How many of you have all the following cleaning products cluttering up that space in the laundry cupboard, under the kitchen sink or in the garage.
In my experience you only need the four products hi-lighted to do most of the cleaning jobs around the home. Toilet cleaner with bleach will do the job of all of the products in the same group. Carpet spot cleaner will double as a pre-wash spray when doing the laundry and in my experience will do it better. Water will do the job of window cleaner, car wash and floor cleaner when used with the right micro-fibre cleaning cloth/mitt. All of the products in the cream cleaser group with do much the same job as one another and the multi-purpose spray will cover most of the other jobs that need doing around the home. Micro fibre really is the key to a clean home not chemicals. So cut down on the chemical, it not only save space it save money as well.
Today's item is another pair of shoes that haven't been worn in the last three years.
Cheers! Can't wait to keep reading!
Tracibub, you should feel proud, good on you for cutting back on toxic chemicals in your home. There are still some in my home but I am hoping to find some alternatives soon that I feel are effective. My problem is that I hate cleaning product that don't really work. I am glad my microfibre cloths take care of much of my cleaning without having to use any products at all.


Chicago Brand 3 piece open end ratchet imperial set.
The Chicago Brand 3 piece imperial set is an ideal companion to your toolbox for those working with imperial fasteners. Constructed of 17-4PH stainless steel these open end ratchet spanners won't rust and will resist chipping that can interfere with sensitive equipment. They will not damage the heads of nuts or bolts and contain NO chromium plating. With a lifetime guarantee you can use with absolute confidence!
Three spanners with six different head sizes!
Perfect when working in limited spaces, designed to save you time and effort, guaranteed to last a lifetime!
Trust Chicago Brand, you will NOT be disappointed!
I'm going to put them on the wall at home as a work of art! I love the look and feel of them, stainless steel all the way.
good for tight bulkheads offshore.
I encountered a problem offshore with instrument fittings that terminate to a common bulkhead. The issue was caused by loose fittings and because of the sheer number of fittings located in such a small area, it made any tightening almost impossible with a conventional shifter or spanner.
I found these online and have since tried them out, and found them to be highly successful in getting into tight spots and also without the need to remove the spanner flip side to gain extra space to continue tightening the nut.
Very rugged, well designed and makes for a quick job. My only regret Is that I didn't buy the full set.
If you like to save time and your sanity I would definitely recommend a set of these tools. God send.
Very pleased with this set, fast delivery and good value for money.
Awesome. Work great and exceeded my expectations.


Hair and Beauty Salon Huntsville AL. Call 256-888-9494 now.
Let your beauty shine this summer. Looking Good is Feeling Good! Your hair is the major part of your beauty. First impression is a lasting impression. The way you look when people meet you for the first time is how they will remember you forever. And you don't know who you will meet on your way to work, mall, stores or anywhere for that matter. Take GOOD care of your hair today.
We are experts in hair care such as braiding, sew-in, weaving, dreadlocks, etc. Visit us today at 2420 Jordan Lane NW, Suite G, Huntsville AL 35816 or call us at 256-888-9494.
We work hard to make sure our customers are satisfy with our service. We take walk-in but we prefer booking appointment by calling us at 256-888-9494 or fill out the form on the right side to book your appointment right away. We do all type of braids, weaves, dreadlocks, sew-ins and more.
We are experts in any type of hair braiding. Tell us what exactly you want to get done and we will get it done for you.
Sew-ins is another area of our expertise. Come in and let make your sew-ins done easily and beautifully.
Weaves look good and it is one of services we render. Our customers can testify to this.
We are more than braiding shop. We provide a lot of other services. Some of them are SPA, Manicure, Pedicure and so on.
Best African Braiding is the best place to get your hair braiding done. They are great people, they take care of their customers. I will continue to get my hair done there!


text:
Carol Couse
Manchester, London
+(44)(0)161 234 8806
Contact Carol
Contact Carol Couse
Mills & Reeve will use the information you provide in this form in accordance with our privacy policy. We may from time to time send you general updates by email or post that we think you will find of interest. This includes notification of upcoming event and updates or alerts containing relevant legal news. You can update your preferences at any time and will be able to easily unsubscribe from anything that you do not wish to receive.
Thank you for your enquiry. We will be in touch shortly.
What can Carol do for you?
Carol advises clients on regulatory and commercial issues in sport, media and entertainment. She has particular expertise in football regulatory matters (player transfers, player contracts, immigration/work permit requirements). She also appears before dispute resolution forums at a domestic and international level, including before FIFA, UEFA and the Court of Arbitration for Sport (CAS).
Carol is an accredited commercial and civil mediator and is a Sport Resolutions mediator and arbitrator. She understands the benefits of alternative dispute resolution for clients, where the need to resolve maters in a confidential and often timely way are paramount, preserving relationships where possible, She also has experience of managing multi million pound high profile cases before the ordinary courts, working alongside our expert team of litigators.
Supporting your ambitions
Having previously worked in-house for Manchester United and the football agency Proactive, and having worked in sports, media and entertainment throughout her career, Carol has an in depth knowledge of the industry and is well placed to understand the needs and expectations of her clients. She presents pragmatic legal advice in a clear and concise way, mindful of the commercial and career demands of her clients and related reputational and PR issues.
Carol also heads our Latin America Desk and works closely with numerous international best friend law firms, so benefits from a wide network of global advisers. This enables her, where appropriate to introduce lawyers in other jurisdictions, who are not only experts in their field, but who are likely to be the 'best fit' for the client's needs.
Much of Carol's work is international in nature. Carol and her team successfully brought a claim for disability discrimination against Newcastle United for the Argentinian player Jonas Gutierrez, who gave the following client reference: "Carol gave me excellent professional support throughout the tribunal proceedings and dealt with matters in a sensitive way, explaining everything to me in Spanish which really made things easier".
What else should you know?
As a Spanish speaker, Carol often advises clients in their mother tongue, which assists them in dealing with complex legal matters.
Carol is regularly ranked as a Top 10 Global Thought Leader in Who's Who Legal.
Legal 500 states "Carol works tirelessly for clients, is a superb communicator, gives clear and practical advice, often on complex multi jurisdictional matters"
Chambers and Partners refers to the following client testimonial: "Her knowledge was immediately apparent and her advice was very sensible, commercial and industry specific and her drafting was good, clear and concise".
Mills & Reeve partner appointed as FIFA mediator
Carol Couse, Mills & Reeve partner in the sports team, has become a FIFA-approved mediator following the successful implementation of mediation within the proceedings of the Football Tribunal.
Mediation and sports law
The number of sports related disputes has increased exponentially in recent years and, while some sports regulations and contract provide for early mediation prior to commencing arbitration or litigation, mediation is generally under-utilised in sport...
She's one Elle of a keeper!
Paddington Women's Football Club has announced the signing of 24 year old goalkeeper Elisa 'Elle' Henry.
Life Cycle webinars
In conjunction with international agents and promoters, JL Romanillos Ltd, we bring you Life Cycle, a two-show webinar series which will analyse and talk you through the key issues affecting sportspeople, artists and celebrities.
Kieran Trippier back with Atlético Madrid after serving FA ban
Mills & Reeve has represented England and Atlético Madrid footballer Kieran Trippier in defending betting related charges issued by The Football Association (FA) .
Women in Sport: Top tips for wealth protection
Carol Couse chairs a panel on protecting private wealth, and highlights specific windows of opportunity for estate planning.
Mills & Reeve scores at Northwest Football Awards
The sports team at Mills & Reeve last night took home a top accolade at the Ladbrokes Northwest Football Awards 2019.
Reevaldo scores for Mills & Reeve at Legal Week Innovation Awards
Mills & Reeve has been awarded Best Marketing Innovation for the second year in a row for their dynamic Reevaldo website at the Legal Week Innovation Awards 2019.
Football Leaks: what are the legal consequences/options?
While it can be extremely difficult to contain information once it has been leaked, there are a number of opportunities to potentially seek redress.
What are image rights in football and how are they taxed?
In light of recent coverage of issues relating to footballers' image rights and the related tax issues, the sports team at Mills & Reeve have put together a summary outlining key legal issues.
Related sectors and services
Women's sport
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redpajama_set_name: RedPajamaCommonCrawl


Go to Flotheme – Pages where you can make a few generic adjustments to the Search, Archive and Not Found Pages.
Overall, this section is pretty simple. When users search for Blog Posts or Galleries on your website, the Search Results layout will be structured according to the one selected.
Each layout has a unique number of settings that can be adjusted. These settings are standard, just as any other Content Block you can adjust Font, Colors, Padding, etc.
Archive Pages are related primarily to Blog Posts and Galleries. Similar to the Search Results Page, you can select a desired layout and then make font and color adjustments if needed.


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Bobby Massie Ranks Out Far Better Than Expected and Could Be Due for a Breakout in 2018
February 6, 2018, by Luis Medina Chicago Bears
Coming into the 2017 season, the Chicago Bears' tackles were generally considered the weak link on what was an otherwise top-tier offensive line. And right tackle Bobby Massie was arguably the most criticized Bears lineman, but perhaps things weren't as bad as we thought.
As part of a series ranking the league's best players, Bleacher Report's NFL1000 scouting team ranking Massie surprisingly high among the NFL's right tackles. Indeed, among the 49 eligible players, Massie checked in as the 14th best at his position. That puts him in the top half of his position group, which is a damn fine place to be all things equal.
BR's scouting report saw Massie bounce back from a rough early season stretch (littered with inconsistencies) and settle in after Week 5. The site's scouts laud his punishing style, range in pass protection, and physicality in the running game. When everything is click, the BR scouts believe Massie "looks like one of the NFL's top right tackles at times."
That's high praise for a much-maligned lineman.
(Photo by Jonathan Daniel/Getty Images)
Massie's blocking in the run game looked to be improved early in the season, too. His space-clearing blocks (yes, blocks plural) helped rookie Tarik Cohen break off a big run in the season-opener against the Falcons. And it's not as though there isn't talent and upside within Massie's 6-6, 317-pound frame, it's just that we haven't seen it consistently just yet. Maybe that will change under the watchful eye of new Offensive Line Coach Harry Hiestand, who's proven capable of getting the most out of his players at both the college and pro level.
And if you reacall, it wasn't too long ago when Massie's star was believed to be on the rise. In 2013, Pro Football Focus' Gordon McGuinness tabbed Massie as the Arizona Cardinals' secret superstar and a breakout candidate to be one of the league's top right tackles. Five years later, Massie is still the inconsistent player he was in Arizona. But if the Bears pass on a chance to choose a tackle early in the 2018 NFL Draft, Massie could be in a position to show Chicago's new coaching staff what he can do in a make-or-break contract year.
Previous PostPrevious post:FanGraphs No Cubs in Top 100, But ZiPS Has a Cubs Prospect in the Top 20(!)
Next Post Next post:Lukewarm Stove: Rangers Sign Oh, Darvish Market Value, Royals and Hosmer, More


Hello there, I do think your site may be having internet browser compatibility problems. When I take a look at your site in Safari, it looks fine but when opening in Internet Explorer, it has some overlapping issues. I merely wanted to give you a quick heads up! Other than that, excellent blog!


"I am the originator, innovator, and the architect of Rock-n-Roll," said Lil' Richard.
He was kicked out of his father's house at 15 years of age for inappropriate behavior. He was shortly doing an act on the Chitlin' Circuit in drag. Richard's bizarre personality was often fueled by drugs, he put more that a million dollars up his nose. Yet, in a singularity in pop music, at the height of his national popularity, Richard walked away from the entertainment industry and became a preacher of the Gospel of Jesus Christ.
Lil' Richard is still alive here is the tribute, and parody he deserves. See the previous post "Molly on the Beach". The lyrics of his songs are generally bawdy and silly, the orchestration of his tunes never knock me out... but his rhythms- bring a smile to my eyes.
Richard was cheated out of millions in royalties, eventually, he was the most notorious litigant in Rock-n-Roll. He also made feature films before the exploitation genre was available.
What Richard did, that no one had before, was bring black and white youth together, the first mixed race youth crowds in American history got together at Lil' Richard events. The Beatles and Rolling Stones opened for Richard in England and no one ever followed him on stage anywhere, Richard brought the house down.
Thank you for your generous support over the years. Keep rocking my friend!
and Rolling....it just kept getting better!
Thanks for stopping by... grand you enjoyed the program.
This rocks ! Bravo !
Riffs that fuelled a thousand songs. Horns sound solid. The hesitant start gives way to classic rock'n'roll. Impressive homage. Thanks.
Lots of energy, lots of fine playing. Plenty going on. Fast-paced entertainment. I like it!
Thanks for stopping by, appreciate your support on the thing. I enjoyed making the piece and it is for a great cause.
I'd love to have been a fly on the wall in your studio when you made this! Great rhythm section, cool keys and punchy brass. Ace production too.
You would not believe how many times I had to play the opening piano riff to get something that worked in this century. The way I phrase and the way Richard heard things are very different... Thank you for the listen and the comment is appreciated.
Your band's in full swing here. Very nice work on the horns and of course the signature key riffs. The life that is injected into this kind of music (and that emanates from it) is spirited and infectious. A fitting tribute, quotation, homage to one of the greats of the industry.
Like the fun music too!
saw him once in Florida, handed out a gospel pamphlet to everybody, told stories and told the the crowd to shut up after each one. and he rocked rocked rocked! and he taught Paul McCartney how to Woooooooh! love it!


Copyright law in Australia has some different features from US, UK and Canadian copyright law.
Copyright in Australia is covered by the Copyright Act 1968 (Cth).
Firstly, there is no requirement for registration, nor does a copyright notice needed to be attached to an image.
While the general rule in Australia is that the first owner of copyright is the creator of a work, with an exception to this being where a work is created by an employee of a business as part of that person's job, the default position on who owns copyright in images taken by a photographer in Australia initially depends on whether the photographs are considered to have been commissioned for a commercial or a private purpose.
Under Australian law, Copyright owners have the exclusive right to: reproduce the work; make the work public for the first time; and communicate the work to the public.
Copyright Owners also have the rights to license the use of their works, in return for a "valuable consideration".
Whilst this most often refers to a financial payment, it can also refer to a bartering arrangement where goods and services are exchanged. Unless an exception detailed in the Copyright Act is applicable, other parties (people or companies) will require permission (i.e. a license) to use copyright material in ways reserved as the exclusive rights of the Copyright owner.
One key distinctive of Australian copyright law is the reservation of moral rights vesting in the creator of a work (the photographer). Moral rights do not depend on whether or not they retain ownership of copyright.
Take legal action if their work is altered in such a way that is prejudicial to their reputation.
Moral rights cannot be assigned to another entity in the same way as copyright, however a creator/photographer may waive their moral rights.
So who owns the copyright by default?
Generally, if photos have been commissioned for a private purpose such as a wedding, then the client will retain the copyright in the photos as a default.
The photographer will also be able to restrain (or prevent) the use of images for a purpose other than which they photographer was contracted.
For example, a bride and groom cannot sell the images for commercial publication without the consent of the photographer.
The following summarizes when the client, rather than the photographer, was the first owner of copyright in a photograph in the absence of agreement about copyright ownership.
Where the client is the government If client indicated purpose of photograph, photographer can restrain use for any other purpose.
Other the other hand, if a photographer is commissioned to do work for another party on a commercial basis, the copyright in the photographs remains with the photographer.
Reproduction of any photograph will require the consent of the photographer. A copyright notice or watermark is a good way to indicate you are the original copyright owner but this is not required to trigger copyright protection. Remember, to operate as a freelancer in Australia, you must have an Australian Business Number (ABN).
Be aware that if photos are taken in the course of employment, the employer will own the copyright unless there is an agreement otherwise.
A contract should limit what a commissioner can use the photo for, and the rights of the photographer as the original copyright owner of the photographs. It is important to have a lawyer licensed in Australia review any contract before signing.
Using commissioned photos beyond the purposes originally agreed would constitute a breach of the photographer's copyright. A photographer making works for, or who allows a government (Commonwealth, State or Territory) to be the first publisher should note that the Australian government owns copyright in the absence of an agreement to the contrary.
For photographs taken before 1 July 1998, the client, rather than the photographer, was the first owner of copyright in a photograph in the absence of agreement about copyright ownership.
If a photograph was taken since 1 May 1969, and the client indicated purpose of photograph, the photographer can restrain use for any other purpose.
For photographs taken after 1 July 1998, if the client has indicated purpose of photograph, the photographer can restrain use for any other purpose. If there is no agreement otherwise, section 35(5) Copyright Act 1968 (Cth), applies to photographs commissioned for a private or domestic purpose, where there is no agreement between the photographer and the client about who owns copyright.
It states that if a photographer makes an agreement with another person for the taking of a photograph for a private or domestic purpose, in exchange for "valuable consideration," and the work is made according to the terms of the agreement, then the photographer is the owner of any copyright remaining in the work.
Make sure that your contract includes the purpose for which the client intends to use the photographs – it will be on this basis that you can assert your statutory right to restrain the use of the photograph for other purposes without a further agreement.
Where the client owns the copyright absent an agreement to the contrary, it would be prudent to write the copyright remaining with the photographer into the contract.
Failing the reservation of copyright by the photographer being secured, then a photographer will need to ensure that there is a license for them to use the images in promotion and advertising written into the agreement.
If you obtain a photography contract written by a lawyer who is not licensed in Australia, you will need to have it reviewed by an Australian lawyer who understands the implications of the Copyright Act 1968 (Cth), and the ways in which to ensure that you retain your copyright and are able to assert your moral rights under the law.


As a father of four daughters himself, Manchester dentist Dr. Stanford enjoys taking care of children. Helping them learn about their oral health and understand its importance is a passion of his. Because of this passion, he has been giving dental presentations at the surrounding elementary schools for over 30 years.
Dr. Stanford also understands how important first visits to the dentist are for setting your child up for success in the future. So you will find that our entire team at Stanford Dental is focused on making your little one's visit to our office a positive and upbeat experience.
Dr. Stanford recommends that your child's first visit take place around the age of three years old. We will start by acclimating them to "the dental chair" and counting and examining their teeth. If they feel comfortable enough to have a cleaning, our hygienists will clean their teeth with special flavored paste. We will never move forward with any procedure until your child is completely comfortable.
We focus on using language that is comforting and not scary for your child; and as they get older, we involve them in learning about their oral health by showing them their x-rays on the television screen and discussing their development with them.
Just like adults, children should see the dentist every six months, and as they get older we will incorporate x-rays into their visits once a year. This allows Dr. Stanford to monitor their growth and development so any necessary recommendations can be made in a timely manner.
Children have unique dental needs, and we may recommend some additional services to help build and protect their teeth as they grow, such as fluoride treatments.
Fluoride is a mineral that occurs naturally and helps to build and strengthen developing teeth. It can also assist in remineralizing teeth that have been damaged by tooth decay. We can easily apply fluoride during your child's routine cleaning and checkup.
Dr. Stanford enjoys taking care of families, and he understands how much more convenient it is when each member of the family is able to see the same dental provider. Our experience leads us to recommend early appointments for children when they are fresh and not tired in order to provide them with the best dental visit possible.
We look forward to the relationship we will build with your child and taking care of your family for many years to come.
If you are an expecting mom or new parent, you might have started your research into children's dentistry. In our Manchester, MO dental office, we always tell our patients that good oral health for kids begins during pregnancy! Mom's dietary choices and oral hygiene will impact those of her child as the first step in a lifetime of healthy smiles.
Early Visits With Your Dentist Help to Form Good Life Long Oral Habits!


The Economic and Financial Crimes Commission (EFCC) and the Office of the National Security Adviser (ONSA), have allegedly discovered $9 million cash at the residence of the sacked Special Adviser on Niger Delta to President Muhammadu Buhari and Co-ordinator of the Presidential Amnesty Programme, Brig.-Gen. Paul Tarelah Boroh (rtd).
directed "a full investigation into the activities of the Amnesty Programme from 2015 to date, especially allegations of financial impropriety and other acts".
In the petition to Buhari dated August 21, 2017 and signed by one Timi Angalabiri, on behalf of the people of Niger Delta for Accountability and Good Governance (NDAGG), the group had requested the president to suspend the ex-Amnesty Programme boss "for a credible investigative inquiry to commence into the non-payment of tuition fees and living expenses of recently graduated Niger Delta students in universities across the United States, the United Kingdom and Nigeria, with many institutions withholding the students' certificates due to the non-payment of tuition fees ranging from nine months to two years, despite receiving over N70 billion within this time frame".


I write about this quite often as it's a really important topic from an environmental viewpoint and a problem that doesn't seem to be getting any better – food waste.
According to a new analysis from the Natural Resources Defense Council, folks in the USA are binning 40 percent of food, the equivalent of $165 billion in uneaten food each year.
The average American family of four tosses an equivalent of up to $2,275 annually in food in the bin.
I was surprised to also learn food waste is the single largest component of solid waste in U.S. landfills – I would have thought it was plastic.
A couple more statistics – there has been a 50 percent jump in U.S. food waste since the 1970s and just a 15 percent reduction in losses in the U.S. food supply would feed 25 million Americans annually.
The USA isn't Robinson Crusoe on this front – I mentioned in July that Aussies were binning over a billion bucks worth of fruit and vegetables a year and $5 billion worth of food annually.
Food waste is a problem in most developed countries.
By reducing food waste, we not only save a bundle of cash, but a lot of resources. Harking back to the NRDC report, it seems 10 percent of the USA's annual energy consumption, 50 percent of its utilised land and 80 percent of all freshwater consumed in the nation goes towards the production of food.
When you consider how much water, land and energy goes into producing food, not binning the food we buy is a very green thing to do – and probably something most of us could make some improvements in. It's a low hanging fruit (excuse the pun) of living a more environmentally friendly life and simple green actions, when multiplied by millions of people performing them, really can make a difference.
NRDC's report – Wasted: How America is Losing Up to 40 Percent of Its Food from Farm To Fork to Landfill (PDF) looks at case studies and government data on food losses and provides examples and recommendations for reducing this waste.


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Unusual primary election in PA: Masks encouraged. Many already voted. Voters split
Kim Strong
York Daily Record
Underlying the peaceful primary election at polling places across York County on Tuesday were the rumblings of unrest and agitation.
As voters carried masks into fire halls and municipal buildings, many were focused solely on one issue: the presidential race.
While President Donald Trump and former Vice President Joe Biden have no significant challengers for each of their parties, some voters showed up just to solidify their stance on who should lead the country – or who shouldn't. Magnifying the divisions are two polarizing camps about the pandemic: those who believe it's been blown out of proportion and politicized by Democrats; and others who favor caution in reopening the economy.
More:Pa. Primary: See live results from presidential, local races
It mattered little to people interviewed that protests blew up across the country through the weekend. Just one day earlier, a small protest in the City of York promised to be a precursor to Tuesday night's Black Live Matters rally, organized by two teenagers.
"This vote is not even about the last few days (of violence); this is about the past four years and the way ... the leadership has been guiding us," said Charles Culver, 59, as he tried to take his mail-in ballot to his polling place in Newberry Township.
Culver's mother just died of the novel coronavirus, so the election is even more personal for him this time. He believes that Trump could have minimized the pandemic if he had acted sooner and kept the CDC funding at the same levels as it had been previously.
"There's research that says this pandemic could have been ... at least minimized more," said Culver, who runs a nonprofit for the homeless in Baltimore.
More:A Pa. presidential primary like no other: 5 things to watch
More:Primary 2020: Who's on the ballot in central Pennsylvania?
Eleanor Lavelle, 58, wore her mask out of the Union Fire and Hose Co. in Dover Tuesday. She's required to wear it every day at work, as a construction worker.
While she understands the infection is real, she believes it's been hyped by the media.
"Now Democrats are using it to keep the current administration (Trump) in the dog house," she said, and she's not happy about that. While she knows he doesn't always say the right things the right way, she forgives him for all of that.
"I love Trump to death," she said. "I see nothing wrong with anything he's doing."
Culver, on the other hand, bristled at Monday night's photo of Trump in front of a Washington, D.C., church, holding a Bible.
"That tells me right then and there, it's not about us. It's about him," Culver said. "This is an important vote for me."
Kenneth Diaz, 50, of Manchester Township, described himself as a Native American, Christian, conservative-libertarian who voted for Trump.
America is at a crossroads, he said, and this election is a pivotal point in the country's evolution. He said that either there will be individuals with "good standards who will govern the country for the citizens ... or there will be a new revolution."
The pandemic pushed Pennsylvania's primary back 35 days, and masks were encouraged. Poll workers used masks or sat behind Plexiglas panels.
Voter turnout was slow starting off the day, in part because of the number of residents choosing mail-in ballots over in-person voting.
"It's definitely 54,000 people less people going to the polls," said York County spokesman Mark Walters about the number of registered voters who requested mail-in ballots. "There's really not that much to vote for, and I think that's just as much of a reason."
As of Tuesday morning, more than 34,000 mail-in ballots had been returned to the York County Voter Registration and Elections Office.
The distance issue
Six York city polling locations and two from the suburbs were consolidated at Memorial Hall in the York Expo Center because of the coronavirus pandemic.
Erika Bryant, who calls herself a fourth-generation poll worker, normally works at the Princess Street Center. "It's pretty difficult with moving our polls out here, and I think it's going to be a big reflection in the numbers ... being disabled, just imagine being on a city bus with the virus … and then having to get off the bus and come this far down," she said.
More:Your polling place likely moved. Here's where to go for Tuesday's primary election
Bryant describes voting at the Princess Street Center as a traditional neighborhood event that brings out people. "For me, the torch has been passed down. The people who are at the Princess Street Center are my neighbors. These people have fought in the riots, they have took care of our neighborhoods, now they are running the election polls."
"We have to do something (about the distance people travel) before the main election, for the people," she said.
"My understanding is that 30 to 40 percent of the city people do not have their personal cars ... a large percentage of minority people and older people living in the city," said Kacy French, a candidate for state representative campaigning in front of Memorial Hall.
"This puts a burden on them (getting to the polls)," she said. French did some research and figured out that a direct route from the Crispus Attucks polling place was hard to find and would drop off a person outside the fairgrounds, requiring an additional quarter-mile walk.
Slow turnout
At the York YMCA polling place, things were slow. By 9:30 a.m., just 33 had voted, according to poll workers.
Marty Glass, judge of elections for two precincts located at the Manchester Township building, said turnout in that location also was slow
"I expect a lot less (voters)," he said. "As you know, primaries are normally low turnout anyhow."
Kawoni Richardson of Manchester Township said one of the people she voted for was write-in candidate Fred Owens, who is throwing his hat in for state representative of the 47th District.
"It doesn't seem right to not have a choice," she said.
A single elderly woman sat behind a cardboard voting booth inside the New Freedom Community Center. Footsteps echoed off the auxiliary gym floor inside as volunteers migrated between tables. A few sat patiently, behind protective gear, in silence waiting for incoming voters.
"We usually have a line out the door," volunteer Mary Smith said.
Low turnouts are not unusual in primary elections, however, polls throughout southern York County experienced a slightly slower frequency than usual.
Masks, however, were plentiful.
"We haven't had any issues with voters not wearing a mask," said New Freedom election official Eric Shaffer. "We have extras in case someone needs one."
The county supplied polling locations with additional masks, sneeze guards and hand sanitizer, he said.
"We're limiting how many people we let inside at a time," said Randy Schultz, a volunteer at Hopewell Township Building in Stewartstown.
Schultz was tasked with keeping incoming voters in line outside. A lenient sense of social distancing was used between voters, who waited eagerly in line. Not much different than primary's past.
The difference this year for many polling locations throughout the southern region of the county was an absence of elderly volunteers and concerns over supplemental votes from mail-in ballots.
Several polling locations noted they had a few elderly volunteers that opted to remain at home due to health concerns amid the coronavirus pandemic.
"Seven of my people dropped out," Shrewsbury election official Daniel Pierce said.
For Pierce, he believes he'll have enough volunteers come November, but his concerns rested with provisional ballots and the elimination of single-party ticket.
"Now we don't know who voted in our district because all of the ballots are sent to the headquarters in York," Pierce said in regard to the mail-in ballots.
Voting in-person, rather than by mail
Tammy Waddell, 36, of Straban Township, Adams County, said that every time she can vote, she does.
Waddell said she also chose to come out to vote rather than doing a mail-in ballot, which was available to Pennsylvanian's this year for the first time, because she wanted to make sure her vote was done right.
"I want my vote to be counted as mine, I don't want to take the risk of someone tampering with it," Waddell said.
Many voters shared the same sentiment throughout Adams County and the Hanover area saying they were afraid of fraud and their ballot getting lost in the mail.
Paul Powers, 56, of Oxford Township, said he used to mail-in his vote when he was in the military but prefers to go in and vote.
"If I'm available, I come out to vote … it just feels like I'm actually voting," Powers said.
Adams County Voter Registration Director Angie Crouse said that the office already began counting mail-in votes as of 9 a.m. Tuesday and was hoping to have those results in by the end of the day.
Polling places also recommended that voters who went in to vote wear masks, but it was not a requirement.
Graham Boudreau, 25, of Straban Township, said that he has not been personally affected by the current pandemic, but he feels that wearing a mask is a minor inconvenience that shouldn't get in the way of preventing others of getting the virus.
"As current events show, not everything is centered around 'me,' there are lots of other people less fortunate … who am I to complain," Boudreau said.
Delayed primary
The primary in Pennsylvania, originally scheduled for April 28, moved back 35 days because of the global coronavirus pandemic.
Fifteen other states delayed their primaries as well, and several states had mail-in ballots only. Pennsylvania expanded its mail-in ballots for this primary, typically restricted to people who have a disability or illness that makes them unable to vote in person or to people who will be out of the area on election day. This time, it was offered to all registered voters as a way to encourage voting without risking public health.
That's not all that makes this primary an unusual one. For the first time, voters were encouraged to wear masks at their polling places.
More:Didn't get your mail-in ballot in time? Here's how you can still vote.
More:York and Adams head to the polls today for primary 2020 voting
The contests
The primary, which sets the stage for the General Election in November, had few contests in Pennsylvania.
The presidential race is already defined. Trump is seeking re-election on the Republican ticket, and Biden is already looking for a running mate.
Candidates for the U.S. House of Representatives were on the ballot along with state attorney general, auditor general, treasurer, and state senators and representatives.
Mail-in ballots were sent by county election offices in the months preceding this election.
Check back for updates throughout the day.
Kim Strong can be reached at kstrong@ydr.com.
Others contributing to this report: Ted Czech, Paul Kuehnel and Neil Strebig


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Music Therapy Success Stories in Mental Health: Songwriting & Song Sharing
2019 Feb.19
Our Music Therapists have meaningful experiences every day when working with their clients. We've decided to share a few of those experiences to help paint a picture of music therapy.
Making a Lasting Impact through Songwriting
I find music therapy rewarding for a lot of different reasons. Probably the most rewarding one is when I get to see that I've been a real, hopeful part of my client's journey to wellness, when they've shown me or told me that an intervention I've done, a song I've written, or a discussion I've facilitated through the music has helped them in some lasting way. I've had clients come up to me on multiple occasions and tell me that they've kept my original song lyrics because they've given them hope, a reminder that they haven't failed and can still move forward.
Earlier this year, I wrote a song with a patient, helping her to express her struggles, fears, goals, and hopes surrounding her visit to the hospital. Not only could I tell that it meant a lot to her in the moment, but when she returned to the hospital about a month later, she asked if we could sing her song again and if we could share it with the other patients on her unit. I got to see her share everything that went into her song with her peers, and see that empathy, support, and connection happen between them as well.
I feel honored to help facilitate these kinds of connections through music therapy – where patients who sometimes have difficulty orienting to reality, finding hope, or extracting themselves from their anxiety find themselves able to be in the present moment through active music making, form connections between themselves and their peers in a shared musical experience, and allow themselves to express themselves honestly in a safe, emotional way.
–Monica Moser, SCMT, MT-BC
Opening up Through Song Sharing with Adolescent Girls
With a group of adolescent girls, I proposed the idea of doing a song communication where each resident shares a song that expresses something about herself. We spent 3-4 weeks trying to get through everyone, and it was a fantastic experience.
Each resident shared a song and talked about why she chose it, then we opened up a discussion with the rest of the group on their reactions to the song. Some of the comments as we processed were very insightful and vulnerable, such as opening up about addiction or relationships, talking about wanting to turn their lives around, and so forth.
On our last week together, I asked what their favorite part of music therapy was, and on every unit, there were multiple comments stating that they loved sharing their music, and that it helped them understand each other more.
–Jared Campbell, SCMT, MT-BC
Songwriting with GarageBand with Adolescents with Autism
I worked with two units of boys who were on the autism spectrum, and one of their favorite experiences was group songwriting. We worked with GarageBand over a few weeks, putting together a soundscape they wanted, and we worked together to write lyrics that were treatment-oriented. We unfortunately ran out of time before we were able to record their songs, but the process of writing was something they were excited about, and they loved the sound/beat they put together.
8 Surprising Benefits of Drumming for Mental Health
Outcomes, Benefits and Drawbacks of Music Therapy with Special Needs Children


Shane Williams talks about why he got involved in The Rugby Site and what skills and tips he wants to pass onto players and coaches about how he plays the game. " The Rugby Site is a perfect opportunity for me to give back to the game and to share what I have learned over the years. Some of it is self taught and some of it is from coaches handed down over the years, it might not be handbook stuff but its what I believe in"
Shane Williams played 87 caps for Wales and 4 for the Lions. He is Wales' most capped winger and with 58 tries to his name is his country's leading try scorer; and third on the list of international try scorers. Shane was first selected for Wales in 2000 by Graham Henry though suffered from injury and doubts over his size in his early years in the national side. He recovered from both and was part of the Wales Grand Slam winning sides of 2005 and 2008, and was named IRB Player of the Year in 2008. The diminutive winger became the darling of the Cardiff crowd as he sidestepped his way around the best defences in the world. Shane retired from international rugby in 2011 and will finish his playing career with the Ospreys at the end of the 2012 season.
Youth and stamina should carry Wales to a Grand Slam despite their poor recent record at home to France.
Shane Williams reflects on the great players who made him want to run down to his local field and pretend he was side stepping for Wales.
Shane Williams explains why a Wales Grand Slam this year would mean far more than when they last triumphed in 2005 and 2008.
Shane Williams breaks the sidestep down, taking you through his skill checklist and showing you how the ball carrier and support runners can manipulate defenders and defensive lines to beat and unlock them. Watch and learn direct from one of the best attacking players the game of rugby has ever seen.
Shane Williams says that Wales will dig out a rare Twickenham victory by exploiting England's lack of a genuine openside.


text:
Synthesis of 4-(2-fluorophenyl)-7-methoxycoumarin: experimental and computational evidence for intramolecular and intermolecular C–F···H–C bonds
Vuyisa Mzozoyana ,
Fanie R. van Heerden and
Craig Grimmer
Vuyisa Mzozoyana
School of Chemistry and Physics, University of KwaZulu-Natal, Private Bag X01, Scottsville, 3209, Pietermaritzburg, South Africa
Fanie R. van Heerden
Associate Editor: J. A. Murphy
Received 16 Oct 2019, Accepted 04 Feb 2020, Published 10 Feb 2020
A non-peer-reviewed version of this article has been posted as a preprint https://doi.org/10.3762/bxiv.2019.124.v1
4-(2-Fluorophenyl)-7-methoxycoumarin (6) was synthesized by Pechmann reaction under mild conditions via a three-step reaction. The solution-state 1H NMR spectra of 6 showed a strong intramolecular interaction between F and H5 (JFH = 2.6 Hz) and 13C NMR suggested that this C–F···H–C coupling is a through-space interaction. The 2D 19F-{1H} HOESY and 1H-{19F} 1D experiments were done to confirm this F···H interaction. The single crystal X-ray structure and the DFT-optimized structure showed that the fluorinated phenyl ring favors the orientation with the fluorine atom closer to H5 than H3. The X-ray structure also showed the existence of the intermolecular C–F···H–C interaction.
Keywords: DFT; F···H hydrogen bond; fluorinated phenylcoumarin; Pechmann reaction; through-space coupling
Coumarins constitute one of the big classes of naturally occurring compounds. The first coumarin was isolated from the tonka bean (Dipteryx odorata) in 1820 and, to date, more than 1300 coumarins have been identified from natural sources [1,2]. Coumarins have been reported to play a vital role as food and cosmetics constituents, cigarette additives, and dye-sensitized solar cells [3,4]. In addition, coumarins possess some biological activities such as anti-inflammatory [5], antitumor [6], anti-oxidant [7], antibacterial [8], hepatoprotective, anticoagulant, antiviral and antithrombotic activities [9]. The variety of uses of these compounds resulted in an increase in demand for large quantities of coumarins. Due to an insufficient natural supply to meet this demand for these compounds, numerous methods for the synthesis of these compounds have been developed, examples are the Pechmann condensation [10,11], Stille coupling reaction [12], Knoevenagel condensation [13], Heck coupling reaction [14], Kostanecki reaction, Baylis–Hillman reaction [15], Michael reaction [16], Suzuki–Miyaura cross-coupling reaction [17], Negishi cross-coupling reaction [18] and Wittig reaction [17]. The concept of the incorporation of fluorine into organic molecules has gained much interest since Fried and Sabo reported the improvement of the therapeutic index of cortisol by the incorporation of a fluorine atom in the 9α position of the structure [19]. Since then, the fluorine-containing drugs have come onto the market and they are amongst the best-selling pharmaceutical drugs, including Lipitor®, Prevacid®, Advair Discus® and Lexapro® [20-22]. The incorporation of fluorine may improve the activity of biologically active compounds as it imparts a variety of properties such as enhanced binding interaction, metabolic stability, and reaction selectivity by changing physical and chemical properties [23-26].
Hydrogen bonds (HBs) are associated with highly electronegative atoms (oxygen, nitrogen, fluorine) and have been observed to govern the conformational structure of some molecules as well as the alignment of the molecules within a crystal structure [27-29]. Moreover, HBs have been reported to play a vital role in a ligand–receptor interaction that determines the biological activity of a molecule. Oxygen and nitrogen have been proven to be good hydrogen-bond acceptors which form strong intermolecular and intramolecular hydrogen bonds, however, fluorine is still denied hydrogen-bond acceptor status by some scientists.
There is evidence of the existence of C–F···H interaction in organic molecules [30,31]. Early reports by Glusker and co-workers in 1983 and 1994 showed C–F···H interactions in structures found in the Cambridge Crystallographic Data Centre database [32]. Similar evidence was reported by Howard, O'Hagan, Desiraju and their co-workers where the C–F···H interaction was observed, although the conclusions of the two groups were different – O'Hagan et al. concluded that fluorine is not a good hydrogen-bond acceptor, whereas Desiraju et al. concluded that the interaction has genuine hydrogen-bond character [24,33-36].
The C–F···H–C interaction is amongst the weakest of hydrogen bonding phenomena because a carbon acid (C–H) is weak, therefore is a weak donor, and the acceptor is non-polarizable, therefore is a poor acceptor [34-36]. Wang and co-workers reported the existence of the C–F···H–C intramolecular hydrogen bond in the structure of aromatic triazole foldmers [37]. In their study, using crystallographic and DFT data, they concluded that their folded conformers are held by C–F···H–C hydrogen bonds. To further these studies, we have synthesized a fluorine-containing phenylcoumarin in order to study the fluorine-hydrogen bond. The crystal structure and solution-state NMR data of the coumarin 6 were studied to examine any C–F···H–C hydrogen bond interactions. DFT calculations were performed to determine the preferred conformations of the structure that might exhibit a C–F···H–C hydrogen bond.
Synthesis of 2-fluorophenylcoumarin 6
4-(2-Fluorophenyl)-7-methoxycoumarin (6) was synthesized under mild conditions via a three-step reaction (Scheme 1) and the first step was the synthesis of the fluorinated β-keto ester 3. Methyl acetoacetate (2) was treated with MgCl2, Et3N and n-BuLi in DCM and then with 2-fluorobenzoyl chloride (1) to yield methyl 2-fluorobenzoylacetate (3) [38,39]. These reactions are very rare in the literature, however, there are similar reactions for the synthesis of β-keto esters as reported by Sijbesma et al. [40] and Anwar [41]. The second step of the synthesis was the Pechmann reaction, commonly used for the synthesis of coumarins [42,43]. Methyl 2-fluorobenzoylacetate (3) was reacted with resorcinol (4) in the presence of H2SO4 at 35 °C, and 7-hydroxy-4-(2-fluorophenyl)coumarin (5) [39,44] was obtained as a light yellow solid. The last step of the synthesis was the methylation of the hydroxy group of coumarin 5 with dimethyl sulfate, to form 4-(2-fluorophenyl)-7-methoxycoumarin (6).
Scheme 1: Synthesis of 4-(2-fluorophenyl)-7-methoxycoumarin (6).
During the synthesis of coumarin 6, solution-state NMR spectroscopy was used to characterize compounds 3, 5, and 6 (1H and 13C spectra are available in Supporting Information File 1). The 1H spectrum of coumarin 6 showed H···F interactions for H3′, H4′, H5′ and H6′ which is typical through-bond (TB) coupling. However, the peaks that caught our particular attention were the singlet peak at 6.25 ppm and a doublet-of-doublets (dd) peak at 7.16 ppm assigned to H3 and H5, respectively (Figure 1). The H5 signal was expected to be a doublet (not a dd) due to 3J coupling to H6, since an H,H-COSY experiment does not show coupling between H5 and H8 (Figure S9, Supporting Information File 1). It became clear that the splitting of the signal from H5 was due to coupling with the 19F atom by comparing the spectra from the 1H and 1H-{19F} experiments (Figure 1) which showed the H5 peak as a doublet with 19F decoupling. While the doublet-of-doublets signal for H5 collapses into a doublet with 19F decoupling, there are no significant changes in the line-shape for the signal of H3 with 19F decoupling (Figure 1).
To determine whether the observation of 19F–H5 coupling for coumarin 6 was a solvent dependent phenomenon, a comparison was made between the 1H and 1H-{19F} spectra in CDCl3 and acetone-d6. Splitting of the H5 signal was observed in both solvents (Figure 1) suggesting that the 19F–H5 coupling for coumarin 6 is solvent independent. A literature report of the NMR characterization of a structurally similar 7-hydroxycoumarin performed in DMSO-d6 has the signal for H5 reported as a singlet [44].
Figure 1: 1H NMR spectra for the "aromatic" region of coumarin 6; comparison of 1H spectrum and 1H-{19F} spectrum in CDCl3 and 1H spectrum and 1H-{19F} spectrum in acetone-d6.
Figure 1: 1H NMR spectra for the "aromatic" region of coumarin 6; comparison of 1H spectrum and 1H-{19F} spec...
Since coumarins 6 and 5 have similar structure, the only difference is at position seven, 6 has a methoxy group while 5 has a hydroxy group, a similar study was carried out for coumarin 5 (Figure S10b, Supporting Information File 1).
The question posed at this point was "is this a through-bond (TB) or through-space (TS) effect"?
To answer this question, we analysed a 13C-{1H} spectrum of coumarin 6 dissolved in CDCl3 and the signal corresponding to C5 was found to be a doublet (J = 1.4 Hz) but the signals corresponding to C4 and C4a were singlets, and this indicates that this coupling is not a TB effect, because if it were a TB effect, the signals for C4 and C4a would also likely be split. Similar splitting of C5 was observed in coumarin 5, also in different solvents as shown in Figure 2 and there was no splitting of the signals corresponding to C4 and C4a as shown in Figures S22 and S21 (Supporting Information File 1). These observations were not found in the similar derivatives of coumarin 5 (7-hydroxy-4-(3-fluorophenyl)coumarin and 7-hydroxy-4-(4-fluorophenyl)coumarin) found in the literature where the fluorine atom is in the third (C3') and the fourth (C4') position, respectively, of the phenyl ring [39]. The spectra for these derivatives showed an H5 signal as a doublet (not doublet-of-doublets as observed in coumarin 5 and 6) and C5 as a singlet, indicating that they do not possess the through-space F···H5 or/and F···C5 coupling since the fluorine atom is a bit further away from H5 and C5.
Figure 2: 13C NMR spectra for coumarin 5 and 6; showing the splitting of the signal corresponding to C5.
To confirm our findings, we further ran a 19F,1H-HOESY experiment and it showed clear H5···19F and H3···19F coupling (Figure 3). Evidence of a HOESY interaction between H5···19F and H3···19F indicates that neither the H3···19F nor the H5···19F interaction limits the C4–C1′ bond rotation.
Figure 3: 19F,1H-HOESY NMR spectrum for coumarin 6 illustrating two through-space interactions.
The geometry of coumarin 6 (single molecule, gas phase) was optimized using the B3LYP functional and the 6-311G basis set, as implemented in Gaussian-09W (Rev. C.01) [45]. The superposition of the single-crystal X-ray structure (red) and the optimized structure (green) is shown in Figure 4.
Figure 4: Superposition of single-crystal X-ray structure (red) and DFT-optimized structure (green); RMSD 0.3 Å (hydrogen atoms omitted for clarity).
Figure 4: Superposition of single-crystal X-ray structure (red) and DFT-optimized structure (green); RMSD 0.3...
The DFT optimized geometric structure is shown in Figure 5 and has a dihedral angle, Φ (C2'–C1'–C4–C4a) of 65.3°. Following the optimization, the dihedral angle Φ was varied through a 360° rotation to examine the effect of changing the relative position of the fluorinated ring and the energy profile for this variation is shown in Figure 6. When Φ = 5°, the F···H5 distance is at its shortest (dF···H5 = 2.0 Å) and the fluorinated ring is almost coplanar with the coumarin ring, and the molecule is at its least stable conformation due to the electron–electron (e–e) repulsion of H5 and fluorine. The second least stable conformation is found at Φ = 185°, with the fluorine atom and H3 in close proximity (dF···H3 = 2.0 Å).
Figure 5: DFT-optimized structure for coumarin (6).
Figure 6: Plots of relative energy (black trace, no units), interatomic distance F–H5 (red trace, Å), interatomic distance F–H3 (blue trace, Å) as a function of dihedral angle Φ C2'–C1'–C4–C4a (°).
Figure 6: Plots of relative energy (black trace, no units), interatomic distance F–H5 (red trace, Å), interat...
Examples of through-space coupling between fluorine and hydrogen atoms in organic molecules are reported in the chemical literature [46,47], with magnitudes as large as 7 Hz for 7JHF [46]
One report of TS-coupling between F and H atoms comments that "...it appears that significant coupling only occurs when the proton–fluorine closest approach distance is within the sum of the van der Waals radii of hydrogen and fluorine (c. 2.55 Å)..." [47]. During rotation of the fluorophenyl ring (Figure 6), the F–H distance (for both F–H5 and F–H3) varies between 2 and 5 Å, so for some part of the rotation, both the distances F–H5 and F–H3 fall inside the limit of ≈2.55 Å, although not simultaneously. For a fixed geometry like that of the crystal structure, this would suggest that through-space F–H coupling would be observed between F and H5 but not between F and H3, as in Figure 1, where there is an obvious change to the shape of the signal corresponding to H5 but a negligible change to the shape of the signal corresponding to H3, with the application of {19F} decoupling. However, the F–H HOESY spectrum in Figure 3 shows coupling between the fluorine atom and both H5 and H3. The authors interpretation of these observations (Figure 1 and Figure 3) is that, in solution, rotation of the fluorophenyl ring (about C4–C1') is permitted but that the average geometry of coumarin 6 has the fluorine atom closer to H5 than H3.
The theoretical NMR data for twenty-four conformations of coumarin 6 were obtained from Gaussian 09W (Rev C.01) at the B3LYP/6-311G level. Geometry optimization and calculation of NMR parameters for TMS and CCl3F at the same level provided reference chemical shifts for 1H, 13C, and 19F. The chemical shifts for the lowest energy structure (Φ = 65.3°) and the most unstable conformer (Φ = 5°) are used as examples (Table 1). The theoretical chemical shifts for the carbons appeared to be shifted downfield relative to the experimental carbon peaks (for both stable and unstable conformers) as shown by 'change' (Δ = −ve, experimental − theoretical) in Table 1.
Table 1: Experimental and theoretical (gas phase) 1H and 13C chemical shift (δ) for atoms within six bonds from fluorine for coumarin 6 and RSMD values.
Atom Exp Φ = 65.3° a Φ = 5° b
C/H δ (ppm) δ (ppm) Δ(ppm)c δ (ppm) Δ(ppm)c
C2 160.9 169.1 −8.2 170.1 −9.2
H3 6.25 6.00 0.25 6.75 −0.50
C4a 112.4 120.8 −8.4 120.2 −7.8
C5 127.8 135.0 −7.2 139.2 −11.4
C1' 123.2 135.2 −12.0 130.6 −7.4
C2' 159.1 172.8 −13.7 173.7 −14.6
C3' 116.3 123.0 −6.7 126.8 −10.5
H3' 7.29 7.20 0.09 7.30 −0.01
C4' 131.5 137.5 −6.0 138.6 −7.1
H4' 7.50 7.52 −0.02 7.46 0.04
H5' 7.35 7.37 −0.02 7.39 −0.04
RMSD values 13C NMR = 8.84 ppm
1H NMR = 0.138 ppm 13C NMR = 8.79 ppm
1H NMR = 0.569 ppm
aConformer with Φ = 65 °. bConformer with Φ = 5 °. cExperimental – theoretical, e.g., C2: 160.9 − 169.1 = −8.2 ppm.
Comparing the experimental and the calculated 13C NMR chemical shifts for both the optimized and least-stable DFT-generated conformations, the RMSD values were found to be 8.84 ppm and 8.79 ppm, respectively. The RMSD value for the calculated 1H NMR chemical shifts of the optimized conformer was found to be substantially smaller (RMSD = 0.14 ppm) than that for the least-stable conformer (RMSD = 0.57 ppm).
The theoretical coupling constants at the same 24 geometries from geometry scan for coumarin 6 were obtained using the same functional and level of theory (B3LYP/6-311G). The coupling constants (F···C or F···H) for selected nuclei of interest were obtained using a scaling factor calculated from the observed and calculated 1JFC value for CFCl3 [48]. Selected graphs of the plots of nJFH and nJFC as a function of rotation of the fluorophenyl ring are included in Supporting Information File 1.
Figures S18 and S19 show the magnitude of 5JFH and 6JFH between the fluorine atom and H3 and H5, respectively. It can be seen that, at the B3LYP/6-311G) level, when coupling between F and either H3 or H5 is large enough to be observed in an NMR spectrum (magnitude ≈1–11 Hz for H5, ≈1–5 Hz for H3), coupling to the other nucleus is near zero and may not necessarily be observed. This is consistent with the idea of an average angle in solution that places the fluorine atom closer to H5 than H3, since F–H5 coupling is obvious in the experimental NMR spectrum (Figure 1), while F–H3 coupling is not. A similar prediction is made for coupling between F–C5 and F–C3 (Figures S14 and S17 in Supporting Information File 1). At angles that would manifest in an experimental F–H5 coupling of ≈2.5 Hz, with near-zero F–H3 coupling, Gaussian predicts small F–C coupling to both C5 and C3. This is consistent with the experimental observation of 5JFC ≈ 1.4 Hz between F and C5 and no observed coupling between F and C3, in the 13C-{1H} spectrum. Gaussian also predicts F–C coupling between the fluorine atom and carbons C4 and C4a, magnitude <1 Hz and 1–1.5 Hz, respectively. While the <1 Hz F–C4 coupling might not be noticeable in the 13C-{1H} spectrum, it should be possible to see F–C4a coupling of 1–1.5 Hz, since the F–C5 coupling is observable at a similar magnitude. The model (B3LYP/6-311G) seems to work reasonably well for coupling between F and H3, H5, C3, C4, and C5 but not for C4a.
The single crystal X-ray analysis of coumarin 6 was carried out as it has not been reported previously [CCDC No.: 1868146]. The crystals of 6 were obtained by slow evaporation of methanol/dichloromethane and were found to be of the monoclinic crystal system with space group C2/c (Figure 7).
The crystal structure shows that the fluorinated phenyl ring is at a torsion angle (Φ, C2'–C1'–C4–C4a angle) of 54.44° to the coumarin moiety. The F···H5 TS-distance of 2.547 Å is small enough to induce some rotational constraint on the C4 and C1' bond, as the constraint was observed at an F···H distance of 2.9 Å [37]. The short contact interactions show that there are C–F···H–C intermolecular interactions to the neighboring molecules (F–H6 and F–H5; different molecules) that play a crucial role in crystal packing (Figure 7).
Figure 7: Short contacts within the single-crystal X-ray structure of coumarin 6.
As mentioned above, the structure of coumarin 6 was optimized and the dihedral angle, Φ (C2'–C1'–C4–C4a) was found to be 65.3° (Figure 5), which is comparible close to that found in the crystal structure (Φ = 54.4°). The TS distance between F and H5 for the optimized structure is 2.807 Å which is relatively close to that of the crystal structure (2.547 Å). Selected comparisons are shown in Table 2.
Table 2: Comparison of some features of the X-ray crystal structure and DFT optimized structure of 6: Through-space (TS) and dihedral angle (Φ).
Run TS distance (Å) Dihedral angle (°)
F···H5 F···C5 H6···H3 Φ
6 (exp) 2.547 2.934 2.535 54.44
6 (DFT) 2.807 3.174 2.874 65.27
difference 0.260 0.24 0.339 10.83
The synthesis of 4-(2-fluorophenyl)-7-methoxycoumarin (6) via the Pechmann reaction was successful. The solution-state 1H and 13C NMR spectra of 6 showed that there is a strong intramolecular interaction between F and H5 (JFH = 2.6 Hz) and suggest that this interaction is through-space C–F···H–C coupling, since C5 is coupled to F (JFC = 1.4 Hz) whereas C4 and C4a are not. The 2D HOESY spectrum shows the F···H5 coupling and also F···H3 coupling, seemingly weaker than F···H5 since splitting of the H3 signal is not observed in the 1H and 1H-{19F} 1D spectra. The single crystal X-ray structure showed that the fluorinated phenyl ring is orientated in a manner that brings the fluorine atom closer to H5 than H3. The same orientation was observed in the DFT-optimized (B3LYP/6-311G) structure. The X-ray data also showed the intermolecular C–F···H–C interactions which, together with other interactions, are resposible for the crystal packing.
All reagents (including solvents) were purchased from the chemical suppliers Aldrich, Fluka and Merck. For all moisture-sensitive reactions, the glassware was thoroughly dried in an oven at ca. 140 °C for 12 h prior to use, and anhydrous solvents were used under inert conditions. Qualitative thin-layer chromatography (TLC, silica gel 60254, aluminum backed) was used to monitor the reactions. Visualization of the TLC plates was achieved using an iodine tank and/or fluorescence on exposure to short wavelength ultraviolet light (254 nm). For purification, column chromatography (silica gel 60, 0.040–0.063 mm) or centrifugal chromatography conducted on a Harrison Research Chromatotron model 7924T (glass plates coated with silica gel 60 PF254 containing gypsum, 2 and 4 mm thick layer) was used.
Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker Avance 400 spectrometer equipped with a 5 mm BBOZ probe at frequencies of 400 MHz, 100 MHz, and 376 MHz for 1H, 13C, and 19F, respectively. High-resolution mass spectrometry (HRMS) was performed on a Waters LCT Premier time-of-flight mass spectrometer.
Synthesis of methyl 2-fluorobenzoylacetate (3): To a stirred mixture of MgCl2 (2.0 g, 21 mmol) and Et3N (2.1 g, 21 mmol) in dry DCM (15 mL) at room temperature, methyl acetoacetate (2, 2.0 g, 17 mmol) was added slowly. The mixture was stirred for 30 min before the temperature was reduced to 0 °C. n-BuLi (20 mL of a 1.6 M in hexane, 32 mmol) was added slowly into the mixture and the mixture was stirred for a further 30 min. 2-Fluorobenzoyl chloride (1, 2.7 g, 17 mmol) was added dropwise into the mixture and the mixture was stirred for 15 min. The reaction mixture was allowed to reach room temperature and was stirred overnight. To the reaction, was added 5 M HCl (8 mL) and distilled water (10 mL) and the mixture was extracted with DCM (3 × 30 mL). The organic layer was dried over anhydrous MgSO4 and the solvent was removed in vacuo. The resulting yellow product was purified by silica gel column chromatography with 10% EtOAc in hexane as eluent and 3 was obtained as a light orange viscous liquid (2.7 g, 81%), TLC Rf 0.50 (hexane/EtOAc, 9:1). 1H NMR (400 MHz, CDCl3) 3.76 (s, 3H, H4), 4.01 (d, 1hJH,F = 3.4 Hz, 2H, H2), 7.15 (ddd, 3JH,F = 12.1 Hz, 3JH,H = 8.5 Hz, 4JH,H = 1.0 Hz, 1H, H3'), 7.26 (t, 3JH,H = 7.6 Hz, 1H, H5'), 7.57 (m, 1H, H4'), 7.95 (ddd, 3JH,H = 7.6 Hz, 4JH,F = 6.2 Hz, 4JH,H = 1.9 Hz, 1H, H6'); 13C NMR (100 MHz, CDCl3) 49.6 (d, 2hJC,F = 8.1 Hz, C2), 52.3 (C4), 116.7 (d, 2JC,F = 24.1 Hz, C3'), 124.7 (d, 3JC,F = 2.9 Hz, C6'), 129.3 (d, 2JC,F = 21.7 Hz, C1'), 131.0 (d, 4JC,F = 2.3 Hz, C5'), 135.5 (d, 3JC,F = 9.6 Hz, C4'), 162.2 (d, 1JC,F = 254.3 Hz, C2'), 167.8 (d, 3hJC,F = 3.0 Hz, C3), 190.1 (d, TSJC,F = 3.7 Hz, C1).
Synthesis of 7-hydroxy-4-(2-fluorophenyl)coumarin (5): To a mixture of resorcinol (2.0 g, 18 mmol) and methyl 2-fluorobenzoylacetate (3.5 g, 18 mmol) was added H2SO4 (8 mL, 75%). The temperature of a stirred mixture was increased to 35 °C. After stirring for 5 h, the mixture was poured into crushed ice and neutralized with a NaOH solution. The mixture was filtered under vacuum and the residue was washed with plenty of water. The resulting product was purified by silica gel column chromatography with 60% EtOAc in hexane as eluent and 5 was obtained as a light yellow solid (4.2 g, 91%), mp 204–207 °C, TLC Rf 0.45 (hexane/EtOAc, 2:3). 1H NMR (400 MHz, DMSO-d6) 6.24 (s, 1H, H3), 6.77 (dd, 3JH,H = 8.6 Hz, 4JH,H = 2.4 Hz, 1H, H6), 6.81 (d, 4JH,H = 2.4 Hz, 1H, H8), 7.03 (dd, 3JH,H = 8.6 Hz, 1hJH,F = 2.6 Hz, 1H, H5), 7.37–7.45 (m, 2H, H3', H6'), 7.50 (td, 3JH,H = 7.5 Hz, 4JH,H = 1.8 Hz, 1H, H5'), 7.61 (m, 1H, H4'), 10.67 (s, 1H, OH); 13C NMR (100 MHz, DMSO-d6) 102.6 (C8), 110.7 (C4a), 112.1 (C3), 113.4 (C6), 116.1 (d, 2JC,F = 21.3 Hz, C3'), 122.7 (d, 2JC,F = 15.3 Hz, C1'), 125.2 (d, 3JC,F = 3.6 Hz, C6'), 127.9 (d, 2hJC,F = 1.6 Hz, C5), 130.8 (d, 4JC,F = 2.9 Hz, C5'), 132.0 (d, 3JC,F = 8.2 Hz, C4'), 150.3 (C4), 155.2 (C8a), 158.6 (d, 1JC,F = 248.6 Hz, C2'), 160.0 (C2), 161.6 (C7); HRMS–ESI+ (m/z): [M + Na]+ calcd for C15H9O3FNa, 279.0433; found, 279.0437,
Synthesis of 4-(2-fluorophenyl)-7-methoxycoumarin (6): A mixture of 7-hydroxy-4-(2-fluorophenyl)coumarin (5 ,0.77 g, 3.0 mmol), dimethyl sulfate (0.76 g, 6.0 mmol) and K2CO3 (0.83 g, 6.0 mmol) was refluxed in acetone (20 mL) for 4 h. The reaction mixture was cooled to room temperature and and brine (50 mL) was added then extracted with ethyl acetate (3 × 40 mL). The organic layer was dried over anhydrous MgSO4 and the solvent was removed in vacuo. The resulting light yellow product was purified by silica gel column chromatography with 60% EtOAc in hexane as eluent and 6 was obtained as a yellow crystalline solid (0.78 g, 2.9 mmol, 97%), mp 167–170 ºC, TLC Rf 0.54 (hexanes/EtOAc, 3:2). 1H NMR (400 MHz, CDCl3) 3.88 (s, 3H, OMe), 6.25 (s, 1H, H3), 6.79 (dd, 3JH,H = 8.9 Hz, 4JH,H = 2.5 Hz, 1H, H6), 6.89 (d, 4JH,H = 2.5 Hz, 1H, H8), 7.16 (dd, 3JH,H = 8.9 Hz, 1hJH,F = 2.5 Hz, 1H, H5), 7.23 (dd, 3JH,H = 7.8 Hz, 4JH,F = 4.5 Hz, 1H, H6'), 7.29 (td, 3JH,H = 3JH,F = 7.8 Hz, 4JH,H = 1.8 Hz, 1H, H3'), 7.35 (td 3JH,H = 7.8 Hz, 4JH,H = 1.8 Hz, 1H, H5'), 7.50 (m, 1H, H4'); 13C NMR (100 MHz, CDCl3) 55.8 (OMe), 101.0 (C8), 112.4 (C4a), 112.5 (C3), 113.5 (C6), 116.3 (d, 2JC,F = 21.9 Hz, C3'), 123.2 (d, 2JC,F = 15.4 Hz, C1'), 124.7 (d, 3JC,F = 3.7 Hz, C6'), 127.8 (d, 2hJC,F = 1.4 Hz, C5), 130.5 (d, 4JC,F = 3.1 Hz, C5'), 131.5 (d, 3JC,F = 7.9 Hz, C4'), 150.5 (C4), 155.7 (C8a), 159.1 (d, 1JC,F = 250.0 Hz, C2'), 160.9 (C2), 163.0 (C7). HRMS–ESI+ (m/z): [M + Na]+ calcd for C16H11O3FNa, 293.0590; found, 293.0587.
Supporting Information File 1: Copies of NMR spectra for compound 3, 5 and 6, single crystal X-ray data for compound 6, Gaussian calculation data of J-values for compound 6 and HRMS for compound 6.
The authors would like to acknowledge the Ph.D. thesis by Vuyisa Mzozoyana (University of KwaZulu-Natal, South Africa) as the main source of this work. The authors would like to thank Dr Rainner Kerssebaum of Bruker-DE for his kind assistance with the programming of a gradient HOESY experiment compatible with Topspin 2.1.
The authors gratefully acknowledge National Research Foundation (South Africa) and the University of KwaZulu-Natal for financial assistance.
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1. Lin, M.-H.; Chou, Y.-S.; Tsai, Y.-J.; Chou, D.-S. J. Exp. Clin. Med. 2011, 3, 126–131. doi:10.1016/j.jecm.2011.04.006
2. Hoult, J. R. S.; Payá, M. Gen. Pharmacol.: Vasc. Syst. 1996, 27, 713–722. doi:10.1016/0306-3623(95)02112-4
7. Vukovic, N.; Sukdolak, S.; Solujic, S.; Niciforovic, N. Arch. Pharmacal Res. 2010, 33, 5–15. doi:10.1007/s12272-010-2220-z
18. Wu, J.; Liao, Y.; Yang, Z. J. Org. Chem. 2001, 66, 3642–3645. doi:10.1021/jo0102157
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6. Marchenko, M. M.; Kopyl'chuk, G. P.; Shmarakov, I. A.; Ketsa, O. V.; Kushnir, V. N. Pharm. Chem. J. 2006, 40, 296–297. doi:10.1007/s11094-006-0113-8
17. Jung, J.-W.; Kim, N.-J.; Yun, H.; Han, Y. T. Molecules 2018, 23, 2417. doi:10.3390/molecules23102417
37. Shang, J.; Gallagher, N. M.; Bie, F.; Li, Q.; Che, Y.; Wang, Y.; Jiang, H. J. Org. Chem. 2014, 79, 5134–5144. doi:10.1021/jo500582c
5. Emmanuel-Giota, A. A.; Fylaktakidou, K. C.; Litinas, K. E.; Nicolaides, D. N.; Hadjipavlou-Litina, D. J. J. Heterocycl. Chem. 2001, 38, 717–722. doi:10.1002/jhet.5570380329
16. Ray, S. K.; Singh, P. K.; Molleti, N.; Singh, V. K. J. Org. Chem. 2012, 77, 8802–8808. doi:10.1021/jo301513x
46. Agranat, I.; Rabinovitz, M.; Gosnay, I.; Weitzen-Dagan, A. J. Am. Chem. Soc. 1972, 94, 2889–2891. doi:10.1021/ja00763a074
3. Hara, K.; Sayama, K.; Ohga, Y.; Shinpo, A.; Suga, S.; Arakawa, H. Chem. Commun. 2001, 569–570. doi:10.1039/b010058g
4. Givel, M. Tob. Control 2003, 12, 401–405. doi:10.1136/tc.12.4.401
47. Adcock, W.; Rizvi, S. Aust. J. Chem. 1973, 26, 2659–2663. doi:10.1071/ch9732659
12. Cherry, K.; Parrain, J.-L.; Thibonnet, J.; Duchêne, A.; Abarbri, M. J. Org. Chem. 2005, 70, 6669–6675. doi:10.1021/jo050638z
14. Barancelli, D. A.; Salles, A. G., Jr.; Taylor, J. G.; Correia, C. R. D. Org. Lett. 2012, 14, 6036–6039. doi:10.1021/ol302923f
45. Gaussian 16, Revision C.01; Gaussian, Inc.: Wallingford, CT, 2016.
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15. Kaye, P. T.; Musa, M. A. Synthesis 2002, 2701–2706. doi:10.1055/s-2002-35984
9. Jung, K.; Park, Y.-J.; Ryu, J.-S. Synth. Commun. 2008, 38, 4395–4406. doi:10.1080/00397910802369513
8. Basanagouda, M.; Kulkarni, M. V.; Sharma, D.; Gupta, V. K.; Pranesha; Sandhyarani, P.; Rasal, V. P. J. Chem. Sci. 2009, 121, 485–495. doi:10.1007/s12039-009-0058-z
13. Heravi, M. M.; Hekmatshoar, R.; Emamgholizadeh, M. Phosphorus, Sulfur Silicon Relat. Elem. 2004, 179, 1893–1896. doi:10.1080/10426500490466814
23. Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320–330. doi:10.1039/b610213c
24. O'Hagan, D. Chem. Soc. Rev. 2008, 37, 308–319. doi:10.1039/b711844a
25. Isanbor, C.; O'Hagan, D. J. Fluorine Chem. 2006, 127, 303–319. doi:10.1016/j.jfluchem.2006.01.011
26. Kirk, K. L. J. Fluorine Chem. 2006, 127, 1013–1029. doi:10.1016/j.jfluchem.2006.06.007
19. Fried, J.; Sabo, E. F. J. Am. Chem. Soc. 1954, 76, 1455–1456. doi:10.1021/ja01634a101
20. Hagmann, W. K. J. Med. Chem. 2008, 51, 4359–4369. doi:10.1021/jm800219f
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22. Gether, U.; Andersen, P. H.; Larsson, O. M.; Schousboe, A. Trends Pharmacol. Sci. 2006, 27, 375–383. doi:10.1016/j.tips.2006.05.003
38. Jeon, M.-K.; Kim, K. Tetrahedron 1999, 55, 9651–9667. doi:10.1016/s0040-4020(99)00585-2
40. Hirschberg, J. H. K. K.; Koevoets, R. A.; Sijbesma, R. P.; Meijer, E. W. Chem. – Eur. J. 2003, 9, 4222–4231. doi:10.1002/chem.200204495
34. Howard, J. A. K.; Hoy, V. J.; O'Hagan, D.; Smith, G. T. Tetrahedron 1996, 52, 12613–12622. doi:10.1016/0040-4020(96)00749-1
35. Pedireddi, V. R.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1992, 988–990. doi:10.1039/c39920000988
36. Thakur, T. S.; Kirchner, M. T.; Bläser, D.; Boese, R.; Desiraju, G. R. CrystEngComm 2010, 12, 2079–2085. doi:10.1039/b925082d
32. Murray-Rust, P.; Stallings, W. C.; Monti, C. T.; Preston, R. K.; Glusker, J. P. J. Am. Chem. Soc. 1983, 105, 3206–3214. doi:10.1021/ja00348a041
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Mzozoyana, V.; van Heerden, F. R.; Grimmer, C. Beilstein J. Org. Chem. 2020, 16, 190–199. doi:10.3762/bjoc.16.22


Upping an arm's race on MBA scholarship aid, Harvard Business School said it is handing out a record $32 million to MBA candidates this year, up 10% from $29 million in fiscal 2013. It is the fifth year in a row that HBS has increased fellowship spending.
Dean Nitin Nohria disclosed the number to Poets&Quants in a recent appearance in San Francisco. The increase in fellowship payouts to MBA students this year will grow at twice the pace of the 5% increase in annual tuition, which is now $56,175. Only four years ago, fellowship spending on MBA students was $25 million. If fellowship spending to doctoral candidates and executive education participants are included in the number, it is even higher: $40 million last year.
No other business school in the world provides more fellowship support than Harvard, though its reputation and prestige means that most applicants would gladly go there even if it meant borrowing more than $100,000 to get their MBA. In contrast, most other U.S. and European business schools have fellowship aid that is generally in the single digits. INSEAD, with an annual intake of 1,024 students vs. HBS' 932, has $4.1 million in annual scholarship aid, with the average grant at $18,350.
HBS, of course, can afford its generosity. Harvard Business School achieved strong financial results in fiscal 2013, with revenues, operating margins, and gift income all coming in higher than expected. HBS reported record revenue of $587 million, up more than seven percent from $546 million in fiscal 2012 (See chart on following page). Most of the revenue gains occurred in the school's publishing and executive education units which account for nearly 56 percent of its revenue and an even larger percentage of its operating income.
The school's publishing revenue for fiscal 2013 increased by $15 million, or nine percent, to $180 million from fiscal 2012, exceeding the school's forecast by three percent. HBS said it sold a record 11,448,076 case studies last year, a significant increase over the 10,603,000 a year earlier. Driven primarily by tuition increases, Executive Education revenue grew by $4 million to $146 million, or three percent, from fiscal 2012, exceeding the school's fiscal 2013 budget by four percent.


Are you new to Canada and British Columbia? Then Columbia Chrysler is the dealership you are looking for to help you get your new or used vehicle. It can be really daunting to get financing as a newcomer, but there is no need to worry, we will get you approved! We are proud to offer BC's best car buying experience! Columbia Chrysler caters to Richmond's domestic vehicle clientele as a new and used retailer for Dodge, Chrysler, Jeep, Ram and Fiat. As a branch of the Go Auto Group, our industry-leading buying power allows us to offer you the most selection, the lowest prices, and the highest quality in the Richmond new and used car market. Visit our dealership to experience the commitment and care of our sales staff. At Columbia Chrysler, we are always happy to help!!


Correct is another key. Eat foods that are really rich in protein and consequently vitamins to strengthen at the very least and give you a lot more energy when doing some exercises. Jack your own protein intake since the actual uses protein in the muscle repair process.
During exercise your biceps and triceps, the muscle building strategies you should count on will include a associated with weights and dumbbell curls, in addition to standard presses.
This entry was posted in Information, News and tagged build, muscle on December 20, 2010 by .
This entry was posted in Information, News on December 20, 2008 by .


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Ostional Mass Arrival of a Different Sort
Under the waning moon in rainy season Olive Ridley sea turtles arrive by the thousands to nest on normally isolated and deserted Costa Rican beaches in what's know as an arribada. Unfortunately in September of 2015 there was a mass arrival of a different sort – hundreds of visitors from San José and all over Costa Rica descended on the beach.
The mob scene on Playa Ostional
Typically only a few intrepid international tourists make the difficult journey crossing rain swollen rivers to observe this amazing natural phenomenon under the careful supervision of the park rangers. The social media images above tell a different story this time. The severe drought in Guanacaste brought on by El Niño dried up the rivers and word spread on social media.
The two rangers on duty didn't stand a chance against the hundreds of weekend visitors who drove down from the capital for a day at the beach and a chance to see one of the most amazing natural occurrences anywhere. Unfortunately the visitors were unaware of the regulations established to protect the turtles and congregated precisely in the nesting zone. Before dawn many were using lights or flash photography to capture the perfect selfie and not surprisingly the rangers reported that many turtles returned to the Pacific without laying eggs.
While the normal behavior was obviously severely disrupted by the mob it probably wasn't the "devastation" or "disaster" described by some. It's not unusual for females to abort a nesting attempt and return a few nights or even a few weeks later. They also lay a huge excess of eggs every season so it's unlikely that this one weekend will have a significant impact on the hatch or population.
SINAC (Sistema Nacional de Áreas de Conservación – the government agency that oversees Costa Rica's parks and reserves) has stated that they will convene a study group to develop a plan for education and crowd control so this sort of scene doesn't repeat. The turtles are quite defenseless forced by their genetics and collective consciousness into putting on the show every year under the last quarter of the moon in the rainy season. Hopefully the human observers can find a more respectful and less disruptive way of enjoying it.
The "good old days" of a few people at a respectful distance are gone from Ostional beach but wherever you are please follow the local regulations and these turtle watching guidelines.
Stop Animal Selfies
Don't Feed the Animals
Turtle Nesting
Bird Feeder Ban
Best Places to See Monkeys & Sloths in Costa Rica
Resplendent Quetzals
Macaws in Costa Rica
Turtle Egg Harvest


Are you finding it more difficult to recruit international students for your school than in previous years? Are your traditional channels for recruiting students starting to dry up? With the total number of international students coming to the U.S. for high school starting to decline and the number of schools with international student programs continuing to rise, how can you best position your school to recruit international students in this changing, increasingly competitive, industry? Learn about changes in the education consulting industry and strategies for reaching your international student recruiting goals.
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Robber's Bridge, or Robbers Bridge, is an old masonry arch bridge in the royal forest of Exmoor near Doone Valley,
carrying the minor road from Porlock Hill to Oare.
It crosses Weir Water and is located down a steep, wooded lane beneath overhanging trees.

Some consider it to be a popular picnic spot, accessible via a narrow, steep, and winding road. In addition, from the nearby carpark, the bridge provides access to a grassland considered suitable for picnicking.

Association with Lorna Doone

The bridge takes its name from the fact that much of this area was dangerous bandit country in past centuries. R.D. Blackmore drew on the history and legends of this area to create his world-famous novel Lorna Doone.

References

Stone bridges in the United Kingdom
Bridges in Somerset
West Somerset
Packhorse bridges
Stone arch bridges

redpajama_set_name: RedPajamaWikipedia


This is a continuation of the flashbacks from the previous chapter, and all I can say is there is no Casey/Luke in it, despite the chapter title (as enjoyable as those are to read!).
[spoiler]The entire story's action so far has taken place in December 2010 (starting with Christmas day) and January 2011. However, there is extensive use of flashbacks to both canon, made-up scenes both pre- and post-Reid, as well as hybrids. It goes off canon roughly in early August. The story begins at Christmas time when Reid gives Luke a trip to a four-week writer's retreat in Iowa.
Yes, the boys have made love – of COURSE. I think I know when their first time was, but that flashback has not been played out yet. Yes, they have said "I love you" (chapter 12 Tuesday at Al's). The boys progressed slowly (per canon) through the summer, dated/had a serious relationship in the autumn, and moved in together in November. When Noah called a few days ago, Luke more or less told him to go stuff it. Reid, who knew only that Noah called, overreacted.
Noah left for USC film school in July; there was a Mona Cross arc; Reid is NOT Chief of Staff – Chris is (I definitely know why, but this has not been revealed yet), and Chris's heart is (and always has been and will be) just fine, thank you very much. Barbara and Henry are together, and Chris and Katie are engaged (Reid is to be "maid" of honor). Luke and Reid have been working together on the surgical wing project (not just neuro).
As of Chapter 31, Luke has now been away for nearly three weeks, with the recent passing of January 19, 2011. This occasion did not go unnoticed (Chapter 28-30) and the present – I won't say what or from whom, in case you haven't read it – causes both of them to think a bit more about their future together.
Or, start from the beginning….
Train? What train. Following their first Christmas together, Luke and Reid embark on journeys of self-discovery. Can two simple gifts lead to a happily ever after?
Extended author's notes will be posted when this mini-arc plays out. As always, thanks for reading. Feedback appreciated.
This entry was posted on Friday, August 12th, 2011 at 10:10 pm	and is filed under Fan Fiction. You can follow any responses to this entry through the RSS 2.0 feed. You can skip to the end and leave a response. Pinging is currently not allowed.
I just recently discovered your Simple Gifts story and I liked it very much. I really enjoy your style of writing. And because I did not know it excists I had the pleasure of reading a a book and did not have to wait for a next chapter. I really enjoy your style of writing. Are you going to continue this story ?
Reid, Luke , Ethan and Natalie waiting for the "wedding" – I wish this is what we could have had on the show – hilarious!


Long time, no write! I'm home and well. I'm just trying to figure out what is next. The end of the One Room Challenge can leave me drained and a little empty. Like, what am I supposed to do without a huge room makeover looming over me. Make printables is what!
Few things make me happier lately than designing stuff in Adobe Illustrator. So I made some stickers. There are 2 pages of printable tropical planner stickers. I made these fun and decorative. Most are light enough to write on, though.
These stickers fit the Big Happy Planner. You can either print them on sticker paper or print them on regular paper and run them though a sticker maker. Then just cut them out. Easy, peasy. Tutorial for cutting out stickers with a silhouette here.
Don't forget to check out my favorite planner supplies. I share my favorite sticker paper and other supplies that I love.
I hope you enjoy the tropical planner stickers.


Win 40 Anne French Tender Care Packs! : 10 Winners Per Week: WEEK 2 - Divassence!
Thank you for the amazing response to last week's contest. The contest continues this week too! Here is a chance to win a pack of the all new Anne French Shea Surprise Depilatory Cream! And we have 10 packs to give away each week for 4 weeks! Yes, you heard it right! 10 winners per week and this contest goes on for 4 weeks which means 40 of you have the chance to win!
Fill in the form with your Name and Email ID and answer a simple question.
The winners of WEEK 2 will be announced on Sunday (24/11/13). Good luck!


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王蓮成
王蓮成(Lian-Chen Wang)
Appointment: Professor
Lab:Immunological Parasitology Laboratory
Education:Ph.D.
University/Nation:Kaohsiung Medical College, Taiwan
Tel: (03)2118800 ext.5092
E-mail: wanglc@mail.cgu.edu.tw
Research website : http://memo.cgu.edu.tw/lian-chen
Tang, P. & Wang, L.C.* 2010. Uptake and utilization of arachidonic acid in infective larvae of Angiostrongylus cantonensis. Journal of Helminthology (SCI) ( accepted)
Tsai, Y.J., Chung, W.C., Wang, L.C., Ju, Y.T., Hong, C.L., Tsai, Y.Y., Li, Y.H. & Wu, Y.L. 2010. The dog mite, Demodex canis: Prevalence, fungal co-infection, reactions to light, and hair follicle apoptosis in northern Taiwan. Journal of Insect Science (SCI)( accepted)
Chung, L.Y., Chen, C.H., Wang, L.C., Chang, S. J. & Yen, C.M. 2010. Oxidative stress in mice infected with Angiostrongylus cantonensis coincides with enhanced glutathione-dependent enzymes activity. Experimental Parasitology 126(2):178-83(SCI)
Chung, L.Y., Wang, L.C., Chen, C.H., Lin, H.Y. & Yen, C.M. 2010. Kinetic change of oxidative stress in cerebrospinal fluid of mice infected with Angiostrongylus cantonensis. Redox Report 15(1):43-8(SCI)
Hwang, K.P., Chang, S.H. & Wang, L.C.* 2010. Alterations in the expression level of a putative aspartic pretease in the development of Angiostrongylus cantonensis. Acta Tropica 113(3):289-94 (SCI)
Wang, L.C., Hwang, K.P. & Chen, E.R. 2010. Enterobius vermicularis infection in schoolchildren : a large-scale survey 6 years after a population-based control. Epidemiology and Infection 138:28-36 (SCI)
Tsai, K.H., Huang, C.G., Wang, L.C., Yu, Y.W., Wu, W.J., Chen, W.J. 2007. Molecular evidence for the endosymbiont Wolbachia in a non-filaroid nematode, Angiostrongylus cantonensis. Journal of Biomedical Science 14:607-615 (SCI)
Wang, L.C., Jung, S.M., Chen, C.C., Wong, H.F., Wan, D.P. & Wan, Y.L. 2006. Pathological changes in the brains of rabbits experimentally infected with Angiostrongylus cantonensis after albendazole treatment: histopathological and magnetic resonance imaging studies. The Journal of Antimicrobial Chemotherapy 57(2):294-300 (SCI)
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Location:8th floor, first medical building
TEL: +886-3-2118800 ext. 5201
E-mail:gibms@mail.cgu.edu.tw


Port of Liverpool owner Peel Ports is to offer training to around 100 existing staff in a £300,000 programme funded via the Apprenticeship Levy.
This is more than five times the 19 employees put through vocational training in 2018 and there training will cover topics from leadership to port operations and involve workers from sits in Liverpool, Manchester, Heysham and eventually Sheerness and Great Yarmouth.
The investment is part a wider programme of professional development that will see nearly 10% of the entire Peel Ports workforce of 1,600 taking part in additional learning throughout 2019.
Peel Ports' chief executive Mark Whitworth said: "It's always been clear to me that we must invest in our next generation of talent, as they will deliver and lead our services in years to come.
Over the last year Peel Ports has continued to grow, increasing its headcount by almost 10%. It has also transferred-in more than 300 agency staff, underpinned by a new three-year pay deal and enhanced terms and conditions.