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Sail on: Darien Junior sailing program survives hurricane and remains popular
Call it the little sailing program that could: After suffering the destruction of its clubhouse in 2012 during Hurricane Sandy, the Darien Junior Sailing Team, now operating out of a storage pod and a tent, is still fulfilling its mission of introducing young people to sailing.
Founded in 1972 at Weed Beach, the sailing program, known as DJST, is a non-profit organization supported by, but not affiliated with, the town of Darien. The town provides the use of Weed Beach, but DJST is self-funded and organized by parent volunteers. The program runs for two three-week sessions, and is open to Darien children ages 8-14, most who come into the program with little or no sailing experience.
"The most amazing thing about this program is we have the ability to take kids who have almost never been out on the water before, let alone sailed, and then put them in boats, and put them in one of the most beautiful places certainly in the East and get them sailing," Jeff Hudson, chairman of the DJST board, said. "And that impact stays with you for life."
Sailors must pass a swim test, and then start sailing in small boats called Optimists, moving through four levels of experience before moving on to the bigger, faster 420s. And while the program, which is a member of the Junior Sailing Association of Long Island Sound, competes in local regattas, racing is not the focus. Here, the goal is to build leadership and community skills while having fun.
"We have great relationships with our fellow yacht clubs, so when I speak about racing it's not a pejorative thing," Hudson said. "But kids are different, some kids are not ready for competitive sports. If you've never been in a sailboat, to go from zero to 60 in terms of getting out and racing is overwhelming. We are dealing with kids who are scared of what's in the Sound. It's a very family friendly, very easy way to get people introduced to a sport I grew up doing."
Central to the program is the longevity of the counselors, many of whom grew up in the program. Cam Cirillo, who graduated from Darien High School in 2016 and now attends Elon College, started sailing with DJST at eight years old; this summer, he is the head instructor.
"This is more of a family feel. A lot of people are intimidated by the yacht club culture — it's extremely demanding and can be intimidating," Cirillo said.
As opposed to a traditional racing program, where the day is structured around training on race courses, DJST counselors build young sailors' confidence on the water by incorporating games, swimming and theme days, while also teaching skills like resilience and collaboration.
According to DJST chairman Hudson, these skills are vital to the mission of the program.
"You watch these kids and they help each other pull the boats out of the water, rig the boats, do everything," Hudson said. "Most of the counselors came through the program themselves and there's a spirit here of 'help and get it done' and I think it has been instilled in the longevity of the program. None of these kids want to let their friends down on anything."
Despite the enthusiasm of the current participants, the effect of the storm remains fresh.
Prior to Hurricane Sandy, in 2012, the program enrolled 170 sailors; this summer, there are 60 sailors. Christopher Deak, who oversees the program as site director, blames the attrition partly on the destruction of the two-story building, which was owned by the town and featured garage storage as well as office space, a boat rack and a deck.
The current Darien Parks and Recreation master plan calls for a new waterfront boating center at Weed Beach.
According to Pamela Gery, director of the Darien Parks and Recreation Department, any decision on a new building is up to the Parks and Recreation Commission. The commission is currently considering several options for the Weed Beach space, including a new facility that could house DJST in the summer, but no decision to build has been made.
"Our travesty is Hurricane Sandy," Deak said. "It came in and broke the back and spirit of the program. The building was the central focus. Imagine if Noroton Yacht Club's building was never built back, what do you think would happen to the club?"
Yet, Deak said, the popularity of the program endures.
"You get an 8-year-old and have them for eight, nine years — I call that a legacy. I have parents who come down here all the time that are in their late 30s, early 40s, and they are bringing their kid who is 10-years-old and they say 'I did this program, I want you to do this," Deak said.
For longtime DJST sailors like head instructor Cirillo, the program remains a vibrant, and important, part of Darien, building or no building.
"There's a lot to learn from the hardships we've had in the past," Cirillo said. "Kids love coming back, and I think people feel at home here. That's how I've felt for the past 12 seasons, with instructors being really open and sailors coming back every year. It creates a bond."


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Jan 3, 2018
This week, we're playing "Would I Rather," a game about predicting each other's hypothetical opinions! It's a great game to play with friends, or with people you've never met, or even with awful people that you never want to see again. Because, hey, you know what they say: "keep your friends close, and your enemies are good for playing games with but not much else, yup, this is that classic quote by me, mister quotes."
Topics include: Captain Smacks, rat surprises, vacationing in the puff, Love Actually 2: It's About McDonalds This Time, David becoming his own parent, and Grapple-Tooth Mike's love of conjuring.
And search for us on SPOTIFY. Because we're there. Too simple. Too easy. Gotta do it.
We love you.

subset: commoncrawl


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Student Disability Services
Programs that provide special assistance and accommodations that support the ability of students with visual, hearing, physical, emotional, learning or other disabilities to achieve their academic goals and participate in, contribute to and benefit from the institution's programs, services and activities. (AIRS HL-8120.7980)
If you know of a Service that should be listed but isn't, please Suggest a New Provider. If you find errors in a listing, please let us know by using the "Suggest an Edit" form on the provider's detail page.


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Number Matching Puzzles with Ten Frames - Dinosaurs {Numbers 1-20}
Number Matching Puzzles with Ten Frames - Dinosaurs
This Number Matching Puzzles set contains 20 mini puzzles that focus on matching numbers 1-20 using ten frames. Simply print out the puzzle pages (six puzzles per page) and cut apart. Students then match the numbers to the corresponding ten frames.
There are both color and black line pages to save ink. Add a pop of color by printing the black line version on colored paper. Print either version on heavy cardstock and laminate for durability.
Thank you! -- Polliwog Place
Look for additional teaching resources in my store:
*Number Matching Puzzles - Sea Life
*Number Matching Puzzles - Sharks
*Letter Matching Puzzles - Building Crew
*Label the Picture Vocabulary Activity - Set 1
*Ten Frames: Making Ten and Twenty {Set 2}
*Spot the Differences Picture Puzzles
*CVC Word Building Pages
More activities
Number Matching Puzzles | Number Matching | Ten Frames | Ten Frame Matching | Ten Frame Puzzles | Number Puzzles | Ten Frame Number Matching | Numbers 1-20


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- Wade Barrett tweeted the following about attacking Kofi Kingston on last night's RAW:
"Felt great to wipe the smug grin off Kofi's face at #Raw. That Bull-Hammer was the sweetest I've ever thrown."
- WWE has announced that AJ Lee and Dolph Ziggler will be special guests for The Miz and MizTV on tonight's live Super SmackDown special. We are looking for correspondents for tonight's show, so if you are attending it, please contact us by clicking here.


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HOT READS: Nippertown's Top 10 Stories of the Week
Yes, yes, yes, we know… We've heard all of the complaints that some of you simply don't have the time to read all of the Nippertown.com news as fast as we write it. And, yes, there was a whole lot of news to write about this week…
So for all of you casual, once-or-twice-a-week readers, here's a summary of the Top 10 most-viewed stories from Nippertown in the past week:
1. It's On: Big Music Fest Coming to Saugerties (by Staff)
2. SPAC Announces New Concert (by Staff)
3. The Egg Announces Three New Concerts (by Staff)
4. Who's Bad? Rockin' On the River? (by Staff)
5. LIVE: Alexis P. Suter Band @ WAMC-FM's The Linda, 3/7/14 (by J Hunter, Rudy Lu)
6. Comin' Soon: New Concert Announcements (by Staff)
7. RIP: Dan Griffin, 1956-2014 (by Greg Haymes)
8. Yet Another New Concert Announced for SPAC (by Staff)
9. FreshGrass Festival Announces Line-Up of Bands (by Staff)
10. Belleayre Music Festival Announces Summer Concert Schedule (by Staff)


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Started as a family business in 1990, Bryndulais Scaffolding has grown year on year to current levels mainly through word of mouth recommendation from existing clients. Providing exceptional service through an honest, reliable and clear focus on your satisfaction from start to finish.
Several major construction and industrial firms across the region have secured our services over long term contracts for the next several years. Something we are proud of and continue to justify on our approach.
Bryndulais Scaffolding provides the safe erection and removal of scaffold structures across Breconshire, Neath Port Talbot, Swansea Valleys and Mid Wales whilst continuing to grow.
What areas do you serve?
We provide Scaffolding services across South Wales between Llanelli, Swansea Valleys, Neath Port Talbot, Brecon and surrounding areas.
Do you provide residential or corporate Scaffolding services?
We provide Scaffolding services to commercial, industrial and residential customers, as well as being the Scaffolding company of choice for many established construction companies and council schemes.
Have a question? Call 01639 700 220 or click here 👉


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About The Bloggers
« Some Straight Talk on Value Billing |
| Chinese Lawyers Lose Their Jobs After Calling for Bar Association Elections »
Beware the Supersize Law Firm
From an in-house counsel's perspective, what's not to like about large law firms? They're chock full of talent, boast dozens of practice groups that allow for one-stop shopping and bring a respected brand name that allows corporate clients to show others that they mean business. But with these strengths come attendant drawbacks, argues Rees Morrison in this article from the New York Law Journal, "Why Law Departments Should Beware Super-Sized Firms."
So what does Morrison believe are the disadvantages to large firms? First, and not surprisingly, is their cost. While law firm associates receive terrific supervision and instruction, that training is subsidized by higher billing rates. And enormous overhead combined with the billable-hour approach gives firms even more incentive to run up their bills. Second, while large firms have great experience, being a go-to firm also increases the probability of conflicts -- and obtaining client waivers up front which can complicate negotiation of engagement agreements. Finally, as law firms specialize, they morph into collections of small practice areas. As a result, they may not have the ability to offer a broad perspective -- only an aggregation of narrow views.
Though Morrison's article just appeared today, it seems that some corporate clients are already applying his advice. According to this story from Bloomberg, a Japanese video game maker chose to abandon its pricey Biglaw representation to take advantage of the 20 percent rate cut offered by Mark Peroff, who moved to Hiscock and Barclay, a 200-attorney firm in upstate New York.
Posted by Carolyn Elefant on November 6, 2008 at 11:37 AM | Permalink
| Comments (0)


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Owning a Home is Still The Dream.
Owning a Home is Still the American Dream
Despite the effects of the Great Recession, people still love their homes and think they're a good investment.
- 81% of adults surveyed believe buying a home is the best long-term investment a person can make.
- 80% of adults surveyed see homeownership as a very important long-term financial goal.
- 81% of renters would like to own a home in the future.
- 54% of first-time homebuyers bought because they were tired of renting.
- 96% of homeowners are happy with their decision to own.


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One million Americans are expected to receive hip and knee replacements in 2013. At an average price tag of $52,063, these procedures are anything but affordable. Medicare negotiates significantly reduced rates with hospitals, but these procedures still cost the government roughly $6B each year.
NerdWallet Health built a Best Hospitals tool to help patients investigate the cost of hospital care in their local areas. Using the tool, we studied the ten most and least expensive hospitals for hip and knee replacements. We asked the following questions:
1) What are the prices and expected quality of the top 10 most and least expensive hospitals for hip and knee replacement?
To determine prices, we looked at 2011 Medicare data for the amount billed by the hospitals and how much Medicare pays.
To predict quality, we relied on a recent study of 2750 hospitals offering hip and knee surgery. We found hospitals performing more than 200 hip and knee replacement surgeries a year have lower rates of infections, heart attacks, serious complications like blood clots and pneumonia, and death – we call this metric the "200 Quality Benchmark". Government data reveals how many Medicare beneficiaries are treated annually at each hospital.
2) Do high hospital prices unfairly affect needy populations, like the poor or elderly?
We looked to the U.S. Census Bureau State & County QuickFacts for median household income, percent of population below poverty level and percent of population over age 65.
3) What are the operating characteristics of the most and least expensive hospitals?
We looked for trends in hospital attributes like number of beds, U.S. News rankings, management structure, and funding sources. We also studied individual hospitals via details published on their own websites.
Top 10 most expensive hospitals for knee and hip replacement and reattachment surgery
1. Monterey Park Hospital, Monterey Park, CA: Average Price $223,373
This partnership-operated, small hospital treated only 15 Medicare patients with hip and knee replacement in 2011. This hospital serves a population that is both predominantly Asian (66.9%) and older than average—19.3% of Monterey Park residents are over the age of 65, compared to the 13.7% nationwide average. Despite skyhigh costs and low levels of patients treated, Medicare pays Monterey Park Hospital 150% of the average national reimbursement for these procedures.
2. Centinela Hospital Medical Center, Inglewood, CA: Average Price $220,881
Centinela Hospital Medical Center is a privately owned corporation and was named a 2013 Truven Health Analytics Top 100 Hospital. Inglewood, CA, is a city in Southwestern Los Angeles County with high percentages of Latino and Black residents and a lower than average percentage of senior citizens.
3. Our Lady of Lourdes Medical Center, Camden, NJ: Average Price $202,777
This not-for-profit teaching hospital is sponsored by Catholic Health East, a multi-institutional health system that is funded by seven religious congregations. Our Lady of Lourdes serves a community of only 7.6% individuals over 65. Median household income in Camden is about half of the nationwide average, and the percentage of Camden residents below the poverty level is almost three times the national average.
4. University of California Davis Medical Center, Davis, CA: Average Price $185,506
This state-funded teaching hospital, which prides itself on being "a leading West Coast center for orthopaedic care," has a relatively high Medicare reimbursement for hip and knee replacements, as is it paid about 80% above the national average. The UC Davis Medical Center is ranked by U.S. News as High Performing in Orthopedics, and features an 'Adult Reconstructive Service' that serves joint replacement patients.
5. Lourdes Medical Center of Burlington Country, Willingboro, NJ: Average Price $177,168
Lourdes Medical Center, like Our Lady of Lourdes Medical Center (number three on this list), is sponsored by Catholic Health East and also receives lower reimbursements from Medicare. In 2001, the hospital opened a long-awaited $20 million same-day surgery center. Unlike its sister hospital, this hospital is located in a relatively well-off area, with a median household income of about 150% of the nationwide average and a poverty rate about three times less than the national average.
6. Hahnemann University Hospital, Philadelphia, PA: Average Price $173,874
This corporately owned teaching hospital is ranked by U.S. News as High Performing in Orthopedics. The 'University Orthopaedic Institute' "specializes in early recognition of implant failures and revisions to previous joint replacements", and prides itself on using the latest materials and being skilled in even the most complicated joint replacements. Hahnemann serves Philadelphia, where the median household income is about 30% below average, putting approximately 1 in 4 residents below poverty level.
7. Temple University Hospital, Philadelphia, PA: Average Price $172,393
This not-for-profit teaching hospital is also ranked by U.S. News as High Performing in Orthopedics. 'Temple Orthopaedics & Sports Medicine' offers the latest treatments in joint replacement and is part of a relatively large (728 bed) hospital. Despite its large size, this hospital only discharged 48 Medicare patients for hip and knee replacements in 2011.
8. University of California Irvine Medical Center, Orange, CA: Average Price $172,023
Yet another that ranks as High Performing in Orthopedics by U.S. News, this state-funded teaching hospital has only one hip and knee surgeon and treated only 11 patients for major joint replacements 2011. Despite being below from NerdWallet Health's 200 Quality Benchmark, UC Irvine was reimbursed twice the nationwide average for these procedures. This hospital serves a more wealthy population, with a median household income of about 150% of the nationwide average.
9. Regional Medical Center of San Jose, San Jose, CA: Average Price $170,730
This partnership-owned medical center boasts a comprehensive 'Orthopedics & Joint Replacement' program. In October 2005, $160-million was spent on an expansion effort that included adding new hospital facilities. Of the Top 10, Regional Medical Center serves the highest earning population, with a median household income of $80,764. It is also well paid by Medicare (72% above average reimbursement).
10. Regional Hospital of Jackson, Jackson, TN: Average Price $161,699
The Regional Hospital of Jackson is a corporate-owned partnership that proudly includes physicians as owners. It charges more for a "unique patient experience", which includes the "latest surgical techniques, a dedicated orthopaedic coordinator, 18 newly remodeled private suites, and flat-screen TVs and wireless Internet." The second smallest hospital in the Top 10, it receives close to the average Medicare reimbursement. This hospital serves Jackson, TN, where slightly less than 1 in 4 people is below poverty level.
Hip and knee replacements are common surgical procedures offered by thousands of US hospitals. Prices vary widely among the 2750 hospitals included in our study. Vice President of Health Christina LaMontagne says, "on average, the top ten most expensive hospitals charged nearly 12 times more than the ten least expensive hospitals." Patients can use free tools to learn more about the costs of hospitals in their local areas. "There is no doubt that California is the most expensive state for hip and knee replacement and reattachment surgery," explained LaMontagne. "On average, procedures in California cost 69% more than the national average, and we find five of the top ten most expensive hospitals are in this state."
All of the top ten most expensive hospitals for knee and hip surgery fail to meet NerdWallet's '200 Quality Benchmark', suggesting patients treated at these hospitals may face increased rates of infection, pneumonia, heart attacks, blood clots and even death. At the same time, four of the least expensive hospitals do exceed the 200 Quality Benchmark, meaning they offer better outcomes to patients.
"We found that many hospitals that perform more than 200 hip or knee procedures each year charge lower rates than do hospitals that fail to reach the 200 Quality Benchmark," remarked Vice President LaMontagne. She suggested that "patients should not consider high price a signal of high quality."
We observed no meaningful correlation between the price a hospital charges for hip and knee surgery and the relative income or age of people living in the nearby community. Likewise, we did not find that hospital size or operating characteristics had any consistent influence on hospital charges.
About NerdWallet Health
NerdWallet Health provides transparency to patients, empowering them to choose better and more affordable health care. NerdWallet Health's newly launched Best Hospitals tool allows individuals to compare prices, experience, and patient satisfaction for hospitals in their region. Please consult a health professional for medical advice.


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GPS for Parents to Track Children 24/7 Launched in Singapore
The Global Positioning System or GPS previously was developed to allow accurate determination of geographical locations by the military and civil users.
Now, GPS has revolutionized our daily life. We frequently use GPS to track for locations we are heading to. Knowing the location of your beloved ones can be easier too when using the GPS.
A tech company in Singapore, myFirst recently launches a service that provides unlimited GPS tracking for parents to track their children. The service also includes messaging, voice, and video call services for S$25 a month.
To allow the users to track for their children's locations 24/7, the "Stay Connected with Your Loved Ones" service comes with a kid's smartwatch, a parent's application, connectivity, data storage, and server application.
The parents have to subscribe to a 12-month plan to be able to rent the smartwatch. The smartwatch, myFirst Fone S2 have specifications of a 2MP built-in camera for video calls. It also has a touchscreen feature that allows children to send texts.
There are a few more features that attract the parents to subscribe to this service. Some of the features are the Classroom Mode, Geo-Fencing, and One-Touch SOS. These features help the parents to monitor the children's safety and life every day and at any time they want.
Source: mothership.sg
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Malaysian Teacher Samuel Isaiah Makes Final 10 For US$1 Mln Global Teacher Prize 2020
English language teacher Samuel Isaiah from Sekolah Kebangsaan Runchang school, Muadzam Shah, Pahang, has been named as one of the top 10 finalists for the Global Teacher Prize 2020, in partnership with UNESCO.
The Malaysian teacher was selected from over 12,000 nominations and applications from over 140 countries around the world, said a statement issued by the Varkey Foundation which the Global Teacher Prize is part of its long-standing commitment to improving the status of teachers.
Samuel introduced many innovations to inspire his Orang Asli students to dream big and crucially connect them to the outside world, including an e-mail exchange project called 'Asli E-Pal', where they communicate in English with adult volunteers all over Malaysia and overseas.
Malaysian teacher Samuel Isaiah has been named a top ten finalist for the Global Teacher Prize 2020, in partnership with @UNESCO. Now in its sixth year, the US$1 million award is the largest prize of its kind. @samuel_isaiah87 #teachersmatter #gtp2020 #tuesdaymotivation pic.twitter.com/8pAuRe9Mrk
— Global Teacher Prize (@TeacherPrize) October 27, 2020
Samuel also introduced the "Speak Up With Poetry" programme where he worked with amateur poets to write poems relatable to Orang Asli culture which his students would then watch in the form of guided videos to learn English.
The school's average pass rate in English had increased from 30 per cent in 2012 to between 80 per cent and 85 per cent in 2015-2018, said the London-based Varkey Foundation.
Other finalists are Ranjitsinh Disale from India, Olasunkanmi Opeifa (Nigeria), Jamie Frost (United Kingdom), Carlo Mazzone (Italy), Mokhudu Cynthia Machaba (South Africa), Leah Juelke (United States) and Yun Jeong-hyun (South Korea).
"Congratulations to Samuel Isaiah for being selected as a top ten finalist from such a huge number of talented and dedicated teachers. I hope his story will inspire those looking to enter the teaching profession and also highlight the incredible work teachers do all over Malaysia and throughout the world every day," said Assistant Director-General for Education at UNESCO, Stefania Giannini.
"The Global Teacher Prize helps put the teachers' voice at the heart of our mission to champion inclusive learning opportunities for children and young people all over the world, especially the most marginalised and disadvantaged, during this sudden and unprecedented disruption to global education.
"Since the coronavirus pandemic first emerged, we have seen 1.5 billion learners across the world impacted by school and university closures. But not all learners are being impacted equally. Governments must learn lessons and act decisively to ensure all children receive a quality education in the age of COVID and beyond."
The remaining two top 10 finalists will be announced one each week in the run-up to the Global Teacher Prize ceremony, which will be virtual for the very first time in its history due to the COVID-19 pandemic.
This year's Global Teacher Prize ceremony will be done virtually and is expected to take place on Dec 3, 2020, where the overall winner will be announced.
It will be hosted by English comedian, actor, writer and presenter Stephen Fry from the Natural History Museum in London.
"The Global Teacher Prize was set up to shine a spotlight on the important role teachers play in society. By unearthing thousands of stories of heroes that have transformed young people's lives, the prize hopes to bring to life the exceptional work of teachers all over the world," founder of the Global Teacher Prize, Sunny Varkey, meanwhile said.
"This year, more than ever, we have seen teachers go above and beyond to keep young people learning throughout the world. Teachers everywhere should be applauded for their creativity, compassion and resolve to fulfil every child's right to a good education."
The Global Teacher Prize winner will be paid the prize money in equal instalments over 10 years.
LATEST: Petrol Price RON97, RON95 Remain The Same
The Malaysian Ministry of Finance recently issued a media statement related to the retail price of petroleum products for the period of 31 October to 6 November 2020.
According to a statement released on Twitter, the retail price of RON97 petrol remains RM1.94 per liter, RON 95 petrol remains RM1.64 per liter, and Diesel also remains RM1.74 liter.
Siaran Media Berkenaan Harga Runcit Produk Petroleum Bagi Tempoh 31 Oktober 2020 Sehingga 6 November 2020. pic.twitter.com/lr6UfnZJeo
— Ministry of Finance🇲🇾 (@MOFmalaysia) October 30, 2020
Sources: MOF
Macau Scam: Remand of Datuk, Two Policemen Under POCA Extended by 38 Days
KUALA LUMPUR, Oct 30 — The remand period for a 'Datuk' and two policemen being investigated under the Prevention of Crime Act (POCA) 1959 in connection to an online gambling syndicate and Macau Scam activities was extended another 38 days by the Magistrate's Court here today.
Magistrate M. Mageswary allowed the police's application to extend the remand period against the suspects aged between 34 and 39 beginning today.
They were previously remanded under POCA for 21 days from Oct 11.
The remand proceedings of the three suspects who wore orange lockup attire began at 10.30 am and ended an hour later.
Lawyer Jacky Loi when contacted by Bernama confirmed that all the suspects were remanded according to Section 4 (2)(a) of POCA. Also representing the suspects were lawyers Gobind Singh Deo and Shahrizal Abdul Manan.
On Oct 13, Kuala Lumpur Criminal Investigation Department chief SAC Nik Ros Azhan Nik Ab Hamid said police had re-arrested the three individuals after the court rejected a remand order applied for by the Malaysian Anti-Corruption Commission (MACC) against them for their suspected involvement in online gambling activities.
He said they were re-arrested immediately after being released by the MACC.
Source: BERNAMA
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Faith Church is a cross-generational congregation of the Presbyterian Church (U.S.A.). In worship we enjoy exceptional music, intelligent preaching, and the Lord's Supper (often called Holy Communion or Eucharist) every week.
At Faith Church we enjoy each other:
People from all walks of life and diverse points of view call Faith "home." We hold to a "better together" philosophy, believing that God has called us into community and so it's better to be together than apart, even though we don't agree on everything all the time. We believe God gifts our community with each individual, and gifts each individual through our community. Come join us!
What We Practice:
Phone: 719-596-4895
Email: firstname.lastname@example.com
Office hours: Mon, Tues, Thurs, 8:15am - 12:00pm


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Ju Park
Attorney at Law
Ju graduated from UCLA law school after attending the US Military Academy at West Point and UT Austin. She worked at a top int'l law… read more firm for 4 years prior to co-founding Parsus LLP.
Practice Areas
Client Reviews
"Ju helped us successfully negotiate and close a $10mm acquisition of a US company. She was clearly competent, knowledgeable and experienced, and her advice was practical and custom-tailored to my team's objectives. We were extremely satisfied with Ju and will definitely use her again."
"As a fast-growing technology company, Parsus filled an important gap for us. For day-to-day matters, our two-person in-house team juggles as best we can. However, during busy periods, we need extra hands to assist (without adding to our headcount). And that's where Parsus comes in. They've spent the time to understand our business; that way, they can quickly jump in to help as and when needed. We have been very happy with Parsus' business-centric, client-first service."
Work History
Parsus LLP
Managing Partner
May 2009 - Present
Co-founded and manages the growth and operations of Parsus LLP, a boutique law firm focused on the practice of corporate transactions and general counsel advice.
Latham & Watkins
Aug 2005 - Apr 2009
Practiced corporate law in Los Angeles and Hong Kong offices of Latham & Watkins.


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When it comes to possible future water crises, B.C. is in a strong position — that is, if we begin talking about water management issues now.
"In Metro Vancouver, we have three large reservoirs that collect enough water to meet our summer demand," said Steven Conrad, a Simon Fraser University doctoral student.
"But if we were to continue to have droughts and these kinds of years, I would expect that water supply to be inadequate to meet our needs. So then what do we do?"
Conrad, who recently completed a study on drought and climate response in the Okanagan, sits on the board of directors for the B.C. Water & Waste Association as a director of the American Water Works Association.
Along with other experts, Conrad will speak about water research at SFU Blue (the Wosk Centre for Dialogue, June 24).
The school is calling the event a "preamble" to the Canada Water Summit on June 25. Now in its sixth year, the Summit brings together leaders from different sectors to discuss a national sustainable water future.
Conrad will also work with the Pacific Water Research Centre, which is part of SFU's Faculty of Environment. The goal of the Centre is to help resolve increasing drought issues that are related to climate change, and to open up a dialogue with communities about water-management issues.
"We can set a research agenda at SFU that will look toward these current and ongoing concerns that communities have," Conrad said. "I expect the citizens of Prince George to have different concerns than Metro Vancouverites or people in Kelowna, and water research needs to respond accordingly."
Last year, Conrad published a study on the attitudes of farmers in the Okanagan about water allocation. Farmers from Vernon to the U.S. border were given a list of options on managing drought.
"They were open to water trading, in some circumstances, with a preference for trading among themselves, with some groups looking to trade with other water users," Conrad said.
Allocation according to crop value, where individuals growing the most high-value crops would get the water first, was least preferred, he says.
"And they wanted to share the pain during drought. They wanted to work together so there would be a small amount of water reduction that every farmer would have to meet to allow them to strategize."
Conrad, who began his education in Arizona, has spent most of his professional and academic life working with communities that have not asked these kinds of questions until the last minute.
That's what we're seeing in California, he said.
"They've waited until they're at a critical point of water shortage before asking individuals to cut back. Some Californians aren't willing to cut back their water use. Then you get into a regulatory perspective."
In B.C., we need to ask how prepared our water systems are for extreme weather events, such as floods and droughts.
"Can we deliver enough water for our growing demand, can we have programs and plans in place to work through the uncertainty that we expect?"
The model of stability that our water infrastructure is based on no longer holds. The current provincial Water Act is 100 years old. (A new Water Sustainability Act will come into effect in 2016.)
"We put systems in place thinking things are going to be stable," Conrad said. "Now we realize that we're going to have more ups and downs, and on a more frequent basis."
B.C. is "at a great point right now," he said.
"It's nice to be here, where we have the opportunity to ask those questions now instead of waiting 10 or 20 years and saying 'Shoot, I wish we'd done this before.'"
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Research Article | Open Access
Ali Chami Khazraji, Sylvain Robert, "Self-Assembly and Intermolecular Forces When Cellulose and Water Interact Using Molecular Modeling", Journal of Nanomaterials, vol. 2013, Article ID 745979, 12 pages, 2013. https://doi.org/10.1155/2013/745979
Self-Assembly and Intermolecular Forces When Cellulose and Water Interact Using Molecular Modeling
Cellulose chains are linear and aggregation occurs via both intra- and intermolecular hydrogen bonds. Cellulose has a strong affinity to itself and toward materials containing hydroxyls groups. Based on the preponderance of hydroxyl functional groups, cellulose is very reactive with water. At room temperature, cellulose chains will have at least a monomolecular layer of water associated to it. The formation of hydrogen bonds at the cellulose/water interface is shown to depend essentially on the adsorption site, for example, the equatorial hydroxyls or OH moieties pointing outward from the cellulose chains. The vdW forces also contribute significantly to the adsorption energy. They are a considerable cohesive energy into the cellulose network. At the surface of the cellulose chains, many intermolecular hydrogen bonds of the cellulose chains are lost. However, they are compensated by hydrogen bonds with water molecules. Electronic clouds can be distorted and create electrostatic dipoles. The large antibonding electron cloud that exists around the glucosidic bonds produces an induced polarization at the approach of water molecules. The electron cloud can be distorted and create an electrostatic dipole. It applies to the total displacement of the atoms within the material. Orbitals play a special role in reaction mechanism. Hydrophilic/hydrophobic nature of cellulose is based on its structural anisotropy. Cellulose-water interactions are exothermic reactions. These interactions may occur spontaneously and result in higher randomness of the system. They are denoted by a negative heat flow (heat is lost to the surroundings). Energy does not need to be inputted in order for cellulose-water interactions to occur.
1. Introduction
The development of materials derived from renewable resources is an important pillar in the drive for the sustainability of our society. Cellulose is the world's most abundant natural, biodegradable polymer and renewable organic material produced in the biosphere. It is widely distributed in higher plants, in several marine animals, and to a lesser degree in algae, fungi, bacteria, invertebrates, and even amoeba. The production of cellulose is estimated to be over .
In a woody plant cell, the linear cellulose chains referred to as microfibrils are approximately in cross-sectional dimension and of indeterminate length. Regardless of its source, natural cellulose [C6H10O5]n; ( 10,000 to 20,000, where depends on the cellulose material) can be characterized as a high-molecular-weight homopolymer of linked anhydro-D-glucose monomers organized into a crystalline structure in which every unit is corkscrewed 180° with respect to its neighbors, and the repeat segment is frequently taken to be a dimer of glucose, known as cellobiose (Figure 1) [1]. Cellulose is composed of β-D-glucopyranose rings that adopt a 4C1 chair conformation, which are linked together by ()-glucosidic bonds [2]. In nature, crystalline cellulose (cellulose I) is found in two forms termed Iα and Iβ, and its structure was established in 1984 by cross-polarization magic angle spinning (CP-MAS) [3, 4].
Cellobiose (C12H22O11) is a disaccharide with the formula [HOCH2CHO(CHOH)3]2O. Cellobiose consists of 2 glucose molecules (two D-glucopyranose units) joined by a 1,4,-beta-glycosidic bond. Cellobiose has 8 free alcohol (OH) groups, 1 acetal linkage, and 1 hemiacetal linkage, which give rise to strong inter- and intramolecular hydrogen bonds (Figure 2). Cellobiose cannot be digested by humans and cannot be fermented by yeast. Its solubility in water is 12 g/100 mL. Cellobiose units are reducing sugars because the anomeric carbons on the right-hand sugar are part of a hemiacetal.
Each cellulose chain possesses a directional chemical asymmetry with respect to the termini of its molecular axis: one end is a chemically reducing functionality (i.e., a hemiacetal unit) and the other has a pendant hydroxyl group, the nonreducing end. The number of glucose units or the polymerization degree (DP) is up to 20,000, but shorter cellulose chains can occur and are mainly localized in the primary cell walls [1]. The cellulose polysaccharide contains considerable energy stored in its C–H and C–C bonds. Cellulose structure favors organization in bundles with the crystalline order held together by hydrogen bonds and disordered regions or amorphous.
In nature, cellulose is mainly found as slender fibrils where a precise number of glucans are organized in a parallel fashion. The lateral size of these fibrils, and consequently the number of its constituting glucan chains, depends on the synthesizing organisms. Extreme fibril lateral dimensions ranging from 2 to 20 nm have been reported in rare species, but the most common cellulose fibrils have diameters in the 3 to 5 nm range. Usually, these fibrils do not occur individually but are hierarchically assembled into bundles, herein referred to as fibril aggregates. Furthermore, the fibril aggregates themselves are organized into larger structures. The organization of the glucan chains within each cellulose fibril leads to a specific crystalline arrangement, defined as cellulose I or native cellulose, where all of the glucan chains are crystallized with their polar heads pointing in the same direction. Two crystalline cellulose I allomorphs have been identified, namely, the triclinic cellulose Iα and the monoclinic Iβ, the former being dominant in some algal cell walls such as those of Valonia and the latter being the major constituent of higher plant cell walls such as those of cotton or wood [5].
Understanding the supramolecular structure of cellulose and the nature of its overall existing interfaces with water is important in many applications. For chemists working with cellulose, its reactivity is a crucial issue, and this is intimately connected to interfacial properties. Cellulose and its derivatives show a notable variation in their capacity to form anisotropic solutions depending on the kind, the degree of substitution, and the solvent. Molecular structures of typical repeat units of cellulose can be found in the book of Fengel and Wegener [6].
2. Objective of This Study
This study will focus on physical and chemical properties of cellulose when it comes into contact with water. We will investigate the crystal structure of cellulose, its electronic properties, and its interactions with water molecules using molecular modeling simulation.
3. Computational Methods
The proposal aims to understand some of the fundamentals behind the properties as well as evaluating their stability using mesoscale modeling of cellulose-water interactions. Mesoscale modeling such as the dissipative particle dynamics and the quantum mechanical modeling to be undertaken in this project are prime candidates for tackling the previous questions. The large size and slow dynamics of mesoscale structures make atomistic modeling techniques such as quantum mechanics or molecular mechanics prohibitively expensive. However, mesoscale structures are critical to the properties of certain materials, and therefore methods have been developed to elucidate mesophase behaviour. At such scales, hydrodynamical behaviour becomes important and must be included in the model.
Dissipative particle dynamics (DPD) is a mesoscale-simulation program available from the Accelrys Materials Studio 6.0 [7]. It provides a dynamics algorithm, which incorporates hydrodynamics, for studying coarse-grained systems over long length and time scales. It also enables us to perform analysis on the results of such dynamical simulations. The effective pair potentials are both short ranged and soft, allowing long dynamical time steps to be used. Since the DPD equation of state does not include cubic density terms, the potential does not produce a van der Waals loop in the pressure. As a result, liquid and vapor phases cannot coexist and only a single fluid phase is obtained. The softness of the potential precludes crystalline phases. The walls of cellulose can be included to study preferential adsorption, and the system may be sheared to observe morphological changes.
DMol3 from Accelrys Materials Studio 6.0 is a modeling program that uses density functional theory (DFT) to simulate chemical processes and predicts properties of materials rapidly and with great accuracy. Because DMol3 predicts processes in gas phase, solution, and solid environments, it is broadly applicable to research problems in chemistry, pharmaceuticals, materials science, and chemical engineering, as well as solid-state physics. Researchers can use the program to investigate the nature and origin of the chemical, electronic, optical, and structural properties of a system without the need of any experimental input. DMol3 performs virtual experiments, leading to tremendous savings in costly experiments and shorter developmental cycles. DMol3 achieves its speed and accuracy by using numerical functions on an atom-centred grid as its atomic basis [8–11]. The atomic basis functions are obtained from solving the DFT equations for individual atoms and are hence quite accurate. The high quality of these basis sets minimizes basis set superposition effects and provides an improved description of molecular polarizabilities [12]. The electron density in DMol3 is expanded in terms of multipolar, atomic-centred partial densities. This provides a compact yet highly accurate representation of the electronic density and provides good scaling with a growing system size.
VAMP module from Accelrys Materials Studio 6.0 uses semi-empirical calculations to determine a molecular wave function. The molecular wave function is constructed according to the LCAO (Linear Combination of Atomic Orbital) method in which molecular orbitals are obtained as a linear combination Slater-type atomic orbitals. Semi-empirical methods use Slater functions by evaluating the two-electron integrals via a multiple approximation, rather than an exact calculation. Other features of VAMP are transient state optimization, solvent models, and the calculation of many electronic properties.
4. Results and Discussion
4.1. First Part: Self-Assembly of Cellulose Chains and Interaction with Water Molecules
The descriptions of polymer systems start with a model of an ideal macromolecule. A polymer built up of repeating units (bonds) with length in a linear fashion can be characterized by its reducing and nonreducing extremities. The bonding phenomenon is the sum of a number of mechanical, physical, and chemical forces that overlap and influence each other. Because both hydrogen bonding interactions and vdW dispersion forces are expected to play important roles in determining the crystal structure of cellulose, the proper inclusion of long-range interactions in the geometric optimization is necessary.
From the DPD and Mesocite Accelrys Materials Studio 6.0 library, we took the carbohydrates 12aD_glucose (Figure 3). First, with this molecule, we built the repeat unit fragment so-called cellobiose (Figure 4) and then cellulose fibres in which the number of chains is 10 and the length of each chain is constructed with 5 repeating units of cellobiose (Figure 5). In this manner, we obtained a fibrous network of cellulose by forming an anhydroglucose polymer connected by β-glycosidic links. In the chemical sense, cellulose is alinearpolymer formed by cellobiose units (two β-glucose units). Cellulose polymer is insoluble in water. Its structure is compact and ordered. Ithasa great physical and chemical stability.
The molecular aggregation of cellulose in the wood's cell walls contributes to its unique polymer properties. The aggregation phenomenon occurs primarily via both intra- and intermolecular hydrogen bonds. The cellulose chains are arranged in a parallel manner and are organized in sheets stabilized by interchain OH–O hydrogen bonds, whereas the stacking of the sheets is stabilized by both vdW dispersion forces and weak CH–O hydrogen bonds [13, 14] (Figures 6 and 7). As result of the vdW dispersion forces, there is a considerable cohesive energy within the cellulose network. The large antibonding electron cloud that exists around the glucosidic bonds induces polarization at the approach of the water molecules. The weak interaction due to CH–O hydrogen bonds enables the dispersion of cellulose in water in small quantities. Remember that the cellulose chains are interconnected by OH–O type hydrogen bonds to form flat chain sheets with weak CH–O hydrogen bonds between them. The hydrophilic and hydrophobic nature of cellulose is based on its structural anisotropy. Yamane et al. proposed that the hydrophilic behaviour of cellulose was due to the location of hydroxyl groups at the equatorial positions of the glucopyranose rings [15].
4.1.1. Description of Interactions between Water Molecules and Cellulose Chains
Within the plant cell wall matrix, water is subjected to a number of interactions caused by the chemical and physical composition of the cell wall. Thus, the structure and composition of the cell wall produce different states and locations of water, all of which may be important for our understanding of cellulose-water interactions.
The behaviour of cellulose surfaces in different media as well as their interactions with different chemicals is of great importance in their current and future applications (papermaking, composites, and nanocomposites). The bonding phenomenon is the sum of a number of mechanical, physical, and chemical forces that overlap and influence each other. Wetting may be attributed to acid-base interactions, weak hydrogen bonding, or vdW dispersion forces (dipole-dipole, orientation, induction and dispersion forces). The extent of wetting depends on the difference in surface free energies of the solid, liquid, and subsequent interface.
Since cellulose has a strong affinity to itself and any hydroxyl-containing materials, especially, water [16], a solvation cage is formed around the cellulose chains after their interactions with water molecules (Figure 8). The cellulose reacts much more with water because of the preponderance of hydroxyl functional groups. In the cellulose model in Figure 7, we added a lot of water molecules. As a result, the water molecules interacted quickly with the cellulose chains by immediately forming hydrogen bonds (Figure 8, blue dashed lines). According to a previous study, only the topmost layer in the cellulose differs in terms of structure and dynamics from the crystal bulk, but even these differences are small. At the surface approximately half of the cellulose intermolecular hydrogen bonding is lost, but this is compensated by hydrogen bonds with water molecules. The potential energy of water molecules in the first hydration layer is lower by 2 kJ/mol. The cellulose surface contains about five exposed hydroxyl groups per square nanometer, which accounts for the good hydration of the surface [17]. In addition, monomeric properties of nanocrystalline cellulose offer high specific surface.
Water is a good solvent due to its polarity. The molecular shape of water allows for this polarity. Cellulose polymer is also a polar compound. Therefore, when the cellulose chains come into the water media, these chains are automatically surrounded by water molecules. The smallness of the water molecules enables them to react easily with the cellulosic chains. The partial negative charge of the dipole of water is attracted by the positive charge of the cellulose chains and vice versa. Cellulose chains may be surrounded by several water molecules. At common ambient environment conditions (room temperature), cellulose chains will have at least a monomolecular layer of water associated with it. Moreover, cellulose is very stable in a variety of solvents and can only be dissolved by the application of strong acids or strong hydrogen-bonding-solvent systems—usually amine-based. The thermal properties of cellulose are such that the cellulose glass transition temperature is in the range of 200 to 230°C, which is close to its thermal decomposition temperature of 260°C [18].
The hydrogen bond is really a special case of dipole forces. A hydrogen bond is the attractive force between the hydrogen attached to an electronegative atom of one molecule and an electronegative atom of a different molecule. Usually the electronegative atom is oxygen, nitrogen, or fluorine, which has a partial negative charge. The hydrogen then has the partial positive charge. To recognize the possibility of hydrogen bonding, examine the Lewis structure of the molecule. The electronegative atom must have one or more unshared electron pairs as in the case of oxygen and must have a negative partial charge. The hydrogen, which has a partial positive charge, tries to find another atom of oxygen with excess electrons to share and is attracted to the partial negative charge. This forms the basis for the hydrogen bond. In other words, The hydrogen on one molecule attached to O that is attracted to an O of a different molecule.
4.1.2. Building a Cellulose Crystal Containing Water Molecules inside
Accelrys Materials Studio 6.0 features a powerful crystal-building tool which enables building the cellulose crystal. The display style of the water atoms changes to large CPK (Corey-Pauling-Koltun) spheres with their radii dependent on the vdW radius of the element they represent. However, most structures look better with a slightly smaller CPK size, so that the spheres do not dominate the structure too much.
Change the range values so that more than one cell is displayed. Three cells are displayed in the x-direction (), and then we increased the B and C values similarly (). The cells are extended in all three directions. The crystals simulated are either isolated or immersed in water. Using the 12aD_glucose dimer (Figure 9), we built the cellulose crystal in which there are water molecules (Figure 10). Within the cellulose chains, the water molecules are shown in large spheres or CPK style and cellulose chains are displayed in stick. For larger structure such as cellulose polymer that we are visualizing, the perspective projection is useful. Water molecules interact with the cellulose chains and by creating hydrogen bonds (Figure 11). Through the capillary forces, water molecules can be found around the fibres, for example, the diffusion of water molecules in porous fibre network in order to understand the permeability to liquids.
The bonding phenomenon is the sum of a number of mechanical, physical, and chemical forces that overlap and influence each other. In addition, water molecules tend to congregate in forming a bulk of hydrogen bonds or clusters (Figures 12 and 13). This bulk does not also prevent the water molecules from binding with cellulose chains. The water could form different kinds of shapes, especially, clusters with the number of water molecules.
4.2. Second Part: Some Physical and Chemical Properties of Interactions between Cellulose and Water
In this section, we tried to highlight some energetic and electronic properties of cellulose using DMol3 from Accelrys Materials Studio 6.0. The purpose is to calculate binding energies and ionization potentials because, between cellulose and water, there are electronic interactions.
4.2.1. Effect of Water Adsorbates on the Field Emission from Cellobiose Tips
Of the various potential application areas of cellulose, field-emission-based flat panel display is the closest to becoming the first commercial application. In these devices, electrons are emitted from tips of cellobiose, which have been aligned parallel on silicon or glass substrates. A practical challenge in making an efficient display is to reduce the operating voltage under which electron emission occurs. One way to achieve this is to introduce adsorbates that might effectively lower the ionization potential (IP) and facilitate the extraction of electrons from the cellobiose tip. Important experiments in this context were recently performed at Motorola [19], showing that the presence of water significantly enhances the field emission current from cellobiose.
In this experiment, we will use first-principles quantum mechanics to compute the binding energy of a water cluster to a cellobiose tip under field emission conditions. We will also compute the ionization potential, a measure of the difficulty to extract an electron from the cellobiose tip. The Accelrys Materials Studio 6.0 module used to do this calculation is DMol3 [20], a first-principles code based on the density functional theory (DFT). In this code, the electronic wave functions are expanded in an atom-centered basis set defined on a numerical grid.
We have built the preoptimized structures of(1)the isolated cellobiose tip (tip.xsd), where only the repeat segment is frequently taken to be a dimer of glucose, known as cellobiose (Figure 14);(2)an H-bonded cluster of 5 water molecules (5water.xsd) (Figure 15); and(3)the cellobiose tip with the water cluster adsorbed on it (tip_5water.xsd) (Figure 16).
In the first structures (tip.xsd and tip_5water.xsd), the axis is aligned along the negative Z-direction. In order to simulate field emission conditions, calculations (1) and (3) are performed in an electric field oriented along the positive Z-axis, while calculation (2) is performed in zero electric field (see [21] for more details).
This modeling covers(i)computing the single point energy for the cellobiose tip + water system;(ii)computing the single point energy for the cellobiose tip;(iii)computing the single point energy for the water system in the absence of an electric field;(iv)computing the binding energy of water to the cap;(v)ionization potential (IP) calculations.
(1) Computing the Single Point Energy for the Cellobiose Tip + Water System On tip_5water.xsd that it is the activated model. On the setup tab: task is set to energy and functional to GGA and PBE. On the electronic tab: integration accuracy is coarse. SCF tolerance is coarse, and basis set to MIN. On the DMol3 electronic options dialog, in the SCF tab, check use smearing. On the orbital cutoff tab custom is selected. In the global orbital cutoff textbox 3.5 is indicated. In the tip_5water.input file, we erased the line symmetry on, and we added the following lines in the document: symmetry c1 fix and electric field 0.0 0.0 0.02. The symmetry line is to make sure that DMol3 does not reorient the molecule away from the current alignment along the Z-direction. The electric field units are in Hartree/Bohr, which implies a field of ~1 volt/Angstrom parallel to the tube axis directed toward the cellobiose tip from above. Once the calculation finishes, in the tip_5water.outmol file, the total energy () is
(2) Computing the Single Point Energy for the Cellobiose Tip With tip.xsd as the activated model, use the same settings in the calculation dialog of DMol3 as tip_5water.xsd. Again, the "symmetry" line is to make sure that DMol3 does not reorient the molecule away from the current alignment along the Z-direction. Once the calculation finishes, the total energy () is
(3) Compute the Single Point Energy for the Water System in the Absence of Electric Field Again, with 5water.xsd as the activated model, use the same settings in the calculation dialog of DMol3 as tip_5water.xsd. After the job finishes, the total energy () is
(4) Compute the Binding Energy of Water to the Tip The binding energy is given by the formula ().
(5) Ionization Potential (IP) Calculations In order to obtain insight into the effect of adsorbed water molecules on the field emission current, it is interesting to compute the ionization potential (IP) of an electron from the cellobiose tip in the presence and absence of water. The IP is defined as the difference in energy between a system with a charge (i.e., 1 electron removed) and the original system with a net zero charge. Also, the system with the charge has essentially the same atomic geometry as the neutrally charged system flowing in from the stem side of the cellobiose. Thus all we need to perform is the single point energy with the same DMol3 settings as before, except that charge has to be set to . On the tip_5water.input file, we changed the charge from 0.0 to 1.0. The energy for the charged system is On the tip.input file, we changed the charge from 0.0 to 1.0. The total energy of the charged cellobiose tip is The IP for the cellobiose tip (in absence of water) is therefore In the presence of water, the IP becomes So, the presence of water cluster lowers the IP by . , thereby enhancing field emission current at a given voltage.
4.3. Third Part: Electronic Properties of Cellulose and Water
In this modeling, we optimized the cellobiose and water molecules, analyzed the results, and calculated molecular properties using DMol3 from Accelrys Materials Studio 6.0. We built an atomistic model of cellobiose and water (Figure 17), and then we modeled them using quantum mechanics.
Since cellulose readily interacts with its environment and in a special way with water molecules, it is best to highlight its electronic properties as the electron density, electrostatic potential field, and molecular orbitals where the reactions take place.
In the DMol3 calculation, in the setup tab, we have set the task to geometry optimization. The quality is set to medium, the functional to GGA (generalized gradient approximation) and BLYP [22, 23]. We have just specified the basis set and the Hamiltonian to be used in this calculation. In the electronic tab, we have set the basis set to DNP (double numerical plus polarization). In the properties tab, we have checked the electron density, electrostatics, and orbitals.
4.3.1. Displaying the Electronic Properties of Cellulose Chains and Water Molecules
We used the DMol3 analysis tool from Accelrys Materials Studio 6.0 to display isosurfaces of cellobiose and water molecules. Initially, we are going to view the electron density as an isosurface. The total charge density is displayed. Once we have an isosurface displayed, we can map different properties onto it, such as the electrostatic potential of cellobiose and water molecules (Figures 18 and 19, resp.). The electrostatic potential is mapped onto the total charge density isosurface using color to represent the variation. Mapping the electrostatic potential in this manner gives insight into the charge distribution over the molecule.
Electrostatic potential:(i) positive regions (red) correspond to electron-deficient areas—subject to nucleophilic attack;(ii) negative regions (blue) correspond to electron-rich areas—subject to electrophilic attack.
We used VAMP from Accelrys Materials Studio 6.1 for these experiments. WAMP is a semiempirical molecular orbital program that has been optimized to be highly numerically stable. We optimized the structures of a cluster of water (4 water molecules), cellobiose, and cellobiose + 4 water molecules, and we analyzed several properties of theirs (Table 1). Polar molecules, such as water molecules, have a weak, partial negative charge at one region of the molecule (the oxygen atom in water) and a partial positive charge elsewhere (the hydrogen atoms in water). Thus when water molecules are close together, their positive and negative regions are attracted to the oppositely charged regions of nearby molecules. The force of attraction, shown here as blue dashed lines, is called a hydrogen bond (Figure 20). Each water molecule is hydrogen bonded to four others. The hydrogen bonds that form between water molecules account for some of the essential and unique properties of water. The graphic shows a cluster of water molecules in the liquid state (Figure 20). Water is a polar molecule, with the oxygen (red) being the negative area and the hydrogen (white) being the more positive area. Opposite charges attract. The bond lengths give some indication of the bond strength. A normal covalent bond is 0.96 Angstroms, while the hydrogen bond length is 1.97 Å. The molecular electrostatic potential is the potential energy of a proton at a particular location near a molecule. Negative electrostatic potential corresponds to an attraction of the proton by the concentrated electron density in the molecules (from lone pairs, pi-bonds, etc.). Positive electrostatic potential corresponds to repulsion of the proton by the atomic nuclei in regions where low electron density exists and the nuclear charge is incompletely shielded. The polarity of the water molecule with the attraction of the positive and negative partial charges is the basis for the hydrogen bonding.
We calculated several properties when cellulose and water interact shown in Table 1. Many chemical reactions release energy in the form of heat, light, or sound. Cellulose-water interactions are exothermic reactions. Exothermic reactions may occur spontaneously and result in higher randomness of the system. They are denoted by a negative heat flow (heat is lost to the surroundings). In the lab, exothermic reactions produce heat or may even be explosive. Cellulose-water interactions describe a process that releases energy in the form of heat. Forming chemical bonds releases energy and therefore is an exothermic process. Energy does not need to be inputted in order for cellulose-water interactions to occur.
The heat of formation for the cluster of water (4 water molecules), cellobiose, and cellobiose + 4 water molecules, as calculated by WAMP, is approximately , , and , respectively. Examples for other properties displayed are the total electronic and the total nuclear repulsion energies. The difference between these two energies gives the total energy. The next two lines contain two convergence criteria, the gradient norm and the root-mean-square force on the atoms. Default convergence criteria for these are 0.01 Ha and 0.4 kcal/mol. The output shows that both convergence criteria are satisfied. Finally, the ionization potential, the number of filled molecular orbitals, and the molecular weight of 4 water molecules, cellobiose, and cellobiose + 4 water molecules are listed.
4.3.2. Modeling Interactions between Cellulose and Water Molecules Using Quantum Mechanics
We used DMol3 tool from Accelrys Materials Studio 6.0 to display electronic properties after interactions between cellulose chains and water molecules. The cellulose chains are very reactive with water molecules. Hydrogen bonds form as soon as the cellulose chains come in contact with water molecules (Figure 21). Hydrogen bonding is often described as an electrostatic dipole-dipole interaction. Electronic density and electrostatic potential fields are mixed up between cellulose chains and water molecules. When cellulose and water interact, the electron clouds surrounding each atom of cellulose and water are combined and they form a single electron cloud. Consequently, cellulose chains and water molecules become a single entity (Figures 22 and 23).
Cellulose chains and water molecules can interact through vdW dispersion forces, hydrogen bonding, stacking electrons, and charge-transfer interactions. The vdW dispersion forces are electrostatic types. They are born from attraction between the dipoles of water molecules and cellulose chains. The attraction forces between the dipoles are lowest in the order of a few kcal/mol (<10). When water molecules come into cellulose chains, it results in an electrostatic attraction between the hydrogen atom carrying a δ+ charge and an electronegative atom of another cellulose chain carrying a δ− charge. Moreover, hydrogen bonds are formed whenever a hydrogen atom is linked to a very electronegative atom. It is both a hydrogen-bond donor and hydrogen-bond acceptor or a hydrogen-bond acceptor and hydrogen-bond donor. It reaches energy of around 10 kcal/mol. The available bond around an atom depends on the arrangement of electron pairs in the valence layer. The arrangement depends on the number of electron pairs. The most likely arrangement is that which minimizes the electronic repulsion, that is, one that separates the maximum electron pairs.
Detailed knowledge from the atomic and electronic levels is of direct scientific interest and provides insight into understanding the interaction/reaction mechanism of much more complex systems. According to the LCAO theory, when water molecules and cellulose chains come together, we can understand the new molecular orbitals (and their energies) in terms of the orbitals (and energies) of the separated species. The interactions of cellulose orbitals of one species with the other orbitals of water generate two new orbitals—one favorable (bonding) combination, which is lower in energy than either of the separate orbitals, and the other an unfavorable (antibonding) combination, which is higher than either of the separated orbitals. The amount by which the energies shift depends on overlap and energy match between the mixing orbitals.
Lewis theory (1916) says that two or more atoms react to give a chemical bond if the entity obtained is more stable (a combination accompanied by a release of energy). The establishment of a chemical bond affects only the outer electrons—valence electrons. Electrons in deep layers are not affected.
As known, a water molecule is formed when two atoms of hydrogen bond covalently with an atom of oxygen. In a covalent bond, electrons are shared between atoms. In water, the sharing is not equal. The oxygen atom attracts the electrons more strongly than the hydrogen. This gives water an asymmetrical distribution of charge. Molecules that have ends with partial negative and positive charges are known as polar molecules. It is this polar property that allows water to separate polar solute molecules and explains why water can dissolve so many substances. Water is a good solvent due to its polarity. The solvent properties of water are vital in biology because many biochemical reactions take place only within aqueous solutions. When an ionic or polar compound enters water, it is surrounded by water molecules. The relatively small size of water molecules typically allows many water molecules to surround one molecule of solute. The partially negative dipoles of the water are attracted to positively charged components of the solute and vice versa for the positive dipoles.
In this experiment, we used VAMP to calculate the Mulliken charges and bond orders of cellobiose and water molecule. The partial atomic charges, as calculated by the Coulson method, are displayed on the cellobiose and water molecule (Figures 24 and 25, resp.). Mulliken charges arise from the Mulliken population analysis and provide a means of estimating partial atomic charges from calculations carried out by the methods of computational chemistry, particularly those based on the LCAO method. The bonds in the cellobiose and water molecule are updated from the VAMP calculation (Figures 26 and 27, resp.).
To calculate the electronic properties of cellulose unit and one water molecule, we used VAMP from Accelrys Materials Studio 6.0. This tool enabled us to calculate the heat of formation of these two reactive entities and other important molecular properties (Table 2).
The heat of formation for cellobiose unit and for one water molecule, as calculated by VAMP, approximately and , respectively. The difference between the total electronic energy and the total nuclear repulsion energy (core-core repulsion) energies gives the total energy.
5. Conclusion
Molecular aspects of the interactive behaviour between cellulose and water are not well known. Molecular modeling simulations are one of the most convenient tools to predict solvent properties of cellulose-water interactions, which are otherwise difficult to predict or measure by experimental means. Cellulose is the most abundant chemical compound on earth, and its natural affinity for self-adhesion has long been recognized. The ease of adhesion that occurs in cellulose has contributed to its use in paper and other fibre-based composite materials.
It is obvious that the structure of cellulose is complex, and its study requires the consideration of many factors. Investigation into the many aspects of the cellulose structure is being continued by research groups worldwide and new results constantly appear in the literature. This trend shall continue as more is learned about cellulose by the application of an increasing number of techniques including molecular modeling and simulation solutions. All knowledge gained about cellulose structure is vital to life today because cellulose and its derivatives are used in so many industrial applications.
Within the plant cell wall matrix, water molecules are subjected to a number of interactions caused by the chemical and physical composition of the cell wall. Structure and composition of the cell wall produce different states and locations for water. Besides a strong affinity to itself, the cellulose has also a strong affinity toward materials containing hydroxyl groups, especially water. Cellulose chains were inter-connected by OH–O type hydrogen bonds to form flat sheets with CH–O hydrogen bonds between them. After the interactions between cellulose chains and water molecules, many intermolecular hydrogen bonds are broken from the cellulose/water interface, but these chains build new connections with the water molecules. The weak interactions also allow the dispersion of cellulose in water even in small quantities. The partial negative charge of the dipole water is attracted by the positive charge of the cellulose and vice-versa.
The bonding phenomenon is the sum of a number of mechanical, physical and chemical forces that overlap and influence each other. Within the plant cell wall matrix, water is subjected to a number of interactions caused by chemical and physical composition of the cell wall. The structure and composition of the cell wall produce different states and locations of water. Cellulose chains can interact through hydrogen bonds, vdW forces, stacking and charge transfer interactions. The vdW is electrostatic forces type. They arise between dipoles. The topmost surface layer of the nanocrystalline cellulose is structurally affected by the water outside the surface, which reflects the rigidity and strength of the cellulose crystal. Cellulose chains are arranged in a parallel manner and organized in sheets stabilized by inter-chain OH–O hydrogen bonds, whereas the stacking of the sheets is stabilized by both vdW forces and weak CH–O hydrogen bonds. Cellulose chains were inter-connected by OH–O type hydrogen bonds to form flat sheets with weak CH–O hydrogen bonds.
6. Future Work and Perspective
(i)The extent of wetting depends on the difference in surface free energies of the solid, liquid and subsequent interface.(ii)In addition of non-bonding interactions, wetting may be attributed to acid-base interactions.(iii)Cellulose-water interactions are exothermic reactions. These interactions may occur spontaneously and result in higher randomness or entropy () of the system. They are denoted by a negative heat flow (heat is lost to the surroundings) and decrease in enthalpy . Energy does not needs to be inputted in order for cellulose-water interactions to occur.
The authors would like to thank NSERC (National Sciences and Engineering Research Council of Canada), the Innovative Green Wood Fibre Products Network, and the CQMF (Centre québécois sur les matériaux fonctionnels) for financial support. They also thank the Compute Canada network and Calcul Québec for their computational resources.
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Copyright © 2013 Ali Chami Khazraji and Sylvain Robert. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


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Logan had so much fun making biscuits last week for valentines day and of course the decorating them part. Growing up my favourite thing about after school club was the easy, quick and yummy activities. Yesterday Logan asked me to do some baking, remembering how much fun it was to just decorate biscuits I suggested we skip the baking part. We went for a walk to get some sweeties and digestive biscuits.
Logan was eager to make Rob some for when he came home so picked some of his Daddy's favourite sweets. we wanted different icing colours so put some icing into three bowls and added some icing dye, Logan helped me mix them.
He forgot that you can eat icing so when it got on his finger he freaked out begging me to wash his hands, I said 'you can eat it'… He happily licked his finger finished with a big grin.
He looked down at the bowls rather confused with what we then had to do, I showed him how simple it all was and before I knew it he was getting busy as I had once done. The best things to do with Logan really are things I remember as a child.
I did have to explain to Logan that one biscuits didn't need ten sweets on it, well if we had more sweets then that would be okay but he kept sneaking them into his mouth. I like that Logan is becoming really interested in getting creative as he use to get bored quick. We have his first Toucan box ordered which I think he will love, we have been rubbish with crafts as well laity so it's my main goal to do more fun things. Do you get creative with your child/ren?
I might not be a master chef but with work and a busy life sometimes we need a quick thing to do, with pay day being a week away we also needed something not to costly. I will be doing this again with Logan, his face filled smile is just heart melting. Rob was greeted with a very excited boy when he came home 'Daddy I made you biscuits' he was shouting while running into the kitchen to fetch his creations.


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CAELESTIS FIRST CLASSIFIED GROWTH brand for WWF
Cælestis (1) is one of the rarest wines in the world – in total only 15 bottles of this unique symbolic biodynamic (organic) wine brand have been created especially for WWF (2). Cælestis is not sold in stores but auctioned annually for WWF in London, New York and Hong Kong. (Out of 176 Bordeaux Classified Growth (Grands Crus Classés) wines only 4 are certified organic including 3 biodynamic) (3).
100% of proceeds from charity auction sales of Cælestis are going directly to local WWF.
Cælestis is the FIRST CLASSIFIED GROWTH (Grand Cru Classé) symbolic biodynamic wine brand created in the long history of Bordeaux Grands Crus Classés (whose first classification in the Médoc dates back to the Napoleonic times in 1855) (4).
It originates from the prestigious Château Fonroque Saint-Emilion Grand Cru Classé (5) biodynamic wine in a region recognized as a World Heritage by the UNESCO (6) and is elaborated by the renowned French producer and oenologist Alain Moueix who autographes Cælestis wine each year.
Cælestis is presented in a special handcrafted case (made of ancient wood) in the shape of a book. The book evokes the educational character of the WWF, the age of the origin of the word Cælestis (from Latin Celestial), and refers to the past history of the Grand Cru Classé Château Fonroque from which our wine originates.
Close to the Stars…, close to the Earth… Each year a different vintage with a unique and original label autographed by a celebrity is offered for charity auctions in London, New York and Hong Kong.
In 2014 Cælestis Grand Cru Classé biodynamic wine (only 15 bottles in total) will be auctioned on three continents (in London, New York and Hong Kong) with 100% proceeds going directly to local WWF as usual.
PETER DOIG (*), the renowned contemporary artist, will design and autograph the outstanding Cælestis wine label. The original will be auctioned for WWF. Will it beat the last auction record of $15.5 million of one of his paintings?
In aid of WWF following in the steps of the world famous painter PETER DOIG ART STUDENTS WORLDWIDE are invited to donate a painting on theme vineyard & wine (deadline 24 October 2014).
In 2013 the Cælestis wine label was autographed by the famous Hollywood star FRANCES FISHER (7).
2013 novelty: specially created rarest organic luxury perfume 'Cælestis fleur de vigne' presented in an exclusive hand-crafted perfume bottles was also auctioned.
The luxury 'Cælestis fleur de vigne' (vine flower) organic perfume was especially created by the Higher School of Perfume in Paris (8) and the beautiful symbolic hand-made bottle was crafted by the French National School of Glass Crafts 'Lycée Jean Monnet' (9) as a 'green' educational project.
In 2012 the first unique Cælestis label was autographed by the Oscar-winning Polish composer, JAN A.P. KACZMAREK ('Finding Neverland') (10), who is also the founder of the "Transatlantyk" – Poznan International Film & Music Festival (11): "Pure wine brings great inspiration to my music". Jan A.P. Kaczmarek generously donated a very special piece of music "Cælestis Impromptu" to enojoy on the Cælestis internet site: http://www.caelestis-bio.com/japk-music.html
Learn more about the project and find out how much money was raised for WWF by visiting the official Cælestis internet site (in English, en français) (1).
About Cælestis :
Cælestis means in Latin Celestial (Céleste – in French, Celeste – in Spanish, Italian) and symbolises the importance of the sky which helps us to formulate our point of view (from the Earth) on everything which surrounds us.
Cælestis was created in 2012 by the non-commercial voluntary association 'Cælestis' based in Saint-Emilion, France, to raise funds annually for WWF (World Widlife Fund) and heighten public awareness about the environmental implications of wine production and consumption: http://www.caelestis-bio.com
"Unsustainable agriculture practice represents one of the greatest threats to the natural world of our generation". David Nussbaum, Chief Executive WWF UK (12)
(1) http://www.caelestis-bio.com
(2) http://www.wwf.org/
(3) http://www.bordeaux.com/uk
(4a) http://en.wikipedia.org/wiki/BordeauxWineOfficialClassificationof1855
(4b) http://en.wikipedia.org/wiki/ClassificationofSaint-%C3%89milionwine
(5) http://www.chateaufonroque.com/en/fonroque/16/philosophy.html
(6) http://whc.unesco.org/en/list/932
(*) http://en.wikipedia.org/wiki/PeterDoig
(7a) http://en.wikipedia.org/wiki/FrancesFisher
(7b) http://www.ema-online.org/board-of-directors/
(7c) https://www.facebook.com/FrancesFisherFanPage
(8a) http://www.ecole-parfum.com/EN/training.html
(8b) https://www.facebook.com/pages/Ecole-Sup%C3%A9rieure-du-Parfum/105781266137199
(9) http://www.lycees-jeanmonnet-yzeure.fr/165Ecole-nationnale-du-verre.html
(10a) http://www.jan-ap-kaczmarek.com/
(10b) https://www.facebook.com/jan.a.p.kaczmarek
(11a) http://www.transatlantyk.org/en
(11b) https://www.facebook.com/Transatlantyk
(12a) http://www.wwf.org.uk/
(12b) http://www.caelestis-bio.com/wwf-uk-thanks-grazyna-lallemand.pdf
About the Club
For WWF supporters, celebrity fans, fine & rare wine, perfume & curiosity collectors - you can contribute by participating in Cælestis annual charity auctions to raise funds for World Wildlife Fund. All funds raised are given directly to local WWF.
Annual charity auctions (usually online) in London, New York and Hong Kong (check Cælestis internet site for exact dates)
Key members
Forthcoming events
In 2014 Cælestis Grand Cru Classé biodynamic wine (only 15 bottles in total) will be auctioned on three continents (in London, New York and Hong Kong) with 100% proceeds going directly to local WWF as usual.
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Product Description
B Braun V5406 - IV Extension Set Peripheral 21" Standard Bore Fem LL Ea
Standard bore Extension Set -Priming Volume: 3 mL Length: 21 in. (52.5 cm)
- Female luer connector.
- Distal SPIN-LOCK connector.
- DEHP-free, Latex-free.
- Application Extension Set.
- Standard Bore.
- Without Filter.
- Flow Control Type: Without Clamp.
- Injection Port Type: Without Injection Port.
- Priming Volume: 3.0 mL Priming Volume.
- Tubing Length: 21 Inch.
- Tubing Type :Non DEHP.
- Priming volume: 3 mL. Length 21 in. (53.3 cm).
Safety Data
- BPA Information: Contains BPA
- Latex Information Components: Do Not Contain Natural Rubber
- PVC Information: Contains PVC.


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Back to School
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*Coupon can not be used for an Emergency Edit
How does this work?
- $50 payment must be paid within September to secure the 15% savings.
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Dwight Fletcher | Christmas Breeze - Change in season (Part III)
As we begin a new year, we often reflect on the year that has past, what went well or what lessons we learned. For the past two weeks we have been talking about Joseph, Jesus' earthly father and the lessons we can learn from him. So far we learnt that Joseph, though he was silent, was a man of action.
Though he was silent, we see him acting and setting an example for us to follow. First, we learned that he did not make rash decisions and second, we learned that he responded with mercy.
Today, we will look at the third lesson we can learn from Joseph. By his actions we learn that:
3. He engaged God
Joseph engaged God through prayer. When he learned of Mary's pregnancy, he would have had to stand up against the culture, the dictates of his family, the talk of his friends and even his own fears. Regardless of things that were against Joseph, when the Angel of the Lord appeared to him and gave him instructions, he obeyed immediately. Sometimes in a situation like Joseph we can't even pray, we can only groan. When we are in distress, we need to call out to God knowing that He has the answer to our problem.
God answered Joseph through a dream in Matthew 1:20-21 (NIV) which says, "… an angel of the Lord appeared to him in a dream and said, "Joseph son of David, do not be afraid to take Mary home as your wife, because what is conceived in her is from the Holy Spirit. 21 She will give birth to a son, and you are to give him the name Jesus, because he will save his people from their sins."
Joseph's motto would have been the same as Nike: "Just do it!". He obeyed God despite the fear he must have had when the angel appeared to him "…do not be afraid to take to you Mary, your wife…".
What is God asking you to do in obedience to Him this year?
Obedience to God may cost us. Sometimes doing the right thing comes with a cost. Obeying God cost Joseph - Matthew 1: 24-25(NIV) says, "When Joseph woke up, he did what the angel of the Lord had commanded him and took Mary home as his wife. 25 But he did not consummate their marriage until she gave birth to a son. And he gave him the name Jesus."
Obeying God's will may have immediate personal consequences. For Joseph, obeying God meant that he would not consummate his marriage until Jesus was born.
Obedience also releases the provision and protection of God for us and our family as evident with Joseph when;
- God protected the family from Herod. "an angel of the Lord appeared to Joseph in a dream. 'Get up,' he said, 'take the child and his mother and escape to Egypt. Stay there until I tell you, for Herod is going to search for the child to kill him.'" Matthew 2:13 (NIV).
- God provided for the journey. The magi "…presented him with gifts of gold, frankincense and myrrh." Matthew 2:11 (NIV).
Disobedience to God carries a high price. Great men and women have got derailed in life because they decided to follow their own desires rather than God's will for them. Joseph was a great man because he was a great follower. He did anything and everything God told him to do. If Joseph had decided to disobey God, not only would he have lost his personal integrity, he would have lost his legacy.
A situation that started out as a crisis ended up being a monumental event in history. Joseph was chosen to be the surrogate father of Jesus because he was pure of heart. He was the kind of man God could use and this quiet man's actions changed the world. Through his actions he became a great example for all of us.
He yielded to the will of the Lord.
"Are you the kind of person that yields to God's will, the person that obeys God and that he could use in a big way? God will never call another man to do what Joseph did. But God has plenty of big jobs left to do, He just needs the people who are willing and qualified to do them. That person can be you.