text:
Teacher resources and professional development across the curriculum
Teacher professional development and classroom resources across the curriculum
I;ve been working on the homework assignments for Workshop 7. The last assignment is to go to http://www.soton.ac.uk/~ingenvir/ and play the game "Escape." I searched the site, and I haven't been able to find the game. Has anyone found the site we are supposed to use for this assignment?
Kristen VanderVeen Chemistry Teacher The Bromfield School 14 Massachusetts Avenue Harvard, MA 978.456.4152
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Top News:
Lee Enterprises / St. Louis Post-Dispatch:
Furcal to have elbow surgery Wednesday — • By Rick Hummel email@example.com 314-340-8196 — JUPITER, Fla. • Ailing Cardinals shortstop Rafael Furcal will have his Tommy John ligament replacement surgery on his right elbow on Wednesday in Pensacola, Fla. …
MLB Daily Dish and HardballTalk
Jeff Gordon / St. Louis Post-Dispatch:
Transition year looming for Cards? — Shortstop Rafael Furcal is finished. Rather than putting off the inevitable any longer, Furcal will undergo Tommy John surgery and depart the Cardinal radar screen. — That nagging storyline has finally run its course. The franchise moves on.
Viva El Birdos and MLB Rumors
Associated Press:
Cards SS Furcal to have Tommy John surgery
Cards SS Furcal to have Tommy John surgery
Viva El Birdos, MLB Rumors, ESPN and MLB Daily Dish
Lee Enterprises / St. Louis Post-Dispatch:
Furcal elects to have elbow surgery
Furcal elects to have elbow surgery
Viva El Birdos
Kristie Ackert / NY Daily News:
Matt Harvey throwing a more consistent changeup after latest outing for NY Mets — Harvey used the changeup very effectively Thursday as he tossed 4.1 nearly perfect innings in the Mets' 4-1 Grapefruit League win over the Marlins at Tradition Field. — Matt Harvey throws 4.1 nearly perfect innings …
Metsblog, NorthJersey.com, New York Post and MLB.com
Bill Madden / NY Daily News:
As broken leg heals, Yankees GM Brian Cashman seems content to sit and wait out injuries to Curtis Granderson, Mark Teixeira, Alex Rodriguez and others — Even though it's spring, when GMs supposedly make only garbage-dumping deals, the word is the Padres are starting to listen to offers for Headley …
MLB Daily Dish and It's About The Money
Joel Sherman / New York Post:
Mo's greatness something to behold — We got the preview of Yankees life without Rivera last year after he tore up his knee in May. But now he is making it final. He is scheduled to announce his retirement — effective following the 2013 season — tomorrow. Thus, 2013 becomes part farewell tour, part victory lap for him.
MLB Rumors, It's About The Money and River Avenue Blues
Lee Enterprises / St. Louis Post-Dispatch:
Cards sign Craig to 5-year deal — • By Rick Hummel email@example.com and Derrick Goold email@example.com 314-340-8196 — JUPITER, Fla. • The Cardinals did something they rarely do when they reached agreement today with first baseman Allen Craig …
MLB Rumors and Getting Blanked
Matthew Leach / MLB.com:
Teixeira: Wrist surgery 'doesn't look necessary' — JUPITER, Fla. — It could have been worse. The timing could have been worse and the injury could have been worse for Mark Teixeira. That doesn't mean the Yankees' first baseman isn't disappointed. — Teixeira spoke with reporters via …
MLB Daily Dish and HardballTalk
John Marshall / Globe and Mail:
Italy scores two in ninth to stun Mexico at World Baseball Classic — Anthony Rizzo hit a two-run double off San Francisco Giants closer Sergio Romo in the ninth inning and Jason Grilli escaped a bases-loaded jam in the bottom half to help Italy rally to beat Mexico 6-5 in the opening game …
MLB, Baseball Prospectus, Camden Chat, True Blue LA and baseballmusings.com
Melvin back to work after scorpion sting — PHOENIX — At this rate, general managers will need their own disabled list. — Brewers GM Doug Melvin was back in his office by 8 a.m. MT on Thursday after being stung by a scorpion Wednesday night. Just three days earlier …
Fox Sports:
Young completes community service — CLEARWATER, FLA. — By May, as long as Philadelphia Phillies outfielder Delmon Young remains on good behavior, his name will be cleared. — Young, 27, was charged with a hate crime last April after he shouted an anti-semitic slur while intoxicated …
Associated Press:
King Felix makes spring debut, solves Royals — Final — Recap — Box Score — Conversation — Mariners' Felix Hernandez helps hand Royals 1st spring loss — SURPRISE, Ariz. — Felix Hernandez waited almost two weeks to get in a game for the Seattle Mariners.
MLB.com, Royals Review and Lookout Landing
Henry Schulman / San Francisco Giants:
Aubrey Huff to the Yankees? Not happening — When Yankees first baseman Mark Teixeira went down with with a sprained wrist, Aubrey Huff's name was tossed about as a possible fill-in, but that is not going to happen. — "I'm pretty much retired," Huff just said by phone.
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Bruce Levine / ESPN:
Source: Chris Sale agrees to deal — GLENDALE, Ariz. — The Chicago White Sox and left-handed pitcher Chris Sale have agreed in principle on a five-year contract extension worth as much as $60 million, according to a league source. — Sale will receive $35 million guaranteed …
Bleed Cubbie Blue, South Side Sox, MLB Rumors and Getting Blanked
Zach Links / MLB Rumors:
Rivera To Retire After 2013 Season — 12:03pm: The Yankees have a 10am EDT press conference scheduled Saturday at which Rivera is set to announce that he'll retire following the 2013 season, Joel Sherman of the New York Post reports (Twitter links). — 11:03am: Yankees closer Mariano Rivera …
Pinstriped Bible, HardballTalk, SportsGrid, Over the Monster and Boston Globe


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I'd love to see them make a smaller ZT 0560 with a 3" ~ 3.25" blade. Maybe change the texture on the G10 scales, and offer these knives in other colors; like blue or orange..
A Tiger Stripe version would be cool, too..
Yes! I would have no problem spending $200 to $300 on such a knife.
Yes, but only if it was less expensive ($100-$199)
No, the only premium KAI products i want are knives built like the current ZT line (tanks)
No, I wouldn't purchase any high priced KAI knives
Alright guys I've heard from a lot of people that they wish ZT made a knife that was more easy to pocket. I want high quality ZTs or Kershaws in the $80 to $200 range with EDC/pocket knife dimensions! Kershaw takes their customers seriously so here's your chance to tell 'em. Let them know that there's a market for these knives. Sound off with your ideas/opinions.
I'd love to see them make a smaller ZT 0560 with a 3" ~ 3.25" blade. Maybe change the texture on the G10 scales, and offer these knives in other colors; like blue or orange..
A Tiger Stripe version would be cool, too..
I have a 561 and love it! But there have been a few times that those around me ask what do you need such a big knife for? All I can say is a 3-3.5" blade would please them.
I would like Kershaw to do what ZT does, only without the military overtones. Basically, make more high end jaw dropping designs more frequently. I like what ZT is doing, but they are always going to be large and overbuilt -because that is their calling card. Kershaw could focus more on high speed light weight EDC type stuff.
I would love to see some higher end material kershaws in the 3"-4" range things like the volt and the tilt, are what i'm talking about but not Limited edition. Maybe mix it up with some different steels like m390,more d2,more s30v,s35v,elmax,s110, etc... I'm not saying that it has to dominate the kershaw lineup but maybe 3 or so in the lineup with these. Another thing i would like to see is full flat ground on a few of these kinfes. Keep the clamshell serrations ( they are the best in the industry in my opinion hands down)and the composited blades, they rule.
Another huge thing would be colors. Different colors would be great. g10, frn, aluminum, micarta I just want some options! I like how they started using different patterns on the g10 but now is the time to take another step forward. Look at the leeks, scallions, and blurs. People like variety! any combination of the above would do well in my opinion especially after listening to everyone over the last couple of yrs.
The other thing is locks. I have been hearing alot about it lately. I like the ti frame locks and the hawk lock is one of my favorites. but i would like something refreshing and different. The stud lock was cool in my opinion. Just looking for something different!
If you do a conglomeration of any of these it would be a hit! i'm sure there are ways to make something like this happen in a way to fill out the price range scale.
Franken Blurer Extraordinaire
Well it seems to me that they already HAVE a good knife in the under 3.5" range- the Blur.
Are the current ZT's too big for EDC? I have carried lots of knives with blades close to 4", some of them pretty beefy, but I've never handled a ZT so I don't know if there is more to it beside just blade length.
I think 3" is too small, there are already a lot of good knives at that size. I would prefer something closer to 3.5", maybe a 3.3" to 3.4" blade.
Yup I would love a smaller ZT. Most are a little too bulky for me but I do not mind it too much. If it has a low rider pocket clip then I'd be in for sure.
Keep the 3.75" to 4" blade, lower the weight to three ounces, no assisted opening, and cost less than $100.
I think the 0780 is going to fit the bill nicely. I would love to see a semi wharncliffe or wharncliffe from Zero Tolerance. I know there is the Talon, but I am talking true wharny .
Experience is simply the name we give our mistakes.
I'm pretty positive that we won't see something like that from zt. Thomas said in a recent post that zt's were going to continue to be big and bad. look at what they debuted at blade , this is what we have to look forward to. He also said if you want something smaller that's what kershaw was for. Your only option is the cryo 2 if you are specifically looking for the 560x type of blade. Sorry I didn't say it he did.
Franken Blurer Extraordinaire
What we have now is awesome, but I wouldn't mind if they made a 5" ZT folder.
Nope. While it may be smaller, it's not what I am looking for..
While they may never make one, I am still keeping my fingers crossed that they may make one down the road.
Heck, even Strider and Rick Hinderer make smaller knives. I don't see why a smaller ZT is out of the question..
I'd like a mini(no longer than 3" blade) ZT0200 at about the same price as the 0200. Perhaps it could have an Elmax blade, since Kershaw has shown the ability to make affordable knives in that steel.
I don't understand what you guys are looking for. Doesn't the 0350 and the 0550 cover these bases? Kershaw makes plenty of knives in smaller sizes which gives ZT the green light to cover big tough blades. Zero Tolerance's motto is "Serious knives for serious missions". This motto doesn't scream small blade to me. If you start making smaller knives you are going to sacrifice toughness.
So do you guys really just want a smaller version of the 0560?
Last edited by Tony8179; 06-13-2012 at 11:45 PM.
i would hope they would keep it around the 3.5 inch blade length but make it slim and sleek
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Datasheet | Specific References | Reviews | Related Products | Protocols |
A polyhistidine-tag is an amino acid motif in proteins that consists of at least five histidine (His) residues, often at the N- or C-terminus of the protein.
Polyhistidine-tags are often used for affinity purification of polyhistidine-tagged recombinant proteins expressed in Escherichia coli and other prokaryotic expression systems.
Learn more about expression Vectors |
Product name | Product name |
Vascular endothelial growth factor (VEGF), also known as vascular permeability factor (VPF) and VEGF-A, is a potent mediator of both angiogenesis and vasculogenesis in the fetus and adult. It is a member of the platelet-derived growth factor (PDGF)/vascular endothelial growth factor (VEGF) family and often exists as a disulfide-linked homodimer. VEGF-A protein is a glycosylated mitogen that specifically acts on endothelial cells and has various effects, including mediating increased vascular permeability, inducing angiogenesis, vasculogenesis and endothelial cell growth, promoting cell migration, inhibiting apoptosis and tumor growth. VEGF-A protein is also a vasodilator that increases microvascular permeability, thus it was originally referred to as vascular permeability factor.


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After the deluxe Obi and Jango pictures... I'll be prepared to possibly cringe.
Hey VT, you should sue Hasbro, they gave KE Jango a new non-gimmickized right arm just like you did.
"Hokey packaging and ancient gimmicks are no match for good detail on your figure, kid."
"I am a Klingot from Oklahoma in human boy form."
"We came, we saw, we conquered... We, woke up!"
I can't wait to see how bad Hasbro screws these AF sets up.
"I'm a simple man, trying to make my way in the universe." - Jango Fett
Jangu I'm sad to say, I agree with you. I'm waiting for a midget rgs with good paint but no playability
I just hope it's not pics of repaints again.
Darth Vader is becoming the Mickey Mouse of Star Wars.
Kylo Ren - came from Space Brooklyn, although he moved to Space Williamsburg before it was trendy.
The use of a lightsaber does not make one a Jedi, it is the ability to not use it.
Thats true jeditricks,
Those cheap people are putting out those repaints are nutt'n but dumb. People barely even bought them when they were released. I did but dang
They're up. The Republic Gunship, Jango's Slave 1, and Republic Assault Ship.
Hmm, I thought they were supposed to come with figures. It worries me that none of those images show figures. The ships look nice but without figures they just will not be as nice as they could be. They won't even look right displayed with my other loose AFs. I haven't even bothered to go to a store and look for the Snowspeder or At-At yet. I haven't heard anything good about them, but if they came with figures I know I would have looked. I will look for these since they are new ships (2 and a half anyways) but probably with a little less effort than I would if they did come with figures.
Gunship - Cool but needs two Pilot figures
Slave 1 - Useless without a Jango figure, now it's just a repaint..
Troop Transport - Ok, lowering landing gear all it does? It better open up even if it isn't realistic.
"Hokey packaging and ancient gimmicks are no match for good detail on your figure, kid."
"I am a Klingot from Oklahoma in human boy form."
"We came, we saw, we conquered... We, woke up!"
The republic gunship looks like it has an opening cockpit but i dougbt that it will fit at least one figure just like the dumb cocpit of the at-te. slave one is just a repaint and the assult ship is so out of scale it's not funny. Let's jus say i give up. O and Whats up with the black paint where it should be clear. Like the rgs cockpit and bubble should be clear instead of black. I hope they change it
I will get the rgs but.... I want figures
Last edited by neonblade; 12-23-2002 at 01:44 PM.


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State health officials say whooping cough is now an epidemic in California and is on pace to break a 50-year record for infections and deaths for the year.
As of June 15, California had 910 recorded cases of the highly contagious disease, and five babies -- all under 3 months of age -- have died from the disease this year.
California Department of Public Health director Dr. Mark Horton said Wednesday that children should be vaccinated against the disease and parents, caregivers and infants need a booster shot.
A typical case of the disease, formally called pertussis, starts with a cough and runny nose for one to two weeks, followed by weeks to months of rapid coughing fits that sometimes end with a whooping sound. Fever is rare.
Published at 11:17 AM PDT on Jun 23, 2010 | Updated at 12:27 PM PDT on Jun 23, 2010


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Current Issue Thursday, July 5, 2012
Normal Lake Level is 322.00 feet above Mean Sea Level. Current level for Cedar Creek Lake is: 320.91 Water Temperature: 85 degrees - top 97 degrees - bottom
Looking for the Sports in Brief and Upcoming Events?
See inside the Sunday NEW E-Edition of The Monitor
main sports news obits lake life events views classifieds
Crowds enjoy Western Week Rodeo Monitor Photos/Sam Epps The action was plentiful, the dirt was flying and the crowds enjoyed a thrilling end to the annual Mabank Western Week as the rodeo wrapped up Saturday night.
Read more in The Monitor in stands now.
Copyright © 2012, MediaOne, L.L.C.


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2013-06-26, 13:23 | Link #3201 | |
Senior Member
Join Date: Apr 2006
A hunter needs to learn to take bigger risks than this. Anyway, why don't we stop with this argument now and wait to see what happens. The next few episodes will surely make everything clear.
2013-06-26, 16:10 | Link #3205 |
Join Date: Aug 2012
Why did power level talk come up in the first place? Morel just brought up you can't SOLELY judge someone's strength by the amount of aura someone has. Nen plays a role no doubt but there are so many other factors to take into consideration when Nen users collide which is why Morel's and Kite's stance are both that it boils down to one's resolve. Someone could be smarter than the opponent or one person could get the jump on another like how Pitou blitzed Kite putting him at a severe disadvantage. The arc keeps hammering that point.
The Ants on the surface have all the advantages 1: More resilient bodies 2: Can adapt fairly quickly 3: The uniform nature of insects fused with the dark side of humans Can't really say anything more except the human race puts up quite a fight. Why is that? By all accounts it looks like the Ants should rule the Earth right? Last edited by HybridBloodsZak; 2013-06-26 at 18:32. |
2013-06-26, 23:33 | Link #3206 |
User of the "Fast Draw"
I guess in that case it was alright because they weren't risking the job. Think the key for Assassins is not taking on a fight they can't be sure to win. Since if you don't win you die and if you die normally that means you failed your job. A very respectable profession really. If you can't get the job done, no point risking your life .
2013-06-27, 02:52 | Link #3207 |
Staring into your soul.
Join Date: Oct 2010
Location: At the darkness beyond time.
zeno was willing to die to complete his work against chrollo, he even ackowledged chrollo's superiority against himself, so they are clearly willing to die if it does allows them to complete the assasination.
2013-06-27, 06:08 | Link #3208 |
Kamen Rider Muppeteer
Join Date: Jan 2012
Location: Unknown
Age: 32
Zeno also admitted that in a one-on-one fight against Chrollo, he honestly believed he would win. (after gauging his abilities)
You are misinterpreting Morel's words. The thing he called Killua out on wasn't that he ran away, it's that he saw no option other than to run away. Correct me if I'm wrong, but I don't think he called him a coward, just a novice. Which he is. Last edited by Dengar; 2013-06-27 at 06:21. |
2013-06-27, 09:38 | Link #3209 | |
Kana Hanazawa ♥
Join Date: Jun 2007
Location: France
Age: 30
Killua is actually a bit of a coward, that's the way he was raised. However, in this particular situation, I think running away was perfectly justified. There's no way they could have defeated Pitou when Kite couldn't. My point is that Morel and Knov shouldn't judge Killua when they don't have all the parameters. For all they know, his assumptions were fully accurate.
2013-06-27, 10:21 | Link #3210 | |
The Mage of Four Hearts
Join Date: Mar 2010
Age: 26
2013-06-27, 10:50 | Link #3211 |
Senior Member
Join Date: Sep 2008
There's no way Killua is going to be calm, I think that's obvious.
But to think it was the best option he thought of the time, it is. It's not only his self-defense mechanism at work here, he also thought about what could have happen to Gon if Gon continued. While that decision looks impulsive, hesitation could have accompanied if he thought that is not the right option. Or worse, he could have just ran away without Gon. And there's also Killua feeling like a coward afterwards. He betrayed Gon's intentions (Gon wouldn't run away) and leaving Kite behind. While he made the right decision, that decision is also a burden to him. It's a life and death choice, and while he did what he could, it's normal to think of "what-ifs" and other ways that could transpire. ________________ It's funny, this also connects to the question and answer during the first episodes. While Hunter are to be the best, there are also times when the situation comes to worse and grave decisions need to be made (what to do and who to save). It's debatable but the decision could only be made when that time comes. |
2013-06-27, 13:43 | Link #3212 | |
You're dead to me.
Join Date: Apr 2009
Location: UK
Age: 26
Considering it's that ambiguous for the us viewers who actually saw it happen, I think it's definitely out of line for Morel to make a judgement when he doesn't know the situation.
2013-06-27, 17:02 | Link #3213 |
That Guy
Join Date: Jun 2013
Location: Road of Life
I personally like the idea that Killua ran away from fear. Its become too much of a cliche where the character despite being scared fights the OP bad guy and wins somehow.
Though the discussion on if it was fear or a rational choice i believe it was a fear based choice at first, but after Gon started his Nen and prepared to fight Killua went Rational. |
2013-06-28, 04:30 | Link #3218 |
Senior Member
Join Date: Jul 2008
I am more disturbed by people saying Morel had no right to say anything about Killua. In that scene, it's obvious that Killua was broken down and had given up. Morel saw this, and as a fellow professional just told Killua that unless he could man up he can't stay a hunter. Which he is totally correct about.
Killua doesn't want to be taken as a kid, but as a professional, after all. |
2013-06-28, 06:20 | Link #3219 |
Senior Member
Join Date: Apr 2006
Killua's perspective is the only one that matters though. What is he going to take from what Morel said to him? What is he going to do about it? That's the issue. Everything else is besides the point.
Last edited by Kazu-kun; 2013-06-28 at 07:15. |
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Margot Kidder
Margot Kidder was born Margaret Ruth Kidder in Yellowknife, Northwest Territories, Canada, to Jocelyn Mary "Jill" (Wilson), a history teacher from British Columbia, and Kendall Kidder, a New Mexico-born mining engineer and explosives expert. Margot was a delightful child who took pride in everything she did. At an early age she became aware of the ...
See full bio »


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hope you will more solo shots. patricia is great.
Curves In A Corset
For someone fairly new at adult modeling, Patricia Gold is a fast learner. "I am a very eager to please woman," says Patricia. "Tell me what to do and I will do it. I have done many things in my life before but my favorite now is modeling and making videos with hot guys. Now I am spoiled for other men."
Patricia wears a corset in this fresh set. "I enjoy wearing elegant lingerie but I am also comfortable in casual clothes. I studied how other models spread their lips and asses and practiced at home in a mirror. Looking at my finished pictures and videos is something I love to do now. I go on the XLGirls website and look for ways to improve. I enjoyed seeing myself have sex.


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BOWLING GREEN - A Perrysburg Township woman admitted Friday that she shot a Northwood man in the head then set his house on fire.
Sarah Bunch, 21, pleaded guilty in Wood County Common Pleas Court to voluntary manslaughter, arson, and attempted tampering with evidence stemming from the Dec. 8, 2008 shooting of Robert Porter, 60, at his West Andrus Road home.
Heather Baker, an assistant Wood County prosecutor, told the court that prosecutors will recommend that Bunch be sentenced to 12 years in prison.
Judge Alan Mayberry accepted Bunch's plea then scheduled sentencing for Nov. 20. Bunch is being held in the Wood County jail in lieu of $500,000 bond.


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Egyptian Arab Spring Organizers Address Occupy Harvard
Two Egyptian activists urge Harvard protesters to stay committed to non-violence
Speaking through the bars of the locked Johnston Gate, Egyptian activists Ahmed Maher and Esraa Abdel Fattah, two organizers of the recent protest movement in Egypt, addressed the protesters at Occupy Harvard Friday and sought to link the Occupy movement to the Arab Spring.
"We are suffering against our regime," said Maher, who was introduced as the "Che Guevara of Egypt." "We believe in people. People can do many things. People can do real change."
"I am very proud to be here," he said. "We are youth like you, searching for democracy."
Although he acknowledged the differences between Egypt and the United States, he encouraged the Occupy movement to believe in themselves.
"You must believe in yourselves to reach real democracy," he said.
"We are here to express our solidarity with you, and with all the youth in all the squares," added Abdel Fattah. "We are activists from Egypt supporting all activists for freedom."
About 130 students and community members gathered on both sides of Johnston Gate to hear from the Egyptian activists.
"Congratulate yourselves on supporting this movement, on keeping it alive, despite the University's attempt to close it off to the general public," said Jocelyn R. Eastman '13, one of the night's facilitators.
Activists chanted "We are the 99 percent" as they marched across the Yard, altering the chant to "You are the 99 percent" when passing HUPD officers, who were stationed by Massachusetts Hall and Johnston Gate in preparation for the rally.
At the gate, protesters slammed the University for closing the Yard and preventing individuals without a Harvard ID from entering.
"The University has decided for us that our protest will be exclusive," Eastman said.
During their address, the two Egyptian activists urged participants at Occupy Harvard to stay committed to non-violent tactics, calling on them to reinvent what they called an "age-old science" in response to a question from one student about when violent tactics can become justifiable.


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The Management Information Systems major at Penn State Behrend prepares students for a variety of IT-related jobs such as systems analyst, business analyst, data analyst, team leader, project manager, consultant, and MIS manager. Since the focus of these jobs is on the application of information technology to business problems and opportunities, the MIS curriculum integrates three main areas of study— business, computers, and MIS. Students take core business courses in order to understand organizational processes and requirements. Computer courses help students to develop technical competencies and understand information technologies. Core MIS courses in database management systems, systems analysis, and systems design and development focus on the tools, processes, and techniques required for successful application of information technology to business problems. These courses are supplemented with a variety of electives and a required internship experience.
Why Major in Management Information Systems?
Want to learn more? Check out the Black School of Business Management Information Systems Newsletter!


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The Blu-ray of Neil Young and Crazy Horse's 'Rust Never Sleeps' concert movie is a chance to see the band at its peak and a concert film which manages to stand the test of time. Read More »
Blu-ray Review: 'George Gently: Series 7' – A Change Is In The Air
"George Gently: Series 7" - still the standard against which all other police procedurals should be judged. Read More »
Blu-ray Review: 'Foyle's War: Set 8' – The Final Episodes
"Foyle's War: Set 8" on Blu-ray marks the end of what was a magnificent piece of television. Read More »
Blu-ray Review: 'Midsomer Murders Set 25' – Celebrating A Hundredth Episode
A police procedural of the highest quality with a human element. Read More »
Blu-ray Review: 'American Horror Story: Coven'
American Horror Story: Coven is a great batch of episodes featuring a stellar cast of women, even if the extras are lackluster. Read More »
Blu-ray Review: 'Lone Survivor'
Berg's powerful retelling of Navy SEAL Team 10's struggle is more than enough to recommend the film, but Universal's first-rate Blu-ray package makes it even easier to praise. Read More »
Blu-ray Review: 'Jack Irish, Set 2'
An example of how good television can be when people put their minds to it Read More »
Blu-ray Review: 'Miss Fisher's Murder Mysteries – Series 2'
A perfect example of balancing character development and plots to create wonderful television. Read More »
Blu-Ray Review: 'Veronica Mars' (The Movie)
For a movie funded by fans and made on a relatively low (for Hollywood) budget, this has all the hallmarks of a professional production. Read More »
Blu-ray Review: 'Philomena'
Does the nearly impossible of going behind the facts and figures to get to the emotional heart of the story without ever descending into sentimentally. Read More »


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Upon exit, reflector now displays a message box "Error saving configuration file: Object reference not set to instance of object."
This started happening at least a month ago, when I updated to the latest version (126.96.36.199).
It has something to do with the fact that the cfg file is read only, but that is necessary for me so that I can add/change assemblies but still have the same starting point if I reopen reflector.
Is there any way to disable this error report, or disable the saving?


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Yulia Tymoshenko to run for Ukraine leader
- 27 March 2014
- From the section Europe
Former Prime Minister Yulia Tymoshenko has said she plans to run for president of Ukraine in May elections.
She was released after serving three years in jail in February following the ousting of President Viktor Yanukovych.
It was followed by a referendum which led to Russia's annexation of Crimea. On Thursday, the UN General Assembly voted to declare it invalid.
Earlier, the International Monetary Fund (IMF) agreed to a loan deal with Ukraine worth $14bn to $18bn.
IMF loan
US President Barack Obama said the IMF announcement was a "major step forward" to help Ukraine stabilise its economy and meet the long-term needs of its people.
Speaking after talks with Italian Prime Minister Matteo Renzi in Rome, Mr Obama said it was a "concrete signal" that the world stood united with Ukraine at a difficult time.
The US Senate and House of Representatives have both passed legislation backing a $1bn loan guarantee to Ukraine, which still has to be signed into law by President Obama.
Ukraine's interim Prime Minister Arseniy Yatsenyuk had earlier told parliament the country was on the ""on the edge of economic and financial bankruptcy".
At the UN General Assembly, 100 countries voted in favour of a resolution declaring the Crimean referendum on 16 March illegal and affirming Ukraine's territorial integrity.
Eleven nations voted against, with 58 abstentions. Given that the resolution was non-binding, the vote was largely symbolic, says the BBC's Nick Bryant in New York.
But Ukraine hopes the resolution will act as a deterrent and dissuade Moscow from making further incursions into its territory, he adds.
'Direct action'
Yulia Tymoshenko announced on Thursday her candidature for Ukraine's presidential elections in May.
Ms Tymoshenko, who has already served twice as prime minister and ran for president in 2010, told reporters she would stand as "a candidate for Ukrainian unity".
She said she had earned the right to be considered a candidate who was against corruption.
Yulia Tymoshenko
- 1960: Born in Dnipropetrovsk, industrial city in eastern Ukraine
- 1990s: Runs United Energy Systems of Ukraine and becomes wealthy
- 1999-2001: Serves in energy ministry but falls out with government of President Leonid Kuchma
- 2004: Kuchma's candidate Viktor Yanukovych elected president, but result widely condemned as rigged
- Huge "Orange Revolution" street protests led by Tymoshenko and ally Viktor Yushchenko defeat Yanukovych
- 2005: Becomes PM but relations sour with President Yushchenko
- 2010: Yanukovych defeats her in presidential election
- 2011: Jailed for seven years for abuse of power over gas deal with Russia
- February 2014: Released from prison hospital where she had received treatment for back complaint
"My presidential campaign will be the campaign of direct action: no promises, but immediate actions, and then - in a couple of days - reporting on what's been done," she said.
Ms Tymoshenko was a major figure in the 2004 "Orange Revolution" that ousted Mr Yanukovych from the presidency after an election widely seen as fraudulent.
She was imprisoned in 2011 for corruption linked to a gas deal she brokered with Russia as prime minister in 2009.
Her supporters say the case was politically motivated and instigated by Mr Yanukovych, to whom she lost the 2010 presidential election.
On Monday she denied the authenticity of a taped conversation in which she allegedly called for Russia to be turned into "scorched earth" and for ethnic Russians in Ukraine to be killed.
Ms Tymoshenko said the recording, which featured prominently on Russian news reports, was produced by Russia's security services.
Former boxer Vitaliy Klitschko and chocolate tycoon Petro Poroshenko are also expected to take part in the presidential election.
Opinion polls suggest Mr Poroshenko, who is one of Ukraine's richest men, is currently the most popular candidate.
The election is expected to take place on 25 May.
'Door of diplomacy'
More than 100 people were killed during protests which overthrew pro-Kremlin President Yanukovych in February.
They followed months of street protests sparked by Mr Yanukovych's decision to reject a planned EU trade deal in favour of closer ties with Moscow.
Since then, Russia has annexed the Crimean peninsula, which last week voted to become part of the Russian federation.
The West has widely condemned the move, with US President Barack Obama warning on Wednesday of further EU and US sanctions against Moscow if there were any further incursions.
Mr Obama said on Thursday that the US hoped Russia would "walk through the door of diplomacy" and resolve the issue in a peaceful way.
In other Ukraine developments:
- Six Ukrainian military officers detained by Russian troops in Crimea have been released, but five remain in custody; those released include Col Yuli Mamchur, the commander of Belbek base which fell on Saturday
- Ukrainian Prime Minister Arseny Yatseniuk says the price Ukraine pays for Russian gas will increase by 79% from 1 April
- Russian President Vladimir Putin announces plans for a new domestic payment system to circumvent financial sanctions imposed by Western nations over the Crimea issue.


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I'm not certain what the official dating waiting period is for normal folks when divorcing, but apparently for the Kardashians (and also my parents – ooh, that's awkward, sorry) it's nonexistent. At least, that's what the rumors would have us believe when it comes to Khloe Kardashian – rumored to already be hooking up with baseball player Matt Kemp. Because she's really the only tolerable Kardashian, I'm skeptical.
As everyone knows, Khloe dropped a super secret awesome album while everyone was sleeping yesterday filed for divorce from Lamar Odom yesterday and since that was just a hair over 24 hours ago, the internet is abuzz with rumors that she's now dating Matt Kemp (whose name I don't know as a baseball player, but vaguely recognize as someone who dated Rihanna a few years ago). Adding fuel to the metaphorical Twitter fire, he posted this pic of the Kardashian Khristmas tree with the caption, "Best time of the year!! It's gonna be a Cali Christmas this year."
Since he's a newcomer to the Kardashian Klan (and only an alleged one at that), we'll forgive him for the severe lack of the letter "K" in his post. I can't say the same for Kris Jenner though, who no doubt is somehow involved in the orchestration of this new, rebound fakelationship. According to "sources", Khloe and Matt have been concert-hopping all over town recently, listening to the sweet soulful sounds of John Legend and Jay-Z.
Regardless of whether these rumors are true, at least Khloe Kardashian has one validating truth to help soothe her broken heart: she was married to her basketball player longer than 72 days. And also we just like her more.
(Photo: WENN)


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Here is Justin Timberlake's 'Take Back The Night' video. The official music video had its premiere in support of the lead single of 'The 20/20 Experience Part 2,' the forthcoming new album from the multi-Grammy winning music superstar. The full clip and more details are below after the jump.
The video is above. Shot on location in New York City, and in keeping with the lyrics, the spirited, upbeat clip features Justin Timberlake in a variety of locales in the nighttime streets and the club scene, as well as in live footage from the recent concert performance at Yankee Stadium, part of the co-headlining 'Legends of Summer' tour with Jay Z.
JT's highly anticipated upcoming album, 'The 20/20 Experience Part 2,' will be released on September 30, 2013. As volume 2, it is a follow-up to the multiplatinum selling first volume of the same title released earlier in 2013.
YouTube VEVO link
via Rap-Up.com
Photo credit: Georges Biard (CC BY-SA 3.0) via Wikipedia
Related posts:
- Jay-Z, Justin Timberlake Legends of the Summer Tour Toronto Concert Video, Set-List, Reviews, Photos July 17, 2013
- Justin Timberlake 'Take Back The Night' New Song (Audio) from 'The 20/20 Experience Part 2' Album
- Justin Timberlake 'Tunnel Vision' Video: Official Music Video Premiere
- Justin Timberlake 'Mirrors' Video: Official Music Video Premiere (from 'The 20/20 Experience')
- Justin Timberlake: SNL Video March 9, 2013 Live Performance 'Suit & Tie' ft. Jay-Z and 'Mirrors'
- Justin Timberlake: 'Suit & Tie' Video: Official Music Video Premiere ft. Jay-Z
Justin Timberlake 'Take Back The Night' Official Music Video Premiere


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By Sid Salter
State Sen. Tommy Gollott, R-Biloxi, has walked the marble floors of the state Capitol Building for 42 years – 12 in the state House of Representatives and 30 in the state Senate.
Like most veteran lawmakers, Gollott sees the handwriting on the wall for the next two years.
That handwriting reads: "Make Draconian spending cuts or raise taxes."
But in introducing Senate Bill 2927 during the just-completed 2010 regular session of the Mississippi Legislature, Gollott chose to interject a third option – raise revenue by maximizing collection of existing taxes.
SB 2927 is the so-called "Amazon Tax" – a measure designed to make online sales by out-of-state retailers subject to state sales or use taxes. Gollott's bill never made it to the Senate floor and died a relatively quiet death in the Senate Finance Committee.
But after enduring a Fiscal Year 2010 with 9.4 percent average budget cuts, adopting a FY 2011 state budget with about 13.5 percent budget cuts and facing a likely FY 2012 state budget not underpinned by federal stimulus funds that could make 20 percent to 23 percent budget cuts necessary, lawmakers are likely to give Gollot's "Amazon Tax" a second look during the 2011 regular session.
Some 16 states considered "Amazon Tax" proposals over the last year. Colorado, North Carolina and New York are deepest in the fight so far.
In Colorado, the state passed a law to require Amazon and other Web retailers to mail notices to customers reminding them of their state sales tax liabilities on purchases made online.
Amazon responded by shutting down their affiliate operations in that state – a program that pays people to advertise Amazon products on their own Web sites.
North Carolina tax officials asked Amazon for the names and addresses of their customers in that state in hopes of using that information to collect unpaid sales taxes. Amazon filed suit against the state and the case is pending.
In New York, Amazon built a huge affiliate business. State officials figured that affiliates based in New York gave Amazon a legal "nexus" in the state and began collecting $70 million in additional sales taxes from Web retailers including Amazon.
But Amazon sued New York over the law and that case is also pending.
Web retailers and state governments alike are watching those lawsuits like hawks.
The argument in favor of applying state sales taxes to online sales is a simple one – tax fairness.
Out-of-state companies that make Internet sales in the state but that have no legal place of business or domicile in the state don't have to collect Mississippi's sales tax from customers here.
Proponents of collecting Mississippi's 7 percent sales tax for online purchases make these arguments:
– Failure to do so subsidizes the growth of distant companies, which contribute little to a community's civic and economic vitality, by giving them a 7 percent price advantage over Mississippi's local stores.
– It undermines state and local governments by reducing tax revenue for schools, police and other services – a revenue loss that will continue to grow as Internet sales continue to displace in-store sales.
– It makes a regressive sales tax more regressive (only those with computers, Internet access and credit cards are able to take advantage of the tax break) on poor people.
Gollott's bill may have died this session, but the political stakes will increase as the 2011 elections approach. Confronted with deep spending cuts and few options for new revenue, Gollott's "Amazon Tax" will likely resurface as a means to raises sales tax revenue without raising sales tax rates.
Contact Sid Salter, Perspective editor, at the Clarion-Ledger (601) 961-7084 or e-mail firstname.lastname@example.com.


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Below you will find a list of discussions in the Sony Xperia Play forums at the Android Forum. The Sony Xperia Play forum is for discussion of: The Sony Xperia Play Forum on Android.net. This forum contains all general Sony Xperia Play discussions..
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Buffalo Wings to host Inline Marathon!
Next Meeting is June 19th at 1pm
May 21st, 2010 at 11:05AM May 24th, 2010 3:04PMThe Buffalo Wings 2nd meeting was held Saturday May 22nd at the Amherst Ice Center. A 3rd meeting is scheduled for Saturday, June 19th at 1pm. Please meet at the Feature rink scoreclock.
Hello Everyone,
Just a summary update after Saturday's (5/22) meeting.
I was nominated to be the Chairperson of the event and after being 2nd and 3rd, I accepted.
Tracy Fitzsimmons will be the Coordinator between Buffalo Wild Wings and Roswell Park. (once the event has been approved by Roswell)
Steve Wright will help with soliciting sponsorships or donations from Buffalo Wild Wings' vendors (* see notation about donations below in red)
Carolyn Angstenberger will be the event Treasurer, with myself as second treasurer. Carolyn will coordinate opening a bank account with a local bank.
Carolyn will also be the Coordinator of Donations, letters, pick up of items.
(* see notation about donations below in red) We will have to recruit a small committee to help with donations.
Kristen Chilcott (a guest of Carolyn's) will assist with the event's printing needs (program, banners, flyers, etc)
Unable to attend was the gentleman from Kohls (dave or dan) who was going to help coordinate donations from Kohls and the mother/son pair (mary and ryan?) – who may be willing to help coordinate the theme tray basket donations from each team. If both of you could please contact me (email or phone – [email protected] or 512-0931) to confirm if you still wish to help coordinate these areas. Thank you.
Thank you to the players that attended, (if I have them correct) Kevin Drum, Randy Krupski and Keith Piatek and for your input.
Thank you also to Fred Angstenberger and Corey Clark.
Gina and Wendell Smith – thank you for taking time to attend the meeting while trying to staff the booth at the same time. Please feel free to contact me as we did not have a chance to talk.
The event date was chosen and will be from 10am on Saturday, November 6 until at least 1pm Sunday, November 7th (will continue hour by hour depending on players and the flight time for the adjudicator for Guinness) at the Kenan Center
**side note – should we check with Guinness and see if there is inclement weather in either city and the adjudicator can't arrive in Buffalo, will they reschedule for the next weekend? What is Buffalo Wings backup plan if the adjudicator can't show?
Starting at 10am will allow for set up to start around 7am or 8am depending on what other activities/food we decide to also have.
There was discussion on how much each player should be charged to play in the event – the final decision was a $50 registration fee and then to try to collect pledges or donations from friends, family, coworkers, etc. Should we have a prize for the player that raises the most pledges/donations, as an incentive. We will also check with Roswell to see if they can assist with links for donations.
How to pay for the Guinness Adjudicator was also discussed. Fred, Mike's brother said he would talk to his employer Admar and see if they would donate any money towards it. This lead into a discussion regarding sponsors and different sponsor levels and how would we 'promote' their sponsorship – logos on uniforms, banners, name on literature, listing in program, etc. Still need to work on sponsorship levels.
We set our next meeting for Saturday, June 19th at 1pm – pending the approval of Roswell and their Executive Board for this event.
My first task as Chairperson was to read the literature Mike A. forwarded to me from Roswell and Guinness.
I will need to talk to Mike and/or Eric for some of the information needed to complete the form.
I have copy and pasted the main guidelines from Roswell
Any event or promotion seeking to use the Roswell Park Cancer Institute name and Team Cure name and/or logo must have approval of Executive Board. Usage of the Team Cure logo must comply with graphic standards.
Before soliciting businesses or individuals for sponsorship, please contact the Team Cure Coordinator at Roswell Park Cancer Institute with a list of companies you would like to approach. Many corporate relationships are established with local companies and businesses. We ask that before approaching any businesses, contact the Team Cure Coordinator first so as not to jeopardize our relationship with these donors.
Organizer(s) must agree to hold harmless and indemnify Roswell Park Cancer Institute and Roswell Park Alliance Foundation from any liability arising from the event and sign the attached liability release and indemnification agreement with completed application.
Roswell Park Cancer Institute and Roswell Park Alliance Foundation cannot ensure staff or patient ambassador representation at an event. Determination for representation will depend on availability and date of event.
If for any reason event plans change, please notify the Team Cure Coordinator at Roswell Park Cancer Institute immediately. If your event is cancelled, please return any materials and/or merchandise provided to you.
The main contact person listed on initial application must ensure that all necessary permits, licenses and insurance are obtained.
Roswell Park Cancer Institute/ Roswell Park Alliance Foundation CANNOT Provide:
· Tax exemption
· Gift recognition letters or letters noting a tax deduction
· Insurance or liability coverage
· Funding or reimbursement for expenses
· A mailing list of donors or vendors
So needless to say I have some concerns after reading the guidelines and I will be calling Roswell for clarification especially with regards to the donation section.
If we do need to submit all companies first, I will need each person to forward to me companies names/addresses and I will include with my list.
Once we have the green light from Roswell, I was wondering if the Buffalo Wild Wings website can advertise for sponsors. Keep it brief, until sponsorship levels and details are finalized but I think we could still ask "if anyone knows of a company/business that would be interested in becoming an event sponsor or in making a donation – please contact (committee name) for more information†That way – we can follow Roswell's guidelines of checking with them first.
If Eric, Mike or Steve (or anyone else) can also provide me with any other anticipated/estimated event expenses that would be appreciated. (rink rental, referees, port a potty, uniforms, rink employee(s) the day of the event, event entertainment, event food/drink, printing costs, mailing costs, security, athletic trainers, etc). These expenses are needed both for Roswell as well as when soliciting sponsors. We need to show perspective sponsors what our costs are – doesn't matter if later down the road we get items donated, as of now they are expenses. Does the organization have any funds designated for this event?
I was also thinking – that since we need a "number†for Guinness in terms of funds we have available for the adjudicator – what if we use the Player Registration fees toward that expense. $50 a player * 32 players = $1600.
Without committed players there is no event, and without an adjudicator there is no event. They go hand in hand. And the players/organization are the ones that will be recognized in the Guinness World Book of Records. A company or sponsors would not be recognized.
Please let me know your thoughts so we can advise Guinness as soon as possible. Thank you.
If anyone has any other comments or info I may have missed/not included, please feel free to contact me via email or phone.
716-512-0931 cell phone
Thank you for your time and commitment to this organization and fundraiser.
Cheryl Walsh
The Buffalo wings had their first meeting last night for the Roswell Park benefit. Things went very well as many ideas were kicked around. We will do a follow up meeting May 22nd at 1pm. Please meet at the Feature rink scoreclock.
The Buffalo Wings Roller Hockey League is about to undertake an exciting 'ROLLER HOCKEY MARATHON' Guinness Book of World Records attempt to benefit Roswell Park Cancer Institute. We are seeking the help of anyone interested in participating, either through; volunteering, playing, donating, or pledging. The current record now stands at just 24 hours and has been so since 2002.
We feel this will be a great way to raise money for the Premier Cancer Research Center in Western New York. If you or anyone close to you has ever had to experience the hardships of a battle with Cancer, or if you just want to help join the fight against Cancer, please take the time to join us for an organizational meeting on Friday, April 23 at 7pm.
Everyone will meet at the Amherst Ice Center's Feature Rink score-box and then head to one of the meeting rooms upstairs. Any help will be appreciated as we will need plenty of volunteers throughout the event. Thank you from the BWRHL for your support of RPCI and the fight against Cancer.
Please feel free to contact Mike Angstenberger at [email protected] for further details or any questions.


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I think that connecting with natural environments is so important. I do my best thinking, innovation, and creation while lost in the woods.
Christopher Golden
About Golden's Research
Researcher Links Health of Planet, Its People
Madagascar researcher Christopher Golden finds surprising connections between the environment and humans.
Why People Eat Dirt
Would you eat sand, chalk, coffee grounds, or chicken poop? Some people do, and it's called pica.
Conservation and Nutrition Collide
Conservationalists cringe when they see a rare aye-aye over a fire, but the lemurs are part of a balanced diet for locals.
Explorer of the Week
Christopher Golden—expert on bushmeat consumption in Madagascar—answers all our questions and provides two sketches of himself in the field.
Health Care Savings, Naturally
For millions of people around the world, being sick doesn't mean making a trip to the local pharmacy.


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Enantioselective synthesis
Enantioselective synthesis, also called chiral synthesis or asymmetric synthesis,[1] is a form of chemical synthesis. It is defined by IUPAC as: a chemical reaction (or reaction sequence) in which one or more new elements of chirality are formed in a substrate molecule and which produces the stereoisomeric (enantiomeric or diastereoisomeric) products in unequal amounts.[2]
Put more simply: it is the synthesis of a compound by a method that favors the formation of a specific enantiomer or diastereomer.
Enantioselective synthesis is a key process in modern chemistry and is particularly important in the field of pharmaceuticals, as the different enantiomers or diastereomers of a molecule often have different biological activity.
Macroscopic manifestations of enantioselectivity[edit]
Many of the building blocks of biological systems, such as sugars and amino acids, are produced exclusively as one enantiomer. As a result of this living systems possess a high degree of chemical chirality and will often react differently with the various enantiomers of a given compound. Examples of this selectivity include:
- Flavour: the artificial sweetener aspartame has two enantiomers. L-aspartame tastes sweet, yet D-aspartame is tasteless[3]
- Odor: R-(–)-carvone smells like spearmint yet S-(+)-carvone, smells like caraway.[4]
- Drug effectiveness: the antidepressant drug Citalopram is sold as a racemic mixture. However, studies have shown that only the (S)-(+) enantiomer is responsible for the drug's beneficial effects.[5][6]
- Drug safety: D‑penicillamine is used in chelation therapy and for the treatment of rheumatoid arthritis. However L‑penicillamine is toxic as it inhibits the action of pyridoxine, an essential B vitamin.[7]
As such enantioselective synthesis is of great importance; but it can also be difficult to achieve. Asymmetric induction can occur intramolecularly when given a chiral starting material. This behaviour can be exploited, especially when the goal is to make several consecutive chiral centres to give a specific enantiomer of a specific diastereomer. An aldol reaction, for example, is inherently diastereoselective; if the aldehyde is enantiopure, the resulting aldol adduct is diastereomerically and enantiomerically pure.
Enantioselective catalysis[edit]
Enantioselective catalysis is widely practiced method for generating chiral compounds.
Enantiomers possess identical enthalpies and entropies and hence should be produced in equal amounts by an undirected process – leading to a racemic mixture. The nonselectivity can be biased using a chiral feature that favors the formation of one enantiomer over another via interactions at the transition state. This biasing is known as asymmetric induction and can involve chiral features in the substrate, reagent, catalyst, or environment[8] and works by making the activation energy required to form one enantiomer lower than that of the opposing enantiomer.[9]
Enantioselectivity is usually determined by the relative rates, k1/k2, of an enantiodifferentiating step. The differing barrier heights, ΔΔG*, for these divergent steps determines the relative rates:
- k1/k2 = 10^(ΔΔG*/(temperature*1.98*2.3))
k1/k2 is also sensitive to temperature, which is more noticeable for modest values of ΔΔG*.
ΔΔG* (kcal) | k1/k2 (273 K) | k1/k2 (298 K) | k1/k2 (323 K) | |||
1.0 | 6 |
.37 | 5 |
.46 | 4 |
.78 |
2.0 | 40 |
.6 | 29 |
.8 | 22 |
.9 |
3.0 | 259 | 162 | 109 | |||
4.0 | 1650 | 886 | 524 | |||
5.0 | 10500 | 4830 | 2510 |
Chiral catalysis[edit]
In general, enantioselective catalysis (known traditionally as asymmetric catalysis) are chiral coordination complexes. Catalysis is effective for a broader range of transformations than any other method of enantioselective synthesis. The catalysts are almost invariably rendered chiral by using chiral ligands.[10] Most enantioselective catalysts are effective at low substrate/catalyst ratios.[11][12] Given their high efficiencies, they are often suitable for industrial scale synthesis, even with expensive catalysts.[13] A versatile example of enantioselective synthesis is asymmetric hydrogenation, which is used to reduce a wide variety of functional groups.
The design of new catalysts is very much dominated by the development of new classes of ligands. Certain ligands, often referred to as 'privileged ligands', have been found to be effective in a wide range of reactions; examples include BINOL, Salen, and BOX. Few catalysts are however applicable to more than one type of asymmetric reaction. For example, Noyori asymmetric hydrogenation with BINAP/Ru requires a β-ketone, although another catalyst, BINAP/diamine-Ru, widens the scope to α,β-olefins and aromatics.
Chiral auxiliaries[edit]
A chiral auxiliary is an organic compound which couples to the starting material to form new compound which can then undergo enantioselective reactions via intramolecular asymmetric induction.[14][15] At the end of the reaction the auxiliary is removed, under conditions that will not cause racemization of the product.[16] It is typically then recovered for future use.
Chiral auxiliaries must be used in stoichiometric amounts to be effective and require additional synthetic steps to append and remove the auxiliary. However, in some cases the only available stereoselective methodology relies on chiral auxiliaries and these reactions tend to be versatile and very well-studied, allowing the most time-efficient access to enantiomerically pure products.[15] Additionally, the products of auxiliary-directed reactions are diastereomers, which enables their facile separation by methods such as column chromatography or crystallization.
Biocatalysis makes use of biological compounds, ranging from isolated enzymes to living cells, to perform chemical transformations.[17][18] The advantages of these reagents include very high ee's and reagent specificity, as well as mild operating conditions and low environmental impact. Biocatalysts are more commonly used in industry than in academic research;[19] for example in the production of statins.[20] The high reagent specificity can be a problem however; as it often requires that a wide range of biocatalysts be screened before an effective reagent is found.
Enantioselective organocatalysis[edit]
Organocatalysis refers to a form of catalysis, where the rate of a chemical reaction is increased by an organic compound consisting of carbon, hydrogen, sulfur and other non-metal elements.[21][22] When the organocatalyst is chiral enantioselective synthesis can be achieved;[23][24] for example a number of carbon–carbon bond forming reactions become enantioselective in the presence of proline with the aldol reaction being a prime example.[25] Organocatalysis often employs natural compounds and secondary amines as chiral catalysts;[26] these are inexpensive and environmentally friendly, as no metals are involved.
Chiral pool synthesis[edit]
Chiral pool synthesis is one of the simplest and oldest approaches for enantioselective synthesis. A readily available chiral starting material is manipulated through successive reactions, often using achiral reagents, to obtain the desired target molecule. This can meet the criteria for enantioselective synthesis when a new chiral species is created, such as in an SN2 reaction.
Chiral pool synthesis is especially attractive for target molecules having similar chirality to a relatively inexpensive naturally occurring building-block such as a sugar or amino acid. However, the number of possible reactions the molecule can undergo is restricted and tortuous synthetic routes may be required (e.g. Oseltamivir total synthesis). This approach also requires a stoichiometric amount of the enantiopure starting material, which can be expensive if it is not naturally occurring.
Alternative approaches[edit]
Alternatives to enantioselective synthesis usually involve the isolation of one enantiomer from a racemic mixture by any of a number of methods. If the cost in time and money of making such racemic mixtures is low (or if both enantiomers may find use) then this approach may remain cost-effective. Common methods of separation are based around chiral resolution or kinetic resolution.
Separation and analysis of enantiomers[edit]
The two enantiomers of a molecule possess the same physical properties (e.g. melting point, boiling point, polarity etc.) and so behave identically to each other. As a result, they will migrate with an identical Rf in thin layer chromatography and have identical retention times in HPLC and GC. Their NMR and IR spectra are identical.
This can make it very difficult to determine whether a process has produced a single enantiomer (and crucially which enantiomer it is) as well as making it hard to separate enantiomers from a reaction which has not been 100% enantioselective. Fortunately, enantiomers behave differently in the presence of other chiral materials and this can be exploited to allow their separation and analysis.
Enantiomers do not migrate identically on chiral chromatographic media, such as quartz or standard media that has been chirally modified. This forms the basis of chiral column chromatography, which can be used on a small scale to allow analysis via GC and HPLC, or on a large scale to separate chirally impure materials. However this process can require large amount of chiral packing material which can be expensive. A common alternative is to use a chiral derivatizing agent to convert the enantiomers into a diastereomers, in much the same way as chiral auxiliaries. These have different physical properties and hence can be separated and analysed using conventional methods. Special chiral derivitizing agents known as 'chiral resolution agents' are used in the NMR spectroscopy of stereoisomers, these typically involve coordination to chiral europium complexes such as Eu(fod)3 and Eu(hfc)3.
The enantiomeric excess of a substance can also be determined using certain optical methods. The oldest method for doing this is to use a polarimeter to compare the level of optical rotation in the product against a 'standard' of known composition. It is also possible to perform ultraviolet-visible spectroscopy of stereoisomers by exploiting the Cotton effect.
One of the most accurate ways of determining the chirality of compound is to determine its absolute configuration by Xray Crystallography. However this is a labour-intensive process which requires that a suitable single crystal be grown.
Inception (1815–1905)[edit]
In 1815 the French physicist Jean-Baptiste Biot showed that certain chemicals could rotate the plane of a beam of polarised light, a property called optical activity.[27] The nature of this property remained a mystery until 1848, when Louis Pasteur proposed that it had a molecular basis originating from some form of dissymmetry,[28] with the term chirality being coined by Lord Kelvin a year later.[29] The origin of chirality itself was finally described in 1874, when Jacobus Henricus van 't Hoff and Joseph Le Bel independently proposed the tetrahedral geometry of carbon;[30] structural models prior to this work had been two-dimensional, and van 't Hoff Le Bel theorized that the arrangement of groups around this tetrahedron could dictate the optical activity of the resulting compound.[citation needed]
In 1894 Hermann Emil Fischer outlined the concept of asymmetric induction;[32] in which he correctly ascribed selective the formation of D-glucose by plants to be due to the influence of optically active substances within chlorophyll. Fischer also successfully performed what would now be regarded as the first example of enantioselective synthesis, by enantioselectively elongating sugars via a process which would eventually become the Kiliani–Fischer synthesis.[33]
The first enantioselective chemical synthesis is most often attributed to Willy Marckwald, Universität zu Berlin, for a brucine-catalyzed enantioselective decarboxylation of 2-ethyl-2-methylmalonic acid reported in 1904.[31][34] A slight excess of the levorotary form of the product of the reaction, 2-methylbutyric acid, was produced; as this product is also a natural product—e.g., as a side chain of lovastatin formed by its diketide synthase (LovF) during its biosynthesis[35]—this result constitutes the first recorded total synthesis with enantioselectivity, as well other firsts (as Koskinen notes, first "example of asymmetric catalysis, enantiotopic selection, and organocatalysis").[31] This observation is also of historical significance, as at the time enantioselective synthesis could only be understood in terms of vitalism.[citation needed] Natural and artificial compounds were fundamentally different, it was argued,[by whom?] and chirality could only exist in natural compounds.[citation needed] Unlike Fischer, Marckwald had performed an enantioselective reaction upon an achiral, un-natural starting material, albeit with a chiral organocatalyst (as we now understand this chemistry).[31][36][37]
Early work (1905–1965)[edit]
The development of enantioselective synthesis was initially slow, largely due to the limited range of techniques available for their separation and analysis. Diastereomers possess different physical properties, allowing separation by conventional means, however at the time enantiomers could only be separated by spontaneous resolution (where enantiomers separate upon crystallisation) or kinetic resolution (where one enantiomer is selectively destroyed). The only tool for analysing enantiomers was optical activity using a polarimeter, a method which provides no structural data.
It was not until the 1950s that major progress really began. Driven in part by chemists such as R. B. Woodward and Vladimir Prelog but also by the development of new techniques. The first of these was Xray Crystallography, which was used to determine the absolute configuration of an organic compound by Johannes Bijvoet in 1951.[38] Chiral chromatography was introduced a year later by Dalgliesh, who used paper chromatography to separate chiral amino acids.[39] Although Dalgliesh was not the first to observe such separations, he correctly attributed the separation of enantiomers to differential retention by the chiral cellulose. This was expanded upon in 1960, when Klem and Reed first reported the use of chirally-modified silica gel for chiral HPLC chromatographic separation.[40]
While it had long been known that the different enantiomers of a drug could have different activities,[41][42] this was not accounted for in early drug design and testing. However following the thalidomide disaster the development and licensing of drugs changed dramatically.
First synthesized in 1953, thalidomide was widely prescribed for morning sickness from 1957 to 1962, but was soon found to be seriously teratogenic,[43] eventually causing birth defects in more than 10,000 babies. The disaster prompted many counties to introduce tougher rules for the testing and licensing of drugs, such as the Kefauver-Harris Amendment (U.S.) and Directive 65/65/EEC1 (E.U.).
Early research into the teratogenic mechanism, using mice, suggested that one enantiomer of thalidomide was teratogenic while the other possessed all the therapeutic activity. This theory was later shown to be incorrect and has now been superseded by a body of research. However it raised the importance of chirality in drug design, leading to increased research into enantioselective synthesis.
Modern Age (since 1965)[edit]
The Cahn–Ingold–Prelog priority rules (often abbreviated as the CIP system) were first published in 1966; allowing enantiomers to be more easily and accurately described.[44][45] The same year saw first successful enantiomeric separation by gas chromatography[46] an important development as the technology was in common use at the time.
Metal catalysed enantioselective synthesis was pioneered by William S. Knowles, Ryōji Noyori and K. Barry Sharpless; for which they would receive the 2001 Nobel Prize in Chemistry. Knowles and Noyori began with the development of asymmetric hydrogenation, which they developed independently in 1968. Knowles replaced the achiral triphenylphosphine ligands in Wilkinson's catalyst with chiral phosphine ligands. This experimental catalyst was employed in an asymmetric hydrogenation with a modest 15% enantiomeric excess. Knowles was also the first to apply enantioselective metal catalysis to industrial-scale synthesis; while working for the Monsanto Company he developed an enantioselective hydrogenation step for the production of L-DOPA, utilising the DIPAMP ligand.[47][48][49]
Knowles: Asymmetric hydrogenation (1968) | Noyori: Enantioselective cyclopropanation (1968) |
Noyori devised a copper complex using a chiral Schiff base ligand, which he used for the metal-carbenoid cyclopropanation of styrene.[50] In common with Knowles' findings, Noyori's results for the enantiomeric excess for this first-generation ligand were disappointingly low: 6%. However continued research eventually led to the development of the Noyori asymmetric hydrogenation reaction.
Sharpless complemented these reduction reactions by developing a range of asymmetric oxidations (Sharpless epoxidation,[51] Sharpless asymmetric dihydroxylation,[52] Sharpless oxyamination[53]) during the 1970s to 1980's. With the asymmetric oxyamination reaction, using osmium tetroxide, being the earliest.
During the same period, methods were developed to allow the analysis of chiral compounds by NMR; either using chiral derivatizing agents, such as Mosher's acid,[54] or europium based shift reagents, of which Eu(DPM)3 was the earliest.[55]
Chiral auxiliaries were introduced by E.J. Corey in 1978[56] and featured prominently in the work of Dieter Enders. Around the same time enantioselective organocatalysis was developed, with pioneering work including the Hajos–Parrish–Eder–Sauer–Wiechert reaction. Enzyme-catalyzed enantioselective reactions became more and more common during the 1980s,[57] particularly in industry,[58] with their applications including asymmetric ester hydrolysis with pig-liver esterase. The emerging technology of genetic engineering has allowed the tailoring of enzymes to specific processes, permitting an increased range of selective transformations. For example, in the asymmetric hydrogenation of statin precursors.[20]
See also[edit]
- Aza-Baylis–Hillman reaction, for the use of a chiral ionic liquid in enantioselective synthesis.
- Spontaneous absolute asymmetric synthesis, the synthesis of chiral products from achiral precursors and without the use of optically active catalysts or auxiliaries. It is relevant to the discussion homochirality in nature.
- Tacticity, a property of polymers which originates from enantioselective synthesis
- ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "asymmetric synthesis".
- ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "stereoselective synthesis".
- ^ Gal, Joseph (2012). "The Discovery of Stereoselectivity at Biological Receptors: Arnaldo Piutti and the Taste of the Asparagine Enantiomers-History and Analysis on the 125th Anniversary". Chirality. 24 (12): 959–976. doi:10.1002/chir.22071. PMID 23034823.
- ^ Theodore J. Leitereg; Dante G. Guadagni; Jean Harris; Thomas R. Mon; Roy Teranishi (1971). "Chemical and sensory data supporting the difference between the odors of the enantiomeric carvones". J. Agric. Food Chem. 19 (4): 785–787. doi:10.1021/jf60176a035.
- ^ Lepola U, Wade A, Andersen HF (May 2004). "Do equivalent doses of escitalopram and citalopram have similar efficacy? A pooled analysis of two positive placebo-controlled studies in major depressive disorder". Int Clin Psychopharmacol. 19 (3): 149–55. doi:10.1097/01.yic.0000122862.35081.cd. PMID 15107657.
- ^ Hyttel, J.; Bøgesø, K. P.; Perregaard, J.; Sánchez, C. (1992). "The pharmacological effect of citalopram resides in the (S)-(+)-enantiomer". Journal of Neural Transmission. 88 (2): 157–160. doi:10.1007/BF01244820. PMID 1632943.
- ^ JAFFE, IA; ALTMAN, K; MERRYMAN, P (Oct 1964). "THE ANTIPYRIDOXINE EFFECT OF PENICILLAMINE IN MAN.". The Journal of Clinical Investigation. 43: 1869–73. doi:10.1172/JCI105060. PMC 289631. PMID 14236210.
- ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "asymmetric induction".
- ^ Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter (2001). Organic Chemistry (1st ed.). Oxford University Press. ISBN 978-0-19-850346-0.Page 1226
- ^ It is also possible to generate chiral-at-metal complexes using simpler achiral ligands, but such species have rarely proven to be useful synthetically. Bauer, Eike B. (2012). "Chiral-at-metal complexes and their catalytic applications in organic synthesis". Chemical Society Reviews. 41 (8): 3153–67. doi:10.1039/C2CS15234G. PMID 22306968.
- ^ N. Jacobsen, Eric; Pfaltz, Andreas; Yamamoto, Hisashi (1999). Comprehensive asymmetric catalysis 1-3. Berlin: Springer. ISBN 9783540643371.
- ^ M. Heitbaum; F. Glorius; I. Escher (2006). "Asymmetric Heterogeneous Catalysis". Angewandte Chemie International Edition. 45 (29): 4732–4762. doi:10.1002/anie.200504212. PMID 16802397.
- ^ Asymmetric Catalysis on Industrial Scale, (Blaser, Schmidt), Wiley-VCH, 2004.
- ^ Roos, Gregory (2002). Compendium of chiral auxiliary applications. San Diego, Calif. [u.a.]: Acad. Press. ISBN 9780125953443.
- ^ a b Glorius, F.; Gnas, Y. (2006). "Chiral Auxiliaries – Principles and Recent Applications". Synthesis. 2006 (12): 1899–1930. doi:10.1055/s-2006-942399.
- ^ Evans, D. A.; Helmchen, G.; Rüping, M. (2007). "Chiral Auxiliaries in Asymmetric Synthesis". In Christmann, M. Asymmetric Synthesis – The Essentials. Wiley-VCH Verlag GmbH & Co. pp. 3–9. ISBN 978-3-527-31399-0.
- ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Biocatalysis".
- ^ Faber, Kurt (2011). Biotransformations in organic chemistry a textbook (6th rev. and corr. ed.). Berlin: Springer-Verlag. ISBN 9783642173936.
- ^ Schmid, A.; Dordick, J. S.; Hauer, B.; Kiener, A.; Wubbolts, M.; Witholt, B. (2001). "Industrial biocatalysis today and tomorrow". Nature. 409 (6817): 258–268. doi:10.1038/35051736. PMID 11196655.
- ^ a b Müller, Michael (7 January 2005). "Chemoenzymatic Synthesis of Building Blocks for Statin Side Chains". Angewandte Chemie International Edition. 44 (3): 362–365. doi:10.1002/anie.200460852. PMID 15593081.
- ^ Berkessel, A.; Groeger, H. (2005). Asymmetric Organocatalysis. Weinheim: Wiley-VCH. ISBN 3-527-30517-3.
- ^ Special Issue: List, Benjamin (2007). "Organocatalysis". Chem. Rev. 107 (12): 5413–5883. doi:10.1021/cr078412e.
- ^ Gröger, Albrecht Berkessel; Harald (2005). Asymmetric organocatalysis – from biomimetic concepts to applications in asymmetric synthesis (1. ed., 2. reprint. ed.). Weinheim: Wiley-VCH. ISBN 3-527-30517-3.
- ^ Dalko, Peter I.; Moisan, Lionel (15 October 2001). "Enantioselective Organocatalysis". Angewandte Chemie International Edition. 40 (20): 3726–3748. doi:10.1002/1521-3773(20011015)40:20<3726::AID-ANIE3726>3.0.CO;2-D.
- ^ Notz, Wolfgang; Tanaka, Fujie; Barbas, Carlos F. (1 August 2004). "Enamine-Based Organocatalysis with Proline and Diamines: The Development of Direct Catalytic Asymmetric Aldol, Mannich, Michael, and Diels−Alder Reactions". Accounts of Chemical Research. 37 (8): 580–591. doi:10.1021/ar0300468. PMID 15311957.
- ^ Bertelsen, Søren; Jørgensen, Karl Anker (2009). "Organocatalysis—after the gold rush". Chemical Society Reviews. 38 (8): 2178–89. doi:10.1039/b903816g. PMID 19623342.
- ^ Lakhtakia, A. (ed.) (1990). Selected Papers on Natural Optical Activity (SPIE Milestone Volume 15). SPIE.
- ^ Pasteur, L. (1848). "Researches on the molecular asymmetry of natural organic products, English translation of French original, published by Alembic Club Reprints (Vol. 14, pp. 1–46) in 1905, facsimile reproduction by SPIE in a 1990 book".
- ^ Pedro Cintas (2007). "Tracing the Origins and Evolution of Chirality and Handedness in Chemical Language". Angewandte Chemie International Edition. 46 (22): 4016–4024. doi:10.1002/anie.200603714. PMID 17328087.
- ^ van't Hoff, Jacobus (September 1874). "Voorstel tot Uitbreiding der Tegenwoordige in de Scheikunde gebruikte Structuurformules in de Ruimte, benevens een daarmee samenhangende Opmerking omtrent het Verband tusschen Optisch Actief Vermogen en chemische Constitutie van Organische Verbindingen (A suggestion looking to the extension into space of the structural formulas at present used in chemistry. And a note upon the relation between the optical activity and the chemical constitution of organic compounds)" (PDF). Archives neerlandaises des sciences exactes et naturelles. (9): 445–454.[permanent dead link][non-primary source needed][non-primary source needed]
- ^ a b c d e Koskinen, Ari M.P. (2013). Asymmetric synthesis of natural products (Second ed.). Hoboken, N.J.: Wiley. pp. 17, 28–29. ISBN 1118347331.
- ^ Fischer, Emil (1 October 1894). "Synthesen in der Zuckergruppe II". Berichte der deutschen chemischen Gesellschaft. 27 (3): 3189–3232. doi:10.1002/cber.189402703109.
- ^ Fischer, Emil; Hirschberger, Josef (1 January 1889). "Ueber Mannose. II". Berichte der deutschen chemischen Gesellschaft. 22 (1): 365–376. doi:10.1002/cber.18890220183.
- ^ Marckwald, W. (1904). "Ueber asymmetrische Synthese". Berichte der deutschen chemischen Gesellschaft. 37: 349–354. doi:10.1002/cber.19040370165.
- ^ Campbell, Chantel D.; Vederas, John C. (23 June 2010). "Biosynthesis of lovastatin and related metabolites formed by fungal iterative PKS enzymes". Biopolymers. 93 (9): 755–763. doi:10.1002/bip.21428.
- ^ Much of this early work was published in German, however contemporary English accounts can be found in the papers of Alexander McKenzie, with continuing analysis and commentary in modern reviews such as Koskinen (2012).
- ^ McKenzie, Alexander (1 January 1904). "CXXVII.Studies in asymmetric synthesis. I. Reduction of menthyl benzoylformate. II. Action of magnesium alkyl haloids on menthyl benzoylformate". J. Chem. Soc. Trans. 85: 1249. doi:10.1039/CT9048501249.
- ^ BIJVOET, J. M.; PEERDEMAN, A. F.; van BOMMEL, A. J. (1951). "Determination of the Absolute Configuration of Optically Active Compounds by Means of X-Rays". Nature. 168 (4268): 271–272. doi:10.1038/168271a0.
- ^ Dalgliesh, C. E. (1952). "756. The optical resolution of aromatic amino-acids on paper chromatograms". Journal of the Chemical Society (Resumed): 3940. doi:10.1039/JR9520003940.
- ^ Klemm, L.H.; Reed, David (1960). "Optical resolution by molecular complexation chromatography". Journal of Chromatography A. 3: 364–368. doi:10.1016/S0021-9673(01)97011-6.
- ^ Cushny, AR (2 November 1903). "Atropine and the hyoscyamines-a study of the action of optical isomers". The Journal of Physiology. 30 (2): 176–94. doi:10.1113/jphysiol.1903.sp000988. PMC 1540678. PMID 16992694.
- ^ Cushny, AR; Peebles, AR (13 July 1905). "The action of optical isomers: II. Hyoscines". The Journal of Physiology. 32 (5–6): 501–10. doi:10.1113/jphysiol.1905.sp001097. PMC 1465734. PMID 16992790.
- ^ Mcbride, W.G. (1961). "THALIDOMIDE AND CONGENITAL ABNORMALITIES". The Lancet. 278 (7216): 1358. doi:10.1016/S0140-6736(61)90927-8.
- ^ Robert Sidney Cahn; Christopher Kelk Ingold; Vladimir Prelog (1966). "Specification of Molecular Chirality". Angewandte Chemie International Edition. 5 (4): 385–415. doi:10.1002/anie.196603851.
- ^ Vladimir Prelog; Günter Helmchen (1982). "Basic Principles of the CIP-System and Proposals for a Revision". Angewandte Chemie International Edition. 21 (8): 567–583. doi:10.1002/anie.198205671.
- ^ Gil-Av, Emanuel; Feibush, Binyamin; Charles-Sigler, Rosita (1966). "Separation of enantiomers by gas liquid chromatography with an optically active stationary phase". Tetrahedron Letters. 7 (10): 1009–1015. doi:10.1016/S0040-4039(00)70231-0.
- ^ Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L.; Weinkauff, D. J. (1977). "Asymmetric hydrogenation. Rhodium chiral bisphosphine catalyst". Journal of the American Chemical Society. 99 (18): 5946–5952. doi:10.1021/ja00460a018.
- ^ Knowles, William S. (2002). "Asymmetric Hydrogenations (Nobel Lecture)". Angewandte Chemie International Edition. 41 (12): 1998. doi:10.1002/1521-3773(20020617)41:12<1998::AID-ANIE1998>3.0.CO;2-8.
- ^ Knowles, W. S. (March 1986). "Application of organometallic catalysis to the commercial production of L-DOPA". Journal of Chemical Education. 63 (3): 222. doi:10.1021/ed063p222.
- ^ H. Nozaki; H. Takaya; S. Moriuti; R. Noyori (1968). "Homogeneous catalysis in the decomposition of diazo compounds by copper chelates: Asymmetric carbenoid reactions". Tetrahedron. 24 (9): 3655–3669. doi:10.1016/S0040-4020(01)91998-2.
- ^ Katsuki, Tsutomu; Sharpless, K. Barry (1980). "The first practical method for asymmetric epoxidation". Journal of the American Chemical Society. 102 (18): 5974–5976. doi:10.1021/ja00538a077.
- ^ Jacobsen, Eric N.; Marko, Istvan.; Mungall, William S.; Schroeder, Georg.; Sharpless, K. Barry. (1988). "Asymmetric dihydroxylation via ligand-accelerated catalysis". Journal of the American Chemical Society. 110 (6): 1968–1970. doi:10.1021/ja00214a053.
- ^ Sharpless, K. Barry; Patrick, Donald W.; Truesdale, Larry K.; Biller, Scott A. (1975). "New reaction. Stereospecific vicinal oxyamination of olefins by alkyl imido osmium compounds". Journal of the American Chemical Society. 97 (8): 2305–2307. doi:10.1021/ja00841a071.
- ^ J. A. Dale, D. L. Dull and H. S. Mosher (1969). "α-Methoxy-α-trifluoromethylphenylacetic acid, a versatile reagent for the determination of enantiomeric composition of alcohols and amines". J. Org. Chem. 34 (9): 2543–2549. doi:10.1021/jo01261a013.
- ^ Hinckley, Conrad C. (1969). "Paramagnetic shifts in solutions of cholesterol and the dipyridine adduct of trisdipivalomethanatoeuropium(III). A shift reagent". Journal of the American Chemical Society. 91 (18): 5160–5162. doi:10.1021/ja01046a038. PMID 5798101.
- ^ Ensley, Harry E.; Parnell, Carol A.; Corey, Elias J. (1978). "Convenient synthesis of a highly efficient and recyclable chiral director for asymmetric induction". The Journal of Organic Chemistry. 43 (8): 1610–1612. doi:10.1021/jo00402a037.
- ^ Sariaslani, F.Sima; Rosazza, John P.N. (1984). "Biocatalysis in natural products chemistry". Enzyme and Microbial Technology. 6 (6): 242–253. doi:10.1016/0141-0229(84)90125-X.
- ^ Wandrey, Christian; Liese, Andreas; Kihumbu, David (2000). "Industrial Biocatalysis: Past, Present, and Future". Organic Process Research & Development. 4 (4): 286–290. doi:10.1021/op990101l.


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Single Moms
Featured Posts
Hi Ladies,
I'm new to this group so I'll share some background. I divorced my ex of 14ish years after learning not only was he cheating on me with a woman he found on Craigslist the last couple of months but he had also been having affairs behind my back the duration of our marriage, having slept with at least 11 other women (that he could remember.) How I never noticed this was ever going on I can only chalk it up to blind love and his really damn good acting skill. Anyway, we have 2 kids together: 15 y/o son and 8 y/o daughter. The last 3 years of our marriage he was barely a full time student and refused to work. When I kicked him out, he was finishing school and still had no job, so in no position to argue for custody of the kids (and in all honesty I think parenting would have cramped his new open social calendar.) I have full custody of both kids, he has 13 hours of visitation and is supposed to pay $500/month in custody.
The issue I am having the most difficulty with has been the manipulation & emotional abuse of my ex to my son. My son loves his father, despite knowing what he did (my son unfortunately knows too many of the details). He doesn't see the hurtful things his dad says, in an attempt to illicit guilty feelings to love him more, as being hurtful. This weekend I got fed up when I found out he had guilted my son over having homework with this: "You're 15 now, you're not a baby. You need to manage your time better if spending time with me is important."
This is my son's first year in HS and he has been struggling with the change. He is failing half of his classes. I've been trying to support him and help him to study and get tutoring. The LAST thing he needs is his father feeling upset over having to do homework on his Sunday-Funday he has planned with them. The man can berate me for not taking them out to do anything fun - (sorry, I work 40+ hours weekly on top of all the other responsibilities parenting entails and at the end of the day, I don't have a lot of disposable income to go take them to fun places. Maybe I would if he paid his child support?) - and say anything he wants to to me and I will deal with it, but I draw the line at him directing it to my kids. When this happened, Mama Bear came out and it wasn't pretty.
We got into a really nasty shouting match in my doorway and my son tried to intervene, siding with his dad, and putting me in the middle, literally. My ex usues opportunities like this to manipulate his emotional 15 y/o and will deliberately say and do things to get to me, as was the case this Sunday. My son flat out refused to do anything I told him and would not leave to the other room no matter what I said, asked, did, or threatened to take away.
I've grounded my son from just about all of his privileges. He's generally a good kid but he doesn't seem to understand I am his parent first, not his friend, and there are certain times that his defiant behavior is unacceptable. I know he will see his dad's true colors eventually after growing up some and I don't feel right bad-mouthing him to my kids because that IS wrong, however, in my house it's my rules and they are not up for discussion or debate, especially in situations that if not controlled, could not only be very stressful and hurtful, but have potential to be dangerous.
Any thoughts in reigning in teenage boys and handling sticky spots with their dad?
God that sucks !!!!! I don't have a teenage boy so I can't assume to relate to what you are going through. I have you tried speaking with him away from his father, I agree you should speak ill of their dad but maybe you can discuss the fact that when you and his dad are having a discussion especially one that is heated, he has to understand that it's not his place as child to come interprut. I would futher explain to him that while his father is in ther lives, you are they main care giver, both financialy, emotionally, and physically, so your rules avoid all is in his best interest and ones that have to be obeyed if this doesn't work maybe family therapy ?
I HATE how some men are able to manipulate any situation and anyone they please. I am so sorry you are going through this. The only thing I can say, is keep doing what you are doing. Make rules and stick with them. Try not to engage in his "father" no matter how mad he makes you, especially in front of son. Your ex will just use that as ammo against you in his manipulations. I know at 15 the last thing he wants is to talk to someone but I think counseling would be a god things for him. Don't talk bad about his dad either, it is up to him to figure out that his father is a pos. I know how hard it is, but if he thinks you are bad mouthing his dad it will only put more distance between you two. Again, I am sorry you are going through this. Just keep your head up and know that you are doing what is best for your son by being a strong, independent working mother. And if you are having a bad day, go in your room and beat up your pillow :) Always helps me!!
My ex does the exact same stuff to our daughter(13). He whines and cries to her about his financial and physical hardships. She's actually begged me to not make him pay child support. Thank god she only has to see him once a year.
Counseling would probably be good for your son. He will see his father for what he is one day.
First, I would like to welcome you to this group!!!
Second, Wow!!! You have a lot on your plate!!! I may not be in your situation but I am hurt that you are going through this. (One of the many reason why I am pursuing to be a child advocate and family lawyer.) You are doing the right thing about not bad-mouthing the father of your children to them. You're son will eventually learn the true colors of his father. Right now, being the mom that you are is the only thing you can do. Be open to showering your children with extra love and care because as much as this situation is hard for you to manage, your son is obviously hurting and it is hard for him to understand the situation. Give him the chance to express himself when he is ready to. When it comes to your sons education, tell your son that you are proud of him and that you know that he is trying his best!!! Let your son know that you are there to help him with homework and with studying so that his homework will be done before spending time with his dad on Sunday. Keep the communication open between you and your son!!!!
Hope this encourages you.... Stay strong!!! I"m here for you!!!
This sounds like a topic I'm all too familiar with.....PARENTAL ALIENATION....
Do yourself a favor and look into Dr Warshak's Welcome Back Pluto DVD. I believe if you manage to get your son to sit and watch it with you, it will greatly improve your relationship with him. You may also want to mention it to your ex, who I'm sure wants no part of the backlash of the abuse.
Time will heal this one in the long one. Don't pressure your son to make a choice but show him you're sustained, gentle love. He'll come running back eventually. -
I know exactly what you are going through. It's hard NOT bad mouthing my ex. He's done so much stuff to me and my DD it's literally incredible. Not sure if you have read my posts about my ex but he's a piece of work. Very manipulative with our DD. He tries to go backhandedly to try and win her over. He's tried to get her to accept his new life - he married the homewrecker and they have two kids together - born out of wedlock. The ex has stopped paying our DD and me the money he agreed to according to our divorce settlement. He gave nothing to our DD for her 18th b-day and graduation. My ex is a bonafide financial loser and always will be. We are going back to court for a contempt of court charge. My ex has failed to prooperly pay us the money he owes and we have no choice but to go after it. I spent the entire 26 years battling my ex about money and him not being a good provider. He's moody, lies, and has severe mental problems. Factor all of this into an almost daily relationship of ups and downs and you have the same life I have. My DD used to stand up for her father - feel sorry for him about his constant money problems, felt bad that she forget his b-day after he berrated her for doing so. Like your son, my daughter will eventually start to see the true light of her father. I wish that I could have given her a better father. I feel bad about this. My DD (and I for that matter) deserve a better father/husband. We got what we got. If my ex can't get his life together he will end up being divorced for a third time and eventually alienate his two kids he has with wife number three. I see the writing on the wall. Ex knows what he's doing. He just ignores it and thinks everyone is against him.


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Cisco Secures Electric Eye Buy
Acquisition-hungry Cisco Systems today agreed to buy video surveillance vendor SyPixx Networks for $51 million in cash and stock.
SyPixx Networks makes software and hardware that converts footage from traditional analog video surveillance systems into digital form and pipes it over a computer network.
SyPixx products include analog to digital video camera encoders, digital to analog video monitor decoders, analog video transmission equipment, video recording and management software and servers.
The point is to make video accessible at any time from any place to ensure real-time response to security threats and incidents, Cisco said in a statement. SyPixx gear will help companies use new security applications and make recorded and live video more helpful.
With its Self Defending Network strategy for weeding out internal and external threats, Cisco already offers several types of security software, including firewall protection and other solutions to protect against denial-of-service attacks, worms and viruses.
In buying SyPixx, Cisco said physical security will become the latest emerging technology area for Cisco, as it seeks to offer business customers video surveillance as part of an "intelligent converged environment."
Should the deal close in April as expected, SyPixx's video surveillance products will be part of a new business unit in Cisco's Emerging Markets Technology Group, reporting to group vice president Marthin De Beer.
"Through the acquisition of SyPixx, Cisco will begin to show how the network can also be a platform for enhancing the safety of people and the protection of physical assets," De Beer said.
SyPixx is Cisco's latest stab at diversifying its portfolio at a time when the company is trying to find new revenue streams after hogging most of the networking gear market. Some of these target areas include video and network convergence for consumers and businesses.
For example, the San Jose, Calif., company last week closed its purchase of Scientific-Atlanta, a leading provider of set-top boxes, video distribution networks and video systems integration.