text: Homer and Marge to end marriage on The Simpsons show 8 Photos . Updated: 11 Jun 2015, 04:04 PM IST Livemint Marge and Homer Simpson of Fox TV's longest-runnin... moreMarge and Homer Simpson of Fox TV's longest-running cartoon show The Simpsons are going to split up again! The couple that also separated legally in season eight and then remarried, is slated for a divorce in the upcoming season 1/8The Simpsons family. Homer and Marge have been married since the show began in 1989, and have seen all sorts of ups and downs of marriage and child rearing. 2/8The couple separated briefly in season eight's episode 'A Milhouse Divided', when Homer realised that Marge deserves better. But the best thing about Homer and Marge Simpson is that they endure. 3/8The world's most beloved animated husband and wife team have endured Homer's drunkenness among other issues. 4/8Or times like when Homer befriended a hipster and called him to stay next door, inviting trouble to Springfield, the fictional town where the Simpsons live 5/8Marge and Homer's marital problems are also nothing unique. Marge's flirtations with bowling instructor Jacques and Homer's flirting with country western singer Lurleen Lumpkin do lead to quarrels, but they always find a way back to each other. 6/8But in the very first episode of season 27 it is discovered that Homer has narcolepsy (a sleep disorder). The disease takes a toll on their marriage, ending in the couple's split. 7/8Homer and Marge will legally separate, and Homer will fall in love with his pharmacist who's voiced by Lena Dunham. 8/8Will their separation this time around be permanent? Guess we'll have to watch the next season of "The Simpsons" that airs on Fox on September 27 to find out.


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subset: commoncrawl


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We SEA the holidays a bit differently...We have the perfect holiday gift for your avid fisherman!
We are slowly but surely getting back to "normal" here in Islamorada and the rest of the Upper Keys. All of the keys were officially open for tourism as of October 1st. Part of that decision to open included having hotels and businesses to accommodate the tourist.
Florida Keys Hurricane Cup, Backcountry Fishing Tournament to benefit The Guides Trust Foundation,
October 28, 2017, The Florida Keys
The Florida Keys are officially open for business on October 1st and the fishing guides are ready to get out on the water! Many hotels are open, most restaurants and businesses are as well, and the guides are definitely excited to start doing what they do best. A quick influx of tourists will help all hospitality and service industries to get back on their feet.
As you have heard on the news the Florida Keys was heavily impacted by Hurricane Irma. What you haven't heard is how quickly we are recovering and how the entire Florida Keys was not totally devasted by this hurricane. I do not want to take anything away from the areas that received the most devastation, but it is important to know that the Upper Keys and Key West are a little battered and bruised, but overall we will be able to recover pretty quickly.
Last Friday Andy and Adam caught 3 tarpon, a permit, snappers for dinner, and jacks and cudas.
So the weather is not always PERFECT here in the Florida Keys. However, sometimes we have to make the best of the situation that we are dealt. Yesterday was calling for some rain and wind but my clients only had this one day to go fishing so we decided we were going to try and get it done before the rain came.
First-time anglers don't always know that catching live bait is an important part of their charter. There are some fish that will eat shrimp and crabs, that we can buy from the bait shop, but if you really want a great day on the water we need to catch live pilchards or mullet before we put our lines in the water. Also, with live bait is allows us to fish for a wider variety of fish during the day.
Tarpon season is one of our busiest times here in the Florida Keys. We catch small tarpon throughout the year, but depending on the weather the big boys start arriving in March or April.
It's a beautiful President's Day Weekend here in Islamorada and the Florida Keys. Today I took out long time client, James Holmes bonefishing.
We've had a terrific June here in the Keys. Fishing has been great, the temperatures have been hot, and the water has been crystal clear.


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Mencari Jejak Benteng 'De Vijfhoek' Di Kota Lama Semarang Melalui Pendekatan Sejarah
Retracing The 'Vijfboek' Fort in The Old Town of Semarang using Historical Approach. At the beginning of the Dutch East Indies Company (VOC) establishment trade activity increased. The trade facilities road, river, harbour as well as fort have to be provided 'in order to maintain trade monopoly along the north coast of Java. Road and river were transportation facilities to transport agricultural products from inland to the harbour, which was the facility of export and import goods while fort was functioned as military defence and security system. Beginning with fort, VO(hun the trade monopoly policy and gradually set up new town as a settlement and offices to acomodate the business. VOC took advantage in conflict between Trunojoyo and Mataram, the biggest kingdom in Java. Military support from VOC gave Mataram victory over Trunojoyo. As a consequence Mataram bad to give Semarang as a trading post ofVOC under the treaty between VOC and Mataram in 1678. As the first step in establishing Semarang, VOC built a fortress as a military defence. This fortress had been renovated and developed overtime up to the end of 18th century.
Fortress, VOC and Semarang
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DOI: http://dx.doi.org/10.24832/amt.v27i1.436
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A have-a-go hero who helped foil a £1 million pound gunpoint jewellery robbery is a partially sighted former wrestler.
Incredible CCTV footage shows the moment three passers by wrestled a robber to the ground as he tried to make his escape.
This week a judge praised the men for their "public spiritedness" and handed them each a £750 reward.
On Monday Alar Kajurand, 44, Taimar Uibopuu, 30 and Rainis Kilk, 26, were jailed for a total of 51 years for two armed raids.
The trio from Estonia had flown over to the Manchester on budget airline Whizz Air to carry out the raids in London and Leeds.
Read more: Delivery driver caught on camera in 'Xbox scam' leaving note but no parcel
The judge praised the actions of the three heroes who stopped them in their tracks; James Pass, Dsoume Diallo and Issa Sila.
After the robbers were jailed, James, 30, told how he was heading for a relaxing afternoon of meditation, when he stumbled upon the jewellery heist.
James, 30, from Ossett in West Yorks., said: "My girlfriend looked into the shop window and said 'Oh my God, they're being robbed.' I thought she meant the prices were too high," he said.
"I looked down at the window display and then this leather-clad gloved hand appeared and this guy started shovelling all this stuff into a bag.
"I looked at the other window and I could see another hand doing the same.
Then I saw the staff all stood together being kept in one place."
Read more: Boy aged 10 threatened with knife during terrifying robbery
One of the raiders was pointing a gun at the workers as two others grabbed the high-end jewellery including Omega and Rolex watches.
James said his girlfriend, Greta Zipperer, 43, then "yanked" him away from the window and he told her to call the police.
Next one of the raiders, Uibopuu, flees the scene and is spotted by a man who starts shouting and pointing at the robber.
He tries to grab the crook's arm but he wriggles free and makes a run for it.
James explained: "At this point he was in my path and was getting away so I grabbed hold of him. I put him in a bearhug and we all tumbled to the ground.
"Because of my wrestling training I knew how to fall.
"As I'm falling over with him and rolling over, I thought 'If he's got a gun or a knife he'll use it now.'
"I put him in an arm lock and held him there until the police came.
"I kept looking over at the jewellers because I was worried his friends would come and help him."
Read more: Watch brave pensioner tackle gun-wielding robber by throwing beer cans at his head
Former gym worker, James, who had to quit as a part-time professional wrestler because of his eye condition caused by diabetes, said: "I was worried I wouldn't see them in time if they were going to come and help him."
Police arrived on the scene shortly after 3pm on March 24 and arrested Uibopuu.
They recovered 64 watches worth a total of £485,000 but Kilk and Kajurand made off with £450,000 worth of jewellery.
They were later tracked down to a Manchester hotel and officers found Kilk's DNA matched a similar robbery at the Watches of Switzerland, in Oxford Street, London, on February 25th.
All three were charged with conspiracy to rob and found guilty after a trial in November.
The court heard Kajurand had previously been jailed for 12 years in his homeland for unlawfully killing a man in a bar fight.
Sentencing him to 18 years in prison Judge Savill said: "You have previous convictions in your homeland of a serious nature and you are no stranger to violence."
Kilk was also sentenced to 18 years for his role in both robberies. Uibopuu was sentenced to 15 years in prison for his role in the Leeds robbery.
Judge Savill said: "One cannot speak too highly of the members of the public involved in this case."
Detective Inspector Phil Jackson, of Leeds District CID, said the criminal gang hadn't bargained for the "very courageous" actions of the three men.
"While we never encourage members of the public to put themselves at risk, their actions proved absolutely vital in bringing these men to justice," he said.
Grounded James, shrugged off his actions, adding: "Some say I'm a hero but others say I'm an idiot."


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"Olga Tokarczuk will be in conversation with translator Jennifer Croft and writer Askold Melynczuk as part of the Transnational Literature Series. For more information, please contact series curator Shuchi Saraswat at email@example.com.
Back to All Events
Earlier Event: September 24Politics & Prose at The Wharf
Later Event: September 26Olga Tokarczuk, "Flights," with Hermione Hoby and Jennifer Croft


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"It had this incredibly large eruption which left a beautiful lake. It's not until you go and see it you realise how big that explosion must have been," she explained. But her favourite card in the deck is of Soufrierre Hills in Montserrat. "It's not necessarily a big winner but it is 'my' volcano!" she said. "I have visited it many times."
She studied geology at university and worked at the Montserrat Volcano Observatory before arriving at the University of East Anglia. She is married to UEA Hogan Rebel Red
erupt yourself in amazement and wonder!" she said.
And the explosive facts and figures behind Volcano Top Trumps were devised by a team led by a Norwich volcanologist.
Jenni's two daughters, 11 year old Morven and nine year old Eilidh, joined the fun. "They play Top Trumps a lot so they gave us some feedback," she said. Now the first edition of Volcano Top Trumps Hermes Shoes Womens New
Jenni is one of the country's leading volcanologists and shared her passion for all things volcanic with BBC viewers, as a presenter of the prime time Volcano Live! series.
"As Top Trumps fans we couldn't believe there wasn't one for volcanoes," said Jenny.
Her fascination with volcanoes began as a child. "My mum has a school project from when I was small, called 'The Violent Earth!'" she said.
The scientists ranked 30 volcanoes around the world for explosivity, deadliness, devastation potential, height, unpredictability and wow factor and then fought Top Trumps battles to fine tune their game.
The newest, fiercest, most fiery and destructive Top Trumps game pits the wow factor of Eyjafjallajkull against the devastation potential of Krakatoa.
It has been a busy year for Jenni. As well as helping create the first ever Volcano Top Trumps, her presentation, Pompei Live, was beamed to cinemas around the country in association with the major British Museum exhibition on Pompei. She also led the team which created a new volcano in Norwich to celebrate UEA's 50th anniversary. The steam hissing, fireworks flaring volcano on the university campus was one of the highlights (literally) of the anniversary celebrations.
professor, Ian Renfrew, an expert in polar weather systems.
"They are the most obvious manifestation of the huge amount of energy within the earth, and they show us some of the amazing processes that take place. It's almost impossible to watch an eruption and not Sneakers Dsquared Ebay
Scientist helps to create hottest card game around
There are no active volcanoes on mainland Britain, but plenty of evidence of extinct volcanoes including Arthur Seat and Castle Rock in Edinburgh and much of the Lake District.
Next month Jenni will revisit her favourite volcano, on the Caribbean island of Montserrat and take her pack of Volcano Top Trumps along. She will be working with local and international researchers on the island as they continue to study the volcano and learn more about how to predict eruptions and get information to those in danger. But during breaks in the serious science, participants will be honing their skills ready for a major Top Trumps tournament.
Volcanologists from around the world contributed stunning pictures of both dormant and erupting volcanoes to use on the cards and Jenni's team decided on the facts and fine tuned the figures used in the game. Her favourite category is "Wow Factor!" and for her, the volcano with the most wow factor is Crater Lake in Oregon.
If it's wow factor you want this Christmas, meet the collection of volcanoes spitting fire and lava erupting into family festivities thanks to Norfolk scientist Jenni Barclay
So she wrote to the company and was thrilled to get the go ahead to create the first volcanic version of the iconic game.
She would have loved the chance to play Volcano Top Trumps as a child but had to make do with sets featuring dinosaurs and cars. Now her daughters are delighted to be able to pit fiery mountains against explosive eruptions but still believe the Dr Who cards trumps even volcanoes.
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is selling fast and the cards don't just focus on the stunning power of volcanoes. They also reveal the devastating trail Gucci Shoes Red of destruction they can create, so all profits will go to people suffering from the effects of volcanic activity.
Jenni leads a group of experts from UEA, and the universities of Oxford and Plymouth, who work together to research volcanoes and help people living in threatened areas. The Strengthening Resilience in Volcanic Areas (STREVA) Project explores ways of predicting and mitigating the impact of eruptions as well as researching volcanic activity. Dr Paul Cole of Plymouth University said: "Through Top Trumps, we are highlighting those serious and important messages in a fun and informative way."
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Discharge Planning Changes Affect Hiring in Healthcare
Hospitals in the United States will be experiencing broad reaching changes this year with proposals by the Center for Medicare and Medicaid (CMS). The new regulations governing Discharge Planning are anticipated to take effect by October or November and are currently in comment review by CMS.
A summary of what we see as the most impactful changes are threefold.
1. All hospitals will be required to apply the discharge planning process to every patient including inpatients, outpatients under observation status, outpatients with sedated procedures or surgery, and emergency department patients that need a discharge plan.
2. All patients will now require a discharge evaluation, not just those at risk for readmission or complications.
3. A new requirement which can challenge complex systems and communication strategies, is that within 48 hours the discharge plan must be sent to the PCP or provider identified to be responsible for follow up care, with test results being made available within 24 hours of availability. Another big change in discharge planning aimed at reducing re-admissions, is a proposed regulation to require all hospitals, including Critical Access, to develop a follow up process after patients return home.
In addition to the changes in practice, is the new design standard that requires that all hospitals discharge planning processes be documented in writing and approved by the organizations' governing body. Strategies to ensure compliance with the goal of better patient care, value based care, and reduction in readmission rates will be at the heart of the planning for the implementation of these new regulations.


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The Mi-Pac NylonPencil Case in Leopard is a tough, durable and water resistant Nylon case. It is fully lined and features branded zip pullers. Perfect for making a statement at school or at work.
Copyright © 2007 - 2019 John Smith & Son
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Paul DeVault
December 5, 1981 ~ July 17, 2015
Born in: Knoxville, TN
Resided in: Johnson City, TN
Memories Timeline
Fly high my friend. You will be missed. Save a seat for me.
I jus wanted to send a prayer I went to school wit Paul he was a great guy and friend jus know he smiling down cause he's in a better place
I offer my deepest sympathy and prayers for the family and many friends of Paul. Paul always made your day brighter when he was in the room. He was quick with a handshake and quicker with a smile. I like so many others will greatly miss him. May God bless you all and keep you close.
I will miss Paul and think of him every time I go to BFG. Paul grew up with my son Bruce Piercy and spent the night at our home. God is in control! Praying!!
Too all the family, you are I our prayers and thoughts.
You are truely missed Paul. My heart and prayers go out to your family and friends.
Our condolences to the family. May you find strength in the God of all comfort who can provide the strength needed to cope during this difficult time (2 Corinthians 1:3).
Paul was a friend to my oldest son Nate, since Jr High. There was never a dull moment when Paul would come over to visit! He was just the kind of person who lit the world up with his smile and his charm. May God embrace the entire family with His gentle love as you search for understanding. I pray your fond memories of this terrific young man bring you peace in the days to come. God bless, Casey Irish
Paul will be sorely missed. He was a huge reason why we are all a family at work. My deepest condolences go out to his family and most particular to Connor.
Paul, you have been an integral part of my life…from feeding Michael grapes when I was pregnant with him 30 years ago …to calling you on your 11th birthday and letting you know you had a new niece ( Kristen ) so now you have birthday twins…to having the same circle of friends because we both work in the service industry. Texting each other from across the room while at family functions… you'll always be my favorite sib. <3
To all the members of Paul's family, we are sorry for your loss. Paul was a complete Gentleman whom seem to always wear a smile. We'll miss you, friend.
We had the privilege to know Paul from The Bonefish Restaurant. We always requested him after our first time there when we moved from PA to TN in 2011. He was so kind and always had a smile for us. We were there Sat. nigh the 7/11 and we could not get him as our waiter, but he saw us and stopped by to say HELLO. God bless and give comfort to his family and friends as they go through this most difficult time. Our thoughts and prayers are with you all. RIP Paul with a great smile!
You touched many hearts…..I pray and ask comfort to Every FRIEND and FAMILY MEMBER….
Paul was one of the best people I've ever known. He was a great friend and always made knew how to make me smile. My deepest sympathies to all his friends and family. May your memories keep you strong during this difficult time.


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An organic mountain farm uses indigenous breeds to produce high-quality meat, while preserving the local environment and genetic resources.
Projects & Practice
A cheese-producing farm used RDP support to set up a new plant for producing speciality cheeses and ensure its long-term financial sustainability.
A dairy company used RDP support to build a new wing on its factory in order to increase its production capacity. This investment strengthened the local supply chains and helps prevent the abandonment of the farming activity in the area.
A community project in which young people actively participated in shaping their environment and strengthened the cohesion of their community.
A modern hen farm producing eggs for human consumption, set up a new unit to process non commercial eggs and therefore increase its competitiveness.
A project that supports the integration of young immigrants into Swedish society and is organised by young immigrants themselves.
Young people from Finland and Scotland came together to create a Youth Manifesto outlining ways in which local actors can engage young people in their activities.
The Rural Broadband project is a national intervention to close the digital divide in remote and sparsely populated rural 'white areas'.
SILTA supports entrepreneurship among young people by providing a cooperative structure through which they can grow their business ideas and receive training, mentoring and peer support.
A young female farmer introduced a blackberry plantation into a wheat and barley production area and created added value by developing a new range of products. This was the winning initiative of the 2019 Rural Inspiration Awards in the 'Improving competitiveness' category.


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Canadian Netflix subscription is required to watch on Netflix
Date Added: 19th April 2019
Want to keep forever? Try looking for 'Lunatics' on Amazon.ca
This mockumentary series follows the peculiar lives of six eccentric -- and sometimes obscene -- misfits who march to their own beat.
Certificate: Suitable for mature audiences only
Year: 2019
Duration: 1 Season
Available Seasons: Season 1 (10 Ep)
Audio: German, Italian, Spanish, French, English - Audio Description, English [Original]
Subtitles: Italian, Spanish, French, English, German
Cast: Chris Lilley
Login or register to get email updates...
This title is available on Netflix in Canada


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- Created: February 21, 2013
- Updated: December 12, 2017
- DistanceInstructions
- Distance54.85 km
- Time0 s
- Speed0.0 km/h
- Min altitude79 m
- Peak263 m
- Climb541 m
- Descent542 m
Stage 17 of the The Ulster Way from Gortin to Moneyneany, also known as the Central Sperrins Way, is a moderate 2 day or strenuous 1 day (37 km) walking route in County Tyrone in Northern Ireland. This hike is through the centre of the Sperrin Mountains and the scenic Glenelly Valley along mostly quiet back roads and paths. The Sperrins are the largest area of upland in Northern Ireland. If you have time don't miss a walk to Sawel and Dart Mountains, the highest points in the County (see this walking route at the bottom of the page). The final section of this walk is along a public road so can be avoided if wished by public transport.
The Ulster Way is a long distance walking trail throughout all 6 counties in Northern Ireland with small sections of the walk in Ireland. It could be considered the longest of Irelands National Waymarked Trails at approximately 1,006 km (625 miles) long but unfortunately it is not a continuous walk. Several long sections are busy road links which can only be completed by car or alternative transport. The walking route officially begins and ends in Belfast but you can join the trail at any number of points along its length. The Ulster Way comprises some great and well known waymarked walks in their own right including the Lagan Towpath in Belfast and the Causeway Coast Way among many others.
Typically the entire route is broken down into 16 seperate walkings stages covering 740 km and 10 road links. At 20km per day, these walks could be undertaken over 6 weeks but it is rare that the entire Ulster Way is attempted in one go. We have broken some of these longer stages into smaller parts to allow everyone irrespective of fitness or time available to experience one of the most varied walks in Ireland.
There are plenty of routes to suit walkers from beginners to advanced so find a route that is right for you or your group. Plan your walk by checking the weather and sunrise sunset times on our website https://www.activeme.ie/useful-info/planning-a-trip/ and please remember you are only as fast as the slowest member of your group!
Use our Map of Ireland and Sat Nav tool to get directions to any of the stage start points and our detailed maps and GPS on our ActiveME iPhone and Android App to find and follow the walking route live on screen and keep on track. At all times, our maps and App should be used in conjunction with proper map and compass navigation techniques. Feel free to send us your photos and add you own star rating, comments or suggestions below.


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Best Decision I've ever made….
Changing my major from Chemical Engineering to Computer Science is the best decision I've ever made. I fell in love with programming when I first watched "24". Chloe O'brian (Jack Bauer's best friend) made me fall in love with programming. I was so impressed by how she used her programming skills to solve serious matters.
I remembered telling myself I want to be like Chloe O'brian, a geek woman! Since that time, I wanted to study computer science but I was so afraid because I did not have any background in programming, I've never wrote a code before. I told myself maybe it would be a huge mistake to change my major to computer science. My biggest fear is to fail in programming, not being able to write a code. But here is the thing, I lacked of self-confidence. I did not believe in myself. I was constantly telling myself that I could not do it, I could never be a programmer.
So guess what I did? Because I was scared, I decided to stick to a major I was not interested anymore. I kinda forced myself to like chemical engineering but as time went by, I did not feel happy anymore, I felt emprisonned. I just could not deal with chemical engineering, so I finally had the courage to change my major to computer science and let me tell you something: "It is the best decision I've ever made" because Programming makes me happy.
"If you're afraid to fail, then you're probably going to fail"
If you like this post, don't forget to recommend and share it. Check out more great articles at Code Like A Girl.


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Host Harlee Lane and her brand new Co-Host, Raine McCellan have a lot to say about the wonderful wardrobes the models are wearing. the designer for our very FIRST episode of the MODA Fashion Primetime show is Elettra Gausman of Orage Creations, one of the most POPULAR fashion designers in Second Life.
On the runway is a whole lot of amazingly, very real and seamless fabric and designs that are just to die for! Elettra's designs are made of sequins, palettes and Jais in a wide variety of fashions from Haute Couture, formal and casual clothes and realistic limited editions skins. What we notice most is quality both in style and in design.
For a designer who is this talented with textures, it would only make sense to add a line of skins to the wardrobe. At Orage Creations you will find an entire line of truly beautiful and very real looking skins to compliment these amazing fashions. You can get the latest information on the Orage Creations website, and visit the Orage Creations store and try them on for yourself.
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Quad LFO
The SSL 1250 Quad LFO combines four dual waveform (sine/square) low frequency oscillators in one convenient 1 MU module. Why tie up four expensive double width VCO modules if all you need are simple vibratos, trills, slowly morphing timbres or repeating gate sources? Give your synth slow subtile variations or wild cacophonous modulations at lost cost and all within a single module width.
This Module is currently available.$275 Price in € submitted Oct 25th 2012, 21:18 by Squiggletronics | last Change Oct 10th 2017, 18:43 by CoreyBairre


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text: Good afternoon. I am currently a senior at my university studying Information Systems & Operations Management. For my semester project, my team and I have to create an app to help solve a business problem. My team and I decided to develop a local navigation app for our university's campus. I was wonder how one would go about developing a navigation app for a university campus and how free GIS software such as ArcGIS can aid in the development of that type of application. Thank you!


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And now a word from the IT dept.
Charles here, with a sobering website update.
For the past 7 days, malicious code has been injected into the laeliasky.com pages. We're still not completely sure what caused this, but it's now largely under control. If you visited the site in the last 7 days, you may have seen some pop-up window come up when you visited the site with something anti-virus related. If you clicked on that link, you may have unwittingly installed malware on your computer.
Here's what this means for you:
- If you're using a different OS from Windows (Mac or Linux), you should be fine.
- If you have an antivirus program installed that includes real-time scanning, you should be fine–the script would have been blocked–but you may want to run a full virus scan just in case.
- If you don't have real-time scanning on your antivirus software or don't have any installed, you should install some and run a full scan. There are many places to go to get free antivirus software, but Avast is what we use, and we're pretty happy with it.
I'm sorry this happened, and I'm especially sorry if you find yourself cleaning a malware infection out of your computer. I'm pretty sure you come to laeliasky.com for updates on our darling daughter, not for a crash course in malware prevention. We may have some downtime over the next couple weeks as we try to clear out the last vestiges of this code; please be patient with us.


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Day Tours
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20 November 2017
Pictures from our latest tours around Iceland. If you are interested in our private tours send us your thoughts at
5 May 2017
Photographs allows you to re-live some of your best moments in live. I was going through my winter shots and saw this one and it took me straight back to the moment when I was at this abandoned place in Snaefelsnes. I still remember how the snowy storm was. It was so blind that I often could not see the road I was driving. This day I was guiding a woman from Brazil and her daughter and I still remember how stunned they were by this weather we got. Maybe they were not as excited as I was with the weather but I loved every minute of it. I hope that my guiding at www.icelandpersonaltours.is create more memories like this one.
Snæfellsnes peninsula in West Iceland is almost a miniature version of the island. In addition to its characteristic Snæfellsjökull glacier, there are black sandy beaches, bird cliffs, spectacular mountains and volcanic craters along with small villages along the coast. This is a place any nature lover needs to visit
Check out these tours:
THE WONDERS OF SNAEFELLSNES - Day Tour
3 May 2017
One of the place I always go to on my South Coast day tours or my trips around the south area of Iceland is Reynisfjara black beach. This is a place that is always interesting. I been there so many times that I have stopped counting but I always find something new and interesting. This composition is one of my favourites where you can see the basalt cliffs of mount Reynisfjall and you can see the Reynisdrangar cliffs standing tall out of the sea. Legend says that the stacks originated when two trolls dragged a three-master ship to land unsuccessfully and when daylight broke they became needles of rock.
When there is a low tight at the beach you can walk straight to the basalt sea stacks of Reynisdrangar and take a selfie of you facing the cliffs. If there is a high tide than you will witness some massive waves reaching far up the shore that it can be dangerous to stand on the beach and people need to be careful.
The black beach is close to the village of Vik and the cliffs can be seen from many other angles. You can see them clearly from the peninsula of Dyrhólaey and it is always interesting to take shot of them from the Víkurkirkja church in Vík.
This is one of the must visit places in Iceland, it takes you around 2 hour to get to it from Reykjavík. If you like to visit this place with me than consider taking a day tour with me as your driver guide or lets include this in a multi-day package.
Check out these tours:
SOUTH COAST ADVENTURE - Day Tour
14 - 20 April 2017
I was just finishing off a 7 day / 6 nights tour and wanted to tell you the itinerary that was packed and we had a wonderful time.
On day 1 the 14th of April I picked up Nathalie and her 19 year old son Tom at Keflavik airport in the afternoon and dropped the of their first overnight stay here in Reykjavik.
On day 2 I picked them up at 09:30 and we did the golden circle tour where we visit Þingvellir, Geysir, Gullfoss, Skálholt and the volcanic crater of Kerið. After that we drove to the lovely village of Eyrarbakki and had a dinner in the town of Selfoss. After our dinner we head to our overnight stay not far from Selfoss.
On day 3 we had a full active day on the south coast where we first stopped at Seljalandsfoss where we walked behind the waterfall, after that we went wearing water boots to the waterfall canyon of Gljúfrabúi. From there we visit the mighty Skógafoss and got a bit of shower from the waterfall. After that shower we drove to Dyrólaey and had a fantastic overview of the south coast and next we stopped at Kirkjufjara to see Arnardrangur cliff. From there we stopped at Reynisfjara and walked to the Reynisdrangar cliffs and sit on the rocks facing the stunning cliffs. After that wonderful visit we went to Vik and took some photos from the church before we went to visit Víkurfjara and then to have a dinner at Halldórskaffi. After the dinner we drove to Kirkjubæjarklaustur for our overnight stay with a quick stop at Eldhraun.
On day 4 we woke up early had a breakfast and then head our way, our first stop was at Skaftafell where we made the walk up to Svartifoss waterfall, after the nice walk we drove to Sólheimajökull and took some photos of the glacier rift. From there we drove to Fjallárslón and got some close up shot of the Vatnajökull glacier. After that wonderful visit we went to Jökulsárslón and the diamond beach of Breiðamerkursandur to get a close up shots of the glacier ice rocks. From there we drove back to Kirkjubæjarklaustur, had a dinner and then to sleep.
On day 5 we drove back to Reykjavik from Kirkjubæjarklaustur. On the way we stopped at fjaðrárgljúfur canyon, from there we stopped at Eldhraun to visit this stunning lava area. After that we drove on and went to Hjörleifshöfði and took some photos around Mýrdalssandur. From there we kept on going and made our final stop at the black beach at Sólheimasandur where we walked to the abandoned DC plane stuck on the black sand. After that visit we drove straight back to Reykjavik.
On day 6 the mother and son had a day off in Reykjavik but I picked them up at 18:00 and we had a 2 and a half our visit at Reykjanes where we went to Krýsuvík, Seltjörn, Gunnuhver, the lighthouse of Reykjanesviti and witnessed the stunning waves on the tip of Reykjanes, next to cliff Valahnúkur. We ended the evening with a relaxing time at the Blue Lagoon.
Day 7. After our relaxing time at the Blue Lagoon we drove back to Reykjavik for few hours of sleep before I picked them up in the middle of night for their early flight back to Luxembourg. This was a very nice time and I had a wonderful time showing them the southern part of Iceland. We took lots of photos, I specially focused on helping Tom to get the best photos he could along with taking photos of my guests. This is a great tour and I am all in on treading my guests as my friends and showing them how you can see Iceland at its best. I truly believe that going on a private tour with me is one of the best ways to experience Iceland with a local and friendly Icelandic guide
26 May 2016
Sunset photography captures the quiet moments of peace when the world is settling down to sleep; quiet, vast, and always beautiful. Sunset or sundown is the daily disappearance of the sun below the western horizon as a result of earth's rotation. Sunsets can be different each time and you can always see something unique in them. To look at a summer sunset is for me similar to looking at a beautiful painting.
When is the sunset/midnight sun
Iceland is famed for its sunsets and long days during summertime (from May to late August) which peaks with the summer solstice on 20th of June (the longest day of summer) when the sun sets just after midnight and rises again just before 3 am. Further north of the country like in the city of Akureyri the day will be even longer.
The slow sunsets during the summertime produce incredible displays of colorful skies that can last for hours. The sunrise is set the only a couple of hours later so for around 3 months during the summer, Iceland has bright nights. The sunlight will though get shorter from just a few seconds up to several minutes per day after June 20th. For me, one of the best times for sunset photography is late in August when there are a couple of pitch black nights that gives you the opportunity to get really dark and interesting red sunsets.
Late night photographing in Iceland
Having nearly 24 hours of light during the summer in Iceland gives you a great opportunity to go sightseeing later in the day. So taking the advantages of these late nights are a must do if you come to photograph in Iceland. Popular places in Iceland have fewer travelers during evenings and late nights and are therefore a great time to visit if you want to have more space and time on your own. Interesting sunset subjects can be for example seashores around Iceland, mountains, waterfalls, ice lagoons, sculptures, and lava fields.
Places to consider capturing during sunset or the midnight sun:
The seashore close to the island of Grotta in the Reykjavik capital area
The sculpture Sun Voyager in Reykjavik
Mountains like Vestrahorn, Hafnarfjall, and Kirkjufell
Jokulsarslon ice lagoon
Hvítarserkur cliff
Waterfalls like Seljalandsfoss, Skogafoss, Brúarfoss and Godafoss
Lava fields like in Reykjanes peninsula
Many lighthouses around Iceland and the house Straumur art center at Straumsvik
If you are staying in Reykjavik it is ideal to leave the city around dinner time and take the so-called Golden Circle Tour which includes Geysir, Gullfoss, and Thingvellir.
The settings
To capture the sunset in the best way you need to be at the right place at the right time, sharp focus in a low light with aperture settings of f/2.8 is recommended. You will then need to change the ISO and exposure settings to get the best result. ISO should be set at 100 but the exposure needs to be adjusted based on the condition outside, not too fast and not too slow either. An exposure setting from 60 up to 200 usually works but you have to adjust it based on how bright or dark it is outside. Remember to shoot in RAW which allows you to change the white balance in your post processing work.
Remember that though it is bright outside the weather often can be chilly so dress accordingly. Tripod is not necessary though it is always recommended to have one, along with extra batteries. It can get dark really fast during the early and late summer so a flashlight can get in handy.
Sunsets happens late in the evening during the summer
The longest day of summer 2016 is June 20th
It is recommended to have aperture settings of f/2.8
You have to adjust the exposure setting based on how bright/dark it is outside
The sunset itself can be quick so be at the right place at the right time but you have nearly 24 hours of light
Iceland is ideal place to photograph late in the evenings and night during summer
If you are staying in Reykjavik consider taking the Golden Circle Tour in the evening to experience more peaceful and quiet atmosphere with fewer crowds.
23 March 2016
During the winter time, many people travel to the northern hemisphere to photograph the Northern Lights, also known as aurora borealis. The best time to capture the stunning lights is from September to mid-April – these are the months where there are full dark nights.
The northern lights are the result of electrically charged particles from the sun colliding with gaseous particles in the Earth's atmosphere, causing displays of bright, colorful dancing lights. They are visible in the magnetic polar regions of the northern and southern hemispheres and they can range in color from white, green, pink and purple. In the northern hemisphere, the lights are best seen from Iceland, Greenland, Norway, Siberia, Canada and Alaska.
To get some great shots of the Northern Lights planning is important
Dark Skies
Without dark skies it is very hard to get nice shots of the Northern Lights, so finding the right dark spot is crucial in your haunt. Blue Marble Light Pollution Map is a great tool to find those dark locations across the northern hemisphere.
Clear skies
You need to be in darkness but without clear sky, it will be hard to get good shots of the Northern Lights so to capture the aurora you need to find some clear skies. MeteoStar Weather Satellite Imagery Maps of the Northern Hemisphere does a great job of showing cloud cover conditions on a large scale.
Aurora Activity
When you have found a dark place with a clear sky you need to check the aurora activity in the sky. The activity is measured on the Kp scale which ranges from 0-9 with 0 being low aurora activity and 9 being the greatest. Aurora Forecast Page provides some great insight on the current aurora forecast and a multi-day outlook. Aurora activity from 3 to 5 is a very good for some great Northern Lights shots. It is necessary to have in mind that aurora activity can be very unpredictable and some days are better than others.
What kinds of gear do a need?
To capture the Northern Lights a full frame (35mm or larger sensor) camera and a wide angle lens is ideal.
Here a few tips you need to have in mind
Bring a tripod with you.
Use a camera with manual mode. You will need to be able to adjust the ISO, Aperture and Exposure time.
A full frame camera with high ISO capability allows you to capture the Northern Lights without significant noise in your images.
Wide angle lens (14-24mm range) with a fast aperture. Aperture settings of f/2.8-f/4 are recommend.
Fully charged battery. In the cold batteries die quickly so be aware of that.
Since the Northern lights are far away up in the space we can focus at infinity and obtain sharp focus. It is good to set up your camera during the day and adjust your lens to focus on infinity, or at a faraway horizon. Place your focus on manual to get the right focus in low light.
To capture the best images of the Northern Lights, shoot in RAW which allows you to change the white balance in your post processing work. Your aperture settings should be as wide as it can go. The aperture of f/2.8 is recommended. You will then need to change the ISO and exposure settings to get the best result. To get the right shot you need to ask yourself, how fast are the northern lights moving and how bright are they? When you have concluded that then:
Set your exposure time between 5 to 30 seconds. If the aurora moves quickly aim for around 5 to 10-second exposures. If it moving slowly use up to 25 to 30-second exposures.
Set the ISO at 400-800 and continue to increase your ISO until the picture is bright enough. ISO at 1.600 is often necessary to capture bright enough images.
Remember that photographing the Northern Lights takes practice and patient. Also, it can be very cold standing outside staring up the sky, so dress warmly and keep in mind that capturing the aurora can take time. It is also often very dark outside so a flashlight can be handy when handling your gear.
Look for the dark and clear sky in the area where there is some aurora activity.
Use a full frame camera and a wide angle lens.
Use a steady tripod.
Use the manual settings on your camera.
focus on infinity, or at a faraway horizon.
Set the aperture settings at f/2.8-f/4.
Set your exposure time between 5-25 seconds.
Set the ISO at 400 to 1600.
Make sure you have a full charged battery.
Dress warmly, It can be cold standing outside during winters.
The flashlight is good to have.


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: Proviron Penile Growth : Use buyer customer feedback in your marketing with video promotion. : Publish genuine communications from true clients of your : respective organization for the most powerful video tutorials : achievable. Other potential clients will spot how loved you : might be by existing clients and when they know how you go out : of your means by company, they will come up with a reason for : searching you up! : Anabolic Fasting : Keep your pressure degree as low as humanly probable. As anxiety : ranges boost as a result of daily problems, so do symptoms of : asthma signs and symptoms. In the event you encounter wheezing : and hacking and coughing several times every day, take into : account tension comfort techniques such as typical exercises and : stretches and breathing workouts. Also, be sure you get enough : rest to deal with the challenges of daily life. : Proviron Mesterolone A Cosa Serve : Try out your greatest to see your property with objective eye. Make : an effort to analyze your own home like you were a buyer. Bear : in mind how you sensed if you have been thinking about buying a : home. Can you, as being a total stranger, see yourself at your : residence? Or else, you might like to purchase a skilled stager. : Buy Masteron Enanthate
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Highly Advanced Treatment for Gallbladder Cancer at World Class Hospitals in India.
Ms. Jemila Abubakar From Nigeria shares her experience about Medical Treatment in India
Thanks for your always prompt responses to my volley of questions and concerns. I could not have managed even a step without your staff's Excellent care. Couldn't be happier with the Indian hospital's Surgeon, physicians and their expertise. Very personable and professional. Would recommend to others.
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Pet Safety Tips for the 4th of JulyCommunity, Featured June 25, 2018
Fire in the Sky over Lake Blue Ridge Saturday June 30thCommunity June 2, 2018
4th of July EventsCommunity June 29, 2017
Sparks in the Motorsports Park – July 4, 2017 – 10:00 AM – 10:00 PM
Website: https://www.facebook.com/events/577177765796892/
Event Description:
Tentative Schedule below:
10:00am AMP Karting is open
4:00 AMP general parking
4-9pm Festivities : food Vendors, crafts, food trucks, popcorn, activities for the family. Dunk tank, snow cones, bouncy houses, Music- Scott Walker of Scott Walker Band, etc…
4:30-4:45 First Super-Cross show
5:00 car show
7:00-7:15 Second Super Cross show
8:30 pie contest
7-9:45 AMP 4k at 9pm. Finish your run under the fireworks. https://raceroster.com/events/2016/9195/fireworks-4k
8:00-8:15 Third Super Cross show
9:00 parachuters/ParaCommandos fly in /Fireworks to follow
10:00 Exit and closure of AMP
Location: Atlanta Motorsports Park, 20 Duck Thurmond Road, Dawsonville, GA 30534
Cruise-In Car Show – July 4, 2017 – 6:00 PM – 9:00 PM Website:http://www.thevarsity.com/locations.php?action=view&store_id=10
Location: Varsity Jr., 73 Bethel Drive, Dawsonville, GA 30534


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Protection for your eyesNational Pharmacies
UV radiation is always present. All year round, all day, in winter and summer, in sunny and even overcast conditions – even on cloudy days. Prolonged UV exposure also poses some serious health risks including your eyes. Constant exposure to UV rays can cause eye diseases such as cataracts, macular degeneration and accelerated ageing of the area surrounding the eyes.
We are surrounded by UV rays whenever we go outside and it's a little known fact that buildings, water and sand reflect up to 85 % of radiation. UV radiation even penetrates the surface of the water, at a depth of one metre, UV-A radiation can still have an intensity of 75% and UV-B radiation an intensity of 50%.
UV can even penetrate your car windows. While most front windscreens provide UV protection, side and rear windows usually offer none and these untreated windows can let in up to 80% of UV-A radiation. Even tinted windshields aren't an effective means of protection, because they only filter out around 40 % of UV-A radiation. But, there are many ways you can protect yourself from the UV rays surrounding you every day.
Clothing is a good form of sun protection for the outdoors. Together with a good quality pair of sunglasses and sun cream for your skin, you'll enjoy effective, protection for your entire body.
When purchasing sunglasses, avoid lenses without UV protection. These can create even more damage than when you don't wear sunglasses at all because they simply give the illusion of protecting your eyes. They reduce the amount of light penetrating through, leading the pupil to dilate.
As a result, light penetrates your eye in an even more damaging way. Not only should sunglasses offer UV protection: clear lenses should always be equipped with effective UV protection as well.
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National Pharmacies Optical stock UVProtect lenses from ZEISS which offer full UV protection in a clear lens.
The content displayed on this webpage is intended for informational purposes and should be used as a guide only. This information does not replace or substitute professional medical advice, diagnosis or treatment. Information contained on this webpage must be discussed with an appropriate healthcare professional before any action is taken based on the content of this webpage.


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Milton Hill shoveled the snow from the front walk of the church next to his small East Baltimore apartment. The 70-year-old helped carry heavy boxes to the food pantry and walked women to their cars after late-night events. He trimmed the church hedges on Thursday, just because it needed to be done.
On Friday morning, Hill was found slumped against a fence, lying in a pool of blood. He had been shot. The scooter he used to get around town — a retirement present he bought himself, according to the church deacon — was gone.
Friends, family and church members stood across the street, consoling one another and praying as city firefighters washed his blood down a storm drain. The red-stained water washed along the sidewalk he helped clear of debris, and down the alley he traversed to get to the ramshackle porch leading to his second-floor apartment in the 1200 block of E. North Ave. above the Ark Church bookstore.
"People are really gonna miss him," 82-year-old Reginald Trusty said. "I can't say it enough how much he'll be missed."
Hill was the city's eighth homicide victim this week, a tally that includes a Johns Hopkins researcher who was stabbed in a robbery Sunday that captured the city's attention, as well as two people killed in nearby Station North and a 19-year-old who was killed during a fight in Northeast Baltimore. And police say they have yet to reach the family members of victims in Southwest Baltimore and a man found dead in a vehicle in East Baltimore.
Public officials, including Gov. Martin O'Malley and Mayor Stephanie Rawlings-Blake, reminded residents during a news conference Thursday in West Baltimore that city homicides are at a 20-year low, but officials acknowledged that much work remains.
Because Hill's scooter and the keys to it were taken, police believe the motive may have been robbery. But no one could understand why anyone would take his life, too.
Family members gathered at the scene said they were too distraught to talk, and church members said they didn't know much about his background other than that he may have worked at a church in Northeast Baltimore, which he biked to until he purchased the scooter.
Here's what they did know: Whenever they needed a hand, they could count on Milton.
"When we needed a good back, it was 'Get Milton,' " said Bishop Darnal Johnson, the Ark Church's executive pastor. " 'It's late and people are going to their cars; get Milton.' "
John Eden, chairman of the deacon ministry, said Hill's efforts didn't seem particularly motivated by spirituality, though he did attend services during the week. He recalled that Hill had a mammoth appetite but stayed thin. He didn't ask for compensation for helping around the church, just a bite to eat from the pantry on occasion.
Eden said he and Hill often spent time together, leaning against the church fence and chatting.
"I'm gonna miss my buddy," Eden said, watching the water wash over the pavement.


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text: Dangerous winter storms, bad weather and sloppy road conditions are a factor in nearly half a million crashes and more than 2,000 road deaths every winter, according to the AAA Foundation for Traffic Safety. The foundation has suggestions for driving and how to prepare in case you get into a winter crash. (more…) Continue Reading →


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The tree lighting ceremony truly brings the Columbia community together, and reminds each of us, every year, that we are unconditionally, irrevocably alone. Here's how to make the most of the beautiful lights when you know there's nothing inside yourself but endless, self-perpetuating darkness:
1. Dress the part: Take the chance to break out your holiday swag, like those "vintage" gloves you cut the fingers off of. Don't worry—we won't tell your friends they're from Marshall's.
2. Do NOT fucking instagram it. You're in the city now. You've re-branded. Maybe the old you would've, but there's no way it's gonna fit into your current street trash-glam-punk aesthetic.
3. Revel in the holiday spirit: Tree lighting means the holidays are upon us! You are sure to be overcome by the holiday spirit and the all-consuming fear that you'll never outshine your brother. Use the final weeks of the year to reflect on everything you're grateful for, like the time your dad told you he was proud of you five years ago.
4. Take advantage of free Columbia goodies! Hot chocolate is perfect for warming up the vile corpse you live in.
5. Accept that your body is merely a vessel for pain, which, in the grand scheme of things, is meaningless. Lie down in the snow naked. Scream at passersby that you're finally ready to surrender to the inevitability of human suffering. Maybe it'll make her come back.
6. Stay hydrated.
"If this is what it takes to mend the racial scars of American society, it's a sacrifice I'm willing to make," said Greenwood.
"Exposing Westchester's kids to this kind of disease is nothing short of morally repugnant," said local activist group FreeEdu. "If you want to do justice to teaching America's colonial past, you should be giving them smallpox instead."
He's also eyeing a presidential run.
Uhhhh, superdelegates?
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Latest Screenshots for Sonic CD Re-Releaseby Tristan Oliver September 15, 2011
Retina Display Confirmed for iOS, XBOX Live Integration Confirmed for WP7
Today, Sega of Europe updated its product page for the Retro Engine fueled re-release of Sonic CD, adding more screenshots from the game. We have the five shots, which appear to be from the mobile edition, in our gallery below.
In addition, Sega revealed achievements coming, not just for PSN and XBLA, but also in the game's PC re-release on Steam. Furthermore, the iOS port will support the Retina display for devices equipped with it, and the Windows Phone 7 port will fully support XBOX Live leaderboards and trophies.
On the whole, the release should be very faithful to, if not an improvement on the original. We still don't have a firm release date for any platform in any region, however. We will update when we know more. Thanks to Tundiam for tipping us. If you have news to share, be sure to share it us by clicking Send News Tips at the top of every page.


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Good Friday evening, temperatures are mild near 60 degrees with partly cloudy skies. Overnight, expect mostly cloudy skies and mild temperatures, with lows in the upper 40's. For Saturday, we could start as some morning fog in spots, but temperatures will soar into the low and mid 60's, possibly upper 60's for our southern counties. It will be a mostly cloudy day, rain showers will move in during the late evening hours. Rain will be in the forecast for Sunday and going into Monday, some of that rain could be heavy.
FeaturedLocal NewsNewsWatchTop Stories
Friday 1/20/17 Weather Update
By Tyler BarkerJan 20, 2017, 17:54 pm816
Tyler Barker
Tyler Barker is currently the Interim News Director and Digital Content Manager for WOAY-TV. I was promoted to this job in Mid-November. I still will fill in on weather from time to time. Follow me on Facebook and Twitter @wxtylerb. Have any news tips or weather questions? Email me at email@example.com


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Egypt Today
Egyptian, Saudi water ministers hold talks
Tuesday، 06 March 2018 - 04:03 PM
Irrigation and Water Resources Minister Mohamed Abdel Aati had talks on Tuesday 6/3/2018 with his Saudi counterpart Abd al Rahman bin Abd al Muhsin al Fadhli on Egypt's efforts to protect beaches as well as early warning systems and protection from the dangers of torrential rains.
The talks also tackled the challenges besetting Egypt to secure its needs of water.
The two sides agreed to exchange visits by high-ranking delegations within the coming weeks to draw up cooperation memos in the water resources domain.


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This thesis describes synthesis of new chiral N,P ligands and their evaluation in two types of asymmetric transition-metal catalyzed reactions.
The first part of the thesis describes studies in iridium-catalyzed asymmetric hydrogenation. A new class of chiral N,P ligands, imidazole-phosphines, was synthesized and evaluated in the Ir-catalyzed asymmetric hydrogenation of olefins (Paper I). The new ligands proved to be highly efficient and enantioselective in the reaction. Because the substrate scope of Ir-catalyzed asymmetric hydrogenation is still limited to certain types of test substrates, new substrate classes with importance in medicinal and materials chemistry were investigated. Vinyl fluorides were efficiently hydrogenated to fluorine-containing chiral centers by the iridium catalysts with imidazole-phosphine ligands (Paper I). To obtain CF3-bearing chiral centers, we hydrogenated CF3-substituted olefins (Paper II). Ir-catalyzed asymmetric hydrogenation was highly enantioselective for the functionalized CF3-substituted olefins and the resulting chiral products can be valuable in design of materials such as LCD screens. Ir-catalyzed asymmetric hydrogenation was also evaluated as a route to diarylmethine chiral centers (Paper III). A wide range of new chiral compounds possessing a diarylmethine chiral center was obtained.
The second part of the thesis deals with asymmetric intermolecular Heck reaction utilizing N,P ligands. The N,P ligand class of thiazole-phosphines was evaluated in the Heck reaction (Paper IV) and gave high enantioselectivity. Further, the intermolecular Heck reaction was examined using computational and experimental studies (Paper V). This study led to a better understanding of the enantioselectivity in the reaction.
Fluorine-containing compounds are useful in many applications ranging from pharmaceuticals to ferroelectric crystals. We have developed a new, highly enantioselective synthetic route to trifluoromethyl-bearing stereocenters in up to 96% ee via asymmetric hydrogenation using N,P-ligated iridium catalysts. We also hydrogenated an isomeric mixture of olefins; this reaction gave the hydrogenation product highly enantioselectively (87% ee), and only the E isomer was present after the reaction had reached 56% conversion.
The asymmetric Heck reaction using P,N-ligands has been studied by a combination of theoretical and experimental methods. The reaction follows Halpern-style selectivity, that is, the major isomer is produced from the least favored form of the pre-insertion intermediate. The initially formed Ph-Pd(P,N) species prefers a geometry with the phenyl trans to N. However, the alternative form, with Ph trans to P, is much less stable but much more reactive. In the preferred transition state, the phenyl moiety is trans to P, but significant electron density has been transferred to the alkene carbon trans to N. The steric interactions in this transition state fully account for the enantioselectivity observed with the ligands studied. The calculations also predict relative reactivity and nonlinear mixing effects for the investigated ligands, these predictions are fully validated by experimental testing. Finally, the low conversion observed with some catalysts was found to be caused by inactivation due to weak binding of the ligand to Pd(0). Adding monodentate PPh3 alleviated the precipitation problem without deteriorating the enantioselectivity and led to one of the most effective catalytic systems to date.
New chiral bidentate imidazole-phosphine ligands have been prepared and evaluated for the iridium-catalysed asymmetric hydrogenation of olefins. The imidazole-phosphine-ligated iridium catalysts hydrogenated trisubstituted olefins with the same sense of enantiodiscrimination as known iridium catalysts possessing oxazole and thiazole as N-donors. The imidazole-based catalysts were shown to hydrogenate vinyl fluorides, in some cases with the highest ee values published to date.
A series of new phosphine-thiazole compounds has been synthesized and used as efficient ligands in the palladium-catalyzed asymmetric intermolecular Heck coupling of 2,3-dihydrofuran with aryl triflates and cyclohexenyl triflate. Microwave heating was used to accelerate the reactions and gave complete conversions in as little as one hour. Products were obtained with good to excellent enantioselectivities.
Diarylimethine-containing stereocenters are present in pharmaceuticals and natural products, making the synthetic methods that form these chiral centers are important in industry. We have applied iridium complexes with novel N,P-chelating ligands to the asymmetric hydrogenation of trisubstituted olefins, forming diarylmethine chiral centers in high conversions and excellent enantioselectivities (up to 99% ee) for a broad range of substrates. Our results support the hypothesis that steric hindrance in one specific area of the catalyst is playing a key role in stereoselection, as the hydrogenation of substrates differing little at the prochiral carbon occurred with high enantioselectivity. As a result, excellent stereodiscrimination was obtained even when the prochiral carbon bore, for example, phenyl and p-tolyl groups.