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No matter if you're pattern making or starting a new and more adventurous project – there's always a new skill to try and master. By keeping your brain active, you'll always be finding new and more creative solutions.
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Coca-Cola Company's beverages are produced, distributed and sold here, including Coca-Cola, Fanta, Sprite, Bonaqua and MER. This means that we produce over 200 million liters every year, of which 83% is produced locally. We also distribute products for Monster Beverages and Capri Sun.
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Here is a box of 36 gift enclosure cards featuring the ever popular Kliban. There are 9 cards of the 4 cat designs displayed on the cover of the box. Envelopes included. Each gift enclosure card is 2 1/4" x 3" when folded. New.


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Search in titles only Search in Cricket Captain 2021 only
Current and Future Games
Cricket Captain 2021
The Impact of Form
Chris_
1st XI All-Rounder
I've always assumed that the star rating for form has an impact on how a player is likely to perform, and rotated out low form players if a suitable in-form replacement is available. This has partly been based on two things being able to be used to increase form:
1. Extra practice in training using coaching slots.
2. Assigning the player to play for the 2nd XI (though this can also reduce form if they do badly, it seems).
I've always tried to keep starting players at 3+ stars of form where possible, feeling that someone at 0-1 stars is a duck waiting to happen. Particularly since the advent of the Hundred this has meant a lot of changing players around in recent versions, as those who go off to play in the IPL, Internationals or the Hundred often return with no form whatsoever. I'm now wondering if I'm making too many changes for this, and would perhaps be better off just sticking with the best players when they're fit regardless of form. I know some people rotate a lot the same as me and others almost disregard it.
One reason for making this topic is that one of my better bowlers (England contracted, great underlying stats) returned from the Hundred with 0 form. I left him out of the team at first but then thought sod it and put him back in to see how he did amongst other bowlers all at 4-5 stars. The other bowlers are decent, but not quite as much ability as him. The others were all failing against a batting side that dug in and he was mostly responsible for ending their first innings, claiming 6-117 at a SR of 39 and 19.5 runs per wicket. That got me thinking exactly what impact the displayed form has on performance, and if I've been overestimating it. I'm now wondering:
Does a player have a flat ability modifier based on their form?
Does high or low form have a chance to affect their ability, but also a chance to have no effect?
Is form purely representative of their past few performances, not actually having an effect on how they'll play the next match?
Do some players have some kind of 'hidden' reliability/consistency attribute that might see some affected massively by poor form while others only see a minor impact?
The CC15 manual did state that "A player's form is based on his recent performances. A good way to increase a player's form is to give him some net practice or even a run in the 2nd XI."
I'm curious to see what others think, but I might have to be less quick to drop my top players when they return in low form and see what difference I can actually spot. Maybe it is just a quick guide to see how they've performed recently without actually influencing their next performance? But then I'd question why you can use coaching and 2nd XI to increase it. Maybe it is just a minor influence.
Just adding a reply as my posts keep getting flagged for review when I make an edit.
The next match I had another FC bowler in a similar situation. Though not quite as bad, he was at just over 1 star form after the white ball season and Hundred ended. I put him in and despite the terrible form rating (I'd almost always leave players benched with that form) he completely dominating, going 10-100 in the match as I won by an innings. Granted, it was cloudy and bouncy, but he was still the star bowler while other 'lesser' bowlers on near full form didn't perform near as well.
Maybe with bowlers form doesn't matter so much if conditions make it easier for them anyway but they'd struggle more than in-form bowlers on flat wickets, and with batsmen if it's sunny and flat they could disregard form but likely get out early and not be able to dig in if it's not a good wicket for batting?
Lynx54321
I tend to ignore form for bowlers in limited overs matches. I think it's judged on wickets taken which is much less relevant in t20 where 0-20 from 4 overs is a great performance. I've had bowlers achieving superb economies whilst not picking up many wickets and seen their form tank in terms of stars with no impact on their economy.
After paying closer attention over this year's matches I also noticed that it seems to affect a bowler's wicket taking ability more than economy.
The same bowler I mentioned before went away to a test match very early in the season and returned with 0 stars, no form at all. I put him in my team and he was nowhere near the performance I expect from him, barely taking any wickets. After 4 matches he was sitting at a 34.42 average with a SR of 73.5, absolutely awful. For comparison, his previous seasons were 20.04 @ 47 SR and 21.58 @ 51 SR, but he was almost always rested when returning from Internationals with low form. That said, despite not being able to take wickets this year his economy was 2.81 which was still 2nd best out of all the bowlers I used in FC matches. So he wasn't throwing the ball all over the place, just not clinical enough to take wickets. I ended up dropping him for the rest of the season as every time I built him back close to 3 star form with training and 2nd XI matches he'd go away again and return at 0 - 0.5 in an endless cycle.
Another bowler started my T20 campaign at 1 star form, which was disappointing as he was my top wicket taker in the format the previous year. The first couple of matches he didn't really take wickets but his economy stayed reasonable so I kept him in the team with extra training practice and after a few matches his form was picking up. Once he started taking wickets again he maintained that momentum and ended up as my top T20 wicket taker for the second season running - though not topping the competition rankings after the slow start. As the economy remained decent at low form it only seemed to need a few wickets alongside the training to get his form stars up and then regular wicket taking resumed.
On the batting side I had an overseas batsman who went off a few times for International duty. His first few FC matches he did great, with an 84 and a couple of centuries, but he also returned from the first duty with barely any stars of form. From then on he was Mr Inconsistent; one match he'd be out for 1 and 8, the next he might get a 43 and then another 1. He was out for under 10 quite a lot and his form just wouldn't pick up. If he did gain a star or so from extra coaching he'd go away for another International and return at 0 again. It was the same thing in T20 and One Day, where he just ended up getting out in his first few overs a disappointing majority of the time and end up with a terrible average. For someone with great averages across the formats and on 62,000 salary he was getting batting averages worse than some of my bowlers.
I have had some players on around 2-star form manage to put in reasonable performances, get back up to 3 or so and then go on a run of good form and great performances but it definitely felt that being down at 0-1 was causing adverse performances overall.
For bowlers they seemed to keep roughly the same economy but struggle to take wickets when completely out of form.
For batsmen being on 0-1 stars seemed to make them much more likely to get out almost straight away. If they did survive the first few overs they sometimes went on to get decent scores and see a jump in form after but there was a high chance of them just getting out for a duck or 1 run.
Jobi1K
I think as has been noted many a time in the threads on T20, it's batting in that format where form seems to have the biggest impact. As Lynx54321 says, bowlers on low form can often at the very least still have a very good economy rate and therefore be used to keep the opposition's score down, and batters in low form I find can often be gently managed to a reasonable score in FC games. But batters in 0-2 star form seem to be highly unlikely to get much into double figures in T20, so are often worth leaving out, even if they're supposed to be star players.
There needs to be a 2nd team allocation for Aus T20 season. Once someone is out of form you can't pick them again in the season
~I Love Lamp~
After another run of tests I'm definitely going to stick with rotating for form when needed.
I have an overseas opening batsman I first signed at 20 and have continued to sign as a main overseas player due to his consistency across all formats. Now he's 26 on 91,000 salary and has had increasing call-ups for NZ over the past few years for Tests. Coming into the current season he'd averaged 46 for me as an opener in FC matches with a high last season of 75. He would've topped the batting runs for the championship but missed 4 matches due to internationals. Luckily that year every time he returned he still had decent form and picked up where he left off, though his compatriot wasn't as fortunate. This year he's been terrible in comparison. He's been away on 3 tests and 2 ODIs and each time returned at 1-2 star form. Each time I tried to put him straight back in he'd get out for single figures and lose even more form. I had to just say enough was enough and drop him, someone who'd been super consistent for 6 years and now was playing like an amateur with a 17 batting average. My 'cheap' backup opener was in 5 star form from 2nd XI matches at that point and performed better. Thankfully the overseas batsman was up to 3 stars from coaching and 2nd XI by the time the Challenge Trophy came around and he got his form back there so I was able to use him for the Division 1 FC matches. He finally performed the way I'm used to seeing and was back in the 50s and 100s again to help me claim the title.
He was the most stark example but pretty much every time this season I used someone on 1-2 star form hoping they'd do ok and get a jump in form they simply under performed.
My two regular England bowlers missed most of the county matches as they were called up for most formats. When they were available they had no form and played pretty rubbish, at 31 Avg / 66 SR and 29 Avg / 61 SR. For comparison, my 'lesser' bowlers maintaining high form all ended the year with averages in the low 20s (or even below 20) and SRs in the low 40s or mid 30s.
So I'm putting my examples from early posts of bowlers who performed great despite bad form down as outliers. It can happen, and if you're lucky a low form player will get settled, score a bunch of runs or take a few wickets and see their form recover quickly. With top class players it is a possibility. But more often than not a low form player is just going to be mediocre or down right poor, and if you have a 5 star 'average' backup player waiting in the wings they can do a better job for a match or two while you use training and 2nd XI to get your starter back to 3 star form ready to play again.
I think I've seen enough now after paying extra attention to be happy that form is important and has a high chance of affecting player performance. Not guaranteed, but more chance the worse/better the form is.
There are some things that don't make sense to me with form. Usually if a batsman has good innings without getting out early or a bowler takes a few wickets their form will go up after the match. Nice and simple.
I'm currently 3 matches into a T20 campaign and I have a bowler who started on 2.5 star form after the initial County Championship matches. He's bowled 9 overs and taken 4 wickets at an average of 9.25 and an economy of 4.11. A bowler with that average and economy is doing very well in T20, yet his form has dropped to only 1 star!
Another bowler started on 4 star form and has bowled 11 overs, taking only 2 wickets at 36.50 average and 6.64 economy. His stats are far worse, yet he's still on the exact same 4 star form he started the campaign with.
Neither player has any kind of extra practice coaching sessions and neither has had to bat. I've won each of the first 3 matches comfortably without my bowlers having to bat.
I'm confused why the bowler with the better performance is losing a portion of a star of form each match, while another who's been the weakest of my 5 bowlers so far remains unchanged.
muhammad ahmad
Youth Player
I love t20 matches. because it is quick and interesting. but all countries starting own cricket it is good things


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Home / MMF Updates / AMRA Join MMF as an Associate!
AMRA Join MMF as an Associate!
MMF Updates
07 Feb 2018 |
By Phoebe
MMF are pleased to welcome AMRA as an associate. You can read more about them below.
AMRA is the first of its kind — a global digital music collection society that takes a direct approach to digital licensing, collection and administration. AMRA is designed to maximize value for songwriters and publishers in today's digital age, while providing the highest level of transparency and efficiency. Global and direct, AMRA is able to provide its publisher and writer clients with the most transparent and accurate reporting in the industry.
AMRA has offices in New York and London. AMRA is owned by Kobalt Music Group. AMRA licenses Kobalt's K-Tech, the world's most advanced rights and content management platform, to directly and efficiently collect, process and account for the billions of micro-transactions in today's complex digital landscape. AMRA operates independently and is entirely business separated from Kobalt's publishing operations.


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Place List
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Top 30 largest localities (total places):
1. Australia (60)
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Professor Cord Heuer has been awarded the 2014 Massey University Research Medal –Supervisor. The award acknowledges the high quality research supervision Professor Heuer has provided over the past 10 years at Massey University.
Professor Heuer was selected from a high quality field - congratulations Cord on this outstanding achievement.


I am in a situation where I need to withdraw from my 401K plan to cover a payment owed back to my former employer. Basically, I left the company after I finished my MBA which they paid for. I now owe them 14k for it. Its too late to get a student loan for it. MY tax question is, if I take out 18k which would come out to 14k after the 20% for early withdraw. Come tax season next year do I pay the 10% fee and taxable income based on the 18k or the amount I actually received? If have them take the additional 10% when I withdraw it would it cover that cost? I have also seen that the 10% can be waived for educational cost purposes. The only problem is my former company paid for it. Any advise would be appreciated.
doz, the 20% is just a withholding rate that most companies use, it doesn't represent your income tax bill. If you have other income, and add the 401k withdrawal to it, you'll probably pay about 38% (28% fed tax and 10% penalty). And if your state has income tax, that will be added - in my state it's about 5%. At any rate the cut is likely to be in the 42% range (you net only about 58%). So you need to take about $24,000.
But I would avoid doing that - instead, borrow the $14k elsewhere and pay the loan interest, it's sure to be less than the $10,000 hit on $24,000.
You will pay the taxes and penalties on the entire $18K. That's $1.8K for the withdrawal, plus opportunity costs.
Why not get a $14K loan from a bank or credit union instead? Even at 10% per year, you'd end up paying less than $1600 in interest over a 2 year repayment period. That's still less than the $1800 penalty, and it doesn't affect your income. You should be able to afford the $650 monthly payments with an MBA.
And assuming you're in the 25% tax bracket, you'd also be paying $4500 in taxes on the $18K. Your total expenses are well over $6K for the $14K you need. That's about a 40% hit, and you'd have to come up with at least $2K from out of your pocket come tax time.
Retirement funds are for retirement. Don't touch them unless you have absolutely no choice.


SENATOR JOHN MCCAIN DIAGNOSED with aggressive brain tumor; family reviewing treatment options. Weekly Standard.
President and First Lady offer thoughts and prayers. Breitbart.
Democrats offer kind words. Independent Journal Review.
TRUMP SAYS HE WOULDN'T HAVE PICKED Sessions as AG if he knew he would recuse himself from Russia probe. Real Clear Politics.
FORMER U.N. AMBASSADOR SAMANTHA POWER emerging as central figure in Obama unmasking investigation. Free Beacon.
MANAFORT, TRUMP JR., KUSHNER to appear before Senate committees next week. Breitbart.
SCOTUS SAYS TRAVEL BAN can remain in place while lawsuits continue. Free Beacon.
TRUMP NOMINATES JON HUNTSMAN for Ambassador to Russia. Hot Air.
DEMOCRATS CONTINUE TO FALSELY CLAIM "voter suppression." Daily Wire.
LIBERAL CNN ANCHOR JAKE TAPPER called "alt-right" by liberal Women's March activist. Twitchy.
AFTER STALLING FOR MONTHS, Wasserman Schultz to cooperate with investigators on IT probe. Free Beacon.
CNN COMMENTATOR HAS GLOWING WORDS of praise for convicted cop killer. Independent Journal Review.
The curious case of Natalia Veselnitskaya. Andrew McCarthy.
Probably not a good idea to underestimate Kid Rock. Vulture.
The real crimes of Russiagate. Patrick Buchanan.
Dem senator Manchin says Benghazi investigation was a witch hunt. NTK Network.
Trump to Sen. Heller: "He wants to remain a senator, doesn't he?" Real Clear Politics.
GOP senator says support is far short even for straight Obamacare repeal. Daily Caller.
Chris Christie abused by fans after catching foul ball at New York Mets game. NJ.com.
(@PrisonPlanet) The Washington Post's first concern after a woman was executed by a cop is to worry about "Islamophobia" & Somali's hurt feelings. Tweet.
(@HashtagGriswold) Weird. Wanted to a link to a mainstream media outlet's coverage of the Women's March embracing a terrorist. Can't seem to find one. Tweet.


Our office provides support to English teachers at public and private secondary schools and universities in Brazil. We have a newsletter, 'English Matters,' which we send out to about 1,000 English teachers and I will include your web site in our next issue - January - March.... Congratulations to you and all those working on this wonderful project.
I loved your site and will share it with Egyptian students and teachers. They will especially enjoy the recordings and the chance to hear the poems and selections read by young Americans.
... how wonderful that you love poetry and literature as much as you do. I will forward your email to Biblioteca Benjamin Franklin here in Mexico City so that they can publicize your web site.
I will share this information with my friends at the International School of Havana. I was the school librarian there and I am sure the English teachers will find this web site very useful for their classes. It is a good example of what kids can do.
Many/many congratulations for the wonderful job you are doing in disseminating for free the extensive material concerning English classics. No doubt you sent the message to the right address and please, make sure that it is being distributed to hundreds of people in need of such information. For your better understanding, please be informed that the agenda of the English (Language) departments in the tertiary education in my country foresees a course in Anglo-American Literature, but resources are a nightmare. You cannot imagine how helpful you are in providing lecturers and students with such valuable information. I am forwarding the website www.RepeatAfterUs.com to the many IRC contacts, including the US Embassy staff for re-distribution on a larger scale. I passed the message to the Head of the English Department of the University of Kinshasa, Ungina NDOMA, PhD, who appreciated... As for me, I checked Abraham Lincoln's "The Gettysburg Address", and enjoyed both the text and Jeff Kiok's reading.
Thank you for this link! I forwarded it to about 50 literacy providers working with both children and adults. I hope you get a lot of hits on the site.
My name is Deepak. I am an Indian. I have browsed your site....It is a great site. It contains many works of great poets and authors and I am sure that I have use for many of them.... I have told about your site to all my friends and fellow students.
Scott F. Gray, Ed. D.
You have developed a very nice Web site that will be very useful. We will certainly make use of it. Great work and thank you for doing this.
Thank you for the information and resources. I have forwarded your message to the appropriate person who is in charge of updating our website.
I will disseminate your address to ELT teachers here in Tunis. I will also pass it to my colleagues in charge of our monthly newsletter to put an insert. It's a great endeavor to English learners in countries where print materials in English are scarce.
I really enjoy reading the essays on the website and those indeed help me on my "Three Principles of the People" class -- a special course required in Taiwan.... Without those articles, I wouldn't have finished my homework.... BTW, I am a 15-year-old girl from Taiwan. I have read a report about your story in the largest newspaper in Taiwan. Mazel tov!... Keep going!
Thank you for the information. We will include it on our website resource list which is updated and distributed regularly to our volunteer literacy tutors. Nice job!
I ... will give your web address to the folks that write our weekly embassy newsletter and plan many of the children's activities here at the embassy.... I think you are doing a wonderful thing and I will spread the word.
I got your web site address from the U.S. Embassy in Montevideo, Uruguay.... Congrats on all the hard work... The Coordinators to whom I had forwarded your site were very impressed as well: by the quantity and quality of material available, and by your positive, can-do attitude. The Alianza, the Bi National Center I direct, has four branches in the Montevideo Metro area and 48 branches in the interior of the country. We have over 8,000 students. We also have a library, a language lab, and two theaters. Our mission is to encourage friendship and understanding between the U.S. and Uruguay through educational and cultural activities. Thank you for helping us further our mission by sharing with us your work on the page.
I heard about your work on a Voice of America broadcast. Keep up the good work. I am an associate professor of English at a Japanese university.
I read about your site on VOA ( Wordmaster) and have only one comment: FANTASTIC! It was exactly what I was looking for to improve my poor English. Congratulations and Thanks a lot!!!
Your site is great -- keep up the good work. I've sent the site address to teachers' associations in Romania.
In Kyrgyzstan (Central Asia) your website will be published in the Peace Corps newsletter, where there are approximately 100 Peace Corps Volunteers teaching English at the high school and university level. Thanks for a great resource.
I am an ESL Teacher in Peru, South America, and have found your site quite interesting. This mail is just to thank you and everyone at school for sharing all of these contents and experiences. I am sure there are lots of people all over the world who think the same as me. Thanks again on behalf of my kids at school.
Your site is fantastic. I love it. Is it true this is done by an 11th grader! Amazing....I teach university students who are going to be elementary school teachers and your site is ideal for them.
I will inform our English staff of your WONDERFUL site! May you go from strength to strength.
I was very impressed with Repeat After Us. For years I have been telling my adult ESL students (from all over the world) to get books on tape and to follow the texts while listening and then to mimic what they hear in order to improve their pronunciation and reading skills and to pick up the noun and verb endings and the small words that ESL students so often omit. I will certainly recommend this site to my students.
I work in the Human Resources department of a non-profit cancer research center, The Burnham Institute. We employ people from 32 different countries, and we provide on-site English courses, but we focus those courses on writing and presentation skills. Repeat After Us fills a gap by providing help with pronunciation.... Your web site is now improving the pronunciation skills of scientists and researchers who are working to cure disease. Ellie Wen, you are making a bigger difference in the world than you realize.
My son had to memorize Antony from Julius Caesar (Friends, Romans, Countrymen). Although he knew the "words", he was just reading. After listening and downloading (to his Ipod no less), he was able to join the proper sentences together and put the proper pauses in his speech. I wont say my age, but this sure beats walking around the house with index cards to help memorize. Thank you for your site..........I expect to visit again.
Ellie, Thank you so much for all of your help, your website has helped my father learn and understand English, he came to America not too long ago and Spanish is all he's ever known, but thanks to our friends and family, and now you, he can read and speak and understand English very well, I just thought you should know that your website is a very positive one, keep up the good work!
Wow! What a terrific and wonderful site and service. I work with persons with developmental disabilities, many of whom have literacy-related disabilites. Your site gives me many ideas. Thank you!!!


A jury ordered the General Motors Corporation today to pay $33 million to the family of a 13-year-old boy who burned to death in 1991 because of a gasoline tank fire.
Jurors agreed with accusations by the boy's parents, Robert and Constance McGee, that the lack of a protective shield over the gas tank had turned their 1983 Oldsmobile Cutlass Cruiser into a potential bomb with the explosiveness of dynamite.
The McGees were awarded $60 million in damages for the death of the McGees' son, Shane. No punitive damages were awarded.


Join the Celebration & Spread the Word!
The Fulbright Program will receive the 2014 Prince of Asturias Award for International Cooperation!
The Award Ceremony will be broadcast live from Oviedo, Spain on the Spanish TV channel TVE with ECA Assistant Secretary Evan Ryan accepting the award on the behalf of the Fulbright Program at 18:30 in Oviedo | 16:30 UTC/GMT | 12:30 EDT. You can watch TVE in Belgium om the following channels: Telenet 181, Belgacom/Proximus: 290, and Voo: 194.
The live stream links to watch in English or Spanish can be found at http://eca.state.gov/fulbright/about-fulbright/prince-asturias-award (this link will go live by October 24).
What is the Prince of Asturias Award?
The Prince of Asturias Foundation was established in 1980 at a ceremony presided over by the then Prince of Asturias and heir to the throne of Spain, now King Felipe VI. The Foundation has convened the Prince of Asturias Awards since 1981 with the aim to encourage and promote the scientific, cultural and humanistic values that form part of mankind's universal heritage. The Awards are presented each year in Oviedo, capital of the Principality of Asturias, Spain. In 2014, the ceremony will be held on Friday, October 24.
The Prince of Asturias Award for International Cooperation is conferred on the individual, institution, group of individuals or institutions whose work in areas such as public health, universal education, environmental protection and social and economic development, among others, constitutes an outstanding contribution at the international level.
The Jury for the 2014 Prince of Asturias Award for International Cooperation conferred the 2014 Prince of Asturias Award for International Cooperation on the Fulbright Program for educational and cultural exchange that enhances and strengthens links and mutual understanding between the world's citizens.
The Jury prized the international nature of the Program, the will to improve the overall education of young people by providing access to institutions of academic excellence, and the ability to engage civil society in each of the nations in which it operates.
This collective effort over more than half a century has resulted, among other things, in the creation of an extensive network of alumni who have contributed to the betterment of society, increasing collaboration and the exchange of ideas in a multicultural context.
Please join in a worldwide celebration of the prestigious Prince of Asturias Award for International Cooperation to the Fulbright Program!


Decorated in red toile and crème' with a queen sized bed, dining area, two sitting chairs, and a work area with desk and Wi-Fi access. The room is cozy and romantic. Flat screen television allows you to keep up with the events of the day.
This space is perfect for the business traveler as well as a romantic get away. Located on the second floor, this room is adjacent to the balcony where you can have a seat outside and enjoy the evening Gulf breezes. The private bathroom has a large window to let in the light, a claw foot tub with shower, antique music stand sink and make-up mirror.


How do I make a icon for my profile on this site?
Discussion in 'Site and Forum Feedback' started by MartinAppleGuy, Oct 5, 2013.
Give thread a look about avatar's.
You can set a profile picture now if you want on your profile page by going to the User CP.
Can't wait till I get that many posts!


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These files are generated from the BOLT repository:
```
$ python3 tools/extract-formats.py 01-*.md 02-*.md 07-*.md  > peer_wire.csv
$ python3 tools/extract-formats.py 04-*.md  > onion_wire.csv
```

redpajama_set_name: RedPajamaGithub


We are proud to be one of a handful of dental offices in the entire province of Ontario that is dedicated exclusively to comprehensive adult dentistry.
We look at the ENTIRE picture of your oral and body health.
Dr. Ali Farahani DDS Comprehensive Adult Dentistry!
We are proud to be one of a handful of dental offices in the entire province of Ontario that is dedicated exclusively to comprehensive adult dentistry. We find long-lasting solutions by looking at the ENTIRE picture of mouth and body health. My team and I take training all over North America to bring the very best oral care to our patients. Our charming office is located in a newly renovated, three-storey, century-old home at the corner of Front Street and Ontario Street in Stratford, Ontario. We service clients all over Southwestern Ontario.


Ryan Blaney (@RyanBlaney22), driver of the No. 29 Cooper Standard Ford F-150, kept his lead in the NASCAR Camping World Truck Series championship standings with a fifth place finish in the Pocono Mountains 150 Saturday afternoon at Pocono (Pa.) Raceway.
Blaney scored his fourth consecutive top five and collected his seventh in 11 races this season. He stretched his lead in the standings to seven points after grabbing his second top five in two starts at Pocono.
Ryan started eighth and ran inside the top 10 during the early stages of the race. He gained track position during the first caution on lap 18 when others chose to pit. Blaney lined up fourth when the race went green on lap 21 and he stayed in the top five until his scheduled green flag stop on lap 33. He was running third when the race went green on lap 52, but the restart wasn't kind to Blaney and he was shuffled back in the running order.
The way the race played out in its closing stages didn't work to Blaney's advantage. The No. 29 Cooper Standard Ford F-150 ran better on longer runs but Blaney overcame two restarts in the final nine laps to scramble back inside the top five by the time the checkered flag waved on lap 64.


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This is a repeating eventJanuary 14, 2023 9:00 amFebruary 11, 2023 9:00 am
Winter Haven Saturday Market
Winter Haven - Central Park Downtown41 5th St NW, Winter Haven, FL 33881
2023Sat28Jan9:00 amSat3:00 pmWinter Haven Saturday Market9:00 am - 3:00 pm Winter Haven - Central Park Downtown, 41 5th St NW, Winter Haven, FL 33881 Event OrganizerCentral Florida Event VendorsPrice Range:Free
Winter Haven Saturday Markets are free and family / pet-friendly. Like a farmers market, but with arts, crafts, jewelry, food trucks, live music, and more! Event hours are 9
Winter Haven Saturday Markets are free and family / pet-friendly. Like a farmers market, but with arts, crafts, jewelry, food trucks, live music, and more! Event hours are 9 a.m. – 3 p.m.
Vendors at this fresh market may include antiques, paint artists, jewelry artists, hand-made soaps, hand-made furniture, balloon artists, local hand-made crafts, local raw honey, local fresh goods, food trucks, great variety of roasted coffee beans, kettle corn, pure natural fresh products, fresh produce and veggies, sauces, lots of home-made products from cottage industry, local farmers offering seasonal and locally grown fruits and vegetables, pecan rolls/brittle, boiled peanuts, lots of cold sweet treats and much more.
SEPT 2022/ JUNE 2023 SEASON DATES:
Oct 8 & 22
Dec 10 & 17*
Jan 14 & 28
Feb 11 & 25
April 8 & 22
May 13 & 27
June 10 & 17*
Typically the 2nd & 4th Saturday of each month from 9am-3pm. No market in July & August
(*Please note that some of the dates do not fall exactly on the 2nd and 4th Saturdays due to conflicts with other events happening in the city)
(Saturday) 9:00 am - 3:00 pm
Winter Haven - Central Park Downtown
41 5th St NW, Winter Haven, FL 33881
Central Florida Event Vendors
February 11, 2023 9:00 am - February 11, 2023 3:00 pmFebruary 25, 2023 9:00 am - February 25, 2023 3:00 pmMarch 11, 2023 9:00 am - March 11, 2023 3:00 pmMarch 25, 2023 9:00 am - March 25, 2023 3:00 pmApril 8, 2023 9:00 am - April 8, 2023 3:00 pmApril 22, 2023 9:00 am - April 22, 2023 3:00 pmMay 13, 2023 9:00 am - May 13, 2023 3:00 pmMay 27, 2023 9:00 am - May 27, 2023 3:00 pmJune 10, 2023 9:00 am - June 10, 2023 3:00 pmJune 17, 2023 9:00 am - June 17, 2023 3:00 pm


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|| 2023
Drama • Crime
Based on Karin Slaughter's New York Times bestselling "Will Trent" series, Special Agent Will Trent of the Georgia Bureau of Investigations (GBI) was abandoned at birth and endured a harsh coming-of-age in Atlanta's overwhelmed foster care system. But now, determined to use his unique point of view to make sure no one is abandoned like he was, Will Trent has the highest clearance rate in the GBI.
"Will Trent" stars Ramón Rodríguez; Erika Christensen; Iantha Richardson; Jake McLaughlin; Sonja Sohn.
-- SERIES • ABC --
Box Office Italy


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A Cell-Penetrating Artificial Metalloenzyme Regulates a Gene Switch in a Designer Mammalian Cell
Fussenegger, M.; Matile, S.; Ward, T.R.
Nat. Commun. 2018, 9, 10.1038/s41467-018-04440-0
Complementing enzymes in their native environment with either homogeneous or heterogeneous catalysts is challenging due to the sea of functionalities present within a cell. To supplement these efforts, artificial metalloenzymes are drawing attention as they combine attractive features of both homogeneous catalysts and enzymes. Herein we show that such hybrid catalysts consisting of a metal cofactor, a cell-penetrating module, and a protein scaffold are taken up into HEK-293T cells where they catalyze the uncaging of a hormone. This bioorthogonal reaction causes the upregulation of a gene circuit, which in turn leads to the expression of a nanoluc-luciferase. Relying on the biotin–streptavidin technology, variation of the biotinylated ruthenium complex: the biotinylated cell-penetrating poly(disulfide) ratio can be combined with point mutations on streptavidin to optimize the catalytic uncaging of an allyl-carbamate-protected thyroid hormone triiodothyronine. These results demonstrate that artificial metalloenzymes offer highly modular tools to perform bioorthogonal catalysis in live HEK cells.
Metal: Ru
Ligand type: Cp; Quinoline
Host protein: Streptavidin (Sav)
Reaction: Deallylation
Achiral Cyclopentadienone Iron Tricarbonyl Complexes Embedded in Streptavidin: An Access to Artificial Iron Hydrogenases and Application in Asymmetric Hydrogenation
Renaud, J.-L.; Ward, T.R.
Catal. Lett. 2016, 146, 564-569, 10.1007/s10562-015-1681-6
We report on the synthesis of biotinylated (cyclopentadienone)iron tricarbonyl complexes, the in situ generation of the corresponding streptavidin conjugates and their application in asymmetric hydrogenation of imines and ketones.
Metal: Fe
Ligand type: CO; Cyclopentadienone
Reaction: Hydrogenation
A Dual Anchoring Strategy for the Localization and Activation of Artificial Metalloenzymes Based on the Biotin−Streptavidin Technology
J. Am. Chem. Soc. 2013, 135, 5384-5388, 10.1021/ja309974s
Artificial metalloenzymes result from anchoring an active catalyst within a protein environment. Toward this goal, various localization strategies have been pursued: covalent, supramolecular, or dative anchoring. Herein we show that introduction of a suitably positioned histidine residue contributes to firmly anchor, via a dative bond, a biotinylated rhodium piano stool complex within streptavidin. The in silico design of the artificial metalloenzyme was confirmed by X-ray crystallography. The resulting artificial metalloenzyme displays significantly improved catalytic performance, both in terms of activity and selectivity in the transfer hydrogenation of imines. Depending on the position of the histidine residue, both enantiomers of the salsolidine product can be obtained.
Metal: Ir
Ligand type: Amino acid; Cp*
Reaction: Transfer hydrogenation
Metal: Rh
An Artificial Imine Reductase Based on the Ribonuclease S Scaffold
Dative anchoring of a piano‐stool complex within ribonuclease S resulted in an artificial imine reductase. The catalytic performance was modulated upon variation of the coordinating amino acid residues in the S‐peptide. Binding of Cp*Ir (Cp*=C5Me5) to the native active site resulted in good conversions and moderate enantiomeric excess values for the synthesis of salsolidine.
Host protein: Ribonuclease S
Max TON: 4
An Artificial Metalloenzyme for Carbene Transfer Based on a Biotinylated Dirhodium Anchored Within Streptavidin
Cat. Sci. Technol. 2018, 8, 2294-2298, 10.1039/C8CY00646F
We report an artificial carbenoid transferase which combines a biotinylated dirhodium moiety within streptavidin scaffold.
Ligand type: Carboxylate
Optimization: Chemical & genetic
Reaction: Cyclopropanation
Max TON: ~60
Notes: Cyclopropanation reaction was also performed in the E. coli periplasm.
Reaction: C-H insertion
An Artificial Metalloenzyme for Olefin Metathesis
Hilvert, D.; Ward, T.R.
Chem. Commun. 2011, 47, 12068, 10.1039/c1cc15005g
A Grubbs–Hoveyda type olefin metathesis catalyst, equipped with an electrophilic bromoacetamide group, was used to modify a cysteine-containing variant of a small heat shock protein from Methanocaldococcus jannaschii. The resulting artificial metalloenzyme was found to be active under acidic conditions in a benchmark ring closing metathesis reaction.
Ligand type: Carbene
Host protein: Small heat shock protein from M. jannaschii
Anchoring strategy: Covalent
Reaction: Olefin metathesis
Notes: RCM
An Enantioselective Artificial Suzukiase Based on the Biotin–Streptavidin Technology
Chem. Sci. 2016, 7, 673-677, 10.1039/c5sc03116h
Introduction of a biotinylated monophosphine palladium complex within streptavidin affords an enantioselective artificial Suzukiase. Site-directed mutagenesis allowed the optimization of the activity and the enantioselectivity of this artificial metalloenzyme. A variety of atropisomeric biaryls were produced in good yields and up to 90% ee.
Ligand type: Allyl; Phosphine
Reaction: Suzuki cross-coupling
Ligand type: Allyl; Carbene
An NAD(P)H-Dependent Artificial Transfer Hydrogenase for Multienzymatic Cascades
J. Am. Chem. Soc. 2016, 138, 5781-5784, 10.1021/jacs.6b02470
Enzymes typically depend on either NAD(P)H or FADH2 as hydride source for reduction purposes. In contrast, organometallic catalysts most often rely on isopropanol or formate to generate the reactive hydride moiety. Here we show that incorporation of a Cp*Ir cofactor possessing a biotin moiety and 4,7-dihydroxy-1,10-phenanthroline into streptavidin yields an NAD(P)H-dependent artificial transfer hydrogenase (ATHase). This ATHase (0.1 mol%) catalyzes imine reduction with 1 mM NADPH (2 mol%), which can be concurrently regenerated by a glucose dehydrogenase (GDH) using only 1.2 equiv of glucose. A four-enzyme cascade consisting of the ATHase, the GDH, a monoamine oxidase, and a catalase leads to the production of enantiopure amines.
Ligand type: Cp*; Phenanthroline
Max TON: >999
ee: >99
Aqueous Olefin Metathesis: Recent Developments and Applications
Beilstein J. Org. Chem. 2019, 15, 445-468, 10.3762/bjoc.15.39
Olefin metathesis is one of the most powerful C–C double-bond-forming reactions. Metathesis reactions have had a tremendous impact in organic synthesis, enabling a variety of applications in polymer chemistry, drug discovery and chemical biology. Although challenging, the possibility to perform aqueous metatheses has become an attractive alternative, not only because water is a more sustainable medium, but also to exploit biocompatible conditions. This review focuses on the progress made in aqueous olefin metatheses and their applications in chemical biology.
Aqueous Oxidation of Alcohols Catalyzed by Artificial Metalloenzymes Based on the Biotin–Avidin Technology
J. Organomet. Chem. 2005, 690, 4488-4491, 10.1016/j.jorganchem.2005.02.001
Based on the incorporation of biotinylated organometallic catalyst precursors within (strept)avidin, we have developed artificial metalloenzymes for the oxidation of secondary alcohols using tert-butylhydroperoxide as oxidizing agent. In the presence of avidin as host protein, the biotinylated aminosulfonamide ruthenium piano stool complex 1 (0.4 mol%) catalyzes the oxidation of sec-phenethyl alcohol at room temperature within 90 h in over 90% yield. Gel electrophoretic analysis of the reaction mixture suggests that the host protein is not oxidatively degraded during catalysis.
Ligand type: Amino-sulfonamide; Benzene
Reaction: Alcohol oxidation
Host protein: Avidin (Av)
Ligand type: Bipyridine; C6Me6
Ligand type: Amino-sulfonamide; Cp*
Ligand type: Bipyridine; Cp*
Artificial Metalloenzyme for Enantioselective Sulfoxidation Based on Vanadyl-Loaded Streptavidin
J. Am. Chem. Soc. 2008, 130, 8085-8088, 10.1021/ja8017219
Nature's catalysts are specifically evolved to carry out efficient and selective reactions. Recent developments in biotechnology have allowed the rapid optimization of existing enzymes for enantioselective processes. However, the ex nihilo creation of catalytic activity from a noncatalytic protein scaffold remains very challenging. Herein, we describe the creation of an artificial enzyme upon incorporation of a vanadyl ion into the biotin-binding pocket of streptavidin, a protein devoid of catalytic activity. The resulting artificial metalloenzyme catalyzes the enantioselective oxidation of prochiral sulfides with good enantioselectivities both for dialkyl and alkyl-aryl substrates (up to 93% enantiomeric excess). Electron paragmagnetic resonance spectroscopy, chemical modification, and mutagenesis studies suggest that the vanadyl ion is located within the biotin-binding pocket and interacts only via second coordination sphere contacts with streptavidin.
Metal: V
Ligand type: Water
Reaction: Sulfoxidation
Artificial Metalloenzymes
Effects of Nanoconfinement on Catalysis 2017, 49-82, 10.1007/978-3-319-50207-6_3
While chemists are developing confined environments for catalysis, nature has evolved highly elaborate compartments to carry out reactions. Proteins offer such catalytic nano-environments that accept specific substrates to yield highly enantioenriched products. Metalloenzymes form a subclass that combines the functional diversity of proteins with the promiscuous activities of metals. In recent years, a variety of artificial metalloenzymes (ArMs) has been created upon incorporation of metal complexes into a protein scaffold. The following chapter discusses some of the protein scaffolds exploited for the creation of artificial metalloenzymes. Focus is laid on artificial metalloenzymes that catalyze abiotic and asymmetric reactions. Each subchapter presents the unique characteristics of a scaffold followed by a description of the reactions that were performed with it.
Notes: Book chapter
Artificial Metalloenzymes as Selective Catalysts in Aqueous Media
Coord. Chem. Rev. 2008, 252, 751-766, 10.1016/j.ccr.2007.09.016
The fusion of homogeneous and enzymatic catalysis has recently drawn attention due to reported novel activities and high selectivities. The incorporation of metal-catalysts into proteins combines the advantages of both catalytic strategies. Herein we summarize recent approaches of artificial metalloenzymes applied to catalysis. The discussion includes different strategies of anchoring and screening for improved selectivity.
Artificial Metalloenzymes Based on Biotin-Avidin Technology for the Enantioselective Reduction of Ketones by Transfer Hydrogenation
Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 4683-4687, 10.1073/pnas.0409684102
Most physiological and biotechnological processes rely on molecular recognition between chiral (handed) molecules. Manmade homogeneous catalysts and enzymes offer complementary means for producing enantiopure (single-handed) compounds. As the subtle details that govern chiral discrimination are difficult to predict, improving the performance of such catalysts often relies on trial-and-error procedures. Homogeneous catalysts are optimized by chemical modification of the chiral environment around the metal center. Enzymes can be improved by modification of gene encoding the protein. Incorporation of a biotinylated organometallic catalyst into a host protein (avidin or streptavidin) affords versatile artificial metalloenzymes for the reduction of ketones by transfer hydrogenation. The boric acid·formate mixture was identified as a hydrogen source compatible with these artificial metalloenzymes. A combined chemo-genetic procedure allows us to optimize the activity and selectivity of these hybrid catalysts: up to 94% (R) enantiomeric excess for the reduction of p-methylacetophenone. These artificial metalloenzymes display features reminiscent of both homogeneous catalysts and enzymes.
Ligand type: Amino-sulfonamide; P-cymene
Artificial Metalloenzymes Based on the Biotin-Avidin Technology: Enantioselective Catalysis and Beyond
Acc. Chem. Res. 2011, 44, 47-57, 10.1021/ar100099u
Artificial metalloenzymes are created by incorporating an organometallic catalyst within a host protein. The resulting hybrid can thus provide access to the best features of two distinct, and often complementary, systems: homogeneous and enzymatic catalysts. The coenzyme may be positioned with covalent, dative, or supramolecular anchoring strategies. Although initial reports date to the late 1970s, artificial metalloenzymes for enantioselective catalysis have gained significant momentum only in the past decade, with the aim of complementing homogeneous, enzymatic, heterogeneous, and organic catalysts. Inspired by a visionary report by Wilson and Whitesides in 1978, we have exploited the potential of biotin−avidin technology in creating artificial metalloenzymes. Owing to the remarkable affinity of biotin for either avidin or streptavidin, covalent linking of a biotin anchor to a catalyst precursor ensures that, upon stoichiometric addition of (strept)avidin, the metal moiety is quantitatively incorporated within the host protein. In this Account, we review our progress in preparing and optimizing these artificial metalloenzymes, beginning with catalytic hydrogenation as a model and expanding from there. These artificial metalloenzymes can be optimized by both chemical (variation of the biotin−spacer−ligand moiety) and genetic (mutation of avidin or streptavidin) means. Such chemogenetic optimization schemes were applied to various enantioselective transformations. The reactions implemented thus far include the following: (i) The rhodium-diphosphine catalyzed hydrogenation of N-protected dehydroaminoacids (ee up to 95%); (ii) the palladium-diphosphine catalyzed allylic alkylation of 1,3-diphenylallylacetate (ee up to 95%); (iii) the ruthenium pianostool-catalyzed transfer hydrogenation of prochiral ketones (ee up to 97% for aryl-alkyl ketones and ee up to 90% for dialkyl ketones); (iv) the vanadyl-catalyzed oxidation of prochiral sulfides (ee up to 93%). A number of noteworthy features are reminiscent of homogeneous catalysis, including straightforward access to both enantiomers of the product, the broad substrate scope, organic solvent tolerance, and an accessible range of reactions that are typical of homogeneous catalysts. Enzyme-like features include access to genetic optimization, an aqueous medium as the preferred solvent, Michaelis−Menten behavior, and single-substrate derivatization. The X-ray characterization of artificial metalloenzymes provides fascinating insight into possible enantioselection mechanisms involving a well-defined second coordination sphere environment. Thus, such artificial metalloenzymes combine attractive features of both homogeneous and enzymatic kingdoms. In the spirit of surface borrowing, that is, modulating ligand affinity by harnessing existing protein surfaces, this strategy can be extended to selectively binding streptavidin-incorporated biotinylated ruthenium pianostool complexes to telomeric DNA. This application paves the way for chemical biology applications of artificial metalloenzymes.
Artificial Metalloenzymes Based on the Biotin-Streptavidin Technology: Challenges and Opportunities
Acc. Chem. Res. 2016, 49, 1711-1721, 10.1021/acs.accounts.6b00235
The biotin–streptavidin technology offers an attractive means to engineer artificial metalloenzymes (ArMs). Initiated over 50 years ago by Bayer and Wilchek, the biotin–(strept)avidin techonology relies on the exquisite supramolecular affinity of either avidin or streptavidin for biotin. This versatile tool, commonly referred to as "molecular velcro", allows nearly irreversible anchoring of biotinylated probes within a (strept)avidin host protein. Building upon a visionary publication by Whitesides from 1978, several groups have been exploiting this technology to create artificial metalloenzymes. For this purpose, a biotinylated organometallic catalyst is introduced within (strept)avidin to afford a hybrid catalyst that combines features reminiscent of both enzymes and organometallic catalysts. Importantly, ArMs can be optimized by chemogenetic means. Combining a small collection of biotinylated organometallic catalysts with streptavidin mutants allows generation of significant diversity, thus allowing optimization of the catalytic performance of ArMs. Pursuing this strategy, the following reactions have been implemented: hydrogenation, alcohol oxidation, sulfoxidation, dihydroxylation, allylic alkylation, transfer hydrogenation, Suzuki cross-coupling, C–H activation, and metathesis. In this Account, we summarize our efforts in the latter four reactions. X-ray analysis of various ArMs based on the biotin–streptavidin technology reveals the versatility and commensurability of the biotin-binding vestibule to accommodate and interact with transition states of the scrutinized organometallic transformations. In particular, streptavidin residues at positions 112 and 121 recurrently lie in close proximity to the biotinylated metal cofactor. This observation led us to develop a streamlined 24-well plate streptavidin production and screening platform to optimize the performance of ArMs. To date, most of the efforts in the field of ArMs have focused on the use of purified protein samples. This seriously limits the throughput of the optimization process. With the ultimate goal of complementing natural enzymes in the context of synthetic and chemical biology, we outline the milestones required to ultimately implement ArMs within a cellular environment. Indeed, we believe that ArMs may allow signficant expansion of the natural enzymes' toolbox to access new-to-nature reactivities in vivo. With this ambitious goal in mind, we report on our efforts to (i) activate the biotinylated catalyst precursor upon incorporation within streptavidin, (ii) minimize the effect of the cellular environment on the ArM's performance, and (iii) demonstrate the compatibility of ArMs with natural enzymes in cascade reactions.
Artificial Metalloenzymes Based on the Biotin–Streptavidin Technology: Enzymatic Cascades and Directed Evolution
Acc. Chem. Res. 2019, 52, 585-595, 10.1021/acs.accounts.8b00618
Artificial metalloenzymes (ArMs) result from anchoring a metal-containing moiety within a macromolecular scaffold (protein or oligonucleotide). The resulting hybrid catalyst combines attractive features of both homogeneous catalysts and enzymes. This strategy includes the possibility of optimizing the reaction by both chemical (catalyst design) and genetic means leading to achievement of a novel degree of (enantio)selectivity, broadening of the substrate scope, or increased activity, among others. In the past 20 years, the Ward group has exploited, among others, the biotin–(strept)avidin technology to localize a catalytic moiety within a well-defined protein environment. Streptavidin has proven versatile for the implementation of ArMs as it offers the following features: (i) it is an extremely robust protein scaffold, amenable to extensive genetic manipulation and mishandling, (ii) it can be expressed in E. coli to very high titers (up to >8 g·L–1 in fed-batch cultures), and (iii) the cavity surrounding the biotinylated cofactor is commensurate with the size of a typical metal-catalyzed transition state. Relying on a chemogenetic optimization strategy, varying the orientation and the nature of the biotinylated cofactor within genetically engineered streptavidin, 12 reactions have been reported by the Ward group thus far. Recent efforts within our group have focused on extending the ArM technology to create complex systems for integration into biological cascade reactions and in vivo. With the long-term goal of complementing in vivo natural enzymes with ArMs, we summarize herein three complementary research lines: (i) With the aim of mimicking complex cross-regulation mechanisms prevalent in metabolism, we have engineered enzyme cascades, including cross-regulated reactions, that rely on ArMs. These efforts highlight the remarkable (bio)compatibility and complementarity of ArMs with natural enzymes. (ii) Additionally, multiple-turnover catalysis in the cytoplasm of aerobic organisms was achieved with ArMs that are compatible with a glutathione-rich environment. This feat is demonstrated in HEK-293T cells that are engineered with a gene switch that is upregulated by an ArM equipped with a cell-penetrating module. (iii) Finally, ArMs offer the fascinating prospect of "endowing organometallic chemistry with a genetic memory." With this goal in mind, we have identified E. coli's periplasmic space and surface display to compartmentalize an ArM, while maintaining the critical phenotype–genotype linkage. This strategy offers a straightforward means to optimize by directed evolution the catalytic performance of ArMs. Five reactions have been optimized following these compartmentalization strategies: ruthenium-catalyzed olefin metathesis, ruthenium-catalyzed deallylation, iridium-catalyzed transfer hydrogenation, dirhodium-catalyzed cyclopropanation and carbene insertion in C–H bonds. Importantly, >100 turnovers were achieved with ArMs in E. coli whole cells, highlighting the multiple turnover catalytic nature of these systems.
Artificial Metalloenzymes: Challenges and Opportunities
ACS Cent. Sci. 2019, 5, 1120-1136, 10.1021/acscentsci.9b00397
Artificial metalloenzymes (ArMs) result from the incorporation of an abiotic metal cofactor within a protein scaffold. From the earliest techniques of transition metals adsorbed on silk fibers, the field of ArMs has expanded dramatically over the past 60 years to encompass a range of reaction classes and inspired approaches: Assembly of the ArMs has taken multiple forms with both covalent and supramolecular anchoring strategies, while the scaffolds have been intuitively selected and evolved, repurposed, or designed in silico. Herein, we discuss some of the most prominent recent examples of ArMs to highlight the challenges and opportunities presented by the field.
Artificial Metalloenzymes: Combining the Best Features of Homogeneous and Enzymatic Catalysis
Synlett 2009, 2009, 3225-3236, 10.1055/s-0029-1218305
By combining homogeneous with enzymatic catalysis, artificial metalloenzymes offer new perspectives for conferring unnatural activities to biomolecules. The article reassembles the important advances in the field of these hybrid catalysts and summarizes the contributions of our group to this continuously growing field of research.
Artificial Metalloenzymes for Asymmetric Allylic Alkylation on the Basis of the Biotin–Avidin Technology
Angew. Chem. Int. Ed. 2008, 47, 701-705, 10.1002/anie.200703159
Palladium in the active site: The incorporation of a biotinylated palladium diphosphine within streptavidin yielded an artificial metalloenzyme for the title reaction (see scheme). Chemogenetic optimization of the catalyst by the introduction of a spacer (red star) between biotin (green triangle) and palladium and saturation mutagenesis at position S112X afforded both R‐ and S‐selective artificial asymmetric allylic alkylases.
Reaction: Allylic alkylation
Artificial Metalloenzymes for Enantioselective Catalysis Based on Biotin-Avidin
J. Am. Chem. Soc. 2003, 125, 9030-9031, 10.1021/ja035545i
Homogeneous and enzymatic catalysis offer complementary means to generate enantiomerically pure compounds. Incorporation of achiral biotinylated rhodium−diphosphine complexes into (strept)avidin yields artificial metalloenzymes for the hydrogenation of N-protected dehydroamino acids. A chemogenetic optimization procedure allows one to produce (R)-acetamidoalanine with 96% enantioselectivity. These hybrid catalysts display features reminiscent both of enzymatic and of homogeneous systems.
Artificial Metalloenzymes for Enantioselective Catalysis Based on the Biotin-Avidin Technology
Chimia 2008, 62, 956-961, 10.2533/chimia.2008.956
Artificial metalloenzymes, based on the incorporation of a biotinylated catalytically active organometallic moiety within streptavidin, offer an attractive alternative to homogeneous, heterogeneous and enzymatic catalysis. In this account, we outline our recent results and implications in the developments of such artificial metalloenzymes for various asymmetric transformations, including hydrogenation, transfer hydrogenation, allylic alkylation and sulfoxidation.
Top. Organomet. Chem. 2009, 10.1007/3418_2008_3
Artificial metalloenzymes can be created by incorporating an active metal catalyst precursor in a macromolecular host. When considering such artificial metalloenzymes, the first point to address is how to localize the active metal moiety within the protein scaffold. Although a covalent anchoring strategy may seem most attractive at first, supramolecular anchoring strategy has proven most successful thus far. In this context and inspired by Whitesides' seminal paper, we have exploited the biotin–avidin technology to anchor a biotinylated active metal catalyst precursor within either avidin or streptavidin. A combined chemical and genetic strategy allows a rapid (chemogenetic) optimization of both the activity and the selectivity of the resulting artificial metalloenzymes. The chiral environment, provided by second coordination sphere interactions between the metal and the host protein, can be varied by introduction of a spacer between the biotin anchor and the metal moiety or by variation of the ligand scaffold. Alternatively, mutagenesis of the host protein allows a fine tuning of the activity and the selectivity. With this protocol, we have been able to produce artificial metalloenzymes based on the biotin–avidin technology for the enantioselective hydrogenation of N-protected dehydroaminoacids, the transfer hydrogenation of prochiral ketones as well as the allylic alkylation of symmetric substrates. In all cases selectivities >90% were achieved. Most recently, guided by an X-ray structure of an artificial metalloenzyme, we have extended the chemogenetic optimization to a designed evolution scheme. Designed evolution combines rational design with combinatorial screening. In this chapter, we emphasize the similarities and the differences between artificial metalloenzymes and their homogeneous or enzymatic counterparts.
Artificial Metalloenzymes for Enantioselective Catalysis Based on the Noncovalent Incorporation of Organometallic Moieties in a Host Protein
Chem. - Eur. J. 2005, 11, 3798-3804, 10.1002/chem.200401232
Enzymatic and homogeneous catalysis offer complementary means to produce enantiopure products. Incorporation of achiral, biotinylated aminodiphosphine–rhodium complexes in (strept)avidin affords enantioselective hydrogenation catalysts. A combined chemogenetic procedure allows the optimization of the activity and the selectivity of such artificial metalloenzymes: the reduction of acetamidoacrylate proceeds to produce N‐acetamidoalanine in either 96 % ee (R) or 80 % ee (S). In addition to providing a chiral second coordination sphere and, thus, selectivity to the catalyst, the phenomenon of protein‐accelerated catalysis (e.g., increased activity) was unraveled. Such artificial metalloenzymes based on the biotin–avidin technology display features that are reminiscent of both homogeneous and of enzymatic catalysis.
Artificial Metalloenzymes for Enantioselective Catalysis: Recent Advances
ChemBioChem 2006, 7, 1845-1852, 10.1002/cbic.200600264
Creating new catalytic function in proteins. Anchoring an organometallic moiety within a protein affords artificial metalloenzymes for enantioselective catalysis. Both chemical and genetic tools can be applied in the optimization of such systems, which lie at the interface between homogeneous and enzymatic catalysis. This minireview presents the latest developments in the field of artificial metalloenzymes.
Artificial Metalloenzymes for Enantioselective Catalysis: The Phenomenon of Protein Accelerated Catalysis
We report on the phenomenon of protein-accelerated catalysis in the field of artificial metalloenzymes based on the non-covalent incorporation of biotinylated rhodium–diphosphine complexes in (strept)avidin as host proteins. By incrementally varying the [Rh(COD)(Biot-1)]+ vs. (strept)avidin ratio, we show that the enantiomeric excess of the produced acetamidoalanine decreases slowly. This suggests that the catalyst inside (strept)avidin is more active than the catalyst outside the host protein. Both avidin and streptavidin display protein-accelerated catalysis as the protein embedded catalyst display 12.0- and 3.0-fold acceleration over the background reaction with a catalyst devoid of protein. Thus, these artificial metalloenzymes display an increase both in activity and in selectivity for the reduction of acetamidoacrylic acid.
Ligand type: Cyclooctadiene; Diphenylphosphine
Notes: Reduction of acetamidoacrylic acid. 3.0-fold protein acceleration.
Notes: Reduction of acetamidoacrylic acid. 12.0-fold protein acceleration.
Artificial Metalloenzymes for Olefin Metathesis Based on the Biotin-(Strept)Avidin Technology
Chem. Commun. 2011, 47, 12065, 10.1039/c1cc15004a
Incorporation of a biotinylated Hoveyda-Grubbs catalyst within (strept)avidin affords artificial metalloenzymes for the ring-closing metathesis of N-tosyl diallylamine in aqueous solution. Optimization of the performance can be achieved either by chemical or genetic means.
Artificial Metalloenzymes for the Diastereoselective Reduction of NAD+ to NAD2H
Org. Biomol. Chem. 2015, 13, 357-360, 10.1039/c4ob02071e
Stereoselectively labelled isotopomers of NAD(P)H are highly relevant for mechanistic studies of enzymes which utilize them as redox equivalents.
Artificial Metalloenzymes: Proteins as Hosts for Enantioselective Catalysis
Chem. Soc. Rev. 2005, 34, 337, 10.1039/b314695m
Enantioselective catalysis is one of the most efficient ways to synthesize high-added-value enantiomerically pure organic compounds. As the subtle details which govern enantioselection cannot be reliably predicted or computed, catalysis relies more and more on a combinatorial approach. Biocatalysis offers an attractive, and often complementary, alternative for the synthesis of enantiopure products. From a combinatorial perspective, the potential of directed evolution techniques in optimizing an enzyme's selectivity is unrivaled. In this review, attention is focused on the construction of artificial metalloenzymes for enantioselective catalytic applications. Such systems are shown to combine properties of both homogeneous and enzymatic kingdoms. This review also includes our recent research results and implications in the development of new semisynthetic metalloproteins for the enantioselective hydrogenation of N-protected dehydro-amino acids.
Artificial Metalloenzymes: Reaction Scope and Optimization Strategies
Lewis, J.C.; Ward, T.R.
Chem. Rev. 2018, 118, 142-231, 10.1021/acs.chemrev.7b00014
The incorporation of a synthetic, catalytically competent metallocofactor into a protein scaffold to generate an artificial metalloenzyme (ArM) has been explored since the late 1970's. Progress in the ensuing years was limited by the tools available for both organometallic synthesis and protein engineering. Advances in both of these areas, combined with increased appreciation of the potential benefits of combining attractive features of both homogeneous catalysis and enzymatic catalysis, led to a resurgence of interest in ArMs starting in the early 2000's. Perhaps the most intriguing of potential ArM properties is their ability to endow homogeneous catalysts with a genetic memory. Indeed, incorporating a homogeneous catalyst into a genetically encoded scaffold offers the opportunity to improve ArM performance by directed evolution. This capability could, in turn, lead to improvements in ArM efficiency similar to those obtained for natural enzymes, providing systems suitable for practical applications and greater insight into the role of second coordination sphere interactions in organometallic catalysis. Since its renaissance in the early 2000's, different aspects of artificial metalloenzymes have been extensively reviewed and highlighted. Our intent is to provide a comprehensive overview of all work in the field up to December 2016, organized according to reaction class. Because of the wide range of non-natural reactions catalyzed by ArMs, this was done using a functional-group transformation classification. The review begins with a summary of the proteins and the anchoring strategies used to date for the creation of ArMs, followed by a historical perspective. Then follows a summary of the reactions catalyzed by ArMs and a concluding critical outlook. This analysis allows for comparison of similar reactions catalyzed by ArMs constructed using different metallocofactor anchoring strategies, cofactors, protein scaffolds, and mutagenesis strategies. These data will be used to construct a searchable Web site on ArMs that will be updated regularly by the authors.


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https://sixerswire.usatoday.com/2020/05/19/tobias-harris-delivers-250-meals-to-healthcare-workers-at-temple/
Tobias Harris delivers 250 meals to healthcare workers at Temple
Philadelphia 76ers forward Tobias Harris came through on his promise from Monday when he said he would help deliver food to the healthcare workers of Philadelphia, as well as pay some mortgages for some families during this time. On Tuesday, he teamed up with Chick-Fil-A to deliver some food to the University of Temple Hospital.
"We're experiencing one of the biggest crises in the history of humankind," said Harris via the press release. "Being able to provide kindness to people putting their lives at risk in hospitals and supporting Philadelphia families in dire need of help is an important responsibility for me."
To all the healthcare workers THANK YOU!!!! Just a small sign of appreciation for all that you do. Much love and blessings! I hope you enjoy the @ChickfilA ❤🙏 https://t.co/Xc09UP4pop
— Tobias Harris (@tobias31) May 19, 2020
This is a time of crisis for everybody in the world. It is times like these that really show the compassion of other people. When others need help, it's that human spirit to rally around and help them. Harris is using his platform in a positive way which is exactly what we all need in a time like this.
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Covid vaccine programme to fully open to those aged 35-39
Anyone born between 01/04/81 and 30/04/86 can book an appointment at a regional vaccination centre or participating community pharmacy.
The Covid-19 vaccination centre in the SSE Arena, Belfast (Liam McBurney/PA)
By Rebecca Black, PA
Northern Ireland's coronavirus vaccine programme will fully open to all those aged between 35 and 39 from Monday.
By Sunday, some 1,247,931 doses of the jab had been administered in Northern Ireland.
No further deaths of patients who had previously tested positive for Covid-19 were notified on Sunday, and fewer than 100 new cases.
Vaccination programme fully opens to 35-39 year olds https://t.co/lMe06MN3jR pic.twitter.com/h3Wh6ITcHa
— Department of Health (@healthdpt) April 25, 2021
Later this week there will be further relaxations of the coronavirus restrictions, with the reopening of non-essential retail, as well as self-contained tourist accommodation and gyms and swimming pools.
Pubs and restaurants will also be permitted to serve customers in outdoor settings, in groups of six, from no more than two households.
Last week there was limited vaccine available for the 35-39 age group.
From 8am on Monday anyone born between 01/04/81 and 30/04/86 can book an appointment at a regional vaccination centre or participating community pharmacy.
Health Minister Robin Swann has encouraged all those who are eligible to book an appointment as soon as possible.
Health Minister Robin Swann receiving his first coronavirus vaccine in Ballymena (Kelvin Boyes/Press Eye/PA)
"This week we will see further easing of restrictions, with the reopening of non-essential retail, gyms, leisure facilities and some tourist accommodation," he said.
"These easements have only been possible because of the success of the vaccination programme, coupled with the actions of the general public.
"Therefore I would appeal to everyone who is eligible for vaccination to get an appointment booked.
"I know there are some younger people that think they don't need the vaccine, but we have seen what this virus can do. So please protect yourself and get the vaccine.
"Vaccination is absolutely vital in helping us move through this pandemic.
The Department of Health #COVID19 dashboard has been updated.
73 individuals have tested positive for COVID-19 in the past 24 hours. No deaths have been reported.https://t.co/UGfvjc8ZtO pic.twitter.com/EcUBIDfVHX
"There is no doubt that there are people in Northern Ireland alive today because they have been vaccinated."
No further deaths of patients who previously tested positive for Covid-19 were notified in Northern Ireland on Sunday.
Another 73 people have tested positive for the virus in the last 24-hour reporting period.
On Sunday there were 60 confirmed Covid-19 patients in hospital, five of whom were in ICU.
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Home People Kagiso Modupe – Biography, Age, Wife, Career & Net Worth
Kagiso Modupe – Biography, Age, Wife, Career & Net Worth
Kagiso Modupe is a South African actor and producer known for his roles in the popular serials Losing Lerato, Gog' Helen and Unpredictable Romance.
Kagiso Modupe Wife
He is married to Liza Lopes who is a film producer and the couple has two daughters. His elder daughter, Tshimollo acted with Kagiso in the film Losing Lerato as the lead role 'Lerato'.
He was one of the main actors in the blockbuster Losing Lerato in 2019, in which he played the character Thami. Kagiso and his wife Liza provided the funding for the project. The film was shown in South African and Swazilandian theatres. There was red tape that prohibited the screening of the film in Botswana.
Craig Hawks - Biography, Age, Career & Net Worth
It earned honors at the Idyllwild International Festival of Cinema in California, with the reviews being extremely positive. Kagiso received a Best Actor Award for his work in the feature film, Samela Tyelbooi received a Best Actress Award for her work in the feature film, and his daughter Tshimollo received the Best Child Performance Award. This picture was also nominated for two Oscars and won three more awards outside the big prizes.
Sipho Pityana Biography, Age, Net Worth & Contact Details
He created the voice of "Tyler Perry" for South Africa. Additionally, he also starred in the critically acclaimed TV drama Scandal! in the role of "Mangaliso 'Mangi' Nyathi." He quit after several years in the post.
Besides performing, he also became a writer by penning a book entitled Along Came Tsakani.
Kagiso Modupe Net Worth
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47 Top PC Games Coming out in 2016
Updated: 25 Jul 2016 2:16 am
Scars on a face so beautiful looks like jewelry forged from experience
BY: Faheem Arif
Discover 47 of the top PC Games releasing in 2016
So, the year of 2015 has passed and we have seen quite a few awesome game releases, but I assure you that it`s just gonna get better from here on. 2016 will be at least as huge, if not bigger, in terms of PC game releases. So, in this list we are going to countdown the best PC games releasing in 2016.
So, let`s get this list rolling.
47. Torment: Tides of Numenera
Looks like a classical RPG with a twist in gameplay mechanics and interesting level designs
This game is one of the many RPGs on this list. It is basically a story driven RPG. But instead of being same as all the other RPGs, this game puts Character design and storyline as its main preference. This, in turn, gives us a game with well written characters and an engaging storyline
The story revolves around an ancient man who found the way to be immortal and uses people as vessels. But once he gets out of the body, the vessel wakes up again and must find his former master. You play as the last vessel left, who must find his master before you are killed by the ones who are hunting the ancient man and his vessels.
Cinematic Trailer :
Gameplay Trailer :
Release Date : TBA 2016
46. Street Fighter 5
Can you guess the 4 new characters?
Street Fighter is a franchise we all know, and one that some of us truly love. Street fighter 5 is the 5th installment in the franchise. The game is a side scrolling action-fighting game, as you would expect, with some changes in the gameplay and mechanics of the game. The changes include transition into real 3-D, addition of "v-gauge" which fills when you attack and let`s you do special attacks, three new skills, 16 overall characters to play with out of which 4 are new and much more. Add cross platform ranked multiplayer matches between Console and PC to all this, and you will get the best Street Fighter ever released.
Release date : Feb 18, 2016
45. Tree of Saviour
Free to play things always look amazing – the 4 classes should work as a team to succeed
Tree of Saviour is a rather peculiar looking RPG. It is made by Kim Hakkyu, the creator of Ragnarok Online. It is basically an MMORPG that looks quite promising. The game is based on traditional Lithuanian culture and mythology and will feature 4 basic classes that branches out and end up as a total of 80 different classes. The 4 basic classes will be Cleric, Wizard, Swordsmen and Archer.
Release date : May 10, 2016
44. Outlast 2
Say your prayers – for the time to pay has come, you`ll be torn from limb to limb
Outlast was a surprise hit in 2015. And it was so big a success that a sequel is in progress. Outlast 2 will also be a survival horror experience and in the same universe as outlast but with different characters and a new setting.
43. Dying Light: The Following
We`re gonna tear you up,We`re coming for you, boy……… AAARGH
Dying light was one of the best zombie game of 2015 and it`s good to see the devs keeping it alive. The following is an expansion pack for the original game which will have a new story campaign, new characters, weapons and new mechanics.
Release Date : Feb 9,2016
42. The Banner Saga 2
A war ravaged land – all our sympathies for the once flourishing
The Banner Saga 2 is a tactical RPG released on 19th of April 2016. It improves on the original banner saga in every aspect. The story is now more engaging and the world will keep you invested in the storyline and the characters for a long time.
Banner Saga 2 starts where the original Banner Saga left off. In a world left in grim darkness as the Dredge overtakes it. It is up to you to remove the threat of these colossal armor clad creatures on your race.
Release date : April 19,2016
41. Grim Dawn
Knights, magic and aliens – what more could you want?
Grim Dawn is an action adventure game, with a dark fantasy feel to it. The game starts off from the ruins of an empire, which once flourished but collapsed during war. And it is not a normal war, It`s a war between two extra dimensional races. One wants to use humans as resources while other wants to destroy humans before that happens. The human Race is pushed to the brink of extinction and it is now up to the survivors to restore the glory of the human race.
Cinematic trailer ;
Release date : Feb 25,2016
Faheem Arif
Currently Playing: Witcher 3
Top 3 Favorite Games:Batman: Arkham Knight, Middle-Earth: Shadow of Mordor, Bioshock Infinite
Lara draws out yet another bolt.
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