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Shutter Island(2009)
Filmmaking giant Martin Scorsese's psychological thriller is set in 1954 at Ashecliffe Hospital for the criminally insane on Boston's Shutter Island.... More
Detectives Teddy Daniels (Leonardo DiCaprio) and Chuck Aule (Mark Ruffalo) are investigating the mysterious disappearance of one of the patients - a murderess. Doctors refuse them access to records and the detectives start to believe illegal and sinister treatments are being undertaken. As a violent hurricane closes in on the isolated asylum and communication is cut off with the mainland, more criminals disappear, the clues multiply and Teddy begins to doubt everything - his memory, his partner and even his sanity.
This is the fourth Scorsese and DiCaprio collaboration (after Gangs of New York, The Aviator and The Departed).Hide
Directed by Martin Scorsese
Starring Leonardo DiCaprio, Mark Ruffalo, Ben Kingsley, Emily Mortimer, Michelle Williams, Max von Sydow, Jackie Earle Haley, Patricia Clarkson
Written by Laeta Kalogridis (based on the novel by Dennis Lehane)
- Drama, Mystery, Thriller
- 138mins
- Rating: R16 Violence, offensive language & content that may disturb
- Official website
- Movie Poster
Out Now (On-Demand,
DVD or Blu-Ray)
The Reviews
Flicks Review
BY Andreas Heinemann Flicks Writer
Legendary director Martin Scorsese's latest offering isn't quite the masterpiece his army of fan boys and film buffs in general may have been expecting. The twist is a tad predictable, it's a touch too long and the experimental nature of the narrative might see some write it off as weird.
Leonardo DiCaprio, however, continues to solidify his claim as one of Hollywood's most talented working actors. He handles every shift in his character's arc – pulpy gumshoe, caged animal, edge of madness – with skill and aplomb. Helping to no end is the fact that his supporting cast, particularly Ben Kingsley and Michelle Williams, are perfect in their roles.
The technical crew deliver in spades. Production design emphasises menace and claustrophobia with a string of impressive sets. These are expertly presented through cinematography that pays tribute to old-fashioned B-grade genre movies while maintaining a decidedly modern aura. A soundtrack that is perfect for a thriller of this ilk lays beneath the visuals, cranking up the tension when necessary.
Of course, there is also Scorsese, conducting like a maestro from the director's chair. Haunting imagery, strong conveyance of story, bold editing choices – he can do it all. Honestly, if you don't like Scorsese's work, maybe movies just aren't your thing.
The Peoples' Reviews
Your rating & reviewRate / Review this movie
Rate and/or review
Shutter Island
BY ineedpants grader
Sorry to say that this movie is overhyped. I went into it expecting it to be mind-blowing, based upon friend's opinions and critic's reviews, but it didn't live up to the hype for me. Don't get me wrong: I loved it, and I think it is a great movie. But for starters, you can see the ending coming from very, very early on in the movie, so the big reveal is kinda wasted...
Excellent acting by all made for a very good movie, well worth seeing.
BY Andrew-Hedley superstar
Loved this B-movie. Really well directed, good music, great acting. The stormy island is a perfect setting. Will be a little unusual for some multiplex junkies, but I'd recommend.
Brilliant actors saved this from being an average film along well known story lines. Lots of blue screen activity which were horrendously obvious - car, cliff and ship scenes - a empty glass slammed on the table seconds after an empty hand went to the mouth? Di Caprio, Ruffalo and Kingsley are too good for this film
Showing 5 of 21 reviews. See all reviews
The Press Reviews
The film's primary effect is on the senses. Everything is brought together into a disturbing foreshadow of dreadful secrets. Full Review
He movie certainly keeps you in its grip from the opening scene: It's a nerve-twisting, tension-jammed exercise in pure paranoia and possibly Scorsese's most commercial film yet. Full Review
Mr. Scorsese in effect forces you to study the threads on the rug he is preparing, with lugubrious deliberateness, to pull out from under you. As the final revelations approach, the stakes diminish precipitously, and the sense that the whole movie has been a strained and pointless contrivance starts to take hold. Full Review
Meticulous chiller. Full Review
DiCaprio, in his most haunting and emotionally complex performance yet, is the vessel Scorsese uses to lead us through the film's labyrinth. Full Review
Even when it's clear Scorsese has decided to employ fakery and allow it to be obvious, it's done with elegance and beauty. Full Review
A brilliantly directed, genuinely gripping and powerfully emotional thriller with a terrific central performance from Leonardo DiCaprio. Highly recommended. Full Review


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One of the most prestigious events at the ABCA Convention is the ABCA/Diamond Hall of Fame Banquet, which is held on the Friday evening of the convention and features the induction ceremony for the ABCA Hall of Fame as well as the presentation of the ABCA/Wilson Lefty Gomez Award.
The 2019 ABCA/Diamond Hall of Fame Banquet took place in the Gaylord Texan on Friday, January 4 at 6:30 p.m. The seven-member ABCA Hall of Fame Class of 2019 was announced on www.ABCAHallofFame.org in July. The Class of 2019 includes:
Joe Carbone, Ohio University
Gary "Bo" Collins, Southern Illinois University-Edwardsville
Ron Davini, Corona del Sol High School (Ariz.)
Pat Doyle, San Joaquin Delta College (Calif.)
Dave Grant, Glendale Community College (Ariz.)
Steve Kittrell, University of South Alabama
Scott Pickler, Cypress College (Calif.)
The ABCA/Wilson Lefty Gomez is named after the great Lefty Gomez and is presented annually to an individual who has contributed significantly to the game of baseball locally, national and internationally. The recipient of the 2019 ABCA/Wilson Lefty Gomez Award was Jim Darby.
The ABCA Hall of Fame Class of 2020 and the 2020 ABCA/Wilson Lefty Gomez Award recipient will be announced in July. The 2020 ABCA/Diamond Hall of Fame Banquet will be held on January 3, 2020. Registration for the 2020 ABCA Convention, which will be held at the Gaylord Opryland Resort & Convention Center, will open on September 1. Tickets to the Hall of Fame Banquet presented by Diamond will also be available for purchase beginning September 1. All tickets must be purchased in advanced -- no tickets will be sold on-site. Attendees to the banquet are requested to wear semi-formal attire.

subset: commoncrawl


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2 killed in fatal motorcycle crash; car driver charged
A man from Ossining, New York, has been charged with vehicular homicide and other felonies after he allegedly struck and killed a couple on a motorcycle on the New York State Thruway.
Following the early morning accident, the man reportedly fled from police. He was found later that day with a blood alcohol content level of 0.07 percent. The police estimate that the man's blood alcohol content level would have been 0.15 percent at the time of the crash. In addition, the man is alleged to have been trying to send a text message at the time of the accident.
In car accidents such as this one where criminal activities such as drunk driving are believed to have occurred, the district attorney's office may choose to pursue criminal charges. Families of the victims of fatal accidents may also choose to pursue civil action against a drunk or negligent driver via a wrongful death claim. Civil actions don't result in jail time, but rather in monetary compensation from the driver who caused the accident or from his or her insurance company.
The standard of proof is different in civil court than it is in a criminal case. Instead of having to prove guilt beyond a reasonable doubt as with a criminal case, civil court cases are decided by a preponderance of evidence. New York has a statute of limitation for filing wrongful death claims of two years.
Monetary damages that may be awarded from a wrongful death claim include such things as any medical expenses between the accident and the death, as well as loss of future income, loss of companionship and pain and suffering.


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SVP-InternationalOptingenstrasse 1CH-3013 BernTel. +41 (0) 31 336 16 26Fax. +41 (0) 31 336 16 25
Please enter the email address for your account. A verification code will be sent to you. Once you have received the verification code, you will be able to choose a new password for your account.
In the light-green colored countries we have members (as per August 2013).In the dark-green colored countries we have a section or a contact person. By clicking on the point you can reach the different national site.
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Apple Computeris market share of the U.S. computer market climbed to 4.3% in the September quarter, according to market research firm IDC. Thatis an increase from 3.3% from the year-ago quarter. Apple was the number five vendor in the U.S. market, behind Dell, HP, Gateway, and Lenova (formerly IBMis PC division), and the company showed a steeper climb in U.S. unit sales, 44.6%, than any other company in IDCis report.
IDC broke Appleis U.S. unit sales at 737,000 units. By comparison, number one vendor Dell shipped some 5.638 million PCs in the US. Dell had 33.2% of the market, well ahead of perennial number two HP, which had 20.3% of the market.
Gateway, a company that worked hard to be allowed to license the Mac OS in the early 1990s, showed what IDC called the second consecutive quarter of significant recovery. In recent years, the company had been seen as being on hard times with declining fortunes. In the September quarter, Gateway was the number three U.S. vendor. The company posted a 35.2% growth in unit sales, second to Apple, and claimed some 6.4% market share.
Worldwide, Apple saw a 48% increase in unit sales, but didnit crack the top five PC vendors (Dell, HP, Lenova, Acer, Siemens). IDC didnit specify Appleis worldwide market share, but extrapolating from Appleis own total Mac unit sales of 1.236 million Macs, a record quarter for the company, the company had some 2.3% global market share.
Such extrapolations are dangerous, at best, because IDC does not rely solely on corporate numbers, but uses its own formulas and research methods to determine units shipped. Using Appleis reported unit sales to determine market share based on IDCis global numbers is therefore an inexact science. Nonetheless, this rough and ready estimate shows Apple is holding its own in the global market.
Total worldwide unit sales increased by 17%, and IDC noted that this was despite increasing energy prices and interest rates. It was the low end of the market, a market Apple addressed earlier in 2005 with the inexpensive Mac mini, that drove overall growth. U.S. total shipments grew by 11%.
[Update: This story was updated with additional information and details. - Editor]


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Michael J. Atkin
Portfolio Manager
Mr. Atkin is a Portfolio Manager in the Global Fixed Income group. He is a Portfolio Manager of Putnam Diversified Income Trust, Putnam Global Income Trust, Putnam Master Intermediate Income Trust, and Putnam Premier Income Trust. In addition, Mr. Atkin leads macroeconomic discussions as part of the Portfolio Construction group and manages a team of analysts who evaluate government securities in G7 countries and emerging markets. He joined Putnam in 1997 and has been in the investment industry since 1988.
Blog posts
How the Japan election may influence global interest rates
October 11, 2017
The Japan election could have consequences for the future leadership of the Bank of Japan and the country's impact on global interest rate trends.
Why Brazil's crisis creates new concerns
May 26, 2017
The revelations of May 17 may pose a threat to President Temer's administration, and therefore a threat to Brazil's short- and medium-term economic outlook.
See the dove in the Fed's dot plot
December 15, 2016
The market sees a more hawkish Fed in the December 2016 rate hike, but we see see signs of a dove in the Fed's dot plot.


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Re: Patton/Smith
In reply to:
Re: Patton/Smith
Tim Gruber 2/09/11
Dear Tim,
Thank you for your reply and suggestions! I have received a copy of grandma,Jennie's OBIT and it doesn't list parents or any siblings, just her children, no birth area listed. I also sent and received a death certificate. That's where I obtained father's name of Geo.Patton, mother unknown. I will work on your suggestion leads. Sincerely, Karen


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Author's Notes
Disclaimer - All the Twilight stuff belongs to Stephenie Meyer. No copyright infringement is intended. I'm just cavorting on her checkerboard.
Summary - I'm tired of the dating scene. I'm tired of trying to be the nice boyfriend. I am letting go of the last scruple I have. I'm going to buy a slave.
This story is going to contain some harsh material. It has reference to human trafficking and sexual slavery, physical and emotional abuse. It does not romanticize sexual slavery or validate it in any way, shape or form. However, it is told entirely from the point of view of the person doing the buying, so you're going to be hearing some of his thoughts on the whole thing. Sometimes his naiveté on what he's doing is going to be a bit comical, but this is not a comedy. His twisted views are not the same as me, the writer, condoning any illegal real-life acts along the same lines, which are obviously heinous.
Surviving Bella is not a story about survival at sea. It is about an alcoholic dealing with his horrific past and trying to find a reason to go on, and the woman who helps him rediscover his soul.
This story is not about sexual slavery. It's about a man who thinks he's entitled to whatever he wants, and how he is going to deal with the consequences of his actions.
If you have read any of my other stories, you may see a bit of a theme when it comes to my Edwards. They ain't all right in the head. They have kidnapped Bella, been abusive, been alcoholics, been nutcases, been murderers, been douche-bags, been self-centered assholes, etc. Actually, the one with physical brain damage is the only one who wasn't an ass. Deeply flawed characters are far more interesting to me as subject material for writing. In the end, they tend to have grown up a bit, and those readers who stuck it out ended up at least having an understanding of why they were they way they were.
That said, if you don't think you are going to like the material, please don't read it. It's not going to hurt my feelings. If you start reading it and don't like it, please feel free to politely let me know why in a review (if you would like to do so), and stop reading. All others, just trust me. Chapters are short, and I'm going to update frequently (thank you QuantumFizzx). Don't dwell too much on the harshness of the beginning and start making assumptions on where this is going to go – everything happens for a reason, there is method to my madness, and at the time I write this (12 chapters in), I seriously doubt anyone will correctly guess where this is going.
Brave, trusting souls – continue on.
I was not a BDSM guy, really.
Could Be Worse, Right?
Could Be Worse, Right?
I want a sex slave.
Fucking sue me.
I watched Kate's delectable backside as it sauntered out of my office and out of my life. I should have known it wasn't going to work from the very beginning, when she wouldn't even let me open the car door or choose the fucking wine. If she refused all that on the first date, I probably should have ended it after the second. She lasted longer than the last few, at least nearly a month. Apparently she had decided I was way to Neanderthal for her tastes. Neanderthal. Nice.
Maybe it was my fucked up childhood, or maybe it was just because there was something fundamentally wrong with me. I didn't really care. I just wanted a beautiful woman at the beck and call of my cock. It's not like I didn't return the orgasms. I'd fucked my name out of the mouth of every woman I'd been with, and usually had them begging for more. The problem was they just weren't always on my time schedule. They had careers, or families or friends or whatever that got in the way of focusing on me and what I wanted. Did that make me a selfish prick?
Fine, it did. I didn't fucking care.
I was not a BSDM guy, really. I didn't have a play room full of canes and shit like that, though I didn't see anything wrong with some silk scarves and maybe a pair of handcuffs. Having a woman listen to what I say and do it when I said it, yeah – I liked that idea. The thought of having a naked woman on her knees when I got home at night, ready to make me dinner or just bend over one of the dining room chairs – I liked that idea, too. I especially liked it when it came to me wanting to have a little stress relief in the form of a blow job in my office. I just wanted a hot chick to suck me off when and where I wanted it, and maybe be willing to take my cock up her ass. That would be a nice bonus.
Damn Kate. She didn't even really consider that it might be fun for her, too.
I sighed and thought about calling Aro. The last three failed relationships had resulted in the same thought, but I had been way to chicken to consider it. I mean – he didn't exactly run a dating business. The guy sold fucking slaves. Even if I managed to transfer the funds without one of my numerous accountants being all up my ass about it, it was still – in every sense of the word – slavery. The illegality of it aside, it was just fucking wrong, wasn't it? Did I have any scruples left?
Aro had been at a New Year's Eve party at the Country Club when I had just been dumped by yet another "I'm not here to be your slave" girlfriend. I had indulged just a bit too much Markers Mark 46 and must have spilled my drunken guts to some degree. Aro ended up having a little private conversation with me, and had certainly gotten my attention. I didn't know where he got them, and I wasn't about to inquire. I did value my life to some degree, and I knew when not to ask any questions.
I shook my head, silently telling myself not to entertain such ridiculous ideas. I wasn't going to sink as low as to support that sort of illegal trade. I had plenty of other shady businesses to keep me a little paranoid – I didn't need to bring my sex life into it as well.
For some reason I thought of Tanya, my high school sweetheart, if you could call her that. She was a strict vegetarian – refusing to eat anything that ever had a face or a mother. It didn't stop her from sucking my cock, but she wouldn't swallow, sighting the same beliefs. I always figured it was pointless – I mean, just because she isn't going to eat the burger doesn't mean it wasn't going to get eaten. She could walk away with her moral nose in the air, but some fucker was going to sit down and bite into that big, juicy chuck of meat. The cow was dead, and her refusal to eat it wasn't going to change that fact.
The girls are already slaves. They could end up with anyone who could use them for anything. It could be some fat bastard who would beat the shit out of them for fun, or some nutcase who makes snuff films. Shit, it really could be something like that. If I didn't take a bite, someone else was going to in my place. If one of his girls didn't end up on the end on my cock, she'd just be servicing another.
My hand was shaking as I pulled my cell phone from my pocket and started dialing the number. I didn't know who she might be, or how she might have gotten herself into such a predicament, but in some ways I would kind of be saving her, wouldn't I? I mean, I wasn't interested in hurting anyone – I just wanted to stop with the dating game and still get my rocks off whenever and wherever I saw fit.
"Volturi here."
"Hey Aro," I found myself saying into the phone. "Edward Cullen here. I would like to talk to you about a purchase."
She had to be better off with me, right?
Chapter End Notes:I know exactly where this is going now. Do not fear! Well...fear a little bit.


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Venue Information
Accessible or ADA seating may be available at this venue through Goldstar. Contact us before buying tickets to make arrangements.
10 Vibiana Tips
This is the second time I've been to Vibiana's when parking next door has been free!
No Value at All ! Bad attitudies of most staff, nobody working looked like they wanted to be there!
Tiny bites, no selection, had to purchase some tastings.
Free parking next door.
A wonderful venue! Check out the exquisite marble in the bathroom!
Expensive event parking in the neighborhood -- cheaper across the street
Tallis Scholars
Water available
Tallis Scholars


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One of the best parts of holiday decorating is seeing how others do it! We gathered up some of our favorite decor inspiration from around the web to inspire any last minute holiday decor adventures you might be embarking on this week.
This holiday scene by Monika Hibbs is everything, and we would totally move into this play house ourselves.
This space by Sean Anderson Design is dark, dramatic, and gorgeous. The greenery brings the space to life!
Hello Fashion Blog
This dinner party is not last minute, but you can definitely take inspiration from it. We love how Christine from Hello Fashion Blog used our hand towels as napkins in her beautiful table setting. She used neutral colors, gold and greenery to make it festive, proving that you don't need to fill your home with Santa themed pieces to get in the holiday spirit.
Melissa's beautiful space is perfectly simple but feels like a winter wonderland. Her doormat works year-round, but the "Well, Come On In" message is especially fitting for the holidays.
Last year's video was pretty cute, if we do say so ourselves!
Park and Oak Design
Millwork, vintage art, and a gorgeous garland! This entrance by Park and Oak Design is everything.
Anissa from House Seven nailed it with her holiday mantel. We love the stockings displayed on one side, balanced with the candlesticks on the other. The Juniper Berry Wreath is fresh and festive, making the space feel alive. The ribbon comes free when you order a wreath from McGee & Co.!
Here are our tips for styling a holiday mantel!
Using your darker toned pillows makes the space feel festive and cozy during the winter time. Velvet is perfect for the holidays because it's dark, textured, but soft.


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Let's talk about something exciting today. Hmmm… now what could that be? Brexit? Trump vs. Hilary? Flying with a stunt pilot in an airplane that runs out of gas? Mercy, no! The raw material used by Archiped to make its hand cast garden statuary and how it differs from cheapo gray concrete is probably the most fascinating topic that you will find on the Internet today. Oh yes, it's true. Cast stone is enthralling!
Author Archives: admin
Archiped Classics Finds Concrete Solution in Rapid Set®
Oftentimes, an abundance of talent and vision alone don't determine a business owner's success. Many times, it's sheer tenacity that takes natural ability to great heights. Take, for example, Archiped Classics Inc., the producer of fine cast stone urns, jardinières, pedestals, and garden ornaments for interior and exterior use, headquartered in Dallas.
Richard Stanzel, co-owner of Archiped Classics, began his concrete-based craft nearly 22 years ago with his wife, Shelley. After a promising first 10 years, Stanzel tried using a cement product in the late 1990s that provided some major challenges to their successful business.
Archiped Makes Planting Flowers in Outdoor Cast Stone Urns and Planters Easy
Not all urns and pots and planters come ready to plant. Anyone could logically think that one could buy a planter, take it home, pour in some dirt, stick in a plant and get ready to hear the oohhs and ahhhs of friends.
Unless you are buying from Archiped, it's not that easy. Archiped's cast stone urns and planters all come with drainage holes so that your flowers won't drown. They don't have to be emptied in the winter or covered to prevent cracking. You don't have to add gravel. In fact, you don't have to do anything. With Archiped cast stone products, you plant it and leave it.™
Does my Blog about Luxury Garden Urns Make me Sound Like I Flunked English 101?
I'd like for you to know that I do practice correct grammar in my compositions for thank you notes and legitimate articles, even though it's much more fun to go with a stream of consciousness flow, write in the vernacular, forget that commas exist, put too many…….. and —– where they don't belong and have v –e – r – y long run on sentences so long that the reader forgets what the sentence is about anyway.
This means that I throw in the kind of words that may not jive with the high-end garden urns and pedestals that we produce and sprinkle some high falutin' words throughout my blog to catch my readers off-guard.
However, it does create an interesting juxtaposition between the elegant outdoor art that we hand cast and the casual, conversational tone of the blog. At least, I think it's an interesting juxtaposition. I don't know if an English professor would agree.
To Use or Not to Use a Luxor Urn? That is the Question.
People always ask me what it's like to work with my husband. Well, it's interesting. We have some feisty fights. Oops! I mean arguments. Double oops! I mean genteel discussions.
No, they're not about using the Luxor Urn in an ad, because we both like it. It's more like trying to agree whether the Luxor Urn—or one of our other unique urns or pedestals—has been featured in our print ads too often.
I, of course, could look through my advertising file, but that would mean that I would actually have to find it in the hard copy netherworld of my personal filing system.
Do Elegant Urns Match with White Pianos?
"It's a Hunk a' Hunk of Burning Love" is a song made famous by …whom? Let me give you a hint: he's the swinging singer with the swiveling hips who shocked the nation when he appeared on the Ed Sullivan show. Stumped? Well if so, I have a sneaking suspicion that you are under fifty.
Those of us who are, ummm, shall we say mature, know immediately that Elvis Presley made the "Hunk a Hunk of Burning Love" song famous.
Side note: My brother is an Elvis fanatic and when he went to Graceland, he stayed in the Hunk a Hunk of Burning Love room at the hotel across the street. According to the hotel's website, the Burning Love Suite features a rich, romantic decor (lots of red). It is inspired by Elvis' 1972 hit record Burning Love and his status as a romantic idol.
I have a sneaking suspicion that our handmade designer urns wouldn't be the best addition to the Graceland décor or to the Heartbreak Hotel across the street.
Looking for Archiped Cast Stone Urns and Statuary: The Ultimate Dream Vacation
I'm thinking about a vacation. Yes, that is V-A-C-A-T-I-O-N. Summer is coming up and hmmmm, I wonder where I'd like to go?
If you are like me—and you probably aren't—I dream of going to see some of Archiped's most impressive fine cast stone installations. The problem is not only are they all over the world, the ones I HAVE to visit just happen to be the most expensive. Expensive, as in rooms that can cost thousands per night. Yes, I wrote THOUSANDS. Just call your favorite Ritz-Carlton, Four Seasons, Waldorf, and Rosewood hotels and resorts, just a few of the places our urns and statuary are, and find out.
You can check out some of my favorite urn and pedestal combos at our installations in Vegas on the cheap, however. Start out at the Venetian and Palazzo to see ten of our Napoleonic Benches, one of my favorite designs from the Jacques Lamy Collection, with some of our other cast stone urns, planters and pedestals scattered throughout.


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Harry L.
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford OX1 3TA, UK. E-mail: firstname.lastname@example.com
First published on 20th January 2017
Three different types of template-directed syntheses of linear porphyrin oligomers are presented. In the classical approach the product has the same number of binding sites as the template, whereas in Vernier reactions the product has the lowest common multiple of the numbers of binding sites in the template and the building block. Mutual Vernier templating is like Vernier templating except that both strands of the Vernier complex undergo coupling simultaneously, so that it becomes impossible to say which is the 'template' and which is the 'building block'. The template-directed synthesis of monodisperse linear oligomers is more difficult than that of cyclic oligomers, because the products of linear templating have reactive ends. All three types of templating are demonstrated here, and used to prepare a nickel(II) porphyrin dodecamer with 4-pyridyl substituents on all twelve porphyrin units. The stabilities and cooperativities of the double-strand complexes involved in these reactions were investigated by UV-vis-NIR titration. The four-rung ladder duplex has a stability constant of about 2 × 1018 M−1 in dichloromethane at 298 K.
In template-directed macrocyclization reactions,17–23 a template which favors formation of a particular ring-size automatically prevents further coupling. However, in the template-directed synthesis of linear oligomers, the products typically have reactive termini, so that it becomes necessary to control the reaction time, or to add a capping reagent, to avoid uncontrolled polymerization. This lack of a "stop" signal makes the template-directed synthesis of linear oligomers more challenging than that of cyclic ones. On the other hand, linear systems present an interesting analogy to DNA replication, and they open up the exciting possibility of coupling along both strands of a Vernier complex, so that there is no longer a distinction between the 'template' and the 'building block'. Here we test the scope of this strategy, which we call 'mutual Vernier templating', in the synthesis of linear porphyrin dodecamers.
(a) Classical templating: A template binds to n molecules of a complementary substrate to form a double-strand 1:n complex. After coupling, the product will be the same length as the template (Fig. 1a).
|Fig. 1 Linear template-directed syntheses of monodisperse linear porphyrin oligomers. (a) Classical template-directed synthesis. (b) Vernier templating synthesis. (c) Mutual Vernier templating: both strands couple. (d) Key to molecular design.
(b) Vernier templating: This strategy uses the mismatch between binding sites of substrate and template to direct the formation of the product with the lowest common multiple of the number of binding sites in the substrate and the template (Fig. 1b).
(c) Mutual Vernier templating: This is similar to Vernier templating, except that now both components undergo coupling, so that two product stands are formed, each controlled by the other (Fig. 1c).
|Fig. 2 The chemical structure of the 4-rung ladder complex NiP4·CPDIPS-ZnP4 (CDCl3, 500 MHz, 298 K) together with key NOEs between the components (left) and complexation-induced changes in proton chemical shift.
|Fig. 3 The ladder complexes and calculation of effective molarities from binding constants. The statistical factors used here, in Fig. 5 and Table 1 were calculated from the symmetry numbers as explained in ref. 39 and 40.
|Fig. 4 UV-vis-NIR denaturation titration of CPDIPS-ZnP4·NiP4 ([complex] = 1.11 × 10−6 M) with pyridine in dry CH2Cl2 at 298 K. (left) Changes in absorption upon addition of pyridine; the spectrum of the initial complex (thick black line) and the final spectra of the pyridine-saturated Zn tetramer and unbound Ni tetramer (red line). Arrows indicate areas of increasing and decreasing absorption during the titration; (right) binding isotherm (open dots) derived from absorption data at λ = 838 nm and calculated isotherm (red line) (Run 1: R2 = 0.9997; Run 2: R2 = 0.9997).
|β 1:1
|β 1:2
|β 2:2
|β 2:3
|Fig. 5 Complex formed between ZnP4 and NiP6. The overall stability constants for the formation of each complex are provided in terms of K1:2, K2:3 and K1:1.
|Fig. 6 (a) UV-vis-NIR titration of ZnP4 ([ZnP4] = 0.73 μM) with NiP6 in dry CH2Cl2 at 298 K. Arrows indicate increasing or decreasing absorption (black, free ZnP4; green, 1:2 complex; blue, 2:3 complex, red, 1:1 complex and magenta, the end spectrum of NiP6-saturated-ZnP4). (b) Zoom-in of the change of isosbestic points in the absorption spectra. Arrows point out three subsequent isosbestic points at 0.5, 0.7 and 1.0 equivalents of NiP6, which is consistent with NiP6:ZnP4 complexes of 1:2, 2:3 and 1:1 stoichiometries, respectively. (c) Binding isotherm (open dots) derived from absorption data at various wavelengths and fit obtained from global analysis with SPECFIT (solid lines). (d) The speciation plots as a function of the ratio [NiP6]/[ZnP4] (black, free ZnP4; green, 1:1 complex; blue, 2:3 complex, red, 1:1 complex and magenta, free NiP6).
|Fig. 7 Reaction design and outcome of linear tetramer templating for the synthesis of NiP4 from NiP2, using PhC2-ZnP4 as the template. (a) Reaction scheme. (b) GPC traces (detection at 646 nm, toluene/1% pyridine) of the non-templated reaction (top) and the templated reaction (bottom) product mixture after removal of the template PhC2-ZnP4. The product NiP4 and unreacted starting material NiP2 were isolated and identified by MALDI-ToF MS and 1H NMR spectroscopy.
Unreacted NiP2 starting material was observed in both these reactions, because they were stopped before completion to prevent the formation of long Ni oligomers, which would be inevitable at high extents of coupling. It is surprising that traces of longer Ni porphyrin oligomers were not observed by GPC in these reaction mixtures; this may reflect the slowness of the coupling reaction; it is also possible that longer oligomers were lost during work-up due to low solubility. We also carried out similar reactions using CPDIPS-ZnP4 as the template instead of PhC2-ZnP4. As expected, changing the capping group does not alter the effectiveness of the template. The desired product NiP4 was isolated in yields ranging from 35% (from 39 mg of NiP2), 42% (from 3.0 mg of NiP2) to 54% (from 22.3 mg of NiP2), all using the CPDIPS-ZnP4 template.
|Fig. 8 Reaction design and outcome of linear tetramer templating for the synthesis of ZnP4 from ZnP2 using PhC2-NiP4 as a template. (a) Reaction scheme. (b) GPC traces (detection at 591 nm, toluene/1% pyridine) of the non-templated reaction (top) and the linear templated reaction (bottom) product mixture after removal of the template PhC2-NiP4 at 3.5 h and (c) at 1.5 h. Products were identified by analytical GPC based on calibrated retention times, MALDI-ToF and 1H-NMR for ZnP2 and ZnP4. ZnP4 was isolated in 23% and 30% yield from the reaction time at 3.5 and 1.5 h, respectively. The percentages in GPC traces represent the % GPC yields of corresponding compounds, calculated by integration of the peak areas.
Reducing the reaction time from 3.5 h to 1.5 h reduced the formation of longer oligomeric byproducts, while increasing the yield of the desired product ZnP4 (Fig. 8c). In the presence of the template, the reaction gave ZnP4 in up to 30% isolated yield (44% GPC yield), together with enhanced amounts of multiple-of-four byproducts (ZnP8 and ZnP12). The template acts as a positive template in this reaction,23 promoting the intramolecular coupling leading to the formation of the desired tetramer from dimers. Surprisingly, under these reaction conditions, zinc porphyrins undergo faster Glaser coupling than nickel porphyrins, despite the fact that nickel is more electron-withdrawing than zinc, which would have been expected to favor the Glaser coupling reactivity.37b,44
|Fig. 9 Reaction design and outcome of linear tetramer templating for the synthesis of NiP6 from NiP2 using THS-ZnP6 as a template. (a) Reaction scheme. (b) GPC traces (detection at 646 nm, THF) of the linear templating reaction product mixture with the template THS-ZnP6. Products were identified by MLALDI-ToF and 1H-NMR for NiP6.
|Fig. 10 Reaction design and outcome of linear Vernier templating for the synthesis of ZnP12 from ZnP4 using PhC2-NiP6 as a template. (a) Reaction scheme. (b) GPC traces (detection at 591 nm, toluene/1% pyridine) of the non-templated reaction and (c) the templated reaction product mixture after removal of the template PhC2-NiP6 at 4 h. Products were identified by analytical GPC based on calibrated retention times.19 The percentages in GPC traces are the analytical yields of each oligomer, from integration of the peaks (absorption at 591 nm).
With no template (Fig. 10b), the reaction produced more polymers and small amount of the desired product ZnP12 (14% analytical yield) as noticed in the previous control experiment for Ni tetramer templated reaction (Fig. 8b). In the presence of template (Fig. 10c), the substrate ZnP4 was converted into two major products: the intermediate ZnP8 in 20% analytical yield and the Vernier product ZnP12 in 21% analytical yield. The unreacted substrate ZnP4 was observed in 17% analytical yield, indicating slower coupling in the Vernier templating reaction than the classical templating reaction. It appears that template-directed formation of ZnP8 is faster than subsequent coupling to form ZnP12. The results show that ZnP12 can be synthesized by the linear Vernier templating, even though there is competing polymerization. The yield of the templated reaction could probably be increased by optimizing the reaction time.
|Fig. 11 The mutual Vernier templating and three control reactions for the synthesis of NiP12 and ZnP12. m and n are the number of the repeat units.
Similarly to the previous experiment, ZnP4 and NiP6 were mixed in a 3:2 stoichiometric ratio in dry dichloromethane and the complexation was confirmed by UV-vis-NIR spectroscopy, then aliquots of the coupling reagents CuCl and 2,2′-BiPy were added every 3 h to maintain the coupling reaction. The reaction was monitored by analyzing aliquots by GPC (eluting with 1% pyridine/THF) at 1, 3, 4, 6, 7 and 8 h. After 8 h, the reaction was further analyzed by MALDI-ToF mass spectrometry.
Three control reactions were set up as follows (Fig. 11):
The results from all reactions are presented in 2D-plots of the retention times versus Q-band absorption spectra, deconvoluted GPC traces and 1D-plots of analytical concentrations that were calculated by peak fitting of resolved GPC peak areas (Fig. 12), and MALDI-ToF mass analysis (Fig. 13), respectively, as follows.
|Fig. 12 The outcome of the mutual Vernier templating and three control reactions of the synthesis of NiP12 and ZnP12. (a) The selected deconvoluted GPC traces fitted to Gaussians by Origin® at 0, 1, 4, 6 and 8 h, respectively (THF/1% pyridine, detection at 479 nm where all species have essentially the same absorption coefficient per porphyrin unit). (b) The plots of analytical yields that were calculated by peak fitting of resolved GPC peak areas. (c) The selected 2D-plots at 0, 1, 4, 6 and 8 h, respectively. The intensity was normalized by rainbow colors from purple (lowest) to red (highest). The retention times of all components were calibrated from known compounds, and their identification was based on the calibrated retention time in GPC.
|Fig. 13 Schematic of MALDI-TOF spectra of the mutual Vernier templating and three control reactions of the synthesis of NiP12 and ZnP12. Red lines represent the zinc porphyrin oligomers while blue lines indicate the nickel porphyrin oligomers. The mixed red-blue color indicates the heterocoupling zinc–nickel porphyrin oligomers. (See Fig. S34–S37† for raw mass spectra.)
At early reaction times (1 h) the mutual Vernier templating reaction shows a weak Q-band for ZnP12 whereas ZnP8 and NiP12 are quite intense, but at later times the three products have similar intensities (Fig. 12a mutual Vernier templating). Although the retention times of NiP12 and ZnP12 are very close, their Q-bands can still be deconvoluted from the absorption wavelengths.
The Q-bands in the Zn control reaction become more red-shifted at shorter retention times as the reaction progresses, reflecting the formation of longer Zn oligomers (Fig. 12a Zn control) while the Q-bands in the Ni control show up at shorter wavelengths and are mostly unchanged, indicating slow conversion from NiP6 to NiP12 and small amount of polymers at shorter retention times (Fig. 12a Ni control).
Strikingly, in the pyridine control, in addition to the expected distinctive absorptions from Ni and Zn porphyrin oligomers, we can see the Q-band absorption in regions where both species absorb, implying the formation of the product ZnNiP10 arising from heterocoupling between ZnP4 and NiP6 (Fig. 12a pyridine control).
At the start of the linear mutual Vernier templating reaction (1 h), the Zn-strand accelerates the coupling reaction of NiP6 yielding NiP12 in 41%, whereas ZnP12 forms only in 7% yield, and partial coupling from ZnP4 to ZnP8 (42%) was observed at the same yield as NiP12. It can be seen that the Zn-strand speeds up the coupling reaction of the Ni-strand as NiP6 is consumed faster than in the Ni control (Fig. 12b and c mutual Vernier templating compared to Ni control). Surprisingly, the Ni-strand appears to slow down the coupling of the Zn-strand compared to the corresponding control (Fig. 12b and c mutual Vernier templating compared to Zn control). Then, while ZnP8 is gradually converted to ZnP12, NiP12 can further couple to form longer oligomers due to the absence of protecting groups at the acetylenic ends. After 8 h, the yields of the three products ZnP8 (24%), ZnP12 (23%) and NiP12 (28%) became almost equivalent (Fig. 12a and b mutual Vernier templating). Both desired products NiP12 and ZnP12 can form longer oligomer while the coupling reagent is still active, providing traces of high-mass oligomers as seen in the GPC traces at longer reaction times (Fig. 12b mutual Vernier templating). The yields of the Vernier products appear to peak at a reaction time of 6 h (38% for NiP12 and 24% for ZnP12).
As expected, the Zn control reaction led to the increasing statistical coupling of the Zn oligomer products as time proceeded, yielding polymers as the major products at the end of the reaction time (at 8 h). After at 1 h, the unreacted substrate ZnP4 was dominant at 48%; ZnP8 and ZnP12 were also observed in 31% and 11% yield respectively. With increasing time from 3 to 8 h, the polymers become the major products and yields of ZnP8 (from 16% to 4%) and ZnP12 (from 14% to 6%) become very low. The highest yield of ZnP12 (14%) is still much lower than from mutual Vernier templating (24%) (Fig. 12b and c Zn control).
On the other hand, the Ni control reaction gradually produced NiP12 and a small trace of polymers due to the slow coupling rate of the Ni porphyrins. However without a template effect, the yield of NiP12 in the beginning (24% at 1 h) is almost two times lower than from the Vernier templating (41%) and then increases to 34% at 8 h (Fig. 12a and b Ni control).
In the pyridine control (Fig. 12a and b pyridine control), homocoupling products ZnP8 (from 28% to 12%) and ZnP12 (from 12% to 13%) were statistically produced at almost the same rate as in the Zn control from 1 to 8 h. NiP12 is not clearly observed in the GPC traces while the new species of the product of heterocoupling between ZnP4 and NiP6 was observed as anticipated, yielding the 10-porphyrin unit oligomer ZnNiP10 in 29% and reducing to 7% yield from 1 to 8 h. After 8 h, polymers become the main products.
Since the retention time of ZnP12 and NiP12 are very close at 28.6 and 29.1 min in the Vernier-mutual templated reaction, there is uncertainty in the fitting area of the corresponding deconvoluted peaks. Thus, to confirm the reliability in the fitting results, yields of the product mixtures at 779 nm (where only Zn species absorb) were determined and compared indirectly by the product-to-substrate ratios of ZnP12/ZnP4 and ZnP8/ZnP4 to those at 479 nm, resulting in a good agreement of the values in both wavelengths as shown in ESI.†
To support the analyses obtained from calibrated GPC time-traces, the products of the Vernier-mutual templating and the control reactions were also analyzed by the MALDI-ToF mass spectrometry (Fig. 13). The mass data are in good agreement with the GPC analysis discussed above.
In comparison to the cyclic Vernier templating synthesis of 12-porphyrin nanoring using the Zn porphyrin tetramer substrate and radial hexapyridyl ligand template (T6),17,18 the linear Vernier-mutual templating approach shows that two distinctive species NiP12 and ZnP12 can be synthesized without a discrete template. Despite the fact that the unprotected end groups of the products NiP12 and ZnP12 can react further to produce polymeric mixtures in the linear route (a problem that does not arise in macrocyclization), the efficiency of the two methods are comparable in term of the range of yields (38% for NiP12 and 24% for ZnP12 compared to 39% for cyclic 12-mer18).
Linear porphyrin oligomers of up to six porphyrin units were successfully synthesized by the classical template approach using complementary templates and substrates with commensurate lengths under oxidative-coupling conditions, in a manner reminiscent of DNA replication. The porphyrin templates in the classical approach can be recovered in high yield (up to 85%) making this method a practical route to the desired oligomers. However, classical templating is not suitable for the synthesis of longer linear oligomers due to the difficulty of synthesizing long templates. To solve this problem, we exploited linear mutual Vernier template-directed synthesis to achieve the construction of two complementary supramolecular porphyrin dodecamers, via the Vernier assembly of two different types of substrates. Mutual Vernier template coupling gives higher yields of the Vernier products than the control reactions, and it favors homo-coupling over cross-coupling (suppressing the formation of mixed Zn/Ni-strands). This approach adds to the toolbox for supramolecular strategies to the controlled synthesis of materials with interesting photophysical properties. In principle, the double-strand structures discussed here should be capable of autocatalytic self-replication, but replication will be strongly inhibited by the high stability of the duplex and the reaction profiles are expected to be parabolic rather than exponential.45 It is interesting to compare these ladder complexes with other designs for self-replicating molecules.45–54 There are also previous reports of synthetic systems in which double strand formation controls polymer growth.55 In the work presented here, we have confined our attention to templates in which all the sites are identical; in future it will be interesting to explore template-directed coupling of oligomers with sequences of Zn and pyridyl/Ni sites, for encoding binary information.56
|† Electronic supplementary information (ESI) available: Synthesis and characterization of new compounds, ladder complexes, UV-vis-NIR titrations and binding data for reference compounds and for the formation of linear oligomer complexes, calculation of effective molarities, analytical GPC calibration and molar absorption coefficients. See DOI: 10.1039/c6sc05355f
|This journal is © The Royal Society of Chemistry 2017


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Space Tomatoes
Tuesday, August 08, 2006
Sony to Launch a New Wireless Handheld
Wow a Sony product I would actually consider buying. Too bad they can go fuck themselves.
My Way News - Sony to Launch a New Wireless Handheld
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The UK Championship 2016 has been a great tournament overall, especially the second week, but it's not all smiles on the player's side…
Earlier in this month Mark King, winner in Belfast, and Anthony Hamilton, semi-finalist, have revealed how hard financially it is on the tour, even for mid-ranked players. This week Jamie Jones, after reaching the QF, also claimed he was skint. Barry Hearn continues to deny the issue, but it is a real issue and I find the contempt he shows for the players, who are his more valuable asset actually, quite shocking. Top players have suggested that the tour should be cut to 96 or 64 and that the structure of tournaments should be changed. The last to do so was Mark Selby in this interview. He is the World and UK Champion, the World n°1 for nearly two years running. Will he been listen to? I wouldn't hold my breath over it …
Ronnie "infamously" spoke about snooker as being perceived by the media as car-boot sales sport and, of course got stick from Barry Hearn for it. Now only days later, the UK Championship 2016 main broadcaster, the BBC, left in the middle of the QF decider between John Higgins and Mark Selby, in order to show some entertainment, not live, program. You can read here what Hector Nunns had to say about that on inside-snooker . So, Hector requested an explanation from BBC, what about Barry Hearn? Because, this, in fact just shows why Ronnie is right in his perception of the general media attitude towards his sport.
Then there were load of complaints about conditions. I just put here a screenshot of a little conversation on twitter between Mark Selby and Marco Fu (not exactly nobodies)
This has been an ongoing issue for years now: big bounces and kicks. Shaun Murphy has some strong ideas about the kicks, and I honestly don't know if he right or partially right, but clearly he won't get his ideas through as explained here by Hector (again) on inside-snooker. Now Jason Ferguson is someone who truly cares for his sport and the players, I'm certain he does the best he can, but it's still a concern that such an important issue can't be addressed after years of complaints. The players deserve conditions that allow them to show the full extend of their skills, and so does the paying public that comes to watch them.
And finally (for now at least), there is the small matter that the German Masters qualifiers start tomorrow in Barnsley and the players haven't been informed yet about the draw or schedule. Which triggered that rather sarcastic tweet by Mark Allen :
Turns out the WPBSA do work on Sundays. I got an email from disciplinary yesterday. Any chance of the draw now? Thanks @WorldSnooker1
Just one many players complaints … they need to arrange travels and accommodations, mind you!
And just as I finish writing this rant, some players apparently finally got that draw… ain't that magic?


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Opinion Extra
Parker: The reluctant warrior
"Our governor is blessed with poor judgment. I regret to inform you of that, but we all know it."
Rep. Walt McLeod, D-Newberry
-- "What people didn't know was that I had asked Mark to leave . . . without permission to see his woman in Argentina or to see her anywhere, and he was to have no contact with the boys or myself for 30 days. And my hope was that he would wake up from whatever he was in the throes of and maybe see what he might lose."
Jenny Sanford
-- "We can't impeach for hypocrisy. We can't impeach for arrogance. We can't impeach an officeholder for his lack of leadership skills. We cannot impeach a public official because the public has lost confidence in his ability to lead."
Rep. Jim Harrison, R-Richland
Commentary from elsewhere
Grady L. Patterson Jr.
Mr. Patterson, who died Monday at age 85, was a model of integrity who kept the state on an even fiscal keel by following the principle "live within your means."
Affable, low-key and single-minded in his pursuit of the state's financial interests, Mr. Patterson provided conservative management for state revenues, both as treasurer and as a member of the powerful Budget and Control Board. ...
Mr. Patterson was first elected as treasurer in 1966 and steadfastly remained a Democrat throughout his decades of service, even as many state conservatives shifted allegiance to the Republican party. But the regard in which he was held crossed party lines, as evident by his electoral success in an increasingly Republican state. ...
Converse Chellis, who now serves as treasurer, succinctly described Mr. Patterson's contributions to the state in his remarks on Monday: "As state treasurer, he served South Carolina with honor and dignity for over 30 years." Mr. Patterson "worked diligently to safeguard South Carolina's finances and make our state a better place. He succeeded."
The Post and Courier (Charleston)
New energy facility
A new energy-producing facility at Savannah River Site will be a winner all the way around - for many in need of employment, for the taxpayer and for the environment.
Ground was broken on the Biomass Cogeneration Facility at SRS that will give employment to 800 construction workers over the next two and a half years and then to 25 permanent workers when the plant is operational.
It will be a green version of the coal powerhouse and oil-fired boilers at SRS, producing both electrical energy and steam for SRS use.
The Aiken Standard
Jim DeMint
Sen. Jim DeMint, R-S.C., is correct when he says that "Senate seats are not about a particular state. They're about our country. Every vote I take is not about South Carolina. It's about the United States of America." ...
DeMint has been castigated for his comments by one of his opponents, Democrat Chad McGowan, who claims DeMint is putting his personal political goals ahead of the interests of the state.
McGowan is wrong. When our system breaks down, it is frequently because a member of Congress has forgotten his duty is to the nation. He focuses only on the narrow interests of his state, usually motivated by re-election.
The Herald-Journal (Spartanburg)
- "Believe those who are seeking the truth. Doubt those who find it."
Andre Gide
- "I think your whole life shows in your face and you should be proud of that."
Lauren Bacall
- "If you can believe, all things are possible to him who believeth."
Mark 9:23


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The semi-final stage is set for the women in Huntington Beach at the Van's U.S. Open of Surfing. If you have been following then you already know that your fantasy picks are probably wrecked. The top three ranked surfers in the world, Steph Gilmore (AU), Sally Fitzgibbons (AU), and Tyler Wright (AU) are all gone. None of them getting out of the quarter finals. All three of these ladies were dispatched by confident upstarts Coco Ho (HAW), who took out Tyler Wright and Sage Erickson (USA) who sent Sally Fitzgibbons home earlier than expected. Throw in trials winner Maud Le Car (FRA) who got past Gilmore in round two. Both Coco How and Sage Erickson will move onto the semi- finals where they will face more of the big guns on the world tour. Coco Ho matches up with fellow Hawaiian Tatiana Weston-Webb in what should be a classic. Sage will see a familiar face in Courtney Conlogue (USA), who she has faced twice in the last week, splitting those match ups with Courtney taking the finals of the Supergirl Pro last week in Oceanside, and Sage getting the win in their first round match up in Huntington Beach.
The first quarterfinal heat of the day featured the last two Van's U.S. Open of Surfing winners, Tatiana Weston-Webb and Johanne Defay. It was a back and forth match-up with an aggressive Tatiana Weston-Webb edging out Defay 12.80 to 11.90. After a rocky start to the 2017 season, Weston-Webb is starting to catch fire and move up the rankings. Defay will regroup and come back to California for the next event at Lowers ready to get back on track.
Heat two of the quarterfinals started with a bang and went back and forth for the entire round, with the last wave as time ran out deciding the outcome. Coco Ho wasted no time putting the pressure on reigning world champion and number one ranked Tyler Wright as she raced to a lead at the opening horn putting up a solid 7.83. Tyler Continued to answer forcing Coco to pull out one more wave at the end to secure an upset win of 12.86 to12.50 in what so far is the biggest win of her year.
The third heat gained more importance to Sally Fitzgibbons who would have a chance to move into number one in the world rankings if she could win out in Huntington Beach. Usually calm under pressure, Sally was quickly put on notice by Sage Erickson who raced out to a lead and then masterfully used her priority to keep Sally Fitzgibbons at bay. As the heat went on the waves seemed to vanish and time ran out on Fitzgibbons, as a confident and crafty Sage Erickson pulls out a close win, 10.74 to 9.10
In the last quarterfinal of the day Pauline Ado (FRA) came in looking for a big win of her own as she matched up with number four in the world, Courtney Conlogue. Little was left to the imagination in ths one as Courney confidently put things out of reach fairly quickly. Pauline did not have an answer and fell victim to Conlgue at her home break 14.87 to 10-47. This however would be Ado's best finish of the year as she claimed an equal ninth place in Huntington Beach
Down to four women who have all taken different paths to the semi-finals. Aggression, speed and power, cunning and wit and of course, confidence will be on display as these ladies charge toward a Van's U.S. Open of Surfing title.


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Wanna find your soulmates?
Wanna know the resonance rate between your friends and you?
This Soulmates App helps to get the answers by observing the drawings by you and your friends.
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User guide:
(1) Player 1 draws a picture.
(2) Press "Next Drawing".
(3) Player 2 draws a picture.
(4) The Soulmates App supports up to seven players.
(5) Press "Complete" when all players have drawn a picture.
(6) The Soulmates App would find the resonance rate of the players according to their drawings.
(7) You can save the final combined picture to the photo album by the "Snapshot" function.


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Monday, July 03, 2006
Today's thought: the problem with English in Japan
The problem with English in Japan is that it's taught by Japanese to Japanese in Japanese from books written by Japanese for entry to Japanese schools.
Posted by Yokohama Michael at 4:28 pm
1 comment:
- Crunchy Peanut-Blogger said...
July 2006 was a long time ago Captain Cassowary - a life time for some - for some insects - many lifetimes for many insects. Empires have risen and fallen - empires of insects.
Awaiting your next missive...
- 2:08 pm
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Since bursting onto the scene with his debut single on El-P's infamous label Def Jux, Pyramid's been churning out hits & working behind the scenes with everyone from The Black Eyed Peas, to members of Wu-Tang Clan, MF Doom and Pete Rock just to name a few. This year, his track "It's So Hot" was featured in the Hollywood blockbuster film 21 & Over, he's performed to a sold-out NYC crowd alongside A$AP Rocky and has seen the Noisey (Vice) debut of his Grandtheft-produced single & video "Friday Nights".
This import-only EP is a limited edition pressing released exclusively by Silk Ivory/ Universal Music Canada and is Pyramid's best work to date. Featuring all-star production & guests including Grandtheft (who's remixed everyone from A-Trak to Diplo), Rich Kidd (who's produced for the likes of Drake, Jay Electronica, Redman & more) & Ben Stevenson (Boi1da, Joe Budden) the up & coming R&B sensation whose smoky vocals can be heard on 2 tracks.


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Aws Solution Architect Professional Training In Bangalore
The AWS Certified Solutions Architect – Professional validates advanced technical skills and experience in designing distributed applications and systems on the AWS platform.
AWS Overview :
- Description of AWS
- History and Evolution of AWS
- Overview of AWS Products and Services
Designing highly available, cost-efficient, fault-tolerant, scalable systems :
- How to Design Cloud Services
- Planning and Designing
- Monitoring and Logging
- Hybrid IT architectures
- Practice Assignment: Designing Hybrid Storage Page
Identity and Access Management (IAM) :
- IAM Overview
- IAM Policies
- IAM Groups
- IAM Users
- IAM Roles
- IAM best practices
Amazon Virtual Private Cloud (VPC) :
- Amazon VPC Overview
- Amazon VPC
- IP Addresses
- Reserved Instance pricing
- Internet Gateway
- NAT Devices
- Security groups
- Choosing the AMI
- Practice Assignment: Designing a Custom VPC
Amazon Virtual Private Cloud (VPC) :
- What is VPC?
- VPC configuration
- VPC security
- Elastic IP's Inbound and outbound ACL's
Amazon Simple Storage Service (S3) :
- S3 Buckets
- Amazon S3 Lifecycle Management
- Security and Encryption
- Import/Export & Snowball
- Amazon S3 Best Practices
- Amazon S3 Costs
- Practice Assignment: Create an Amazon S3 bucket
CloudFront :
- Use of cloudfront
- Creating a cloudfront distribution
- Hosting a website of cloudfront distribution
- Implementing restrictions
- Configuring origins and behaviors
EBS(Elastic Block Storage) :
- Create EBS volumes
- Delete EBS Volumes
- Attach and detach EBS volumes
- Mounting and unmounting EBS volume
- Creating and deleting snapshots
- Creating volumes from snpashots S3(Simple Storage Service)
Route53 :
- Creating zones
- Hosting a website
- Understanding routing policies
- Weighted simple and failover policies
Direct Connect :
What is S3 :
- RRS(Reduced Redundancy storage)
- S3 durability and redundancy
- S3 Buckets
- S3 Uploading Downloading
- S3 Permissions
- S3 Object Versioning
- S3 Lifecycle Policies
- Create EBS volumes
- Attach and detach EBS volumes
- Mounting and unmounting EBS volume
- Creating and deleting snapshots
- Creating volumes S3(Simple Storage Service)
- S3 Lifecycle Policies
Glacier storage :
Relational Database Service (RDS) :
- Selecting the Database type
- Configuring the database
- Creating database
- Configuring backups
- Configuring the maintenance windows
- Connecting to the database
Dynamo DB :
- Creating a dynamo db
- Configuring alarms
- Adding data manually
Aws Solution Architect Professional Sysops:
- Creating Users and Groups
- Applying policies
- Password Policy
- Roles
- Directory Service
- Cloud Watch
- Cloudwatch dashboard
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- Setting thresholds
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- Creating a cloudwatch alarm
- Getting statistics for ec2 instances
- Monitoring other Aws Solution Architect Professional services
- Configuring Notifications
- Integrating cloudwatch with Autoscaling
- Cloud Formation
- What is cloud formation?
- Deploying template
- Create Stack
- Delete Stack
- Monitoring the resources
- Cloud Trial
- Trust Advisor
- Create an Application Load Balancer
- Create a Network Load Balancer
- Create a Classic Load Balancer
- Auto Scaling
- Boot strapping
- Create a launch configuration
- Create an Auto Scaling group Create a policy for your Auto Scaling group
- Set up an auto-scaled, load-balanced Amazon EC2 application
- Simple Notification Service (SNS) :
- What is SNS
- Creating a topic
- Create subscription
- Subscribed to the subscription
- Bootstrapping Ec2 With OPS Work Chef
- Billing Analysis
To know Schedule & Prices, please write to us at firstname.lastname@example.com
Call at 080-610 12345/9035353007/9036363007
|Trainer Name
|Cloud Architect
|About Trainer
|Sameer has more than 13+ yrs of Industry Experience on pure Infrastructure Cloud Services. He has worked in Wipro, TCS, HP as the past Working Experience. He has been awarded by Citrix as Best Citrix Trainer in India. He has written so many technology blogs on Cloud Services. He has did more than 25+ Industry Certificates and he has guided lot many students on career counselling. He has Masters from Madras University. He is a Quick Learner and technical Evangelist. His Hobbies are watching Youtube Videos and Cracking jokes when ever get free time.
|Available Timings
Register Now! for demo Download Full Syllabus
Cloud Products
Amazon Web Service VMWare Cloud Service Devops Sales Force Microsoft Azure


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Priamry Teacher Gateshead
|Job Title:
|Priamry Teacher Gateshead
|Contract Type:
|£90 - £125 per day
|Start Date:
|2019-01-30 00:00:00
|Contact Name:
|Beth Pearson
|Contact Email:
|Job Published:
|January 30, 2019 13:12
Job Description
We are able to offer you work to suit your schedule - whether that be full-time or part-time - and we will take into account your preferences for key stage/working pattern (e.g. PPA cover, intervention). You never know what a school is going to need and for how long, so we are confident that we can find something to suit you!
* QTS in the UK
* Recent and relevant experience as a primary teacher in UK schools
* Ability to teach and reflect upon engaging lessons which produce quantifiable pupil progress across a range of abilities
* Excellent behaviour management skills and the ability to build strong professional rapports with children and staff
* Effective use of AfL and formal assessment strategies to track pupil progress and inform future planning
* A full understanding of safeguarding procedures and the responsibilities of a primary teacher
*Secure working knowledge of the Development Matters and/or primary National Curriculum
If you think that you could be suitable for the role of supply primary teacher, then please apply directly to this advert for more information about the registration process; we look forward to hearing from you!
If you have not heard form us within 3 working days, then your application for the role of primary supply teacher has been unsuccessful.
Get similar jobs like these by email
By submitting your details you agree to our T&C's


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It was only a matter of time before Miley Cyrus got snapped up for a major fashion campaign, and it's no surprise Marc Jacobs was the one to grab her to be the face of his spring/summer 2014 collection.
Focusing on his solo career after 15 years at Louis Vuitton, Marc has got the Wrecking Ball singer to test out her fashion credentials, tweeting: "Secret's out, @MileyCyrus stars in the MJ SS14 Campaign shot by David Sims", gaining nearly 5,000 retweets and 7,000 favourites showing how excited everyone is about this cool new collaboration.
With Miley usually stealing the headlines with her raunchy performances and barely-there clothing, she's finally put her foam finger away and stripped back her look to be the star of the show in this killer campaign. And there isn't a tongue in sight.
Sitting in a desert, wearing a stunning navy blazer and burgundy shorts – with nothing but bed hair and minimal make-up to complete her look – Miley has got us all wondering what fashion steps she's going to take next. Watch this space.
By Harriet Davey
Got a tablet? You can now download LOOK magazine straight on your
(just search the store for 'LOOK magazine'),
. And don't forget to rate and review!


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I have had fantastic energy levels, have lost 12kg in a week and my milk supply is ample, so consequently my little man is thriving! Also I managed to escape the day 3 "baby blues", I 100% contribute these amazing results on the fact I am taking placenta capsules. Fiona, first time mum, Tingalpa
I'm so happy I had my placenta encapsulated the main thing I notice is energy levels, I've missed taking my capsules a few days and feel a lot more tired then the days I'm taking them. I will do it for every pregnancy! Corinna, 2nd time mum, Sunshine Coast
Carla, I'm so pleased to have found you quite literally 'moments' before my planned c-section. It certainly was the best decision I made to assist in my recovery post partum. Thank you for making everything so easy and for providing such a service. These first 8 weeks have been easier on me (emotionally as well as physically) compared to my first and I know it's down to the capsules providing me with a boost of needed energy…will miss them when they run out. Katie, 2nd time mum, Brisbane
I am so glad I chose placenta encapsulation. My doctor described me as a 'sitting duck' for postnatal depression but I've had a really positive post-birth experience. I've got energy and great milk supply. Carla was great to deal with too! First time mum, Brisbane.
Fantastic speedy service, that went beyond expectations. Thank you!. Bronwyn, 4th time mum, Brisbane
Thank you for your wonderful service. We found it so easy to arrange everything with you and it all went so smoothly and efficiently. Kate, first time mum, Brisbane.
At first I wasn't sure encapsulation was right for me and I umm'd and ahh'd about it for most of my pregnancy. When I voiced it to family/friends they were very quick to tell me not to. 1 week prior to my c section I just decided to do it and boy am I glad I did. I didn't get any post natal blues which I had for several days with my first birth, I felt fantastic and my energy levels were awesome! I also found I was extremely calm in a few stressful situations. Carla was brilliant and I can only recommend her. Have been telling my friends and family all about her and the encapsulation and have even converted some pregnant friends! Anna, second time mum, Brisbane
The service was exceptional and fast, I recieved my capsuals within 24hours of birth. I felt my energy levels were higher especially with a 3yr old to run around after also. I noticed I wasn't as emotional as I normally am. Will definitely recommend to friends and family. Melissa, second time mum, Caboolture.
My recovery has been amazing. Bleeding has been minimal, energy levels good and mood seems to be stable. I'm no where near as emotional or anxious as I was with my first child. However most importantly for me is the difference in my milk supply. I am so grateful for this as my bub has an upper lip tie and this accompanied with my previous breast surgery made breast feeding very difficult and extremely painful. This lead to to the decision again to pump for her as I did with my first child (she also has a tie). The difference between both times is huge! With my first child I only pumped for the first few months and total average pumped in 24hour period was 60ml max, this time I'm getting approx 1ltr per day which means we are not needing to supplement with formula. I now can see us having a long and successful pumping journey. I am so grateful I found you and went ahead with the encapsulation. Your service was wonderful, great communication, very fast to collect placenta and drop off pills and the instructions were easy to follow ( important for sleep deprived mums). Thanks again, Skye, second time mum, Brisbane.
I found my recovery much smoother (emotionally and mentally) and speedier (physically) this time around. I had more energy, I coped much better with fatigue and didn't get as physically run down as I did previously. I didn't have my placenta encapsulated with my first child as the service wasn't available where we were living at the time. I had huge problems with milk supply with my first, and while I still had to mix feed my son I had a better supply this time around and managed to maintain breast feeding for twice as long. Your service was excellent and so very prompt, I have and will continue to recommend your service to others. Taryn, second time mum, Brisbane.
Super impressed with the service from Trudy and Carla. All my questions were answered promptly leading up to the birth of my son and my placenta was collected within 60 min of getting back to my room. I'm excited to give encapsulation a try. I wouldn't hesitate to recommend these ladies ♡ Thank you Trudy!! Jess, third time mum, Bellmere
Service was fantastic! Trudy arrived hours after the birth and I had my capsules delivered the next day at home. I have a history of postpartum depression with my previous children but this time I took the capsules and didn't even experience the baby blues! I also had quite a significant hemorrhage after the birth and have recovered amazingly well. Would not hesitate to recommend placenta encapsulation! Lyndal, 3rd time mum, Caboolture.
I found using the capsules to be ultra beneficial! I seemed to bounce back quickly and felt more like myself before I knew it. I would (and have) without a doubt recommend Carla. Brittany, 1st time mum, Brisbane.
I keep telling myself I am tired as I am so sleep deprived but when I think about it I am feeling just fine – the encapsulated placenta must be the difference as it's the main change this time around. Belinda, 2nd time mum, Brisbane.
Thank you Carla for the great service provided! Stephanie, 2nd time mum, Brisbane.
Encapsulating my placenta is definitely something I would do again! Maddie, 1st time mum, Brisbane.
My post natal recovery was amazing! Shannon, 2nd time mum, Brisbane.
I would recommend Carla and her placenta encapsulation to anyone considering it. The service I received was great and the placenta pills themselves did great for my energy levels. I wish I had of done this with my first baby! Belinda, 2nd time mum, Brisbane.
I've had PPD with both my first two births, so decided to give placenta encapsulation a try this time round! I am amazed, no PPD and not even baby blues at the start. I felt happy and lots of energy for the first time ever after giving birth. I wish they would last forever! 3rd time mum, Sunshine Coast.
Excellent service, I have been telling anyone that will listen about placenta encapsulation. I think hospitals should offer this service or at least have information on it. Its hard to explain the benefits so I will explain what I do on a weekly basis. Gym 5xdays a week, have loads of energy left over for playing with my busy 3yr old. The house is clean and I'm energetic and happy. Im a normal mom, no family in Australia and my partner works away. I got this though!! thanks to my placenta pills. I have missed a day here or there and I don't fall flat on my face I'm just not as calm/relaxed. Can't thank Trudy enough for her amazing customer service. Forever grateful. 2nd time mum, Sunshine Coast.


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Product Details
- beautifully hand made product
- ash
- upholstered
- nordic
- velvet
Product description
Simple, chic Scandi styling, combined with comfortable, soft velvet upholstery creates a practical chair perfect for a contemporary dining area.
Questions about the Velvet Button Dining Chair in Blue
Hi. My question was about the height of the seat, not the overall height of the chair. Please can you reply. Thank you. Regards, Tanya
by Tanya 2018-05-15 12:11:06
Hi Tanya, sorry for the misunderstanding. The seat height is 46cm.
Hello. Some questions about Velvet Button Dining Chair in Blue: What is the seat height (back of the chair) ? Is it possible to order a swatch? Does the chair require assembly? Thank you
by Tanya 2018-05-14 23:48:50
Hi Tanya, The seat height for the back of the chair is 83cm and the chair comes fully assemble. We can also order swatches for you. Kind regards Siobhan
We're here to help! Fire away.


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If you're like most of the adult population and spend a lot of your time sitting in front of a computer screen or in a office cube somewhere, you need to be aware of the risk this has on your health. If you sit for more than six hours a day then your chance of developing heart disease increases by a whopping 64%! Now that's certainly no joke.
How Can Exercise Help?
Regular exercise boosts your mood, your immune system, increases energy levels and protects you against heart disease and health problems.
"I've got too much work to do & no time for exercise!"
Do you find yourself saying that a lot? No excuse! I've got good news for you – there are various "on-the-go" exercises you can do almost anywhere and anytime (yes, some can even be done right at your desk!) that can boost your circulation and alleviate any pain associated with sitting for long periods of time. Some of these are even great to do on the plane or in your hotel room if you travel a lot.
The bonus? They take up hardly any time at all! Here are 7 simple and quick exercises you can do on the go:
Number #1 – Wrist Stretches
If your job involves typing on a computer all day then you are at risk for repetitive strain syndrome, which can lead to Carpal Tunnel syndrome, which is a painful condition of the hands and fingers due to compression of a major nerve.
This exercise done throughout the day or whenever your wrists hurt or feel strained will help with the pain and prevent against future damage.
Number #2 – Front Body Lift
Great for working your legs and tightening your stomach. Here's how it's done…
- Lie face-down on the floor.
- Support your body on your forearms, elbows and hands.
- Lift the rest of your body off the floor and hold to a count of 5.
Repeat as necessary.
Number #3 – Shoulder, Back & Triceps
This is a great stretch for back pain and to alleviate tension in the shoulders.
- Cross your right arm in front of your chest.
- Use your left arm to pull your right arm towards your body and hold to a count of 10.
Repeat with your other arm.
Number #4 – Quadriceps Stretch
This stretch works your quadriceps.
- Stand up straight.
- Bend your right knee, bringing your right foot up towards your buttocks.
- Hold your foot with your hand to a count of 5.
Repeat with your other leg.
Number #5 – Back Strengthener
This one is great for the lower back…
- Lie face-down.
- Extend your legs behind you.
- Extend your arms in front of you.
- Raise your chin off the floor.
- Slowly raise your left leg above and hold for a few seconds (as long as you are able to, comfortably).
Repeat with your other leg.
Number #6 – Half Frog Yoga Pose
This yoga pose works your thighs, shoulders and upper back, which are prone to tightness from prolonged sitting.
- Lie face-down with your arms flat on the floor.
- Raise your torso and head.
- Bend your right knee and bend your heel towards the right buttock.
- Turn your elbow to face the ceiling.
- Now press your foot towards your buttock (as comfortably as you can).
- Adjust your shoulders and rest your body on your forearms if you find that easier.
- Hold for about 5 deep breaths.
Release and repeat with your other leg.
Number #7 – Simple Leg & Foot Stretches
When sitting on a plane for more than 4 hours, this a great exercise to boost circulation and prevent blood clots.
- Extend your leg out.
- Slowly start moving your foot in small circles in a clock-wise motion.
- Do this for about thirty seconds before turning in anti-clockwise for another 30 seconds.
Repeat with your other foot. Do this at least once an hour.
While we should all aim for at least 30 minutes of physical activity a day, these exercises will help to boost your circulation and give instant relief from pain as well as an instant energy boost and mood boost to help you get through the rest of your day. Start them today and you will feel the difference right away!