins National Title
January 25, 2014
The UK Forage Bowl team took the top spot at the National Forage Bowl.... Read More
Gift to Fund Purdue Equine Diagnostic, Surgical Center
December 25, 2013
A $2.7 million gift will help Purdue University build an equine diagnostic and surgical center. ... Read More
AAEP Foundation, Markel Award Scholarships to Vet Students
December 12, 2013
The program awards financial support to students who are advocates for equine welfare and academic achievers.... Read More
Tuesday's Top Tweets from the 2013 AAEP Convention
December 10, 2013
View some of the top tweets from Tuesday at the 2013 American Association of Equine Practitioners' Convention.... Read More
Monday's Top Tweets from the 2013 AAEP Convention
December 09, 2013
View some of the top tweets from Monday at the 2013 American Association of Equine Practitioners' Convention.... Read More
Sunday's Top Tweets from the 2013 AAEP Convention
December 08, 2013
View some of the top tweets from Sunday at the 2013 American Association of Equine Practitioners' Convention.... Read More
UK College of Agriculture, Food, & Environment Has New Dean
November 27, 2013
Nancy Cox, PhD, has accepted the position as dean of the UK College of Agriculture, Food, and Environment.... Read More
Zoetis Provides $1.2 Million to AAEP, FFA, AABP Programs
November 26, 2013
Zoetis raised $1,231,243 to benefit students through the AAEP Foundation, FFA, the AABP Foundation.... Read More
UK Graduate Student Spotlight: Laurel Mastro
November 23, 2013
Mastro's research focused primarily on pituitary pars intermedia dysfunction (PPID).... Read More
Lessons in Agriculture from the Land Down Under
November 22, 2013
Kentucky-based professionals visited Australia to observe the country's agricultural practices.... Read More
UCB Course Providing Horse Care Experience
November 17, 2013
The module covers feeding, stable management, first aid, health care, exercise methods, and more. ... Read More


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Get ready to go retro at the WCHS
Get ready to go retro at the WCHS
Dig through your closet and pull out those 1960's togs, as Wednesday night during the Kentucky State Fair is Go-Go night! The Museum will celebrate its 50th Anniversary and turn back the clock to the 1960's at "50 Years A-Go-Go!" The Saddlebred Café next to Freedom Hall will time travel back to 1962, as friends of the American Saddlebred Museum have organized a waa-a-ay groovy party!
As the World's Championship horse show passes the halfway point, exhibitors and spectators can take a break and party the night away! They will turn back the clock to enjoy all things sixties, including a 60′ menu. Everyone is invited to join in the fun! The event begins at 9:30 pm in the Saddlebred Café, in the new North Wing adjacent to Freedom Hall.
Entertainment will abound, as guests can dance the twist, the mashed potato and the swim, see if they can still hula hoop, play twister with their friends, have their picture made at the on-site photo booth and hear our own Ricky Cook's latest Naashville recordings!
The event benefits the American Saddlebred Museum. To that end, a special auction has been organized. Four exclusive and unique items will be offered up at live auction:
HAWAIIAN SURFING EXPERIENCE – Courtesy Elisabeth Goth and Garrett McNamara
Have you dreamed about riding the big one? If so, be the final bidder on a custom surfing experience with the world's foremost big wave surfer and living legend, Garrett McNamara, i.e. a "GMAC Experience" for two people. Enjoy 3 days and 2 nights at the luxury Turtle Bay Resort on Oahu's famed north shore, including one dinner for two. You will have the privilege of spending one full day on the water with GMAC. Choose from a beginner experience to an extreme experience – Garrett will tailor the day to your preferences. Use your two additional days to relax and savor Oahu's magical sites and tastes. Turtle Bay Resort offers a host of amenities, including two 18-hole golf courses, horseback riding, tennis, whale watching and even a swim with sea turtles! December is the recommended month for this experience.
"DANCING WITH THE STARS" EXPERIENCE – Courtesy Carson Kressley.
The final bidders on this package will enjoy a once-in-a-lifetime experience as they will receive two tickets (not available to the public) to a taping of ABC's top-rated "Dancing With the Stars" All-Star season 15. Included is air fare for two to Los Angeles from anywhere in the continental U.S. and one night at the Beverly Wilshire Four Seasons for the night of the show. Tapings are held on Mondays and Tuesdays Sept – Nov. Final bidder will have their choice of taping dates!
Polo Riding/Carriage Driving Experience – Courtesy James and Misdee Miller
Ever wondered if you could hit a ball with a mallet from atop a galloping horse, or if you can maneuver a team of horses from atop a carriage? Now's your chance to try! Spend a week in luxury accommodations at the Hyatt Siesta Key Beach Resort, which can sleep 4 adults and up to 4 children. Attend a world class polo match at the famed Sarasota Polo Club, complete with a tailgating contest and half time entertainment; receive a polo lesson; enjoy a carriage tour of the polo grounds; take a carriage driving lesson. This package is customizable! Full range of water activities and amenities available at the resort. Package is suitable for couples or for a family. Your choice of 2 dates: Jan 5 – 12, 2013 or Mar 23 – 30, 2013.
ENGLISH COUNTRY EXPERIENCE – Courtesy Georgia Bulmer Ferreira
Want to see how the English really live? The final bidder on this package will stay one week at Monnington Court, England, home of the John Bulmer family. Monnington is a 13th c. Manor House set in the picturesque and historic Wye Valley in Herefordshire, 3 hours west of London. The medieval home is surrounded by 25 acres of parkland, lake and herb gardens, with the famous mile-long avenue of pines and yews planted in the mid 17th c. Dotted around the tranquil gardens and private walkways are examples of Angela Bulmer's kinetic sculptures and bronzes. Guests will enjoy all the modern amenities, a swimming pool, carriage rides through the countryside, the ability to take day trips to the Cotswolds, London, Wales and other points of interest such as the local pub! See firsthand the historic charm of English country living in this special, customizable experience. Can accommodate up to four people.
A limited number of tickets are available for the event, so advance purchase is recommended. Special VIP seating areas for groups of 4, 6 or 8 are still available. These areas, located around the dance floor, provide comfortable seating and come with complimentary spirits and amenities, wait service and front row seating for all the entertainment. Call the Museum for availability and pricing. General admission tickets are available for $50 per person. With every admission comes heavy hors d'oeuvres, two complimentary drink tickets, great music, access to all games and activities and an evening of fun and entertainment.
Join fellow exhibitors, hipsters, peace-lovers, go-go dancers and Museum supporters for 50 Years A-Go-Go. All proceeds go to support the mission of the American Saddlebred Museum to collect, preserve and display the history of the breed. The Museum is a 501 (c) 3 organization and donations are tax deductible to the full extent of the law. Call the Museum for reservations at 859-259-2746, ext. 305.


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Sheridan, Wyoming: Country Homes, Houses, and Rural Real Estate
2,187 acres Sheridan, WY2187.00 acres Beaver Creek Rd, Sheridan, WY 82801- Sheridan County
Status: Active Type: Acreage w/House 5 Beds | 5 Baths | 5528 SqFt
Beaver Breek Ranch for sale near Big Horn and Sheridan Wyoming. Unspoiled, spectacular, exceptional, private: The Beaver Creek Ranch, just west of Big Horn and Sheridan, WY and perfectly situated in the foothills of the beautiful Big Horn Mountains, is truly unspoiled, spectacular, exceptional and private. The word legacy is perhaps too often used when describing ranches, but in this case, a true legacy ranch will be passed on to the next steward. In an area where true legacy ranches seldom come on the market, this offering represents an opportunity of a lifetime for someone who has their heartstrings pulled by the Big Horn Mountains and her lovely foothills. It's the consummate Big Horn ranch, complete with unparalleled privacy withou
John Chase or Galen Chase Chase Brothers Properties, LLC
2,400 acres Sheridan, WY2400.00 acres Sheridan, WY 82801- Sheridan County
Status: Active Type: Acreage w/House
Great Wyoming cattle and hunting ranch for sale very near Sheridan, Wyoming. This one-owner ranch is being offered for the first time since Patent. Productive and scenic, this excellent ranch is located only 7 miles east of Sheridan, WY right off US Highway 14. This rare offering is 2,400 +/- deeded acres and very nicely located. This ranch has a nice mix of irrigated meadows, brushy draws and hearty rangeland, all in a diverse topography ranging from flat meadows to hills and draws that provide protection and habitat for livestock and wildlife. Hunting is very good on the Willey ranch. The Willey Ranch is only 10 minutes from Sheridan, WY, which is continually rated as one of the preferred western towns in the United States. Sheridan is
John Chase or Galen Chase Chase Brothers Properties, LLC
0 acres Sheridan, WY0.00 acres 35 Canyon View Drive, Sheridan, WY 82801- Sheridan County
Status: Active Type: Residential 4 Beds | 4 Baths | 3364 SqFt
The quality of this new custom executive home for sale in the Powder Horn is at the very top end. The builder is Evergreen Dwellings, known for impeccable quality homes. This home is no exception. Every detail captures the quality of life found in the Sheridan area at the Powder Horn Golf Community. Cowboy-cosmopolitan might be a good description for this elegant, but rustic reflection of the refined, but western lifestyle found in the Sheridan Area. It has reclaimed Douglas Fir floors, travertine slab and soapstone counter tops, high-end custom Huggy Bear cabinets, Hansgrohe faucets and fixtures throughout, a steam shower, a custom theater room with HD projection and 110 TV, Lutron RadioRA lighting and electronics, just to name a few of
John Chase or Galen Chase Chase Brothers Properties, LLC


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Post Content
Anna Waclawiczek
Chief of Staff, Department of Agricultural Resources (DAR)
There are nearly 7,500 Massachusetts farms busy tilling, sowing, feeding, and caring for the fresh, local food soon available at the over 200 soon-to-open farmers' markets and farm stands across the state. With the growing season gearing up, maybe you'd like to try your hand at some activities sure to whet your appetite as well as your horticultural interests!
Nibbling on Natives in your Backyard and Beyond in Framingham tonight, April 8th might be your first stop. Learn about the many native species that are edible such as the delicious Juneberry – a cross between cherries and almonds. You'll also learn which edible wild plants are suitable for enhancing your home landscape, seasons of availability, and preparation methods.
On Saturday, April 17th, from 1-5 pm, the Waltham Fields Community Farm is offering a 'Spring Into Gardening: Festival and Seedling Sale with afternoon activities and presentations that will inspire and inform your own gardening efforts this season!
Recent Posts
2015 DAR Agricultural Calendar: February posted on Feb 25
February's contest winner was Amanda Bettle, who photographed sheep at The Natural Resources Trust of Easton. This photo features Dog, a former 4-H show animal and sole male sheep among the nine ewes in the Natural Resources Trust of Easton (NRT) flock. It is the mission …Continue Reading 2015 DAR Agricultural Calendar: February
2015 DAR Agricultural Calendar: January posted on Jan 26
January's contest winner was Renee Finnegan, who photographed a pensive Highland cow at Oak Meadows Farm & Garden in Rutland. Glenn and Mary Kauppila have been farming 100 acres of land in Rutland for approximately 15 years. With the help of their three adult children, they …Continue Reading 2015 DAR Agricultural Calendar: January
Visit Winter Farmers' Markets for Holiday Gifts posted on Dec 5
While performers serenade shoppers with upbeat or easy-listening music, farmers and food producers sell a wide variety of local food throughout the winter at over 40 winter farmers' markets this season. Those who have not yet visited a winter market might be surprised by …Continue Reading Visit Winter Farmers' Markets for Holiday Gifts


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Dr. Paul J. Harton Jr, MD
- 702 Bankhead Hwy
Carrollton, GA 30117
- 2 Locations
- (770) 832-6272
Dr. Paul J. Harton Jr graduated from the Ohio State University College of Medicine in 1991. He works in Carrollton, GA and 1 other location and specializes in Ophthalmology. Dr. Harton Jr speaks English and Spanish.
Gender: Male
Languages Spoken: English, Spanish
Medical School: Ohio State University College of Medicine; Graduated 1991
*This physician has multiple office locations. See Office Information for details.


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Other Alumni
Commemorate your accomplishments or congratulate a 2015 graduate with a chance to win UMass License Plate #UM 15.
February 10—May 31, 2015
If you want "real world" answers and advice on the next steps in your life after UMass, just ask someone who has been there!
April 8, 2015
6:00 pm-8:00 pm
Mullins Center, Massachusetts
The Department of Hospitality & Tourism Management invites you to their Annual Awards Dinner.
April 16, 2015
6:00 pm-10:00 pm
Boston Harbor Hotel
Join faculty and staff of Commonwealth Honors College to celebrate our students' achievements.
April 24, 2015
5:00 pm
Student Union, Ballroom
The School of Computer Science invites you to join fellow alumni, students, faculty and staff at the top of the Campus Center for the 7th Annual Outstanding Achievement and Advocacy (OAA) Awards.
May 1, 2015
5:00 pm-9:00 pm
Campus Center - Marriott Center
The UMass Amherst Alumni Association and the Greater Boston Alumni Network invite you to join them at the UMass Club in Boston for an interactive workshop designed to help you enhance your networking skills.
May 14, 2015
6:00 pm-8:30 pm
The University of Massachusetts Club in Boston
Reconnect with former classmates and meet current students while playing an exciting round of golf at the McCormack Classic Golf Tournament at Cold Spring Country Club in Belchertown, Mass.
May 15, 2015
9:00 am
Cold Spring Country Club
Join the UMass Amherst Cape Cod Alumni Network at our 20th Anniversary Scholarship Golf Tournament.
June 8, 2015
10:30 am
Willowbend Country Club
Please join us for the 2015 Isenberg Business Leadership Awards, an annual event honoring two outstanding graduates of the Isenberg School of Management.
June 17, 2015
6:00 pm
The Colonnade Hotel
Family and friends of Project 10 are welcome to attend our 42nd reunion!


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Pronunciation: шуышмалы
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FC Barcelona Football Stadium Tour and Museum Tickets
Read what other Viator.com travelers think about the FC Barcelona Football Stadium Tour and Museum Tickets. What they loved, what they liked and what they think could be improved, it's all here to help you make the most of your next trip.
Click here for tour details, schedule and pricing
Impressive stadium - lots to see and do.
I am an avid and very passionate fan of Barcelona Football Club so this tour was a must for me. I must say that this tour exceeded all of my expectations. Every bit of history from the club's foundation until present day is available and properly portrayed.From signed jerseys from club legends all the way to Champions League Trophies. Its all there. The experience inside the Camp Nou stadium was beyond memorable. The place is very clean and the tour runs very smoothly with little interruption. I highly recommend this tour for any football fan of any age. It was well worth the time and the money. I am honored to have been able to go to the Camp Nou and look forward to my next visit. Visca Barca!!
This tour was amazing and would love to do it again!!
Could not get near to the items in museum due to amount of people. However it was well worth the visit and thoroughly enjoyed it.
Fantastic day out, worth every penny. Easy to collect tickets and fast entry to the stadium.
Superb great museum and your around the stadium.
It was the most fascinating tour for us being FC Barcelona fans. Loved every moment there.
Best experience and jump the queue is well worth it!
Interesting day but more expense 're hire of audio tour and photo opportunities were good fun but expensive too
If you are a soccer (football) fan, then this tour is definitely recommended!!!
Was great and our guide Margherita was amazing and very knowledgable and gave us all individual attention and good relaying of facts. We were on the tour on aug 2 it was a group of two plus another person. The only thing was that we were on time and had to call your office as couldn't find guide
Took my 14 year old son. He loved it and as a not particularly keen football fan I enjoyed it too!!
Would recommend to anyone even slightly interested in football. The trophy room is a must!
Lots of time to look around the stadium and take photographs. A good tour for football fans!
Awesome tour of this prestigious home of FCB. Very comforting to know we would not have to wait in a line.


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Fusion Power Breakthrough Near At Sandia Labs? 358
from the i'll-order-a-dozen dept.
We've improved Slashdot's video section; now you can view our video interviews, product close-ups and site visits with all the usual Slashdot options to comment, share, etc. No more walled garden! It's a work in progress -- we hope you'll check it out (Learn more about the recent updates).
What do you call something that smashes things together but doesn't exist?
Two flying cars?
How much energy goes into the production of the liner tubes, which are apparently eaten away throughout the course of the fusion reaction? Obviously this is all preliminary research, but I still think I'm missing something.
Of course not, they buy out and extinguish the evidence, duh!
I made a working engine that ran off of tap water. Then the oil companies had me killed.
> No, see as you approach feasibility, your likelihood of being bough by a competing producer to be extinguished (see gasoline) becomes multitudes greater.
I'm not necessarily disagreeing, but do you have a reference?
My own suspicion is that as you approach feasibility, government grant money tends to increase, but if you *achieve* practical feasibility, grant money evaporates. Therefore, to maximize funding, you must asymptotically approach feasibility.
But I'm willing to hear a different theory.
You were lucky. The oil companies beat me around the head and neck with a broken bottle, sliced me in two with a bread knife, then danced around my grave singing "Hallelujah!"
Although both terms are hot... one is several million degrees hotter than the other
Both take 40 years to begin production.
It's the same way God planted Dinosaur bones to test our faith...
With your bare hands?!?


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No respite yet for the Golden Eaglets until the 11th African Under-17 Champions draw to a conclusive end as the team return to training Sunday morning at the Stade Municipal in Niamey. 176 more words
Tags » Niamey
Golden Eaglets Qualify For Chile U17 World Cup
The U-17 National Team, Golden Eaglets became the first African country to qualify for this year's FIFA U-17 World Cup after a 3-1 defeat of Zambia in Niamey on Saturday. 175 more words
Golden Eaglets Draw 1-1 With Guinea
Nigeria's U-17, Golden Eaglets on Wednesday forced their Guinean counterparts to a 1-1 draw at Stade Général Seyni Kountché (SGSK) at the on-going African U-17 Championship in Niamey. 376 more words
Thousands March Against Boko Haram in Niger
NIAMEY: Niger's President Mamahadou Issoufou on Tuesday told thousands of people protesting at deadly raids by Boko Haram that "Niger will be the tomb" of the Islamists from neighbouring Nigeria. 175 more words
NFF Assures Golden Eaglets Over Niger 2015
The Nigeria Football Federation (NFF) has for the umpteenth time, reiterated its commitment to the Golden Eaglets over their participation at the 11th African Under-17 Championship which opens on Sunday in Niamey. 362 more words
11th AJC: NFF Tidies Up Arrangements For Eaglets' Successful Campaign
In its determination to ensure a very successful for the U-17 National Team, Golden Eaglets, at the 11th African U-17 Championship in Niger Republic, the Nigeria Football Federation has been actualizing plans to make the team's stay in that country comfortable. 307 more words
Desertification: 20 year old publication
Photo credit: WVC 1998-02
Niamey, Niger – Reforestation project "Friendship Wood" 1997
Desertification – a threat to the Sahel
Desertification is a man-induced process that leads to soil nutrient depletion and reduction of biological productivity. 254 more words


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TurboTax- Free Federal File
Use TurboTax and e-file your federal taxes for free. (State returns are an additional fee or you can paper file them for no cost.) With TurboTax you'll get your biggest tax refund guaranteed, with 100% accurate calculations, free help, and step by step guidance so you are confident your taxes are done right. TurboTax has also been the #1 Rated, Best-Selling tax software brand year after year.
Here's what reader Courtney had to say about her experience with TurboTax:
I agree that it's fairly easy to file taxes. I'm an independent contractor and I've been filing my taxes on my own for years. TurboTax has an easy navigation system that asks specific questions to allow for the greatest return. I also tested this to make sure I was getting the correct amount by taking my taxes to a professional and they came up with the same number.
Filing our own taxes is one of the easy ways we save money. Some of you might question the easy part, but unless you have complicated taxes it's really quite doable. In fact I've done my own taxes ever since I've started filing them. When I was single my Dad uses to help me do them and we paper filed back then. Talk about time consuming! Once I was off at college I learned about filing online for free and took advantage of that and that's what we've been doing since we are married too.Add a Comment
Tags: thrifty ideas | Categories: Freebies, Money-Saving Ideas, Must Read, Online Deals
Must Read
by Arby's: Free Curly Fries April 15th | The Thrifty Frugal Mom
On April 14, 2014 at 9:26 am
[...] need to file your taxes? Use Turbo Tax as an easy online way to file your federal taxes for free! Add a [...]


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December 28, 2013
Devon Peet, second from right, is in the percussion section of the Georgia Tech band. The second youngest in the family, Devon is a College of Computing student at Tech. (Special Photo)
Stories this photo appears in:
Peachtree Corners siblings make Ga. Tech band a family affair
A Peachtree Corners family has four children in the Georgia Tech band, the same school where their parents and other relatives graduated.
Use the comment form below to begin a discussion about this content.


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A method of removing ammonium ions or amines from contaminated water includes treating the water with sodium tetraphenylborate under acidic conditions. Advantageously, the tetraphenylborate is immobilized on polymer beads and the water is contacted with the beads or passed through a bed of the beads.
1. A polymer for removing a nitrogen-containing species selected from ammonium ion and amines from contaminated water, which polymer comprises a polymer backbone having a tetraphenylbotate salt immobilized thereon.
2. A polymer according to
3. A polymer according to
4. A polymer according to
x being present in a mole percent of from 0 to 50, z being present in a mole percent of from 1 to 10, and y being present in a mole percent equal to [100−(x+z)], and wherein R 2 is a carbon-to-carbon bond or C1 to C6 alkyl, and M is a cation.
8. An article for use in the removal of ammonium ion or amine from contaminated water, which article comprises a containment vehicle having associated therewith a quantity of a polymer as defined in
9. An article according to
10. An article according to
11. An article according to
12. A polymer according to
13. A polymer according to
14. A polymer according to
This application is a continuation of Provisional Application Ser. No. 60/078,046, filed Mar. 16, 1998, and a divisional of application Ser. No. 09/267,610 filed Mar. 15, 1999, now U.S. Pat. No. 6,171,503.
This invention relates to the extraction of ammonia and amines from aqueous solution using tetraphenylborate salts, in particular sodium tetraphenylborate.
Contaminants may enter the environment through discharge of industrial waste into a local water source, thereby imparting damaging and potentially devastating effects to the ecosystems which are dependent on the water source. Various methods have been proposed and implemented to reduce the level of contaminants present in water. However, such methods tend to be complicated and expensive, There is a need for alternative innovative technologies for removal of contaminants from waste water.
U.S. Pat. No. 4,695,387 (Berry et al.) discloses a process for continuous removal of ammonia from waste water using adsorption of ammonium ions to zeolite, and formation of ammonium phosphate from the adsorbed ammonium ions. The method employs a complex separation device having a plurality of chambers through which waste water must circulate. Although ammonium ion concentrations are reduced in waste water using this method, the removal of other nitrogen-containing contaminants from waste water is not addressed.
U.S. Pat. No. 5,641,413 (Momont et al., 1997) teaches removal of nitrogen from waste water having a high chemical oxygen demand. This method involves high temperature, high pressure oxidation and thermal denitrification to convert nitrogen-containing contaminants essentially to nitrogen gas. The process of U.S. Pat. No. 5,433,868 (Fassbender) employs a hydrothermal technique for removal of ammonia from water derived from sewage plant effluent. U.S. Pat. No. 5,407,655 (Sarritzu) discloses a process for recovery of pure (non-aqueous) ammonia from waste water through reaction with carbon dioxide, which also involves thermal decomposition, However, the high temperatures and pressures required in these processes necessitate the use of specialized tanks and equipment and thus tend to be expensive to conduct on a large scale.
U.S. Pat. No. 5,640,840 (Heitkamp et al., 1996) discloses a method for treatment of a liquid waste stream using microbial biodegradation whereby nitrogen-containing organic contaminants are ultimately converted to ammonia and carbon dioxide. The process involves flowing oxygenated waste water through a bed reactor supporting microbes capable of such biodegradation. This method requires the on-site presence of such a reactor, and recovery of purified water from the reactor may be a lengthy process.
Tetraphenylborates, particularly in the form of their alkali metal salts, are useful as counter ion components of cationic polymers in the field of non-linear optics (EP-A2-0 490 385), as polymerization initiators (U.S. Pat. No. 5,124,235), and as hydrophobic anionic functional groups dissolved in a polymeric matrix that is used in the separation of cesium and strontium from nuclear waste (U.S. Pat. No. 5,666,641). No work has heretofore been conducted to incorporate the use of tetraphenylborates in precipitation of ammonium ion or amines from waste water. All patents and publications referred to herein are expressly incorporated by reference.
An object of the invention is to provide a method of extracting ammonia and organic amines from water in an effective and environmentally acceptable manner.
One aspect of the invention provides a method for treatment of contaminated water to remove a nitrogen-containing species selected from ammonium ion and amines, which comprises contacting the water with sodium tetraphenylborate under acidic conditions, preferably weakly acidic conditions such as a pH value of between 3 and 7, and separating the treated water from the resultant precipitate of a salt of tetraphenylborate and the nitrogen-containing species.
Another aspect of the invention provides a method for treatment of contaminated water to remove a nitrogen-containing species selected from ammonium ion and amines (which hereinafter includes imines and any other species wherein the nitrogen atom will receive a proton), which comprises adjusting the pH value of the water to the acidic range, providing a polymer comprising a polymer backbone having a tetraphenylborate salt immobilized thereon, contacting the water with the polymer to dissociate the tetraphenylborate salt to tetraphenylborate ions and cations, whereby the nitrogen-containing species binds with the tetraphenylborate ions, and separating the treated water from the polymer having the nitrogen-containing species bound thereto. Preferably, the tetraphenylborate salt is a salt of Li+, Na+, K+, H+, Ca+2 or Mg+2. More preferably, Na+ is the cation.
A further aspect of the invention provides a polymer for removing a nitrogen-containing species selected from ammonium ion and amines from contaminated water, which polymer comprises a polymer backbone having a tetraphenylborate salt immobilized thereon in the form of dissociated tetraphenylborate ions and cations.
According to another aspect of the invention, there is provided an article for use in the removal of ammonium ion or amine from contaminated water, which comprises a containment vehicle having associated therewith a quantity of a polymer as defined above. The polymer may be, for example, in the form of cross linked beads or inert particles, e.g. silica, surface treated to be coated with tetraphenylborate groups, and the containment vehicle comprises, for example, a porous bag for the beads, a structure for supporting a bed of the beads, or a bed of sand having the beads entrained therein.
The invention also provides an article which comprises a means for introducing a solid or gaseous contaminated water source containing ammonia or amines, and converting said source to aqueous state.
The term contaminated water should be understood to encompass any water source containing ammonium ion or amine, and the invention is contemplated for use in the removal of ammonium ion or amine from any such water source. Thus, the method may be used, for instance to remove ammonium ion or amine from ground water, non-point run-off water, mine infiltration water, industrial effluent, and any other type of contaminated water or waste water.
In the case where ammonium ions or amines may be air-borne, or found in any other gaseous medium, such compounds may be captured and converted from the gaseous medium to an aqueous medium and removed according to the invention. An example of such an application is in the case of volatile ammonia and amines which arise from animal waste in an environment such as an enclosed chicken barn. Additionally, ammonium ion or amines derived from a solid source, such as animal waste, could be solubilized in water and removed therefrom according to the invention.
The invention may also be used as a pre-concentration method for extracting and concentrating small traces of amines or ammonium ion before analysis therefor. The invention can thus be employed for test methods to quantify amines or ammonium ion. The invention may be used for analysis of street-drug mixtures, most of which are amines, whereby the amine component can be sequestered from an admixture. The invention may also be used for recovery of any amine which can be converted into a quaternary (charged) nitrogen system. Even (CH3)4N+ and related species having no N�H bond can be extracted using the method of the invention.
Amines which form insoluble salts with the tetraphenylborate anion and can be removed from aqueous media according to the invention include aliphatic amines such as alkylamines including methylamine, ethylamine, and propylamine, as well as guanidine and biguanidine; diamines of the formula NH2 (CH2)nNH2 where n is an integer, such as ethylene diamine and propylene diamine; aromatic amines such as aniline and benzylamine; heterocyclic amines such as optionally substituted pyridine, pyramidine and pyrazine; polycyclic amines such as tropane and 1,4-diazabicyclo [2.2.2] octane (DABCOH), and also caffeine and nicotine.
The method is based on the formation of ammonium tetraphenylborate (NH4BPh4), a salt which is very insoluble in water. When a slightly acidic aqueous solution of ammonia or an amine is added to an aqueous solution of sodium tetraphenylborate, an immediate, thick, white precipitate is formed. This precipitate of NH4BPh4 is non-gelatinous, powdery but granular and is easily filtered. While NH4BPh4 is insoluble in water, it is soluble in acetone and acetonitrile. It can be recrystallised from acetone/water mixtures (or from acetonitrile) and the crystals appear to be stable indefinitely, Preferred pH values for the aqueous solution range from about 3 to 7, particularly from about 4 to 6.
The nitrogen-containing species in the contaminated water is normally in the form of a soluble inorganic or organic ammonium salt or an amine and the method of the invention is particularly suited to the treatment of waste water streams, such as water polluted with industrial effluent or acid rain. Mine infiltration water also contains a high ammonia concentration when derived from prehistoric sources. Removal of ammonia is required prior to release of mine infiltration water into the environment.
Simple, apparently uncomplicated, salts of ammonia are rarely insoluble. When the crystal structure of NH4BPh4 was completely determined (Cand J Chem 58 (1980) 1355), it was shown to be a most extraordinary system, The NH4 + and BPh4 − ions stack in columns, alternating . . . NH4 + . . . BPh4 − . . . NH4 + . . . BPh4 − . . . with the NH4 ions trapped in a cage produced with a pair of phenyl groups from each of the two adjacent BPh4 − ions.
In itself this is not unusual, but within the columns the NH4 + ions form four hydrogen bonds to the planes of the four phenyl rings in the surrounding cage. The short contact N�H . . . Ph, the careful IR work in the paper cited above and elegant thermodynamic measurements by L. Stavely in Oxford in the 1960's (ref in Cand J. Chem paper) makes it clear that this N�H . . . Ph interaction is a significant hydrogen bond. The favorable lattice energy for NH4BPh4, which is the source of its insolubility, comes then not only from a most favorable ion packing but also has a contribution from these hydrogen bonds.
The contribution from the hydrogen bonds is crucial and instrumental in the unique properties of NH4BPh4. Our subsequent X-ray structure determinations have shown that the N�H . . . Ph hydrogen bond (or a variant thereof is present in every case where the organo-ammonium salt has an N�H bond while the very favorable cage arrangement has often been seriously degraded. We have ascertained that the charge interaction (cation/anion) is necessary as is the N�H . . . Ph interaction, but the symmetrical cage is less vital.
In order to verify the efficiency of the method of the invention, model systems were examined with NH4 + ions present in solution in concentrations ranging from 10 to 200 ppm. These solutions were treated with stoichiormetric quantities of NaBPh4, dissolved in water and then one additional drop of NaBPh4 solution was added to ensure the presence of NaBPh4 in excess. The solutions were allowed to settle and the residual ammonium ion concentration in the supematant was estimated by (a) Nessler's reagent, and (b) electrospray mass spectrometry seeking to detect the chloramine ion.
The Nessler's reagent studies gave consistent readings of a total residual NH4 + concentration in the supernatant liquid ranging between 3 and 5 ppm. The mass spectrometric measurements confirmed these results since no ammonium ions were detected in the supematant liquid.
Thus, we concluded that NH4BPh4 is so insoluble a material that when equimolar quantities of NH4 + and BPh4 − ions are mixed in solution, the concentration of residual NH4 −; ion (ions not complexed with BPh4 −) is very low, probably below 1 ppm.
The supematant liquid was examined by mass spectrometry over a period of several days. The boron species present in solution were easily identified by the natural isotopic abundance of boron. Over a period of a week, the levels of boron species in water stayed unchanged, and no new species were observed to emerge. These results confirm that the NH4BPh4 solid is stable over an extended period of time when left in contact with water. These experiments were conducted at two representative temperatures, 25 and 35� C. and both experiments showed the same stability.
Following extraction of the ammonium ion or amine, the NaBPh4 can be regenerated as outlined below.
The method depends on the fact that although NaBPh4 is soluble in water and KBPh4 is insoluble, KBPh4 is isomorphous with NH4BPh4. This is not surprising since NH4 + and K+ occupy roughly tile same space in a crystal and are often mutually exchangeable in crystal structures.
While the two structures are isomorphous, the KBPh4 system does not have the added advantage of four N�H . . . Ph hydrogen bonds. Thus, when KBPh4 is stirred in a solution containing the NH4 + ion, the equilibrium:
is strongly displaced to the right, that is towards the formation of NH4BPh4(solid).
The process involves stiring excess KBPh4 in the NH4 + solution until the concentration [NH4 +] starts to rise. The �spent� KBPh4 is then filtered off. The spent KBPh4 is then stirred with a mild base such as K2CO3, and the ammonia and amines are released, since once the ammonia or amine is neutralized it loses its charge and the main component of the lattice energy of the NH4BPh4 salt is also lost. This simply reverses the equilibrium equation given above by the removal of the NH4 +(soln) species from the system.
KBPh4 is reformed by this process and the regenerated KBPh4 can then be filtered and re-used. The filtrate contains the amines (and ammonia dissolved as NH3) in solution. Acidification of the filtrate, followed by evaporation produces the solid ammonia and amine salts which can be collected and separated by differential vacuum sublimation.
In an alternative embodiment, sufficient Na2CO3 solution is added to the separated NH4BPh4 to neutralise all the ammonia and amines. NaBPh4 remains in solution and the ammonia and amines can be removed by distillation (reduced pressure distillation to preserve the BPh4 − ion). The NaBPh4 already in solution is then available for re-use.
Another aspect of the invention relates to the use of functionalized polymers or surface modified particles for separation of ammonium ions and amine salts from water. In the former case this involves the use of a polymer which incorporates the BPh4 − moiety. Such a polymer is preferably synthesized in the form of beads that consist of a lightly cross-linked network onto which BPh4 − groups are attached. In the latter case, a suitable material such as particles of silica, alumina or titania, for example, are subjected to a surface modification so as to chemically attach BPh4 − groups. Since it is important to maximize the interactions of the ammonium species with the BPh4 − groups, it is necessary to employ a polymeric backbone with suitable hydrophobicity. Many backbones may be used ranging from somewhat hydrophobic polystyrene to the more hydrophilic polyethers.
Preferred polymer backbones include polystyrenes, polyethers and polyacrylamides, as well as silica, which is an inorganic polymer. Further copolymers including these and other hydrophobic and hydrophilic monomers may also be used. Particularly advantageous polymers include a porous, lightly cross-linked polystyrene resin that is functionalized to contain the tetraphenylborate functional group, and a more hydrophilic polyether polymer system also functionalized to contain the desired functional group. In addition, silica particles may be used as the support (or polymer) and may be surface-coated so as to feature the desired functional group as the active entity.
In all three cases, the tetraphenylborate functional group is preferably neutralized as the sodium salt. The binding of the ammonium species occurs by the displacement of the sodium ions, as in normal ion exchange processes. Alternatively, the other suitable cations may be used such as LI+, K+, H+, Ca+2 or Mg+2. The cations bound to the tetraphenylborate ion are herein referred to generally as M. Regeneration of the materials can be accomplished by washing with concentrated Na2CO3(NaCl) solution, sodium bicarbonate solution or carbonic acid, for example, using methods known to those skilled in the art.
The phenyl groups of the tetraphenylborate group can optionally be substituted in para position by halo, e.g. fluoro or chloro, lower alkyl, e.g. methyl, or lower alkoxy, e.g. methoxy.
The following embodiments are presented as detailed examples of polymers for use in the invention.
All embodiments contain the active binding unit, tetraphenylborate, attached directly or indirectly to a polymeric backbone as shown schematically in formula (I) below. The tetraphenylborate moieties may be present as surface modifying agents or incorporated into a cross-linked resin. In formula (I), the tether (R1) may be a lower alkyl group or simply a carbon-to-carbon bond, and M is a cation.
In a first embodiment, a polymer comprises cross-linked, functionazed polystyrene to which tetaphenylborate is tethered, and has the general formula:
wherein x refers to a styrene comonomer and is from 0 to 50 mol %, z refers to a cross linking agent and is from 1 to 10 mol %, y refers to a comonomer having the tethered tetraphenylborate group and is [100−(x+z)] mol %, and R2 is a carbon-to-carbon bond or C1 to C6 alkyl, and M is a cation.
In a second embodiment, a polymer comprises a cross-linked polyether backbone with tetraphenylborate tethered thereto, and has the following repeating unit:
R3 is C1-C6 alkyl
R4 is H or C1-C6 alkyl,
R5 is a carbon-to-carbon or C1-C6 alkyl, and M is a cation.
More specifically, according to the second embodiment, a polymer comprises a polyether backbone with tetraphenylborate tethered thereto, and has repeating units as follows:
each R3 independently represents C1-C6 alkyl,
R4 is H or C1-C6 alkyl,
R5 is a carbon-to-carbon bond or C1-C6 alkyl,
R6 is phenyl or C1-C6 alkyl
R7 is phenyl C1-C6 alkyl or cross linking unit,
M is a cation,
m is 0-50 mol % (comonomer),
p is 1 to 10 mol % (cross linking agent), and
n is [100−(m+p)] mol % (comonomer having the tethered tetraphenylborate group).
In a third embodiment a polymer comprises a silica backbone having pendant tetraphenylborate groups as shown below:
wherein R8 is a carbon-to-carbon bond or C1-C6 alkyl, and each R9 independently represents C1-C6 alkyl or H, and M is a cation.
FIG. 1 shows schematically the reactions involved in the preparation of a polystyrene derivatized with tetraphenylborate;
FIG. 2 shows the reaction schematics for preparing a polyether; and
FIG. 3 illustrates the formation of a silica with tetraphenylborate derivatization.
The use of functionalized cross-linked polystyrene beads as ion-exchange resins is a well-established industry (e.g., D�rfner, �Ion Exchangers�). Thus, the chemical techniques used in their preparation are well known in the art. Generally, the polystyrene-type (e.g. chloro-methylated) beads are prepared by suspension free radical polymerization techniques, generally using an organic initiator such as benzoyl peroxide or azobisisobutyronitrile (AIBN). Subsequent reactions can then be used to attach the desired functional group to the polystyrene backbone.
Free radical polymerization of p-bromostyrene, by suspension polymerization techniques known in the art, is used to prepare polymer beads approximately 100 to 400 microns in diameter. The bead size may be controlled by appropriate choice of surfactant and stirring design. Divinyl benzene is used as the cross-linking agent, In amounts varying between 1 and 10% by weight. A pore forming agent, such as butyl ether, ensures that the resulting beads are highly porous, as desired for effective sorbents. The density of functional groups, i.e., the number of sites/unit volume of resin, may be varied by copolymerization with styrene such that the resulting polymer will be a random copolymer of p-bromostyrene and styrene. The use of the comonomer serves to minimize additional cross-linking that could accompany subsequent functionalization reactions described below.
The brominated sites of the polymer beads are reacted with magnesium metal in ether to produce a Grignard reagent that reacts subsequently with BF3 to form the polymer BF2 derivative. This reaction of the polymer Grignard reagent with BF3 requires careful control of reaction conditions, particularly stoichiometry, so as to minimize additional cross-linking. Such additional cross-linking has two adverse effects; (i) it decreases the density of functional groups, hence the ultimate binding capacity of the sorbent; and (ii) it makes the polymer more rigid, hence it is more difficult for the sorbate to penetrate the beads. Finally, reaction with another Grignard reagent, for example phenylmagnesium bromide, results in the formation of the desired tetraphenylborate functional sites. To remove the magnesium cations this polymer is washed with concentrated aqueous NaCl solution which results in the sodium salt, as desired. This sequence of reactions is shown in FIG. 1. The individual reactions are efficient so that essentially 100% yield can be obtained at each stage.
Alternatively, a polymeric bead containing phenyl bromide groups is reacted with an alkyl lithium reagent to form the corresponding aryl lithium intermediate which may be reacted directly with triphenyl boron to give a polymeric matrix with pendant tetraphenyl borate groups.
The synthesis of cross linked beads with a more hydrophilic polyether is shown schematically in FIG. 2. While styrene oxide is commercially available, the cross-linking agent used for the synthesis of the polyether resin beads, namely 1,4-diepoxybenzene, must be synthesized. Since epoxides are easily generated from alkenes by reaction with peroxy acids (e.g. peractic acid or, more commonly, meta-chloro-perbenzoic acid) the desired cross-linking agent can be obtained by the oxidation of divinyl benzene, These oxiranes, styrene oxide and 1,4-diepoxybenzene can be polymerized, for example, by a base-catalyzed ring opening mechanism. Thus, beads of poly(styrene-oxide) can be synthesized in a biphasic system using hydroxide and a phase transfer catalyst with styrene oxide and 1,4-diepoxybenzene. If desired, pore-forming agents may be included in the polymerization process.
The resultant polymer, or copolymer, can be brominated by reaction with bromine and iron (III) bromide. Finally, the triphenylboron moiety is added as described earlier using Grignard chemistry. The hydrophilicity of this system can be maximized, for example, by co-polymerizing propylene oxide to increase the relative oxygen to hydrocarbon ratio.
In another embodiment, a free-radical type polymerization can be used for this system. Controlling bead-size and tetraphenylborate density involves optimization of bromine, catalyst, and monomer concentrations as well as the solvent system and the practical aspects, such as stirring rate.
In yet another embodiment of the invention, silica particles are treated so that immobilized tetraphenylborate groups are attached to or synthesized on the surface of the silica particles. The use of silica as the support for functional groups is a common practice, for example, in the preparation of packing materials for chromatography columns. Hence, the chemistry is well developed and will be familiar to those skilled in the art.
Silica particles of various sizes are readily available from various commercial sources, e.g., Cabot. The surface hydroxyl groups are commonly used as reactive sites that can be used for the synthesis of various surface layers. For the preparation of silica that is surface-coated with the tetraphenylborate functional groups a chlorosilane coupling agent is synthesized that possesses the tetraphenylborate functional group. This coupling agent is then attached to the silica particles by reaction with the surface hydroxyl groups thereof. Alternatively, a commercially available bromophenyl silane coupling agent (RxCl(3−x)SiPhBr) can be attached to the surface of the silica. By a series of subsequent reactions, similar to those described above for polystyrene, the bromo group is converted to form the tetraphenylborate. This is shown schematically in FIG. 3.
The commercially available silane coupling agent RxCl(3−x)SiPhBr can be converted to a Grignard reagent by reaction with magnesium metal in ether or a lithium reagent with an alkyl lithium. These intermediates can then be converted to the tetraphenylborate as described above. In a subsequent reaction with the surface hydroxyl groups of the silica particles chemical attachment of the modified tetraphenylborate moiety is attained.
The commercially available silane coupling agent RxCl(3−x)SiPhBr is attached chemically to the silica surface and subsequent reactions at the bromo site, similar to those described above, result in the formation of the tetraphenylborate moiety.
Once the BPh4 − ion is securely tethered to a polymer backbone it can be recycled relatively easily and cost effectively. The polymer is not water soluble but is water wettable. It is preferably in the form of small beads. A waste water stream may be passed, for instance, through a column containing the polymer, or a bag containing polymer beads may be dropped into water. Alternatively, the waste water can be passed through a bed of sand having the silica beads dispersed therein. The NH4 + (and organo-ammonium) ions are bound by the tethered BPh4 − ions. M2+ ions will not be bound, and the BPh4 − will bind all organo-diamines as mono-protonated species.
The ammonium and organo-ammonium species are released from the BPh4 − interaction once the surrounding solution is made basic. Thus, once the spent polymer is washed with, for instance, Na2CO3 solution, the ammonia and amines are released and the starting material regenerated. Alternatively and cheaper, the material can simply be swamped with Na30 ions by washing it with concentrated NaCl solution. This expels the ammonium ions by force of Na+ concentration. Washing the material with CO2 in water (carbonic acid) is also feasible. This washes out ammonia as (NH4)2CO3, the amines as amine carbonates/bicarbonates and regenerates an acidic material. The acidic material then later exchanges H+ for NH4 +.
Reagents and reactants were prepared as follows:
Ammonia-free Water
Ammonia-free water was used in preparation of all solutions and reagents in all experiments. Ammonia-free water was obtained as follows. Distilled water (1000 ml) was added to potassium permanganate (2.01 g) and anhydrous sodium carbonate (2.04 g). The solution was refluxed for approximately 1 hour. The intense purple initial solution boiled rapidly for 1 hour. The first portion (100 ml) of clear distillate was discarded and the remaining distillate was collected at a rate of about 100 ml/30 minutes.
Preparation of Standards and Solutions
Standard solutions of NH4Cl were prepared having different concentrations between 1 and 200 ppm NH4 +. Standard curves for NH4 + were determined via mass spectrometry, spectrometric analysis at wavelengths from 400 to 425 nm (412 nm preferred) using Nessler's reagent (an alkaline solution of mercuric iodide and potassium iodide), and by measurements obtained from NH4 + specific electrodes. Standard solutions of sodium tetraphenylborate having between 1 and 200 ppm tetraphenylborate ion were also analysed via mass spectrometry.
Experiment 1
Formation of Ammonium Tetraphenylborate
A 100 ml aliquot of an NH4Cl solution having 200 ppm NH4 + was added to a 100 ml aliquot of a sodium tetraphenylborate solution having 200 ppm equivalent tetraphenylborate ion. A small aliquot (about 5 ml) of the sodium tetraphenylborate solution was added to ensure excess of tetraphenylborate ion. The mixture was allowed to stand overnight to permit the ammonium tetraphenylborate salt to precipitate and settle. The mixture was additionally centrifuged and a clear supernatant was removed and analysed for NH4 + using the above-described methods.
No ammonium ion was detected in the ammonia-free water using Nessler's reagent. Mass spectrophotometric methods detected ammonium ion in distilled water but not in the ammonia-free water prepared according to the above method.
During the formation of ammonium tetraphenylborate, a milky white precipitate was immediately formed when each of the sodium tetraphenylborate solutions was mixed with each of the ammonium chloride solutions. The supernatant derived following formation of ammonium tetraphenylborate was also found to be free of ammonium ion when analysed using mass spectrophotometric methods. This indicates that all of the ammonium ion present in the solution was precipitated out as the tetraphenylborate salt.
It was noted that during mass spectrophotometric analysis, at approximately pH 10, in the presence of chlorine. NH4 + forms Cl�NH2. Cl�NH2 binds to the tetraphenylborate ion. Thus, the removal of this molecule and other similar inorganic nitrogen-containing compounds from waste water through insoluble salt formation with the tetraphenylborate ion falls within the scope of the invention.
Experiment 2
Effect of pH, Temperature and Time on Formation of Ammonium Tetraphenylborate
Aliquots (100 ml) of solutions having either 100 or 200 ppm ammonium ion were adjusted with dilute HCl to pH values between 4 and 6. An aliquot (100 ml) of a solution containing the equivalent strength of sodium tetraphenylborate was added to each solution of ammonium ion. An extra 5 ml of the sodium tetraphenylborate solution was added to each mixture to ensure excess of the tetraphenylborate ion. The solutions were allowed to settle overnight and thereafter the supernatant was tested for ammonium ion spectrophotometrically using Nessler's reagent. Table 1 shows the resulting ammonium ion content of the supernatant for each solution.
All ammonium ion solutions having pH values ranging between 4 and 6 showed nearly complete clearance of ammonium ion from solution when sodium tetraphenylborate was added.
Solutions of 100 and 200 ppm ammonium ion were again combined with sodium tetraphenylborate solutions, as above. pH values were adjusted to between 4 and 6. Aliquots of each solution were incubated for between 2 and 5 days in a thermostatically controlled water bath at 30� C., 35� C. or 40� C. When supernatants were analysed for residual [NH4 +] using Nessler's reagent, all fell within the range of from 2 to 4 ppm.
Long term stability of the ammonium tetraphenylborate salt in aqueous solution was tested by mixing a 200 ppm solution of ammonium ion with a 200 ppm sodium tetraphenylborate solution, as described above. Initial residual [NH4 +] was determined as 6 ppm. The mixture, including the ammonium tetraphenylborate precipitate was allowed to sit for 48 hours, and for an additional 1 week. No change in residual [NH4 +] occurred in this time period, and no change in the boron content of the supernatant was detected (as determined by mass spectroscopy), indicating that free boron was not arising from the precipitate and that the precipitate is thus relatively stable over time.
It was noted that the ammonium ion specific electrode did not provide reliable readings when the tetraphenylborate ion was present in the solution. Thus, the spectrophotometric analysis using Nessler's reagent was used to assess ammonium ion concentration.
Experiment 3
Synthesis of Polystyrene Having Tethered Tetraphenylborate
Poly(4-bromostyrene) was synthesized directly from the monomer by standard free-radical techniques. 240 mg (1.3 mmol aryl bromide) of vacuum-oven dried poly (4-bromostyrene) was dissolved at room temperature in 20 ml of dry tetrahydrofuran freshly distiled from a standard sodium/benzophenone complex all in an ultrapure nitrogen atmosphere. The reaction temperature was reduced to −78� C. in a dry ice/acetone bath and 1.1 ml of a 1.3M solution of sec-butyl lithium (1.4 mmol or ca. 10% excess) was added dropwise over 1-2 minutes.
The reaction was left to stir at low temperature for four hours whereupon an aliquot was removed and quenched in acidified water. The poly (styryl lithium) intermediate product crosslinked suggesting a terpolymer of cross-linked styrene, debrominated styrene and possibly unreacted 4-bromostyrene. A new peak in the phenyl fingerprint infrared spectrum at 700 wavenumbers, when paired with a peak at about 820 wavenumbers indicated the formation of the �proton-trapped� lithiation intermediate (polystyrene).
6.0 ml triphenyl boron solution (0.25M in THF or 1.5 mmol�used as received from Aldrich) was added to the reaction mixture at −78� C. and the reaction mixture was allowed to warm to ambient conditions overnight. A sandy colored precipitate with a faintly cloudy supernatant was observed 12 hours after the triphenyl boron addition.
The reaction was quenched in rapidly stirred distilled water giving rise to small polymeric particles (295 mg dry mass) which give IR spectra indicative of successful functionalization (eg mono-substituted phenyl groups). The particles were swellable on immersion in tetrahydrofuran, but did not redissolve indicating a cross-linked resin. Based on I.R. analysis, the product was determined to be a cross-linked polystyrene having a minimum of 25% functionalization by tethered tetraphenylborate. Both the polymeric starting material and regular homopolystyrone are very soluble in tetrahydrofuran. The aqueous fraction was blue-tinged and otherwise transparent. On evaporation of the water, a film and some solid residue remained, indicative of tetraphenylborate side reactions and non-crosslinked polymer.
The results of I.R. spectral analysis for intermediate and final products are as follows:
Lithiation quenched in acidified water
Cloudy supernatant 15 hours after triphenyl boron addition (film-dried in vacuo)
Precipitate in water dried vacuo pellet
The precipitate was tested in the following manner: (Test 1); 2 ml of an aqueous solution of ammonium chloride (115 ppm) was stirred overnight with 30 mg of the polymeric precipitate in an airtight vial. (Test 2): 5 ml of the ammonium chloride solution were added to 20 mg of the aqueous fraction residue from the above reaction. (Control): stock ammonium chloride solution was reserved.
Two aliquots (300 microliters) were then withdrawn from the liquid of each of tests 1 and 2 and the control and were tested with one drop of Nessler's solution. The control and test 2 assays (four total) turned red/orange on addition of Nessler's solution (yellow) indicating high concentrations of ammonium cations. The final colour of the test 1 assays was yellow/orange, indicating a lower concentration of ammonium cations. This test confirms that the polymeric product sequesters ammonium cations from aqueous solutions.
Experiment 4
The high-angle, low temperature, X-ray crystal structures of four representative organo-ammonium tetraphenylborate salts were studied for the purpose of defining the N�H . . . (π)phenyl interaction. More specifically the structures of the ammonium, guanidinium [(NH2)3C]+, biguanidinium [((NH2)2C)2N]+, and DABCOH+ (mono-protonated 1,4-diazabicyclo[2.2.2]octane) [HN(CH2)3N]+, tetraphenylborate salts were examined by X-ray diffraction using the charge-density, multipole refinement techniques. The X-ray data were collected on a R-Axisli imaging plate system at −120� C. with Mo�Ka radiation to sin(θ)/λ=1.0 cm−1.
The X�H . . . π(phenyl) interactions were observed in the resulting deformation density maps. The parameters from the multipole refinements were then used to determine and quantity the topological features of the interaction, using Bader's theory of �Atoms in Molecules� (Bader, R. F. W. Atoms in Molecules�A Quantum Theory OUP, England, 1990; Bader R. F. W. Chem. Rev. 1991, 91, 893; Bader, R. F. W. J Phys. Chem. (A) 1998, 102, 7314). This showed that there was a definite, identifiable N�H . . . π(phenyl) hydrogen-bonding interaction between the ammonium or organo-ammonium cation and the (π) system of the phenyl ring(s). The XDPROP program in the XD package (Koritssnszky, T.; Howard, S. T.; Richter T. Mallinson, P. R.; Su, Z.; Hansen, N. K. XD, A Computer Program Package for Multipole Refinement and Analysis of Charge Densities from X-ray Diffraction Data 1995) was used for this. In the four salts there are 14 N�H . . . π(phenyl) interactions and in every N�H . . . π(phenyl) interaction, a (3-1) bond critical point was found between the (H) and π(phenyl) species. XDPROP was then used to locate the bond path (path of maximum electron density) on either side of these critical points. In every case, the path traveled in one direction back to the N�H system and traveled smoothly on to the (X) species in the opposite direction. The value of the electron density (pb(r)) and the Laplacian (∇2pb(r)) were calculated at each of the critical points. The values of the Laplacian ((∇2pb(r)) in all cases are positive, indicating the expected closed-shell nature of the interactions The values place the N�H . . . π(Ph) interactions as slightly weaker in energy than the conventional N�H . . . N hydrogen bonds but from both the topology and the critical point values the N�H . . . π(Ph) interactions are clearly hydrogen bonds.
The geometries of these four salts are representative of all the organo-ammonium tetraphenyl borates salts and the formation of this N�H . . . π(phenyl) interaction is characteristic in the formation and precipitation of the organo-ammonium tetraphenylborate salts.
In conclusion, according to the invention, NH4 + and amines can be removed from waste water through insoluble salt formation with the tetraphenylborate ion. The ammonium tetraphenylborate salt is stable over long periods in aqueous solution. Tethering the tetraphenylborate ion in a polymer is useful in the removal of NH4 + and amines from waste streams. Tetraphenylborate ion which is tethered to a polymeric backbone can be used for removal of NH4 + and amines from waste water and can be regenerated by release of the NH4 + and amines therefrom, thereby providing inexpensive and beneficial means to environmentally treat industrial, agricultural and other waste water or streams.
While the invention has been described in detail with reference to certain preferred embodiments thereof, it will be apparent to those skilled in the art that modifications and variations are within the spirit and scope of that which is described and claimed.
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Whanaungatanga: Sybil-Proof Routing With Social Networks
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Executive Summary
Decentralized systems, such as distributed hash tables, are subject to the Sybil attack, in which an adversary creates many false identities to increase its influence. This paper proposes a routing protocol for a distributed hash table that is strongly resistant to the Sybil attack. This is the first solution to this problem with sublinear run time and space usage. The protocol uses the social connections between users to build routing tables that enable Sybil-resistant distributed hash table lookups.
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