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Matthew gdovin News - Latest matthew gdovin News, Information & Updates - Health News -ET HealthWorld
Matthew Gdovin news
A Russian woman was arrested by the customs officials at the Delhi airport for allegedly trying to smuggle into the country growth hormone medicines worth Rs 32 lakh, according to a statement issued Friday.
Inequities are bad for humanity and in IVF it becomes a rich man's treatment. I would like to make it equal and bring it to the ground level so that every couple in our country can access it.
Clove Dental recently had the opportunity to host a team of students from Harvard Business School in New Delhi for one week as part of a required first-year course at Harvard Business School called the FIELD Global Immersion.
Hyderabad : Braunwald Hospitals chairman arrested for not paying salaries
Rachakonda police have arrested the chairman of Braunwald Hospitals Pvt Ltd for allegedly not paying salaries to the employees of one of the hospitals managed by them in city.

type: global

value: Times Internet is an Indian internet technology company, based in Gurgaon, which owns, operates and invests in various internet-led products, services and technology. It is the digital arm of the Times Group, the largest media conglomerate in India.


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Amazon.com: How to License Your Million Dollar Idea: Everything You Need To Know To Turn a Simple Idea into a Million Dollar Payday (9780471204015): Harvey Reese: Books
Comment: This item is listed as acceptable and has probably been well used. It could have considerable writing or highlighting throughout but is still usable and has been priced accordingly. Please do not buy if you are expecting a perfect copy. It has a couple more reads left before its time to be recycled. We ship within 1 business day and offer no hassle returns. Big Hearted Books shares its profits with schools, churches and non-profit groups throughout New England. Thank you for your support! This item is gently used in good or better condition. If it is a textbook it may not have supplements. It may have some moderate wear and possibly include previous ownerâ€TMs name, some markings and/or is a former library book. We ship within 1 business day and offer no hassle returns. Big Hearted Books shares its profits with schools, churches and non-profit groups throughout New England. Thank you for your support! Fulfillment by Amazon (FBA) is a service we offer sellers that lets them store their products in Amazon's fulfillment centers, and we directly pack, ship, and provide customer service for these products. Something we hope you'll especially enjoy: FBA items qualify for FREE Shipping and .
TURN YOUR GREAT IDEA INTO A GREAT BIG FORTUNE...We all have great ideas, and every day, ordinary people turn their simple, clever ideas into products or services that earn them millions in royalties. So what separates those who earn money exploiting their ideas from those who don't? The answer is in your hands; this book gives you all the information and all the motivation you need to turn your ideas into money without investment or financial risk. In How to License Your Million Dollar Idea, Second Edition, Harvey Reese, a successful new product developer, consultant, and licensing agent, reveals his system for creating commercially profitable ideas and his secrets for turning them into lucrative licensing agreements. Not only will you find nuts-and-bolts information on the licensing process, you'll also learn how to formulate an idea and find the motivation to grow that idea into a fortune. Totally revised and updated, this Second Edition covers recent changes in patent law and how the Internet has impacted modern licensing. Reese includes his proven step-by-step process for formulating an idea that manufacturers are willing to pay for, researching its authenticity, obtaining patents, finding prospects, negotiating the deal, and beyond. Filled with examples of successful, well-known licensing ventures, How to License Your Million Dollar Idea, Second Edition also features an expanded appendix of sample patent forms, licensing agreements, disclosure statements, publications, contact information, and more.
Hardcover$14.04 Prime The Inventor's Bible (Inventor's Bible: How to Market & License Your Brilliant Ideas)
Paperback$18.26 Prime The Independent Inventor's Handbook: The Best Advice from Idea to Payoff
Paperback$12.34 Prime One Simple Idea for Startups and Entrepreneurs: Live Your Dreams and Create Your Own Profitable Company
TURN YOUR GREAT IDEA INTO A GREAT BIG FORTUNE... We all have great ideas, and every day, ordinary people turn their simple, clever ideas into products or services that earn them millions in royalties. So what separates those who earn money exploiting their ideas from those who don?t? The answer is in your hands; this book gives you all the information and all the motivation you need to turn your ideas into money without investment or financial risk. In How to License Your Million Dollar Idea, Second Edition, Harvey Reese, a successful new product developer, consultant, and licensing agent, reveals his system for creating commercially profitable ideas and his secrets for turning them into lucrative licensing agreements. Not only will you find nuts-and-bolts information on the licensing process, you?ll also learn how to formulate an idea and find the motivation to grow that idea into a fortune. Totally revised and updated, this Second Edition covers recent changes in patent law and how the Internet has impacted modern licensing. Reese includes his proven step-by-step process for formulating an idea that manufacturers are willing to pay for, researching its authenticity, obtaining patents, finding prospects, negotiating the deal, and beyond. Filled with examples of successful, well-known licensing ventures, How to License Your Million Dollar Idea, Second Edition also features an expanded appendix of sample patent forms, licensing agreements, disclosure statements, publications, contact information, and more.
Publisher: Wiley; 2 edition (July 9, 2002)
ISBN-13: 978-0471204015
Amazon Best Sellers Rank: #545,091 in Books (See Top 100 in Books)
#77 in Books > Law > Intellectual Property > Patent, Trademark & Copyright > Patent
#348 in Books > Law > Legal Self-Help
#439 in Books > Business & Money > Small Business & Entrepreneurship > Marketing
60 of 62 people found the following review helpfulA Step by Step Guide For Turning You Ideas Into Income
Let me start by saying what this book is not. This book is not a detailed step by step guide to patenting. Nor a detailed legal guide to structuring a licensing agreement.This book is a guide to help everyday people make money by designing and licensing nearly anything to companies looking for new or differentiated products. Mr. Reese offers up a clear and fresh perspective on the whole process from idea development to setting up meetings to contractual agreements. He covers how to patent & copyright, and guides you through when and how to contact an attorney.Mr. Reese challenges the reader to become product developer, not an inventor. What this means is that if you can help companies make money and gain an edge on their competition, they will be more than happy to give you a percentage of the sales. There are lots of inventors that are good inventors but weak in the selling and licensing of their hard work. This book articulates what steps there are between an idea in your head and money in the bank.This is by far the single greatest collection of practical wisdom I have found relating to everyday products and their licensing. My only complaint is that I wish I had discovered this book sooner.
34 of 36 people found the following review helpfulVery Inspirational yet not complete
I found this book to be very inspirational. It does have a lot of good information that is presented at a level that's great for those who are just getting started in the invention business. Having an encouraging book is very useful. My only concern is that the book is lacking in detail. I still strongly recommend it, and also recommend "From Concept to Market", which is a little more tempered in mood but provides a great deal of detailed information including a lot of sample forms and documents that are merely referred to in this book. The two make an excellent combination.
65 of 75 people found the following review helpfulSane, sensible and honest
Harvey Reese gives excellent and straightforward advice on what I used to think was an awesomely complex topic. Structurally, the book is well organized, simple to follow and written in language anyone can understand. His style is intelligent and interspersed with humor, examples, and concrete information. He not only details the steps, (he loves lists) he also tells the reader what to avoid and why. And he addresses the human issues. He talks about frustration, disappointment, commitment.Reese demystifies the legal mumbo-jumbo and makes the subject of licensing understandable to anyone. I've read hundreds of "how-tos" in the business genre, many that vastly oversimplify difficult subjects. This one tells it all - the good, the bad and the ridiculous. Ultimately, it is both believable and usable. Reese's book is an outstanding and inspiring resource for anyone with ideas.
21 of 24 people found the following review helpfulVery Encouraging and Informative
This book was a great read. It tells you that you can easily make money by selling your ideas, and the author tells you how to make sure it is original, how to protect your idea, how to spark companies' interest with your idea, how to make the deal, and then the money starts rolling in. He explains that not EVERY idea you sell to companies will make you millions, but if you have sold several ideas and are getting royalty checks for all of them, it all adds up and you could make a lot of money, and ho knows? Maybe one of your ideas is one of those multi million dollar Ideas? The best thing about the book is that he tells you anyone (including idiots) can do it. Its not hard, all you need is the confidence and motivation to see it through. Give it a read!
28 of 33 people found the following review helpfulPacked with useful, 'You can do it!' information
22 of 27 people found the following review helpfulSimply excellent... I've read it three times...
Even though I know I should I usually don't take the time to contribute to Amazon's book reviews but...This book was so fantastic that I just had too! I loved Harvey Reese's no-nonsense tell-it-like-it-is style... no fluff or touch-feely BS. He explains exactly how to come up with ideas for new products, how to assess their true merit, how to bring them to reality (via licensing)... and most importantly, how to make $$$ doing it. This last part is a salient point, as Mr. Reese is a professional product developer himself and sees this as a "business" just like any other. The book is loaded with plently of real life examples of incredible success stories involving everyday people that made millions from products that started with ideas... Teenage Mutant Ninja Turtles, Post It notes, Cabbage Patch Kids... Mr. Reese himself came up with over 100 licensed products in the market today, including those little reindeer horns you see dogs wearing around Christmas time. You can easily read this book one Saturday... and the info you'll glean from it will prepare you to make some real $$$ from your next million dollar idea.
I will not recommend this book to anyone
I will not recommend this book to anyone. About ninety-six percent of the book is about how to come up with a million dollar idea, not how to license it.
Published 3 months ago by cooldirt
Published 8 months ago by Lamar Mauldin
Great book with a lot of good information...I really love it.
Good ideas if your into inventing.
Published 11 months ago by Joe Loera
The information shared by Harvey Reese makes this a valuable tool for anyone considering working with large companies to get their idea into the public's hands.
Published 16 months ago by Mr. Sanford
Sounds like 1970's business advice
The author is extremely nonchalant about how easy/smart it is to license ideas. His portrayal reminds me of Mr.
Published 19 months ago by Werckmeister
Very helpful book, great deal!
So glad I read this book, exceptionally reasonable price for so good of information! Will save you a lot of money and headaches in the future! Kimberly
Published 20 months ago by Kimberly S.
$14.04 Prime How to License Your Million Dollar Idea: Cash In On Your Inventions, New Product Ideas, Software, Web Business Ideas, And
$18.11 Prime One Simple Idea: Turn Your Dreams into a Licensing Goldmine While Letting Others Do the Work
Check out these pages to see more: how to sell an invention, books a million franchise, you can keep your money, the angels don't forget

value: Amazon.com, Inc. ( AM-ə-zon) is an American multinational conglomerate which focuses on e-commerce, cloud computing, digital streaming, and artificial intelligence.


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The Green Weenie: Wandy, Pedro Tag Team Cards 5-0
Pittsburgh took the series from St. Louis 8 games to 7, the first time they've won the season set from the Cards since 2008 and only the second time this century. Their last plus series before that was in 1999. Steve Berthiaume of ESPN noted that Pedro Alvarez's 7 HR and 23 RBI vs the Cards this season is the best showing against them by a Bucco since Ralph Kiner had 9 long balls and 23 RBI against them in 1950. Pedro, GI Jones and McCutch are the second NL trio with 70+ RBIs; the Cardinals have four. Neil Walker is in the clubhouse and feeling better, but he hasn't taken a swing yet. His achy back is still inflamed and a couple-to-a-few days from recovering after tightening up on Monday. There is no point in DL'ing The Kid with IF Chase d'Arnaud now in the dugout and the rosters expanding Saturday. Josh Harrison, subbing at second, has been 6-for-14 starting the last four games and turned a pair of DP yesterday, so the club hasn't missed a beat yet.
Tonight's attendance was 19,398. More interesting news: the Bucs have promoted Gerrit Cole from Altoona to Indy according to the Altoona Mirror's Corey Giger. That gets him some high level playoff experience and provides an arm to replace whomever the Bucs call up Saturday. Yadier Molina said that he felt J-Hay banging into him at home last night was a "clean play," and that he thinks he'll be back Thursday or Friday. That's good news; for our money, he's the NL's top guy behind the plate, although Buster Posey has got his foot in the door.

value: Blogger is an American online content management system (CMS) which enables multi-user blogs with time-stamped entries. Pyra Labs developed it before being acquired by Google in 2003.


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Daily World Buzz: Berlusconi uses the nuclear referendum to the Constitutional
The vote is doubly dangerous for a prime minister who is on the ropes. That same day, citizens must approve or reject the repeal of the law of legitimate impediment, allowing the prime minister argued efforts of Government to curb their cases pending, and also answer two questions about the privatization of water, which was formerly in management hands of municipalities.
Berlusconi has been defined as "useless and demagogic" the four questions of the referendum, organized by the listed firms promoted by Italy of Values. The People of Freedom, in an attempt to not turn the query into a new referendum on Berlusconi, has freedom of conscience to its members.
Still, the quorum-half plus one of the 46.6 million counted, seems a difficult task to achieve. Among other things, because the votes of the 3.5 million living abroad may not be counted. The Supreme Court decision authorizing the nuclear question on changing the wording to fit the new rule came when thousands of immigrants had sent their ballots to Rome.
Struggling Silvio Berlusconi brushes off referendum worry (03/06/2011)
Meendum Meendum Va-vikram song lyrics(kamal hassan) (24/04/2011)
Italians, not government, to decide on nukes and water privatization (via COTO Report) (04/06/2011)
Berlusconi keeps on staging 'bunga bunga' parties (05/06/2011)
Berlusconi after Milan: wrecked or weakened? (04/06/2011)


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Amazon.com: Buying Choices: Ender's Game (The Ender Quintet)
Ender's Game (The Ender Quintet) (Mass Market Paperback) by Orson Scott Card
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Wonderful mail…. – kviltstina
Friendship, Pay it Forward
Wonderful mail….
27 August, 2009 17 April, 2013 Stina
…arrived yesterday…
a package with sprayed gold stars on….
MY PIF gift from
…Mary at Quilt Hollow….
Ohh.. it is sooo fun with packages….
and this was a really really fun one!!!!
A little peek of whats inside…
I picked up wonderful items after items….
Now I can sew myself a new pretty apron…
make some lovely vintage kitchen towels…
and sew a new bag for me …
….and this beauty was double folded and
squeezed in the package…
Have to redecorate some this weekend…
with all the wonderful gifts I have received now!!
But wait ..there was more…
I bet some of you saw a backside of something at the first picture…
and you were right..
Do you want a peek???
You can see me infront of your eyes now…cant you…
A silly big smiling face…
Do I have to say I love it???
It is adorable…
Love the fabrics…and I love rag quilts…
Thankyou …thankyou……
for all the quilty gifts!!!
I sure have been spoilt again…
haven´t I???
Today I used bloggers new new post edit….
and there are a lot of new functions…
So if it does look strange..
it would be me not knowing what I´m doing…lol
Previous postGot a pink themed package….
Next postLast weekend…
30 thoughts on “Wonderful mail….”
27 August, 2009 at 9:11 pm
Beautiful gifts Stina. Lucky you.
27 August, 2009 at 9:15 pm
Stina,Love your quilt, pillow….Oh my your whole package is wonderful.Enjoy it, its just wonderful!!
27 August, 2009 at 9:29 pm
wow you got spoiled again with lovely gift..I really like the quilt you got..Take care!
27 August, 2009 at 9:38 pm
what a great package – you have some good friends don't you!Karenhttp://karensquilting.com/blog/
Do I see a bit of pink came in that package?
27 August, 2009 at 10:01 pm
Truly hope you'll enjoy them. I love the way you blog the photos!
27 August, 2009 at 11:29 pm
You have been spoiled rotten these last couple of days! Enjoy all your new lovelies.
28 August, 2009 at 12:07 am
Those are such lovely and thoughtful gifts. How fun to open up packages two days in a row!That quilt is just lovely!
28 August, 2009 at 12:53 am
Gorgeous PIF gifts from Mary. Lucky you, Stina. Enjoy them all!
28 August, 2009 at 12:59 am
Oh I love the raggy quilt! You are one lucky duck to receive a gorgeous piece like that!!
How lovely for you and wow to the gifts. Mary did a lovely thing making you the cushion and a fabulous quilt!
28 August, 2009 at 1:29 am
Wow Stina, you received some really nice gifts, love, love your quilt. It looks so soft and cuddly. Looks like your having fun at your sewing machine too!
28 August, 2009 at 2:02 am
Oh my gosh Stina! That quilt is awesome!!! Love your new blog header pic too!
28 August, 2009 at 2:37 am
What a wonderful package and I love the way you blog has been presented!Hugs – Lurline♥
28 August, 2009 at 2:50 am
Wow what a great gift package. I love it all but wow that quilt is just lovely!! Aren't you the lucky girl this week 🙂
28 August, 2009 at 8:04 am
Stina, you must be on cloud 9. The packages you've received lately are gorgeous and with so much thought in each one. Mary and Pat do beautiful work. Can't wait to see all the goodies you make with it.Keep Stitchen'Bonnie
28 August, 2009 at 11:38 am
Oh Stina, what gorgeous gifts!!!! The rag quilt is absolutely lovely! And the pillow, too, it is unbelievable how lucky you are!Love your new header, it so nice to see you sewing! Have a lovely sunny weekend!
28 August, 2009 at 12:54 pm
Such a lovely post with so many beautiful gifts to show. Love your new banner!
28 August, 2009 at 3:10 pm
WOWZER, that's a delightful box from Mary!
28 August, 2009 at 9:42 pm
Wowee, Mary send you some fabulous gifts. She knows how to pay it forward.
29 August, 2009 at 7:02 am
What a lovely care package Mary has sent to you, Stina! Beautiful quilt and some handstitching goodies besides. Wonderful, you deserve to be treated to such fine gifts. 🙂
29 August, 2009 at 4:49 pm
Wow…you have had some wonderful past days with all those goodies coming in the mail!! Everything is lovely…..and your 'pink' coveringturned out great!!Love your new blog header…..there you are practicing your free motion!!!
29 August, 2009 at 5:17 pm
Such a beautiful gift for such a sweet lady. love that packaging to very neat .Have a good week-end sweetie!!!HugsRenae
30 August, 2009 at 12:35 am
Hi Stina!It feels so good to visit your blog again !! I love your new header and your raggy quilt it's just gorgeous!!! Lucky girl!!!Hugs,Sandy-
30 August, 2009 at 5:26 am
Stina…what a wonderful new header you have there!!! Oh that package…it is just so perfect…Enjoy my Friend♥x
30 August, 2009 at 8:30 am
WOW! Gorgeous gifts … the quilt is stunning.
1 September, 2009 at 11:01 pm
Oh, how fun! Enjoy, you deserve every bit of happyness this yummy package brought to you!
2 September, 2009 at 3:00 am
Good for you!! Lovely gifts!
Hello Stina,such a lovely package to receive, the quilt is gorgeous…hugs lyn
6 September, 2009 at 4:06 pm
Love this quilt so were would one find the pattern??

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New & used cookware for sale in North Cornelly, Bridgend - Gumtree
0 ads in Cookware for Sale in North Cornelly, Bridgend
Red Crofton Food Mixer
Marksman Portable Gas Stove, preowned and in great condition, collection only. Come down to cash generator in Bridgend for your bargain. Collection only.
2 brand new large frying pans
Bought brand new from Costco but doesn’t work on our induction hob Buyer to collect from bridgend area
Never ever used, still in original box and packaging. Save 60% off the rrp.

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Bread Crumb LinkHome > eBay Stores > Steve's Musclecars and Parts > Original 60-72 GM Car PartsSave this seller|Sign up for Store newsletter Steve's Musclecars and PartsMaintained by:Member id steves_musclecar_parts ( Feedback Score Of 11565) We are a family owned business specializing in high quality original parts for your Classic American Musclecar. Our speciality is clean Southern parts for your 62-74 MOPAR A B C E Body and 64-72 GM A Body. We ship very promptly and professionally package so you can buy with confidence. Thanks, Steve
Store searchEnter your search keywordin titles & descriptionStore categoriesStore homeOriginal 55-61 Mopar Parts (18)Original 62-76 Mopar Car Parts (160)Original 72-91 Dodge Truck (1)Vintage Mopar NOS Parts (27)Original 60-72 GM Car Parts (17)63 64 65 Buick Riveria GS (1)60-72 Impala SS Biscayne (1)64 65 66 67 GTO LeMans Tempest (2)64 65 66 67 Olds Cutlass 442 (4)64 65 66 67 Chevelle ElCamino (1)68-72 Olds Cutlass 442 W-30 (1)67 68 69 Camaro Z28 RS SS (5)70 71 72 Camaro Z28 RS SS (1)53 - 62 Corvette C1 Parts (1)Vintage GM NOS Parts (2)Original 55-75 Ford Car Parts (9)Vintage Automotive Literature (3)Vintage Street Rat Hot Rod (5)55 56 57 Chevrolet Bel Air 210 (1)NOS Vintage Chervrolet (1)NOS Pre-55 Mopar (3)Other (7)DisplayGallery viewView time leftStore pagesAbout the sellerInternational BuyersWe gladly sell and ship Vintage Original and NOS Auto Parts WORLD WIDE and always utilize the most economical shipping methods available. Whenever possible we use USPS First Class International or USPS Priority Mail International. On items too large or heavy for USPS we use BAX Global or FedEx.
Thank you very much, Steve. Most Recent Listings Listings Ending Soon View: All Items | Buy It Now13 results found in Original 60-72 GM Car Parts View as:ListSort by:Price: lowest firstPicture [hide]Item titlePrice Time Left 1967 Oldsmobile Dealer Brochure Cutlass 442 Vista Cruiser 98 88 $17.95Free shippingTime left:27d 8h 47m 67 68 Camaro RS Headlight Door Cover $19.95Time left:14d 7h 45m Vintage Hurst 4 Speed Shifter Tee Handle Camaro Chevelle GTO Nova Firebird $19.95Time left:27d 8h 47m Chevrolet 1111015 Distributor 1965 Nova Chevelle Impala 283 Small Block $24.95Time left:14d 6h 11m 66 67 Cutlass 442 Chevelle GTO Lemans Skylark Rear Seat Side Panels Trim $34.95Time left:14d 6h 12m 67 68 Camaro Dash Center Trim Bezel Woodgrain No A/C $34.95Time left:14d 7h 38m 67 68 Camaro Z28 NEW Parts Lot Seals Light Gaskets Firewall Kit $49.95Time left:14d 7h 55m 1964 64 Pontiac Catalina Bonneville Spinner Hubcaps $79.95Time left:27d 8h 35m 67 68 69 Oldsmobile Dog Dish Poverty Hubcaps Cutlass F85 442 $124.95Time left:29d 6h 7m 60 61 62 63 Buick Dog Dish Poverty Hubcaps $129.95Time left:29d 7h 58m 55 56 57 58 59 Chevrolet 265 283 327 Small Block Valve Covers Staggered Holes $149.95Time left:27d 10h 27m 68 Camaro Interior Door Trim Panels Standard with Original Set For Parts $229.95Time left:15d 5h 24m 1965 65 Oldsmobile Cutlass 442 Wire Spoke Spinner Hubcaps 14" Wheel $249.95Time left:29d 2h 10mWhy don't we show the price?Sellers have the right to set their own prices independently, but some manufacturers place restrictions on how these prices will be displayed or communicated to others.Start of LayerEnd of LayerPage 1 of 1Previous1|2|3|4|5|6|7NextGo to page

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I've been looking forward to this exhibition for a while as I love paper (!) and it features the fantastic work of Rob Ryan. What I didn't anticipate was that it would also feature work by the very talented Su Blackwell and that there'd be some pieces I'd be familiar with from books on papercutting.
The piece by Rob Ryan was especially created for this exhibition. It's huge! [note: I don't know those people, I just thought it gave a good idea of scale with them there!]
When you enter the exhibition you pass through this enchanted forest. The branches are suspended from the ceiling and hover just above the floor.
The above piece is one I've seen in a book or on the internet. I love it and it was great to see it 'in the flesh' as it were!
Labels: manchester art gallery, paper cutting exhibition, rob ryan, su blackwell, Sue Roddis, the first cut
Labels: distress marker, faded jeans, free machine embroidery, hydrangeas, julia jowett, Julie Ranae Murray, mixed media tag, PDcc154, Ranger, the play date cafe challenge, tim holtz
Labels: cabinet of curiosities, extreme composition, Jane Davies, mixed media sketchbook, the sketchbook challenge
Labels: abstract painting, extreme composition, Jane Davies, mixed media tag
Labels: anna collette hunt ceramics, cheryl ewing ceramics, Julia Dunnit, julia jowett, kate lulham, lindsey tyson, mixed media tags, the great northern contemporary craft fair 2012, woyww 175
Labels: claire baker, holly levell, julia jowett, liz cooksey, sarah heaton, the great northern contemporary craft fair 2012, unit twelve gallery


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text: New mixtape: B Magic - You Got It For Free Volume 2 Intro by B MagicI posted a couple tracks from this already but here's the whole mixtape (bandcamp streaming player above):Download B Magic - You Got It For Free Volume 2 (Produced by Dj DviousMindZ) HERE. [usershare link]I know most of y'all who come here are comment averse for some crazy reason but DJ DviousMindZ and B Magic would like feedback if you check this out. Email them or leave it on his Bandcamp page.Online:B Magic - bandcamp | Dj DviousMindZ - twitterLabels: Its a T.dot Thing, mixtapes


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Best Seller Red Electric Guitar With White Binding,Flame Maple Veneer,Rosewood Fingerboard,Offer Customized As You Request UK 2019 From Inbeijin, GBP ￡170.86 | DHgate UK
DHgate > Musical Instruments > Guitar > Electric Guitars > Best seller Red Electric Guitar with White Binding,Flame Maple Veneer,Rosewood Fingerboard,Offer Customized as you request UK
Best seller Red Electric Guitar with White Binding,Flame Maple Veneer,Rosewood Fingerboard,Offer Customized as you request
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Product Name:Best seller Red Electric Guitar with White Binding,Flame Maple Veneer,Rosewood Fingerboard,Offer Customized as you request

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Patent US5650101 - Complexing a lock micelle molecule including atleast one engineered acceptor ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA lock unimolecular micelle includes at least one engineered acceptor specifically binding a ligand (or specifically a "key" unimolecular micelle) thereto. A key unimolecular micelle comprises a core molecule and a plurality of branches extending therefrom, at least one of the branches including a shank...http://www.google.com/patents/US5650101?utm_source=gb-gplus-sharePatent US5650101 - Complexing a lock micelle molecule including atleast one engineered acceptor with a solution containing key micelle molecule including core and plurality of branches; used for drug delivery systemAdvanced Patent SearchPublication numberUS5650101 APublication typeGrantApplication numberUS 08/280,591Publication dateJul 22, 1997Filing dateJul 25, 1994Priority dateJul 25, 1994Fee statusLapsedAlso published asCA2195980A1, DE69534845D1, DE69534845T2, EP0771190A1, EP0771190A4, EP0771190B1, EP1749516A2, EP1749516A3, WO1996003114A1Publication number08280591, 280591, US 5650101 A, US 5650101A, US-A-5650101, US5650101 A, US5650101AInventorsGeorge R. Newkome, Charles N. Moorefield, Gregory R. BakerOriginal AssigneeUniversity Of South FloridaExport CitationBiBTeX, EndNote, RefManPatent Citations (13), Non-Patent Citations (69), Referenced by (9), Classifications (43), Legal Events (10) External Links: USPTO, USPTO Assignment, EspacenetComplexing a lock micelle molecule including atleast one engineered acceptor with a solution containing key micelle molecule including core and plurality of branches; used for drug delivery systemUS 5650101 AAbstract A lock unimolecular micelle includes at least one engineered acceptor specifically binding a ligand (or specifically a "key" unimolecular micelle) thereto. A key unimolecular micelle comprises a core molecule and a plurality of branches extending therefrom, at least one of the branches including a shank portion extending therefrom having a terminal moiety at an end thereof for binding to a complimentary acceptor of a lock unimolecular micelle. Together, the lock and key micelles form a unit, either irreversibly or reversibly bound wherein the lock micelles is a soluble receptor engineered to specifically bind to the specifically engineered key micelle.
What is claimed is: 1. A method of generating a molecular complex by combining a lock micelle molecule including at least one engineered acceptor with a solution containing a key micelle molecule including a core molecule and a plurality of branches extending therefrom, at least one of said branches including a shank portion extending therefrom having a terminal moiety at an end thereof for binding to a complementary acceptor of a lock unimolecular micelle; and selectively binding the terminal moiety to said acceptor to selectively form a bimicellar complex.
2. A method as set forth in claim 1 wherein said lock micelle includes multiple acceptors, said method being further defined as selectively binding a plurality of terminal moieties to said acceptor to form a multiple micellar complex.
3. A method as set forth in claim 1 wherein said key micelle includes multiple shank portions, said method being further defined as selectively binding a plurality of acceptors to said terminal moieties of said key micelle to form a multiple micellar complex.
4. A method as set forth in claims 2 or 3 further defined as binding multiple key micelles with multiple lock micelles to form a crosslinked multi-micellar complex.
5. A method as set forth in claim 1 wherein the lock micelle includes at least one core atom and arms branching from said core atom forming an outer surface surrounding a void area containing the acceptor, said method further including the step of reversibly changing the solubility of the outer surface of the lock micelle in an environment while reversibly extending the arms of the micelle to expand the micelle and expose the void area to the environment complimentary key micelles therein and contract the micelle to mask the void area within the micelle.
6. A method of delivering a guest molecule to a target binding site having a predetermined affinity by delivering a lock and key micellar complex bound together through a guest having a predetermined affinity for an acceptor region of the lock micelle which is less than the affinity for the target binding site to the binding site and competitively releasing the key micelle bound to the guest from the lock micelle and binding the guest portion of the key micelle to the target binding region.
7. A method as set forth in claim 6 including the step of shielding the guest from an environment within the lock micelle during said delivering step.
8. A method as set forth in claim 7 further defined as protecting the guest from enzymatic degradater.
9. A method as set forth in claim 7 further defined as rendering a relatively insoluble guest to be soluble as it is shielded within a relatively soluble lock and key micellar complex.
BACKGROUND OF THE INVENTION Neat and orderly arrays for micellar systems have been reported,1,2 and are structurally based on the original work of Vogtle et al.,3a who delineated "cascade" construction. The U.S. Pat. Nos. 4,435,548, issued Mar. 6, 1984; 4,507,466, issued Mar. 26, 1985; 4,558,120, issued Dec. 10, 1985; 4,568,737, issued Feb. 4, 1986; 4,587,329; issued May 6, 1986; 4,631,337, issued Dec. 23, 1986; 4,694,064, issued Sep. 15, 1987; and 4,737,550, issued Apr. 12, 1988, all to Tomalia et al., relate to branched polyamidoamines. The polyamidoamines include a plurality of pendent aminoamide moieties exhibiting properties which are related to linear polyamidoamines from which the branched polymers are derived. These compounds can be characterized as high molecular weight, highly-branched, multi-functional molecules possessing a three-dimensional morphology. Synthetic strategies employed for the realization of such "cascade polymers"3b require consideration of diverse factors including the content of the initial core, building blocks, space for molecules, branching numbers, dense packing limits, and desired porosity, as well as other factors.4 The selection of the building blocks govern the type of branching desired from the core molecule, as well as the technology used to attach each successive layer or "tier" of the cascade polymer.
Applicants have found6 that the dialkylacetylene moieties of the cascade polymers set forth herein are also specifically located within accessible void regions. Applicants have shown that molecular guest probes, including diphenylhexatriene (DPH), phenol blue (PB), naphthalene, chlortetracycline (CTC), and pinacyanol chloride (PC) can be used as micellar probes to access the infrastructure of such cascade polymers utilizing known chemistry.20-24 Demonstrations of accessibility of void regions to chemical modification has led to the development of the ability to manipulate internal moieties within the spherically symmetrical dendritic macromolecule, after construction, to allow easy incorporation of internally located sensitive and/or reactive groups which otherwise would be difficult to introduce or protect during cascade construction. Specifically, the introduction of metal and metalloid centers at the interior of cascade infrastructures has been accomplished. Such derived compounds; referred to generically as metallospheres, superclusters, unimolecular Metallomicellanes and Nonmetallomicellanes, Metalloidomicellanes, derivatized Micellanes, or Micellanes, can be utilized for drug delivery of various metals and nonmetals, which are presently difficult to deliver in pharmacologically efficacious matters. The use of carrier-metal combinations as pharmacotherapeutic agents has had the problem of not being able to deliver sufficient metal/nonmetal to a site at a sufficiently low dose of the carrier of the metal/nonmetal per se.
For example, the U.S. Pat. No. 5,422,379 to Applicants provides a means of delivering high concentrations of the metal/nonmetal moiety(ies) to a site at a relatively low dose of carrier (Micellane system).
FIG. 4 depicts a versatle method for the construction of four-directional cascade locks containing four diaminopyridine units (A) equidistant from the central core (II and III). The aminopyridinetriester building block used for the construction of the dendritic arms is prepared via high dilution methodology that allows the incorporation of various alkyl chain lengths separating the triester and aminopyridine moieties. This feature allows the design of building blocks that introduce varying degrees of lipophilicity to the interior cascade superstructure. Standard formic acid mediated tert-butyl ester conversion to acid functionalities allows the formation of water-soluble locks as well as generates the poly(acid) precursor for the addition of another tier, or layer, of cascade building block [in the depicted case, the aminotris(tert-butyl ester)] via standard peptide-type coupling conditions. It should be noted however that other amino/ester building blocks can be added to the poly(acids), such as the previously described aminopyridinetriester, via the same technology.
Micelles made in accordance with the present invention can be described as having at least one core atom, preferably a carbon atom, and arms branching from the core atom. At least one acceptor is an integral part of at least one of the branches for binding at least a portion of the ligand within the void region. At least some of the branches can extend about the acceptor defining a predetermined pocket containing the void region. Accordingly, the pocket is a lipophilic container of the void region and acceptor and defines an opening to the exterior of the micelle from the void region. That is, the branches form a lipophilic wall of a cave in which the acceptor is exposed. Such a pocket can be engineered to include one or more acceptor sites as described below. Further, the acceptor sites can be engineered into any branching tier or tiers as needed to engineer a specifically defined receptor or docking site which is complementary to the tertiary and quartenary structure of the ligand to be bound. As it will be described below, the ligand can be in the form of a specifically engineered key micelle such that the key inserts into the pocket and includes a terminal moiety which binds specifically to the acceptor site(s).
It has been found that with significant increases in length of branches or arms, the arms or branches may fold into the micelle thereby not necessarily exposing the terminal end of the arm or branch but rather, a mid-section. Accordingly, hydrodynamic groups exposed in this manner can also effect expansion and contraction of the micelle. The above description of expansion and contraction in response to changes in the environment related to the solubility of the branching of the micelle is further described in U.S. Pat. No. 5,422,379 to Applicants assigned to the assignee of the present invention.
For example, pH, immiscibility or other factors described in the above mentioned patent application U.S. Pat. No. 5,422,379 to Applicants can be utilized. For example, an aqueous solution of an acid terminated lock micelle at pH ≧7 would be in an extended (open or porous) configuration. Substrate (guest) molecules are readily encapsulated (dissolved) within the lipophilic micelle interior; lowering the solution pH (<4) will collapse the lock micelle (close the pores) and entrap the key (guest) molecule. This lock-key (host-guest) complex can be isolated from the solution via filtration methods (such as, dialysis, ultrafiltration, or gel permeation). Dissolution of the isolated lock-key complex in a solution with pH ≧7 will facilitate the release of the entrapped key molecule. The lock micelle imparts its solubility characteristics onto the entrapped key molecule and should serve as a protective "sheath", which can protect labile functionalities on the key molecule.
Besides carboxyl groups, hydroxyl groups, and amines, other acidic, neutral, and/or basic functionalities can be incorporated onto the surface or on interior dendritic arms adjacent to the void regions of these unimolecular micelles as set forth in U.S. Pat. No. 5,154,853. The void areas of these unimolecular micelles made in accordance with the present invention have been characterized. The expanded and contracted nature of such dendritic arms defining the micelles have also been characterized. U.S. Pat. No. 5,422,379 to Applicants discloses various structures capable of expansioning contraction for exposure of void regions and masking of void regions which can be utilized for masking and shielding the opening to the pockets of the micelles made in accordance with the present invention, and are incorporated herein by reference.
For example, the gatekeeper molecules can be selected from the group including, but not limited to, amino acids (such as tryptophan, phenylalanine), carbohydrates and sugars, charged or ionizable groups (including carboxyls, amines, sulfonic acids), metal chelators (including pyridine, phenanthroline, crown ethers, azacrowns), and host moieties such as β-cyclodextrin. A particularly useful example is a gatekeeper moiety which is a chiral molecule for favoring a single enantiomer of a guest molecule which can enter the opening of the pocket to bind the acceptor. Accordingly, the present invention can be utilized as a filtering mechanism for removing a specific enantiomer of a molecule from a solution.
For example, a lock micelle having an R or S configuration can be used as either a soluble form or insoluble form bound to a matrix. Tryptophan is an example of a chiral molecule which can terminate a dendritic macro-molecule as disclosed in the paper entitled "Polytryptophane Terminated Dendritic Molecules", Newkome et al. Tetrahedron Asymmetry Vol 2., No. 10, pp. 957-960, 1991, incorporated herein by reference. Chiral gatekeeper molecules will allow binding of only one of the oppositely active components of a racemic mixture. Accordingly, pursuant to drug industry standards regarding separation of enantiomers (an active drug component from an inactive drug component) the present invention can be used as a filtering system. For example, an aqueous solution of the acid terminated chiral lock micelle at pH ≧7 would be in an extended (open) configuration. Upon addition of a racemic mixture of a complimentary key, only one enantiomer will interact with the lock micelle. Lowering the solution pH (<4), will collapse the lock micelle and entrap the preferentially complexed chiral key molecule. This chiral lock-key complex can be separated from the solution via filtration methods (such as, dialysis or ultrafiltration), removing the remainder of the racemic mixture and other impurities. Dissolution of the isolated chiral lock-key complex in a solution with pH ≧7 will facilitate the release of the chiral key molecule.
A key micelle molecule comprises a core molecule and a plurality of branches extending therefrom a predetermined distance and at least one of the branches including a shank portion extending therefrom having a terminal moiety at an end thereof for binding to a complimentary acceptor of a lock unimolecular micelle. Such a shank portion can consist essentially of a multicarbon chain, the multicarbon chain including zero to 22 carbon atoms. Of courser such a shank portion can be made by various molecular mechanisms known in the art. But it must provide a spacing allowing access of a terminal binding region to an acceptor region within a pocket of a micelle. Examples of such key micelles or molecules are shown in FIG. 2.
The terminal moiety of the key micellar molecule includes the tertiary structure including at least one partially charged portion, either negative or positive or a combination of the two. Such terminal moieties can be selected from the group including barbiturates; such as Allobarbitol, Aminoglulehimide, Amobarbitol, Barbituric acid, Barbital, Bemgride, 6-Azauridine, Phenobarbitol, Primidone, Secobarbital, Pentobarbitol, Diazepam, Flurazepam, Methaqualone, Meprobamate, and also carbohydrates, such as sucrose, alditols, mannitols, hexoses and amino acids and peptides such as trytophane, phenylalanine, glycine and nucleotides and nucleosides such as purines and pirymidines, guanine, cytosine, thiamine, and adenine. As discussed above, the terminal moiety can be chiral.
Based on all applicants' all-carbon unimolecular micelle model, the acetylene moiety is replaced by the appropriate (poly) functionality. Alternate and more simplified incorporation can be envisioned in FIG. 4, utilizing other related dendrons, or cascade building blocks, (specifically, the aminotris(tert-butyl ester)) previously described in the applicants' patent application U.S. Pat. No. 5,422,379 to Applicants for the said dendritic building block. Such a process incorporates the acceptor units(s) in the lock; however, the processes herein described are not limited to only the first tier of construction with four binding loci (as depicted in FIG. 4), but can be incorporated at higher generations using known chemistry.
To illustrate the key/lock principle, four equivalents of the key are added to the dendritic macromolecule possessing the four lock locii. Each key fits the lock perfectly, resulting in the molecular incorporation of four specific guest molecules within the void domain of the macromolecule (FIG. 5). Proof of this concept is by standard spectroscopic procedures. The introduction of other keys possessing the same complimentary portion but different shaped handles on the "bit" region of the key has been shown to give analogous inclusioned and docked guest within the lock structure. FIG. 6 shows other related examples in order to establish the facile ability to molecularly secure reagents within the cavities of these spherical polymers. The use of different attachments (Z; FIG. 6) to the barbiturate's unique "bit" region, via an appropriate connector moiety such as an alkyl chain, permits the molecular entrapment of diverse materials within the lipophilic core of these precursors to the water-soluble spheres or the water-soluble unimolecular micelles. hydrolysis of the lipophilic macromolecules, e.g. II, to the hydrophilic counterparts does not alter the docking region within the core. Treatment of III (R═H) which can be obtained by simply the hydrolysis of V (R-tbu). Either route gives rise to a water soluble material processing the inclusioned (locked) guest (key).
The terpyridine ligand is non-discriminatory in complexation with metals; it does, however, form strong complexes and the metal centers can be electrochemically modified creating a potential catalytic center. The use of bipyridine and related bis-amines can generate enhanced selectivity in the recognition process. Lehn and Potts have shown the bis-, tris-, and tetrakis-bipyridines recognize only their counterpart such that the bis-bis, tris-tris, and tetrakis-tetrakis are formed selectively even though there may be a mixture of ligands. FIG. 9 depicts the key-lock combinations necessary to generate the complexed structure; the lock would be treated initially with the metal salts followed by the introduction of the key. If the alternative formation of the metal-key it is possible to create boloamphiphile in which two keys are complexed to one (or more) metal ion(s).
It is anticipated that most organic molecules have one or more complimentary binding structures. Thus, initially the use of a locus with two or three hydrogen bonds are capable of bonding the complimentary guest with formation of the desired hydrogen bonds. Nucleic bases are used in nature to template or replicate, eg. DNA/RNA. The introduction of these same essential bases with specific locii within the void domain of these cascade macromolecules would synthetically mimic the base pairing; thus, Guanine-Cytosine (similar to the diacylaminopyridine model with the creation of three hydrogen bonds between the bases), Adenine-Thymine (2-hydrogen bonds) would act as the key/lock complimentary locus holding the complex together,
EXPERIMENTAL SECTION Description of the Synthesis for the H-bonding Locks and Keys General Procedure for the Preparation of Aminopyridine Triester Building Blocks for the Incorporation of Bis(amido)pyridine Acceptor Moieties within Cascade Superstructures. [This Procedure can be used with any bis(acid chloride)]
A solution of aminotris(tert-butyl ester) (10 g, 0.024 mol)and diisopropylethylamine (3.11 g, 0.024 mol) in tetrahydrofuran (THF, 50 mL) was added to a cold (5� C.), stirred solution of glutaryl dichloride (4.07 g, 0.024 mol) in THF (900 mL) over a period of 3 h. The mixture was stirred an additional 3 h at 0-5� C.; subsequently, a mixture of THF (50 mL), 2,6-diaminopyridine (7.9 g, 0.072 mol), and diisopropylethylamine (3.11 g, 0.024 mol) was added in one portion. After stirring for another 12 h and allowing the temperature to rise to 25� C., the solvent was removed and the residue dissolved in CH2 Cl2 (200 mL). Upon washing with H2 O and saturated brine (2�200 mL portions of each), the organic phase was dried (Na2 SO4), filtered, and the solvent was removed. Chromatography of the crude product using silica gel and EtOAc/CH2 Cl2 as an eluent afforded (5.8 g, 38%) the pure aminopyridine triester.
13 C NMR(CDCL3) δ 21.3 (CH2 CH2 CH2), 27.9 (CH3,CH2 CO2), 29.7 (CH2 CH2 CO2), 35.7, 36.1 (CH2 CONH), 57.3 [(C(CH2)3 ], 80.5[C(CH3)3 ], 103.0, 104.1 [(CH(2,4)3 ], 139.7 [CH(3)PYR ], 149.7 (CNHCOPYR), 157.2 (CNH2 PYR), 171.1, 171.8, 172.7 (C═O);
1 H NMR(CDCL3) δ 1.30 (CH2 CH2 CH2), 1.43 (CH3), 1.97 (CH2 CO2), 1.30 (CH2 CH2 CH2, m, 2 H), 1.43 (CH3, s, 27 H), 1.97 (CH2 CO2, m, 6 H), 2.21 (CH2 CH2 CO2, CH2 CONHALKYL, m, 8 H), 2.40 (CH2 CONHARYL, t, 2 H, 6.7 Hz), 4.56 (NH2, br s, 2 H), 6.09 (NHALKYL), 6.23 (H3 (PYR), d, 1 H, 7.6 Hz), 7.44(H4 & H5 (PYR), m, 2 H), 8.46 (NHARYL, br s, 1 H)
General Procedure for the Preparation the First
Tier Poly(pyridino) Cascades (FIG. 4; structure II)
A solution of aminopryidine triester (3.0 g, 0.0048 mol) and diisopropylethylamine (0.624 g, 0.0048 mol) in THF (10 mL) was added in one portion to a solution of tetraacid chloride (0.512 g, 0.0012 mol) in THF (5 mL) at 0� C. After stirring for 12 h, the solvent was removed and the residue was chromatographed over silica gel using combinations of EtOAc/CH2 Cl2 with increasing polarities as an eluent to afford (1.6 g, 48%) the pure dodecaester (first tier lock).
13 NMR(CDCL3) δ 21.5 (CH2 CH2 CH2), 27.9 (CH3, CH2 CO2), 29.7 (CH2 CH2 CO2), 35.8, 36.1 (CH2 CH2 CH2), 37.8 (OCH2 CH2), 57.3[C(CH2)3 ], 66.9, 69.5 (CH2 OCH2), 80.5 [C(CH3)3 ], 109.4, 109.6 (C3,5 (ARYL)), 140.4 (C4), 149.5, 149.7 (C2,6), 170.5, 171.6 172.0 172.7 (C═O)
1 H NMR(CDCL3) δ 1.42 (CH3, s, 108 H), 1.98 [C(CH2 CH2)3, CH2 CH2 CH2, m, 32 H], 2.22 [C(CH2)3, CH2 CH2 CH2EXT, m, 32 H], 2.46, 2.59 (CH2 CONHPYRNHCOCH2, 2x br t, 16 H), 3.46[C(CH2)4, br s, 8 H], 3.70 [(OCH2)4, br t, 8 H],6.27 [NHC(CH2)3, br s, 4 H], 7.62 (PYRH4, t, J=8.1 Hz, 4 H), 7.84 (PYRH3 & H5, m, 8 H), 8.81, 8.89 (NHPYR, 2 br s, 8 H)
General Procedure for the Conversion of Poly (tert-butyl esters) to Poly (acids) via hydrolysis with formic acid.
The (first tier) dodecatert-butyl ester (1.0 g, 0.36 mmol) was stirred at 40� C. for 15 h in 95% formic acid. The solvent was removed and the residue was dissolved in hot H2 O (150 mL) with added charcoal and celite. The mixture was filtered through a celite pad and the clear colorless filtrate was evaporated to dryness to afford (0.70 g, 95%) the pure dodeccaacid.
13 C NMR(CD3 OD) δ 22.7 (CH2 CH2 CH2), 29.2[C(CH2 CH2)3 ], 30.4[C(CH2)3 ], 36.6, 37.1 (CH2 CH2 CH2), 38.6 (OCH2 CH2), 46.5 C4�), 58.6 (CONHC4�), 68.3 (C4� CH2), 70.6 (OCH2), 110.6, 110.7 (C3 & C5)PYR, 141.4 (C4)PYR, 151.2, 151.3 (C2 & C6)PYR, 172.8, 174.0, 174.9, 177.2 (C═O).
1 H NMR(CD3 OD) δ 1.95-2.52 (CH2 CONPYRINT, CH2 CH2 CH2, CH2 CH2 CO2 H, m, 80 H), 3.35 [C(CH2 O)4, s, 8 H], 3.71 [C(CH2 OCH2)4, m, 8 H], 7.70 (H3,4,5(PYR), m, 12 H), 8.1 (NH, s)
A mixture of the (first tier) dodecaacid (0.5 g, 0.24 mmol), the aminotris(tert-butyl ester) building block (1.2 g, 0.0028 mol, 12.1 eq), dicyclohexylcarbodiimide (DCC, 0.59 g, 0.0029 mol, 12.1 eq) and 1-hydroxybenzotriazol (HBT, 0.39 g, 0.0029 mol, 12.1 eq) was stirred in dry N,N-dimethylforamide (DMF, 10 mL) for 12-15 h at 25� C. After removal of the solvent, the residue was dissolved in toluene/diethyl ether (100 mL, 1:1 v/v) and washed with saturated brine (3�100 mL). The organic phase was separated, dried (Na2 SO4), filtered, and the solvent was removed. The crude material was chromatographed over silica gel eluent (EtOAc/CH2 Cl2) aliquots of increasing polarity to afford (0.77 g, 48%) the pure second tier, 36-t-butyl ester.
13 C NMR(CDCL3) δ 21.6 (CH2 CH2 CH2), 27.9 (CH3,CH2 CO2 R), 29.7[(CH2 CH2 CO2)G2, (CH2 CON)G1 ], 31.5 (CH2 CH2 CON)G1, 36.1, 37.7 (CH2 CH2 CH2), 46.5(C4�), 57.4 (CONHC)G2,G1, 67.0 [C(CH2 OCH2)4 ], 69.6 [C(CH2 OCH2)4 ], 80.5 [C(CH3)3 ], 109.8 [(C3 & C5)PYR ], 140.3 [(C4)PYR ]. 149.8 [(C2 & C6)PYR ], 70.8, 172.7 (C═O)
1 H NMR (CDCL3) δ 1.42 (CH3, s, 324 H), 1.82-2.70 (CH2 CH2 CO, CH2 CH2 CH2, CH2 CONHPYR, m, 224 H), 3.45, 3.63 (CH2 OCH2, 2 br s, 16 H), 6.40, 7.30 (NHC4�), 7.68 (C4(PYR), m, 4 H), 7.88 (C3 & C5(PYR), m, 8 H), 8.95, 9.15 (NH.sub.(PYR), 2 br s, 8 H)
Preparation: please see the general procedure for the conversion of tert-butyl esters to acids via formic acid.
13 C NMR (CD3 OD) δ 22.6 (CH2 CH2 CH2), 29.2 (CH2 CO2), 30.4 (CH2 CH2 CO2, CH2 CONG1), 31.7 (CH2 CH2 CON)G1, 36.9 (CH2 CH2 CH2), 38.6 (OCH2 CH2 46.4 (C4�), 58.5 (CONHC)G2,G1, 68.2 [C(CH2 OCH2)4 ], 70.4 [C(CH2 OCH2)4 ], 110.6 [(C3 & C5)PRY ], 141.5 [(C4)PYR. 151.0 [(C2 & C6)PYR ], 172.9, 174.2, 175.6, 177.3 (C═O);
1 H NMR (CD3 OD) δ 1.63-2.65 (CH2 CH2 COG1,G2, CH2 CH2 CH2, m, 200 H) 3.35 (C(CH2 OCH2), CH2 CONcore, CH2 CH2 CH2, br s, 32 H), 3.64 (C(CH2 OCH2, br s, 8 H), 7.73 [H3,4,5 pyr, br s, 12 H], 7.35, 7.49, 8.15 (NH).
SYNTHESIS AND CHARACTERIZATION OF BARBITUIC ACID BASED KEYS 11-Bromoundecanamide-triester. A solution of 11-bromoundecanoic acid (10.00 g, 37.7 mmol) dissolved in CH2 Cl2 (30 mL) was slowly added to a solution of SOCl2 (7.0 mL, 94.0 mmol) in CH2 Cl2 (25 mL). The mixture was refluxed for 5 h, then concentrated in vacuo to give 11-bromoundecanoyl chloride, which was used without further purification:
1 H NMR (CDCl3) δ 1.26 (bs, (CH2)5, 10 H), 1.34 (m, CH2 CH2 CH2 Br, 2 H), 1.67 (m, CH2 CH2 COCl, 2 H], 1.81 (m, CH2 CH2 Br, 2 H), 2.85 (t, CH2 COCl, J=7.2 Hz, 2 H), 3.36 (t, CH2 Br, J=6.8 Hz, 2 H);
13 C NMR (CDCl3) δ 24.89 (CH2 CH2 COCl), 27.95 (CH2 CH2 CH2 Br), 28.21, 28.52, 28.84, 29.02, and 29.12 ((CH2)5), 32.64 (CH2 CH2 Br), 33.80 (CH2 Br), 46.92 (CH2 COCl), 173.47 (COCl).
A solution of 11-bromoundecanoyl chloride (10.68 g, 37.7 mmol) dissolved in CH2 Cl2 (15 mL) was added to a stirred solution of di-tert-butyl 4-amino-4-[2-(tert-butoxycarbonyl)ethyl]-1,7-heptanedioate (15.7 g, 37.7 mmol), (i-Pr)2 EtN (7.32 g, 56.7 mmol), and CH2 Cl2 (15 mL) at 0� C. The reaction mixture was stirred for 2 h at 25� C., filtered, and the CH2 Cl2 solution washed successively with brine (50 mL), cold 10% HCl (50 mL), water (50 mL), saturated NaHCO3 (50 mL), then dried over anhyd MgSO4, and concentrated in vacuo to give (93%) 11-bromoundecanamide-triester, as a white solid: 23.24 g; mp 61.7�-63.9� C.;
1 H NMR (CDCl3) δ 1.24 (bs, (CH2)5, 10 H), 1.32 (m, CH2 CH2 CH2 Br, 2 H) 1.39 (s, OC(CH3)3, 27 H), 1.47 (m, CH2 CH2 CONH, 2 H), 1.81 (m, CH2 CH2 Br 2 H), 1.92 (t, CH2 CH2 CO2, 6 H), 2.06 (m, CH2 CONH 2 H), 2.18 (t, CH2 CH2 CO2, 6 H) 3.36 (t, CH2 Br, 2 H), 5.81 (s, CONH, 1 H);
13 C NMR (CDCl3) δ 5.67 (CH2 CH2 CONH), 27.98 (OC(CH3)3), 28.05 (CH2 CH2 CH2 Br), 28.63, 29.17, 29.19, 29.25, and 29.28 ((CH2)5), 29.75 (CH2 CH2 CO2), 29.92 (CH2 CH2 CO2), 32.74 (CH2 CH2 Br), 33.88 (CH2 Br), 37.48 (CH2 CONH), 57.18 (CONHC), 80.52 (OC(CH3)3), 172.48 (CONHC), 172.86 (CO2 C).
Dimethyl malonatoamidotriester. A mixture of 11-bromoundecanamide (10.00 g, 15.1 mmol), dimethyl malonate (5.00 g, 37.8 mmol), NaI (0.565 g, 3.77 mmol), and anhyd K2 CO3 (6.25 g, 45.2 mmol) in dry DMF (50 mL) was stirred at 90�-100� C. for 15-24 h. Upon cooling, the mixture was filtered through celite and concentrated in vacuo to give a residue, which was dissolved in C6 H6 (100 mL), washed with water (3�100 mL), dried over anhyd MgSO4, and evaporated. The resulting crude material was column chromatographed on basic alumina (C6 H12 /EtAc; 85/15) to give (56%) the desired malonatotriester, as a thick oil: 6.03 g;
1 H NMR (CDCl3) δ 1.27 (bs, (CH2)7, 14 H), 1.44 (s, C(CH3)3, 27 H), 1.59 (m, CH2CH2CONH, 2 H), 1.87 (m, CH2 CH2 CHCO2 Me, 2 H), 1.97 (t, CH2 CH2 CO2, 6 H), 2.11 (t, CH2 CONH, 2 H), 2.22 (t, CH2 CH2 CO2, 6 H), 3.36 (t, (MeO2 C)2 CH, J=7.5 Hz 1 H), 3.73 (s, CO2 CH3, 6 H);
13 C NMR (CDCl3) δ 25.50 (CH2 CH2 CONH), 26.61, 27.02, 27.77 (C(CH3)3), 28.55, 28.87, 28.96, 29.04, 29.11 (CH2 CH2 CO2), 29.14, 29.51 (CH2 CH2 CO2), 29.64 (CH2 CH), 37.17 (CH2 CONH), 51.39 (CH(CO2 Me)2), 52.07 (CO2 CH3), 56.97 (CONHC), 80.20 (C(CH3)3), 169.62 (CO2 Me), 172.36 (CONH), 172.58 (CO2 C(CH3)3),
Barbituric Acid Key--First Tier Ester.
A stirred solution of the malonatotriester (1.00 g, 1.40 mmol), urea (84.1 mg, 1.40 mmol) and potassium tert-butoxide (314 mg, 2.80 mmol) in tert-butanol (5.0 mL) was refluxed for 2 h; water (10 mL) and saturated aqueous NH4 Cl (2 mL) was added and the mixture was concentrated in vacuo. The resulting material was extracted with CH2 Cl2 (25 mL), dried over anhyd Na2 SO4, and evaporated to give (90%) the barbituric acid key, as a thick oil:
1 H NMR (CDCl3) δ 1.18 (bs, (CH2)7, 14 H), 1.36 (s, OC(CH3)3, 27 H), 1.47 (m, CH2 CH2 CONH, 2 H), 1.88 (m, CH2 CH2 CO2 and CH2 CH2 CH, 8 H), 2.14 (m, CH2 CH2 CO2 and CH2 CONH, 8 H) 3.18 (m, CH2 CH, 1 H), 5.8-6.2 (br s, NH, 1 H), 8.7 (br, NH, 2 H);
13 C NMR (CDCl3) δ 25.75 (CH2 CH2 CONH), 27.90 (C(CH3)3), 29.09 (CH2 CH2 CO2), 29.64 (CH2 CH2 CO2), 37.29 (CH2 CONH), 53.10 (CH), 57.29 (CONHC), 80.60 (C(CH3)3), 162.38 (NHCONH), 172.91 (CO2 C), 173.48 (CONHC), 174.71 (CHCONH).
Barbituric Acid Key--First Tier Acid.
Triester (200 mg, 0.422 mmol) was stirred with HCO2 H (5.0 mL) for 24 h at 25� C., concentrated in vacuo; the last traces of formic acid were removed azeotropically via addition of toluene (3�30 mL) to give the desired triacid, as a thick oil: 150 mg;
1H NMR (CD3 OD) δ 1.35 (br s, (CH2)7, 14 H), 1.63 (m, CH2 CH2 CONH, 2 H), 1.89 (m, CH2 CH, 2 H), 2.05 (t, CH2 CH2 CO2 H, J=6.8 Hz, 6 H), 2.21 (t, CH2 CONH, J=7.3 Hz, 2 H), 2.31 (t, CH2 CH2 CO2 H, J=6.8 Hz, 6 H), 3.21 (t, CH, J=7.3 Hz, 1 H), 5.75 (brs, NH, 1 H), 7.41 (brs, NH, 2 H).
EXPERIMENTAL DETAILS FOR H-BONDING LOCK AND KEY COMPLEXES Preparation of the complexes: Four to one complexes were prepared for 1 H NMR analysis by mixing four equivalents of Key with one equivalent of Lock in the appropriate NMR solvent.
Barbituric acid key (1st tier ester)+First tier dodecaester lock: 1 H NMR (CDCl3) δ 8.98, 9.10 [NH (pyridinocarboxamides), 2 x br s, 8 H (these signals were observed to be shifted downfield by at least 0.2 ppm (J. P. Mathias, E. R. Simanek, and G. M. Whitesides, J. Am. Chem. Soc. Vol 116., pp 4326-4340, 1994)], 7.63, 7.84 (pyr-H3,4,5, sharp multiplets, 12 H, these absorptions were observed to sharpen relative to the parent Lock) All other pertinent absorptions were obsevered at chemical shifts listed in the experimental section.
SYNTHETIC METHOD AND EXPERIMENTAL DETAILS FOR THE PREPARATION OF METAL COORDINATED LOCKS AND KEYS General Procedure for the coupling of the hydroxyalkylacids with Cltpy.
General Procedure for the Amid-Coupling.
A mixture of the lock-0-acid (1.34 g, 4 mmol), dicyclohexylcarbodiimide (DCC; 866 mg, 4.2 mmol), and 1-hydroxybenzotriazole (1-HBT; 567 mg, 4.2 mmol) in 20 ml DMF was stirred at 25� C. for 1 h. Di-tert-butyl-4-amino-4-[2-(tert-butoxycarbonyl) ethyl]-heptanedioate (1.66 g, 4 mmol) was added to the mixture, which was stirred at 25� C. for additional 23 h. After filtration of dicyclohexylurea, the solvent was removed in vacuo to give a residue, which was dissolved in EtOAc and filtered through a short Alumina column. The filtrate was concentrated in vacuo, and chromatographed (SiO2 column) eluting with CH2 Cl2 /EtOAc to give the pure lock-3-ester as a colorless solid 1.26 g (43%).
General Procedure for the Ester-Hydrolysis.
Preparation of the key-Ru-complex.
Preparation of the key and lock complexes.
EXPERIMENTAL DATA The following compounds were made and analyses in accordance with the present invention.
1 H-NMR (CDCl3 /MeOD): δ=2.21 (CH2, m, J=6.9 Hz, 2H), 2.59 (CH2 CO, t, J=7.3 Hz, 2H), 4.33 (CH2 Otpy, t, J=6.2 Hz, 2H), 7.46 (C5 H, tm, J=5.6 Hz, 2H), 7.93 (C3' H, s, 2H), 7.98 (C4 H, tm, J=8 Hz, 2H), 8.60 (C3 H, dm, J=8 Hz, 2H), 8.67 (C6 H, dm, J=4.9 Hz, 2H).
13 C-NMR (CDCl3 /MeOD): δ=25.73 (CH2), 31.63 (CH2 CO), 68.63 (CH2 Otpy), 108.68 (C3'), 123.16 (C3), 125.48 (C5) 138.75 (C4) 150.01 (C6) 157.26 (C2), 158.38 (C2'), 168.60 (C4'), 177.00 (CO2 H).
1 H-NMR (CDCl3): δ=1.40 (C(CH3)3, s, 27H), 1.98 (CCH2, t, 6H), 2.15 (CH2, m, 2H), 2.21 (CCH2 CH2, t, 6H), 2.35 (CH2 CON, t, 2H), 4.26 (CH2 Otpy, t, 2H), 5.99 (NH, s, 1H), 7.32 (C5 H, tm, 2H), 7.82 (C4 H, tm, 2H), 8.00 (C3' H, s, 2H), 8.60 (C3 H, dm, 2H), 8.67 (C6 H, dm, 2H).
13 C-NMR (CDCl3): δ=25.06 (CH2), 28.02 (C(CH3)3), 29.83 (CH2 CO), 30.05 (CCH2), 33.43 (CH2 CON), 57.46 (C-quat), 67.22 (CH2 Otpy), 80.63 (OCC(CH3)3), 107.37 (C3'), 121.28 (C3), 123.74 (C5), 136.70 (C4), 148.99 (C6), 156.10 (C2), 157.12 (C2'), 167.02 (C4'), 171.48 (CON), 172.86 (CO2 C(CH3)3).
1 H-NMR (MeOD): δ=2.10 (CH2 ; CCH2, m `br`, 8H), 2.38 (CCH2 CH2, t, 6H), 2.43 (CH2 CON, t, 2H), 4.12 (CH2 Otpy, t, 2H), 7.47 (C5 H, t, 2H), 7.70 (C3' H s, 2H), 7.93 (C4 H, t, 2H), 8.35 (C3 H, d, 2H), 8.60 (C6 H, d, 2H).
13 C-NMR (MeOD): δ=26.21 (CH2), 29.60 (CH2 CO), 30.81 (CCH2), 33.75 (CH2 CON), 58.96 (C-quat), 69.47 (CH2 Otpy), 109.26 (C3'), 123.53 (C3), 126.45 (C5), 139.94 (C4), 149.62 (C6), 154.42 (C2), 155.87 (C2'), 169.47 (C4'), 174.87 (CON), 177.42 (CO2 H).
1 H-NMR (CDCl3): δ=1.40 (C(CH3)3, s, 81H), 1.95 (CCH2, m, 24H), 2.17 (CH2 ; CCH2 CH2, m, 26H), 2.38 (CH2 CON, t, 2H), 4.26 (CH2 Otpy, t, 2H), 6.13 (NH, s `br`, 3H), 6.17 (NH, s `br`, 1H), 7.28 (C5 H, tm, 2H), 7.80 (C4 H, tm, 2H), 7.98 (C3' H, s, 2H), 8.58 (C3 H, dm, 2H), 8.65 (C6 H, dm, 2H).
13 C-NMR (CDCl3): δ=25.14 (CH2), 27.99 (C(CH3)3), 29.76 (CH2 CH2 CO), 33.42 (CH2 CON), 57.41 (C-quat), 67.49 (CH2 Otpy), 80.46 (OCC(CH3)3), 107.44 (C3'), 121.20 (C3), 123.64 (C5), 136.59 (C4), 148.94 (C6), 156.09 (C2), 157.00 (C2'), 167.05 (C4'), 172.38 (CON), 172.76 (CO2 C(CH3)3); 172.99 (3CON).
1 H-NMR (MeOD): δ=2.00 (CH2 ; CCH2, m, 26H), 2.30 (CCH2 CH2, m, 24H), 2.48 (CH2 CON, t, 2H), 4.28 (CH2 Otpy, t, 2H), 7.50 (C5 H, t, 2H), 7.85 (C3' H, s, 2H), 7.98 (C4 H, t, 2H), 8.52 (C3 H d, 2H), 8.68 (C6 H, d, 2H).
13 C-NMR (MeOD): δ=26.53 (CH2), 29.56 (CH2 CO), 30.76 (CCH2), 34.18 (CH2 CON), 58.87 (C-quat), 69.33 (CH2 Otpy), 109.19 (C3'), 123.54 (C3), 126.13 (C5), 139.55 (C4), 150.02 (C6), 156.07 (C2), 157.07 (C2'), 169.20 (C4'), 175.30 (CON), 175.80 (3CON), 177.45 (CO2 H).
1 H-NMR (CDCl3): δ=1.33 (CH2, s `br`, 12H), 1.50 (CH2, m, 2H), 1.65 (CH2, m, 2H), 1.85 (CH2, m, 2H), 2.32 (CH2 CO, t, 2H), 4.21 (CH2 Otpy, t, 2H), 6.9 (CO2 H, `br`, 1H) 7.34 (C5 H, tm, J=4.9 Hz, 2H), 7.85 (C4 H, tm, J=7.9 Hz, 2H), 7.97 (C3' H, s, 2H), 8.60 (C3 H, dm, J=7.9 Hz, 2H), 8.72 (C6 H, dm, J=4.9 Hz, 2H).
13 C-NMR (CDCl3): δ=24.79 (CH2), 25.77 (CH2), 28.87 (4CH2), 28.97 (2CH2), 29.15 (CH2), 34.21 (CH2 CO), 68.23 (CH2 Otpy), 107.58 (C3'), 121.56 (C3), 123.82 (C5), 136.95 (C4), 18.90 (C6), 156.17 (C2), 156.85 (C2'), 167.42 (C4'), 178.06 (CO2 H).
1 H-NMR (CDCl3): δ=1.18 (CH2, s `br`, 12H), 1.24 (C(CH3)3, s, 27H), 1.30 (CH2, m, 2H), 1.45 (CH2, m, 2H), 1.70 (CH2, m, 2H), 1.82 (CCH2, t, 6H), 2.00 (CH2 CON, t, 2H), 2.08 (CCH2 CH2, t, 6H), 4.04 (CH2 Otpy, t, 2H), 5.99 (NH, s, 1H), 7.15 (C5 H, t, 2H), 7.67 (C4 H, t, 2H), 7.82 (C3' H, s, 2H), 8.44 (C3 H, d, 2H), 8.50 (C6 H, d, 2H).
13 C-NMR (CDCl3): δ=25.65 (CH2), 25.79 (CH2), 8.87 (CH2), 2913 (2CH2), 29.19 (CH2), 29.33 (CH2), 29.37 (2CH2), 29.67 (CCH2), 29.85 (CCH2 CH2), 37.39 (CH2 CON), 68.04 (CH2 Otpy), 80.40 (OC(CH3)3), 107.25 (C3'), 121.16 (C3), 123.57 (C5), 136.56 (C4), 148.81 (C6), 156.03 (C2), 156.85 (C2'), 166.90 (C4'), 172.47 (CON), 172.74 (CO2 C(CH3)3).
1 H-NMR (CDCl3): δ=1.28 (CH2, s `br`, 12H), 1.38 (CH2, m, 2H), 1.58 (CH2, m, 2H), 1.72 (CH2, m, 2H), 2.08 (CCH2, m, 6H), 2.20 (CH2 CO, t, 2H), 2.34 (CCH2 CH2, m, 6H), 4.00 (CH2 Otpy, t, 2H), 7.41 (C5 H, t, 2H), 7.68 (C3' H, s, 2H), 7.90 (C4 H, t, 2H), 8.40 (C3 H, d, 2H), 8.60 (C6 H, d, 2H).
13 C-NMR (CDCl3): δ=27.08 (CH2), 27.31 (CH2), 29.51 (2CH2), 30.10 (CH2), 30.47 (2CH2), 30.57 (2CH2), 30.73 (6 CCH2 CH2), 37.89 (CH2 CO), 58.68 (C-quat), 69.99 (CH2 Otpy), 108.90 (C3'), 123.26 (C3), 126.03 (C5), 139.39 (C4), 149.73 (C6), 155.36 (C2), 156.55 (C2'), 169.17 (C4'), 176.12 (CON), 177.29 (CO2 H).
1 H-NMR (CDCl3): δ=1.20 (CH2, s `br`, 12H), 1.30 (C(CH3)3, s, 81H), 1.38 (CH2, m, 2H), 1.50 (CH2, m, 2H), 1.76 (CH2, m, 2H), 1.86 (CCH2, m, 24H), 2.10 (CH2 CO; CCH2 CH2, m, 26H), 4.12 (CH2 Otpy, t, 2H), 5.98 (NH, s, 1H), 6.07 (NH, s, 3H), 7.21 (C5 H, t, 2H), 7.73 (C4 H, t, 2H), 7.90 (C3' H, s, 2H), 8.50 (C3 H, d, 2H), 8.58 (C6 H, d, 2H).
13 C-NMR (CDCl3) δ=25.61 (CH2), 25.74 (CH2), 27.86 (C(CH3)3), 28.83 (CH2), 29.22 (2CH2), 29.36 (3CH2), 29.58 (18CH2), 29.75 (6CH2), 31.56 (CH2), 31.89 (CH2 CO), 57.16 (C-quat), 67.98 (CH2 Otpy), 80.26 (OC(CH3)3), 107.15 (C3'), 121.07 (C3), 23.53 (C5), 136.51 (C4), 148.77 (C6), 155.95 (C2), 156.79 (C2'), 167.11 (C4'), 172.43 (CO2 C(CH3)3), 172.72 (3CON), 172.81 (CON).
Lock-9 -ester-Ru-key-9 -ester C198 H314 N14 O46 Ru (3723)
1 H-NMR (CDCl3): δ=1.30 (CH2, s, 12H), 1.40 (C(CH3)3, s, 81H), 1.43 (C(CH3)3, s, 81H), 1.60 (CH2, m `br`, 4H), 1.93 (CH2, m `br`, 48H), 2.20 (CH2, m, `br`, 52H), 2.55 (CH2, m `br`, 4H), 4.10 (CH2 Otpy, t, 4H), 6.03 (NH, s `br`, 1H), 6.18 (NH, s `br`, 3H), 6.46 (NH, s `br`, 4H), 7.19 (C5 H, m, 4H), 7.38 (C4 H, m, 4H), 7.65-8.80 (C3' H; C3 H; C6 H, m, 12H).
13 C-NMR (CDCl3): δ=25.89 (CH2), 28.07 (C(CH3)3), 29.79 (C2), 31.78 (C2), 32.20 (CH2), 33.59 (CH2), 57.21, 57.36 (C-quat), 80.36, 80.52 (OC(CH3)3), 111.13, 111.55 (C3'), 124.52 (C3), 127.72 (C5), 137.82, 138.18 (C4), 151.98 (C6), 155.99, 156.12 (C2), 158.24 (C2'), 166.23, 168.26 (C4'), 172.70, 172.77 (CO2 C(CH3)3), 172.95 (CON).
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Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS4435548 *Apr 27, 1981Mar 6, 1984The Dow Chemical CompanyBranched polyamidoaminesUS4468499 *May 26, 1982Aug 28, 1984Lehigh UniversityThermoplastic interpenetrating polymer network composition and processUS4469621 *Jun 22, 1981Sep 4, 1984Asahi Kasei Kogyo Kabushiki KaishaMolecular aggregate having an ordered structureUS4507466 *Jan 7, 1983Mar 26, 1985The Dow Chemical CorporationPolyamines and acrylate copolymersUS4558120 *Dec 27, 1983Dec 10, 1985The Dow Chemical CompanyIncreased terminal groupsUS4568737 *Aug 17, 1984Feb 4, 1986The Dow Chemical CompanyDemulsifiers for oil in water emulsionsUS4587329 *Jul 19, 1985May 6, 1986The Dow Chemical CompanyDense star polymers having two dimensional molecular diameterUS4631337 *Jul 15, 1985Dec 23, 1986The Dow Chemical CompanyHydrolytically-stable dense star polyamineUS4694064 *Feb 28, 1986Sep 15, 1987The Dow Chemical CompanyRod-shaped dendrimerUS4713975 *May 30, 1986Dec 22, 1987The Dow Chemical CompanyDense star polymers for calibrating/characterizing sub-micron aperturesUS4737550 *Dec 8, 1986Apr 12, 1988The Dow Chemical CompanyBridged dense star polymersUS5154853 *Feb 19, 1991Oct 13, 1992University Of South FloridaAlkylating branches of multi-branch core alkyl compound with alkyne building lbock having ether side chains; reducing; deprotecting; functionalizingUS5221534 *Feb 4, 1991Jun 22, 1993Pennzoil Products CompanyHealth and beauty aid compositions* Cited by examinerNon-Patent CitationsReference1Bochkarev et al., "Polyphenylenegermane--a new type of polymeric" Journal on Organometallic Chemistry, 195-200 (1987) [not translated; only copy available].2 *Bochkarev et al., Polyphenylenegermane a new type of polymeric Journal on Organometallic Chemistry, 195 200 (1987) not translated; only copy available .3Bochkov et al., "Synthesis of Cascadol, A Highly Branched Functionalized Polyether" translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2394-2395, (1989).4 *Bochkov et al., Synthesis of Cascadol, A Highly Branched Functionalized Polyether translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2394 2395, (1989).5Buhleier et al., "Cascade-and Nonskid-Chain-Like Syntheses of Molecular Cavity Topologies" Synthesis, 155-158 (1978).6 *Buhleier et al., Cascade and Nonskid Chain Like Syntheses of Molecular Cavity Topologies Synthesis, 155 158 (1978).7Hawker and Frechet, "Control of Surface Functionality in Synthesis of Dendritic Macromolecules. . . 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"Building Blocks for Dendritic Macromolecules" Aldrichimica Acta, 25:31-38 (1992).32 *Newkome et al. Building Blocks for Dendritic Macromolecules Aldrichimica Acta, 25:31 38 (1992).33Newkome et al., "Alkane Cascade Polymers Possessing Micellar Topology: Micellanoic Acid Derivatives" Angew. Chem. Int. Ed. Eng. 30:1176-1180.34Newkome et al., "Unimolecular Micelles" Angew. Chem. Int. Ed. Engl. 30:1178-1180 (1991).35 *Newkome et al., Alkane Cascade Polymers Possessing Micellar Topology: Micellanoic Acid Derivatives Angew. Chem. Int. Ed. Eng. 30:1176 1180.36 *Newkome et al., Unimolecular Micelles Angew. Chem. Int. Ed. Engl. 30:1178 1180 (1991).37Padias et al., "Starburst Polyether Dendrimers", J.Org.Chem., 55:5305-5312 (1987).38 *Padias et al., Starburst Polyether Dendrimers , J.Org.Chem., 55:5305 5312 (1987).39Pessi et al., "Appl. of Cont-flow Polyamide Method to Solid-phase Synth. of Multiple Antigen Peptide (MAP) based on Deq. of Malaria Epitope" J.Chem.Soc. Chem. 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Silicone Dendrimers", J.Am.Chem.Soc., 112:7077-7079 (1990).65 *Uchida, General Strategy for Systematic Synthesis of Oligosiloxanes. Silicone Dendrimers , J.Am.Chem.Soc., 112:7077 7079 (1990).66Wooley, "Polymers with Cont. Molecular Architecture: Cont. of Surface Functionality in Synthesis of Dendritic Hyperbranched Macromolecules" J.Chem.Soc.Perkin Trans.1, pp. 1059-1075 (1991).67 *Wooley, Polymers with Cont. Molecular Architecture: Cont. of Surface Functionality in Synthesis of Dendritic Hyperbranched Macromolecules J.Chem.Soc.Perkin Trans.1, pp. 1059 1075 (1991).68Young et al., "Smart Cascade Polymers. Modular Syntheses of Four-Directional Dendritic . . . " Macromolecules 1994, 27, 3464-3471.69 *Young et al., Smart Cascade Polymers. Modular Syntheses of Four Directional Dendritic . . . Macromolecules 1994, 27, 3464 3471.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5863919 *Aug 28, 1996Jan 26, 1999University Of South FloridaLock and key micelles and monomer building blocks thereforUS5994534 *Mar 11, 1996Nov 30, 1999Lek Pharmaceutical And Chemical Co. D.DProcess for the preparation of pharmaceutically acceptable salts of clavulanic acidUS6130209 *Apr 24, 1998Oct 10, 2000University Of South FloridaCascading polymersUS6207428Oct 8, 1999Mar 27, 2001Lek Pharmaceutical & Chemical Co. D.D.Process for the isolation of clavulanic acid and of pharmaceutically acceptable salts thereof from the fermentation broth of streptomyces sp. P 6621 FERM P 2804US6224935Jan 21, 2000May 1, 2001Cornell Research Foundation, Inc.Forming film on substrateUS6566106Jan 3, 2001May 20, 2003Lek Pharmaceutical & Chemical Co., D.D.Process for the isolation of clavulanic acid and of pharmaceutically acceptable salts thereofUS6566409May 8, 2000May 20, 2003University Of South FloridaLock and key micellesWO1998008491A1 *Aug 26, 1997Mar 5, 1998Univ South FloridaLock and key micellesWO2007048423A1 *Oct 26, 2005May 3, 2007Stichting Dutch Polymer InstUnimolecular micelles containing metal nanoparticles and their use as catalyst for synthesis of carbon-carbon-bonds* Cited by examinerClassifications U.S. Classification264/4.3, 428/402.21, 424/1.53, 424/DIG.16, 525/903, 424/497, 428/402.22, 525/936International ClassificationC07D239/64, A61K47/48, C08G73/02, C08G73/06, C07D239/62, C07D213/75, C07C233/47, C08J3/02, C07D213/68, A61K9/107, A61K47/30, B01F17/30Cooperative ClassificationY10S424/16, C08G73/0627, A61K47/488, C07C233/47, C07D239/62, C08G73/028, C07D213/75, B82Y5/00, Y10S525/903, C07D213/68, Y10S525/936, C07D239/64, A61K47/48961European ClassificationB82Y5/00, C07D239/62, C07C233/47, C08G73/06E1, A61K47/48W6B, A61K47/48W18, C08G73/02R, C07D239/64, C07D213/68, C07D213/75Legal EventsDateCodeEventDescriptionSep 8, 2009FPExpired due to failure to pay maintenance feeEffective date: 20090722Jul 22, 2009LAPSLapse for failure to pay maintenance feesJan 26, 2009REMIMaintenance fee reminder mailedJan 19, 2005FPAYFee paymentYear of fee payment: 8Mar 12, 2002PRDPPatent reinstated due to the acceptance of a late maintenance feeEffective date: 20020204Feb 8, 2002SULPSurcharge for late paymentJan 14, 2002FPAYFee paymentYear of fee payment: 4Sep 25, 2001FPExpired due to failure to pay maintenance feeEffective date: 20010722Feb 13, 2001REMIMaintenance fee reminder mailedJul 25, 1994ASAssignmentOwner name: UNIVERSITY OF SOUTH FLORIDA, FLORIDAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NEWKOME, GEORGE W.;MOOREFIELD, CHARLES N.;BAKER, GREGORYR.;REEL/FRAME:007104/0498Effective date: 19940725RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google

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Summer Towels - Shop The Best Brands Today - Overstock.com
Great Deal towels
A great towel set. The colors are right in for summer
It took while to find towels that actually cover the length of the chair and these are great! All summer long we got asked where we got these towels!
The grandkids used this towel almost every day during the past summer and it held up fantastically. Nice and soft to the touch but very absorbent. Held up to weekly washings. At end of summer design was slightly worn, but being used every day was to be expected. Still in good shape and ready and waiting for next summer.
I ordered 3 of these, in different fun colors. All very pretty. These will be perfect for the kids, come summer. Good size and seem like they'll be absorbent. Also will roll up nice and small to stuff in a beach bag and tote off to the beach. I love these towels ! I just might order a few more !
Fouta Turkish Beach Towel - Just Right
We have a pool, and two children in their twenties. They both love to bring friends and/or families over to swim all summer long. We have always had plenty of regular beach towels/bath sheets on hand for guests. However, that also means plenty of laundry to be taken care of. These towels are generously sized, nice to dry off with, and comfortable to lay on over a lounge chair. Best of all, they cut the laundry loads by at least half!! Yippee!!
Love these towels. I ordered 3. They will be a cute summer beach item!

value: Overstock, excessive stock, excess2sell, B-stock, or excess inventory, is the result of poor management of stock demand or of material flow in process management. Excessive stock is also associated with loss of revenue owing to additional capital bound with the purchase or simply storage space taken.


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Deux Lux Mystery Box Review | boxesfordays
May 5, 2015 LifestyleDeux Lux, Reviewboxesfordays
Deux Lux Mystery Box
Cost: $50 (free UPS shipping!)
“3 items randomly selected from our NYC sample sale! “
Ziggy Card Case in Gunmetal (RV: $30) – This is actually not a bad mystery item to receive! It’s more substantial (heavier) than my J Fold card case that I received last year in a Birchbox Man box. The color is actually what I would have chosen for myself so I’m glad this was the one I got. 🙂
The cool thing is that it’s see-through!
Anguilla Cosmetic in Ecru (RV: $38) – This is gorgeous! I love the cream color and the bird print on this cosmetic case! It could also be used as a very expensive pencil case. XD But seriously, I love this one.
The lining is gorgeous too!
I really loved that every single item came in a dust bag!
Shinjuku Messenger (RV: $90, on sale for $63) – I was so excited when I first realized I was getting a messenger bag… but then I pulled it out and I was like wait… uh… no. XD It’s a shame but I really don’t like the beehive pattern or this type of material. It just looks like a weird bubblewrap kind of bag.
I do like the size and the length of the bag though!
My Deux Lux Mystery box!
Overall value: $131.00 (with the sale price of the messenger)
Overall enjoyment: Not a bad mystery box at all! I just really wish I loved the messenger bag. XD But at least it’s better than some of the other “big ticket” items that I’ve seen other receive, which I really would not want to use. I’m on the fence about keeping/trading the messenger bag but I’ll give it a few days and see what offers pop up on the swap boards. :p
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Ooo! That cosmetics case is glorious! The black bag… not so much. I’m glad you were brave and did this one, I was so curious about what might be in this Mystery box.
I was too curious to pass this one up! But I’m hoping the black bag will grow on me. XD
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