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Breakfast both mornings was perfect - Review of Killeen House Hotel - TripAdvisor
“We even had a drying room that we were free to...”
“The room was beautiful, immaculately clean and...”
“When asking around I talked to a few that...”
“After a day of golf, coming back to Killeen House...”
“Breakfast was simply delicious and dinner at the...”
“Wonderful warm and welcoming hospitality from...”
“We ate every dinner and breakfast full Irish...”
“The golf suites are huge with large bathrooms...”
“Having stayed at this hotel early in October 2011...”
Breakfast both mornings was perfect - Review of Killeen House Hotel
See the most recent reviews taliphoc
3 helpful votes “'Excellent Stay'”
I must say Killeen House Hotel is fabulous. We stayed here for two nights in April. From the moment we arrived the staff couldnt do enough for us. We dined in the cosy bar on the first day. One the second night we had an amazing meal in Rozzers restaurant. The food is top notch. We had Rack of Lamb and Fillet Steak for main course which didnt dissapoint. breakfast both mornings was perfect. We climbed C'touhal on the saturday and the day was perfect. Views are unreal but a tricky climb at times. After our climb we came back to hotel and Michael arrange a trip to a spa. What more could we ask for....The following day we a had a competition and after breakfast we were given a packed lunch. We could not fault this hotel and look forward to going back. Thanks Geraldine and Michael and all the staff.
Thank taliphoc Report Ask taliphoc about Killeen House Hotel
Hi and thank you both very much for the super review - we are very grateful to you. Delighted you enjoyed your stay with us and hopefully now that you've discovered us, you'll start spending a bit more time here in the KingdomAnd we'll always do whatever we can to help and assist you, but please don't ask us to climb mountains or play badminton with you!! Thanks again and all the best, Michael & Geraldine
Danish first Dutch first English first French first German first Italian first Russian first Spanish first Swedish first Any olneymd
24 helpful votes “You'll love it”
My golf buddies and I stayed here for 5 nights as part of a golf trip in Ireland. The location was perfect, in that it was close to great golf and Killarney, but rural enough to showcase some of the beauty of this gorgeous country. The rooms were clean and quiet. Breakfasts were fabulous and the chefs did everything they could to prepare what you liked. The staff was great. Dinner in the restaurant was first rate. And topping it off were the owners, Geraldine and Michael. Anyone who is considering running a guesthouse should watch them operate theirs. They love what they do and it shows. They were great and made our trip memorable.
Thank olneymd Report Ask olneymd about Killeen House Hotel
Well thank you very much for such a kind and thoughtful review - we really appreciate it. If anybody ever deserved to have a good time in Ireland, you guys certainly did, given your first foray on O'Mahony's Point on day 1. Only fools (me) and Tourists (you) were stupid enough to be on the course that day...! And by the way you remember I had never heard of Luggage Forward? Well, in the last few days, we've had two different groups advising us they were shipping their clubs to us with them. Coincidence or what? All the best and thanks again for everything. And know that you have our full permission to tell all your golfing friends about the Killeen House! M+G
2 reviews 3 helpful votes “The high point of our trip”
From the moment we drove into Killeen House we were greeted by one of the friendly staff members who helped us with our bags and directed us to our room. The rooms were very spacious, spotlessly clean and were all individually decorated. Geraldine and Michael told us immediately to think of this as "as home away from home" and that is exactly what it felt like. The hotel is around a 10 minute drive into Killarney with beautiful views of the lakes on the way, you can choose to eat in town however Killeen House have a fabulous choice of food regardless of your budget. The bar menu was delicious and the restaurant Rozzers has food to die for, well worth the little bit extra money. Breakfast was plentiful, a great selection of hot and cold dishes, we always were off to a good start. The hotel also has a great little bar where you are free and encouraged to 'pour your own'. The whole atmosphere was so relaxed and comfortable which suited the area and environment you were in. This was by far the best B&B I have found in Ireland and I cannot wait until I return. Just to add... THE WATER PRESSURE WAS OUTSTANDING! Thanks again Michael, Geraldine and the staff at Killeen House, from the Seymour's.
Thank Alana156 Report Ask Alana156 about Killeen House Hotel
G'Day mates...! Thank you so much for the great review - we really and truly appreciate it. It was a sheer pleasure looking after you all - and watching a real bartender at work! Hope the birthday boy doesn't feel toooo old and that he and his boss are handling the rest of the trip OK without you youngsters to mind them. Hopefully we will see you two again here in the Killeen House - we do great honeymoon deals! Keep well and all the best from the Home of GWP (great water pressure). M+G
Roisinalan
Very nice cosy little hotel. It was spotlessly clean. Room perfect. Breakfast was tasty, lots of choice even for me as a veggie! Owners Geraldine and Michael very friendly. Two bar men very helpful. It's a lovely setting. With views of the mountains. 10 to 12 euro for a taxi into town which is a bit expensive. Only down turn was, but would have loved to try it, the food was out of our budget. But hear it's great. We got a great deal on booking.com for b&b. Glad we came!
Thank Roisinalan Report Ask Roisinalan about Killeen House Hotel
Hi and thank you very much for your review, which we really appreciate. We're glad you enjoyed your brief visit with us and that everything you experienced in the Hotel itself was to your satisfaction. Just in case some readers might get a wrong impression from your comments (the prices part!!) about our food offering, I'd like to point out that as well as our Rozzers restaurant here in the Killeen House, we also operate an extensive Pub menu from noon to 9.00pm daily. In the Pub, prices range from €5.00 to €17.50 per menu item. And in Rozzers, as well as A La Carte prices from €6.50 to €28.50, we have three different fixed price, multi-choice Menus, priced at €37.50, €47.50 and €55.00 respectivelyAs for the cost of the taxi into the Town centre, considering it's nearly four miles from us, I don't really think €10 to €12 is overly expensive. (This price is for the car, not per person). And as you point out in your review above, we're blessed to be in a great location, with great views, which we certainly wouldn't have if we are closer to TownThanks again for the review and all the best to all in the West!. Michael & Geraldine
My wife and I have just returned from one of the best breaks we have ever had. This was our first visit to Killarney and we had perfect weather for the drive around the Ring of Kerry, the Dingle Penninsula including Sleagh Head. Killeen House is the perfect base from which to see Kerry in all it's splendour. Killeen House is run by Michael and Geraldine and together with their staff they show off Irish hospitality at it's best. Our room had an ensuite and was furnished to a high standard and was kept spotlessly clean. The food in the restaurant was superb. The menu had most of my favourite dishes including scallops, lobster,rack of lamb and chateaubriand. Michael and Geraldine treat everyone as friends rather the guests and do everything to make your stay memorable. We look forward to making a return trip later this year.
Room Tip: All the rooms are great. Each room individually decorated.
Thank Michael C Report Ask Michael C about Killeen House Hotel
This review is the subjective opinion of a TripAdvisor member and not of TripAdvisor LLC. AtlanticalMan, Owner at Killeen House Hotel, responded to this review,
Glad you discovered us and glad you enjoyed us! It was great to meet you and I hope you were duly impressed with the weather we organised for you as well. As you know now, we take particular pride in the food in our Rozzers restaurant, and we take it as a great compliment the fact that you dined with us on all three nights of your stay. Mind you, you still have one or two more favourite dishes on our menu that you have to sample, so hopefully we'll see you both again before the sun sets on our summer season in October. All the best Michael & Geraldine
14 helpful votes “True and genuine hospitality”
Michael and Geraldine are the embodiment of what hospitality should be. A fantastic stay in more than comfortable rooms. The Guinness from the tap is not too shabby either! I can only recommend anybody to be their guest; you won't be disappointed.
Thank Jan Z Report Ask Jan Z about Killeen House Hotel
37 helpful votes “A great place for golfers”
If you go to Ireland to play golf, this is a great place to stay. Good food, great atmosphere. Usually guests are golfers from around the world. After golf, you can sit in their bar and exchange golfing stories, have a pint and smoke a Cuban cigar. Like a home away from home.
Helpful? Thank Shivas_8 Report Ask Shivas_8 about Killeen House Hotel
TripAdvisor is proud to partner with Orbitz, Booking.com, Hotels.com, Expedia, Travelocity, TripOnline SA, Priceline, Cheap Tickets and Hotwire so you can book your Killeen House Hotel reservations with confidence. We help millions of travelers each month to find the perfect hotel for both vacation and business trips, always with the best discounts and special offers.
Explore similar hotels Lake Hotel2,158 ReviewsShow Prices 4.0 miles The Killarney Park Hotel1,386 ReviewsShow Prices 3.1 miles The Brehon2,193 ReviewsShow Prices 3.5 miles See all Aghadoe hotels Browse nearby


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Patent US4658086 - Photovoltaic cell package assembly for mechanically stacked photovoltaic cells - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA mechanically stacked module package is described. The package permits the effective mechanical stacking of two solar cells in a compact arrangement. The design also permits the easy wiring of the package into a voltage matching configuration for module wiring thus eliminating the problems of current...http://www.google.com/patents/US4658086?utm_source=gb-gplus-sharePatent US4658086 - Photovoltaic cell package assembly for mechanically stacked photovoltaic cellsAdvanced Patent SearchPublication numberUS4658086 APublication typeGrantApplication numberUS 06/740,362Publication dateApr 14, 1987Filing dateJun 3, 1985Priority dateJun 3, 1985Fee statusLapsedPublication number06740362, 740362, US 4658086 A, US 4658086A, US-A-4658086, US4658086 A, US4658086AInventorsPaul S. McLeod, John A. Cape, Lewis M. Fraas, Larry D. PartainOriginal AssigneeChevron Research CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (4), Referenced by (23), Classifications (22), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetPhotovoltaic cell package assembly for mechanically stacked photovoltaic cells
US 4658086 AAbstract
A mechanically stacked module package is described. The package permits the effective mechanical stacking of two solar cells in a compact arrangement. The design also permits the easy wiring of the package into a voltage matching configuration for module wiring thus eliminating the problems of current matching the top and bottom cells. The package design can be used with any mechanically stacked cells although the design is most suitable for concentrator solar cell configurations where the removal of heat to avoid degradation and shortening of lifetime is a major concern.
1. An apparatus comprising mechanically stacked solar cells, comprising:a base support having opposed major surfaces; a first heat spreader-electrical contact contacting said base support on a major surface thereof which is incident to solar radiation; means for electrically contacting said first heat spreader-electrical contact; a first insulating spacer surrounding said heat spreader-electrical contact, said first insulating spacer having a space therein for a photovoltaic cell; a first photovoltaic cell having opposed major surfaces and electrically contacting said heat spreader-electrical contact on its major surface opposed to solar radiation, said first photovoltaic cell having a band gap energy responsive to solar radiation of predetermined wavelengths; means for electrically contacting the other major surface of said first photovoltaic cell which is incident to solar radiation; a second insulating spacer contacting said first insulating spacer and having a space therein for a second photovoltaic cell; a second photovoltaic cell having, opposed major surfaces, said second photovoltaic cell having a band gap energy responsive to solar radiation of shorter wavelengths than said first photovoltaic cell; means for electrically contacting the major surface of said second photovoltaic cell which is opposed to solar radiation; a second heat spreader-electrical contact contacting said second insulator and the major surface of said photovoltaic cell which is incident to solar radiation, said heat spreader-electrical contact having a space therein to provide for the passage of solar radiation to said first and second photovoltaic cells; and means for electrically contacting said second heat spreader-electrical contact. 2. The apparatus according to claim 1 where said means for electrically contacting said first and second photovoltaic cells and said first heat spreader-electrical contact comprise metallizations on said base support and said second insulating spacer.
3. The apparatus according to claim 2 wherein said means for electrically contacting the incident surface of said first photovoltaic cell and said means for electrically contacting the major surface opposed to solar radiation of said second photovoltaic cell each comprise at least two metallic tabs in electrical contact with each other and in respective contact with said metallizations on said base support and said second insulating spacer.
4. The apparatus according to claim 3 wherein said second heat spreader-electrical contact and said first and second insulating spacers have a circular washer shaped configuration.
5. The apparatus according to claim 4 wherein said means for electrically contacting said first and second heat spreader-electrical contacts and said first and second photovoltaic cells have a Y-shaped configuration.
6. The apparatus according to claim 5 wherein said second photovoltaic cell is a GaAs.sub.(x) P.sub.(1-x) solar cell on a GaP substrate and said first photovoltaic cell has a band gap lower than said GaAs.sub.(x) P.sub.(1-x) cell.
7. The apparatus according to claim 6 wherein the composition of the GaAs.sub.(x) P.sub.(1-x) cell is adjusted to provide an output voltage under illumination which is twice the voltage of said first photovoltaic cell.
8. The apparatus according to claim 7 wherein said first photovoltaic cell is a silicon solar cell having a band gap of about 1.1 eV and said GaAs.sub.(x) P.sub.(1-x) solar cell has a band gap of about 1.75 eV
9. The apparatus according to claim 8 further comprising wiring four silicon solar cells in series for every two GaAs.sub.(x) P.sub.(1-x) solar cells wired in series to form a module of predetermined output voltage under illumination.
10. A kit having component parts capable of being assembled in conjunction with first and second photovoltaic cells to form a mechanically stacked photovoltaic device, said kit comprising:a base support; a first heat-spreader-electrical contact adapted to be electrically joined to said base support; first and second insulating spacers adapted to contain photovoltaic cells; a second heat spreader-electrical contact adapted to electrically contact the photovoltaic cell which is incident to solar radiation; and means for electrically contacting said first and second photovoltaic cells. 11. The kit according to claim 10 further including a GaAs.sub.(x) P.sub.(1-x) photovoltaic cell and a silicon photovoltaic cell.
This invention relates to photovoltaic cells. More specifically, this invention relates to mechanically stacked photovoltaic cells.
To increase the overall efficiency of photovoltaic devices and extract the maximum amount of energy from solar radiation, researchers have investigated various multi-color photovoltaic devices. These multicolor photovoltaic devices can be divided into two general categories. The first category covers monolithic multicolor solar cells. A monolithic multi-color solar cell is a solar cell which has distinct regions optimized to absorb different portions of the solar radiation spectrum in a single device. U.S. Pat. Nos. 4,404,421 and 4,451,691, incorporated herein by reference for all purposes, describe suitable monolithic devices. Although these monolithic devices are attractive from a system and manufacturing point of view, they will require considerable materials research to bring them to commercialization.
A second approach involves tandem mechanically stacked two-color solar cells. These devices comprise independent photovoltaic devices which optimized to different portions of the solar spectrum and are mechanically and electrically interconnected. These tandem mechanically stacked two-color solar cells offer a shorter path to commercialization primarily because the low-band gap cells, such as silicon solar cells, are already developed cells. U.S. application Ser. No. 645,456 filed Aug. 28, 1984, incorporated herein by reference for all purposes, describes a suitable high-band gap solar cell. Examples of high-band gap solar cells are GaAsP or AlGaAs or GaAs solar cells, and the like.
These mechanically stacked cells often fall into the category of solar cells known as concentrator solar cells. A concentrator solar cell is a high efficiency solar cell which utilizes some sort of a focusing optics to concentrate solar radiation from a strength of one sun to many suns, i.e., on the order of 50 to 1000 or more suns. The concentration of the solar radiation permits the solar cells to produce a greater amount of electricity per unit area than lower efficiency flat plate solar cells. This makes them especially useful for space applications where weight is of great concern and in jobs which require maximum electrical output with a minimum amount of surface area. However, a drawback to concentrator solar cells is a means for interconnecting the two mechanically stacked solar cells and dissipating the heat generated by the concentration of the solar radiation. Thus, it would be highly desirable to have a mechanically stacked apparatus which can interconnect two solar cells while minimizing the effects of heat generated by the concentrated solar radiation.
In conventional mechanical stack designs, in particular, those using thin top cells, the heat generated in the top cell must be transmitted through the transparent adhesive bonding the two cells together. This can lead to undesirably high cell temperatures. To avoid this difficulty, it would be highly desirable to have a package design wherein heat spreaders incorporated therein are used both for the bottom and top cells. A further advantage would be to incorporate a wafer for the top cell that is thick enough to conduct the heat laterally to the second heat spreader. A still further advantage or object would be to have a design which isolates the cells so that the effects of thermal expansion are reduced or minimized.
In mechanical or monolithic cell designs, the top and bottom cells must generally be current matched or the performance of the device is limited by the cell having the lower current. Since current matching different bandgap solar cells can be extremely difficult, it would be desirable to have a package which permits voltage matching of the two cells. Voltage matching is beneficial because the voltages of the cells change very little with variations in solar spectrum or with the cell degradation with space radiation damage. Thus, it would also be highly desirable to have a package design which can dissipate the heat and permit the easy wiring of numerous mechanically stacked cells into a module wiring configuration for voltage matching instead of current matching.
We have invented a mechanically stacked photovoltaic cell package assembly for mechanically stacking solar cells which incorporates the above enumerated desirable features and other benefits which are readily apparent to the ordinary skilled artisan. The mechanically stacked apparatus includes top and bottom heat spreaders, insulating means to separate the two solar cells and means for forming electrical contacts to the exposed surfaces of each of the photovoltaic devices incorporated into the assembly. The means for forming electrical contact permit the easy interconnection of the completed device in a voltage matching scheme to avoid the requirements of current matching the individual photovoltaic cells.
FIG. 1 illustrates an exploded view of the photovoltaic cell package assembly for mechanically stacked photovoltaic cells of our invention.
FIG. 2 illustrates a cross sectional view of the assembly.
FIG. 3 illustrates a top view of the assembly.
FIG. 4 illustrates a voltage matching module wiring diagram incorporating eight mechanically stacked photovoltaic assemblies.
The invention will be more clearly illustrated by referring to the figures. FIGS. 1, 2, and 3 illustrate an exploded view, a cross sectional view and a top view, respectively, of a mechanically stacked solar cell package 10. The package 10 includes a base support member 12 of a suitable insulating material such as alumina (Al2 O3). The base support member 12 contains regions of metallization 12a and 12b. These regions provide a means for forming electrical contact to the bottom solar cell 30 through the bottom heat sink 14 and the electrode leads 32, 34, and 36. The metallization regions 12a and 12b can have any shape which permits the formation of electrical contact thereto, although the illustrated configuration is preferred for the contacts and heat sinks illustrated. A suitable metallization is gold, silver, nickel plating, and the like. The insulating base member can be soldered to a suitable heat sink, not illustrated, such as a nickel-plated heat sink.
Contacting the base support means 12 through the metallization 12a is an electrically conductive heat spreader 14. A suitable bottom contact heat spreader is fabricated from a suitable thermal expansion matching conductor such as molybdenum. The heat spreader 14 also functions as a part of the means for forming an electrical contact to the major surface of the solar cell which is opposed to solar radiation. Surrounding this bottom contact heat spreader 14 is a spacer means 16. Preferably the spacer 16 is fabricated from an insulating material such as alumina or high temperature plastic and provides a space therein surrounding the bottom contact heat spreader 14 in which to position a low-band gap solar cell illustrated as photovoltaic device 30. The bottom cell 30 is in electrical contact with the heat spreader 14 and an electrode or lead 32 for wiring into a module.
The bottom solar cell 30 is electrically contacted with suitable means for forming an electrical contact to the portion of the solar cell opposite to the incident surface. This combination comprises the heat spreader 14, metallization 12a, and a lead 32. The incident surface of the solar cell is electrically wired into a module through top leads, i.e., contacts 34 and 36. Lead 34 electrically contacts the incident surface of solar cell 30 and the outer lead 36 through the metallization 12b. This preferred configuration permits the solar cell 30 to be isolated from the rest of the package 10 and thus minimizes the thermal expansion strains placed upon the cell 30 during the heating thereof caused by solar radiation. Although less preferred, the contacts 34 and 36 can be configured if desired as a unitary piece. Of course, if leads 34 and 36 were a single piece of metal then the metallization 12b would be unnecessary. The preferred configuration of the top and bottom leads to the bottom cell 30 is illustrated. Of course, depending upon the packaging the leads 32, 34, and 36 need not be opposed but could be fabricated over but separated from each other. A further option, not illustrated, would be to have the metallization illustrated as 12b on support 12 applied instead on the insulating spacer 16. This option would avoid the tab portion of lead 34 from having to bend down from the incident surface of solar cell 30 to the metallization 12b on support member 12.
A second insulating spacer means 18 such as alumina, a high temperature plastic, and the like, separates the bottom cell 30 from the top cell 50. The top cell 50 is electrically contacted on the bottom, i.e., the major surface opposite the incident surface through leads 54 and 56 and the metallization 18a on the spacer 18. These bottom leads can also be configured as a single unitary piece. The incident surface of the solar cell is in electrical contact with an incident heat spreading means 20 for spreading the heat from the top solar cell 50 and the lead 52. A suitable heat spreader means 20 is a molybdenum heat sink in contact with top cell 50. The lead 52 can be any suitable metal. Of course, the incident heat spreader 20 has a hole therein, as illustrated, for the passage of solar radiation.
Although the package assembly 10 has been described and illustrated with spacers and heat spreaders, i.e., heat sinks, having a circular washer shaped configuration, any suitable configuration for the spacers and heat sinks is possible provided they contain a space therethrough for which the solar radiation to enter into the top cell 50 and pass to the bottom cell 30. The contacts have preferably been illustrated having a Y-shaped configuration; however, any suitable configuration for contacting the appropriate tops and bottoms of the cells is possible such as a rectangular a square tab shape. Furthermore, their thicknesses can be adjusted to provide a more compact or robust assembly as required for a particular application.
The selection of the top and bottom cells is a function of that portion of the solar radiation spectrum for which the package assembly is to be optimized. A preferred top solar cell would be a gallium arsenide phosphide (GaAs.sub.(x) P.sub.(1-x)) solar cell having a band gap of about 1.75 eV fabricated on a gallium phosphide (GaP) substrate with a larger band gap, i.e., about 2.25 eV so that it appears transparent to solar radiation which would pass therethrough and into the bottom cell 30. A suitable preferred bottom cell would be an IR enhanced silicon solar cell having a band gap of about 1.1 eV.
A benefit of the package design 10 permits module wiring configurations illustrated in FIG. 4. The package design 10 avoids the requirement for current matching of the top and bottom cells and replaces it with a voltage matching configuration. This wiring scheme benefits from the advantage that the voltage changes very little with variations in the solar spectrum or device degradation. It requires four independent leads from the cell package which is consistent with the package design described above.
More specifically, if the stacked cells were designed for series connection with currents matched at the beginning of life, the currents would be mismatched at the end of life, with performance loss greater than the efficiency loss of the individual cells. Voltage matching provides a longer life design since the device voltages only vary logarithmically with current changes. FIG. 4 illustrates a four by two module wiring diagram for voltage matching of top and bottom cells whose output voltages differ by a factor of 2. In the arrangement of FIG. 4, four silicon solar cells are wired in series for every Ga Asx P1-x solar cells wired in series. A voltage factor difference of 2 can be achieved with a gallium arsenide phosphide top solar cell 50 selected to have a band gap of about 1.75 eV and a bottom solar cell 30 of silicon selected to have a band gap of about 1.1 eV. For the eight element configuration illustrated, four of the bottom and two of the top cells are connected in series to provide voltage matching. Different voltage ratios for different solar cells would require other series and parallel connection schemes for voltage matching, e.g., four by three, seven by five, five by three, etc. The only limitations on the interconnection schemes are the voltages of the different cells. Of course, different modules having specific output currents and voltages can be connected in series or parallel to provide any desired overall voltage or current output for a particular application.
The solar cell package design has been described with reference to particularly preferred configurations and embodiments. Modifications which would be obvious to the ordinary skilled artisan, such as selection of particular top and bottom solar cells and configuration of the spreaders and insulators are contemplated to be within the scope of the invention.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS4094704 *May 11, 1977Jun 13, 1978Milnes Arthur GDual electrically insulated solar cellsUS4338480 *Dec 29, 1980Jul 6, 1982Varian Associates, Inc.Stacked multijunction photovoltaic convertersUS4461922 *Feb 14, 1983Jul 24, 1984Atlantic Richfield CompanySolar cell moduleUS4547622 *Apr 27, 1984Oct 15, 1985Massachusetts Institute Of TechnologySolar cells and photodetectors* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4746371 *Dec 18, 1986May 24, 1988Chevron Research CompanyMechanically stacked photovoltaic cells, package assembly, and modulesUS4776893 *Oct 21, 1986Oct 11, 1988Chevron Research CompanyGaAs on GaSb mechanically stacked photovoltaic cells, package assembly, and modulesUS4830678 *Jun 1, 1987May 16, 1989Todorof William JLiquid-cooled sealed enclosure for concentrator solar cell and secondary lensUS4830979 *Aug 1, 1988May 16, 1989Sundstrand Corp.Method of manufacturing hermetically sealed compression bonded circuit assembliesUS4954876 *Aug 1, 1988Sep 4, 1990Sundstrand CorporationHermetically sealed compression bonded circuit assembly having flexible walls at points of application of pressure for compression bonding circuit elementsUS4985752 *Aug 1, 1988Jan 15, 1991Sundstrand CorporationHermetically sealed compression bonded circuit assembly having a suspension for compression bonded semiconductor elementsUS5034803 *Aug 1, 1988Jul 23, 1991Sundstrand CorporationCompression bonded semiconductor device having a plurality of stacked hermetically sealed circuit assembliesUS5248346 *Feb 24, 1992Sep 28, 1993The Boeing CompanyPhotovoltaic cell and array with inherent bypass diodeUS5389158 *Jul 26, 1993Feb 14, 1995The Boeing CompanyLow bandgap photovoltaic cell with inherent bypass diodeUS5959787 *Nov 26, 1996Sep 28, 1999The Boeing CompanyConcentrating coverglass for photovoltaic cellsUS6091020 *Oct 16, 1997Jul 18, 2000The Boeing CompanyPhotovoltaic cells having a concentrating coverglass with broadened tracking angleUS7148417Mar 31, 2003Dec 12, 2006The United States Of America As Represented By The Administrator Of The National Aeronautics And Space AdministrationGaP/silicon tandem solar cell with extended temperature rangeUS7557290May 16, 2003Jul 7, 2009Schripsema Jason EPhotovoltaic module with adjustable heat sink and method of fabricationUS7994417 *Feb 23, 2007Aug 9, 2011Jx Crystals Inc.Optimal cell selection for series connection in Cassegrain PV moduleUS8138410 *Oct 1, 2008Mar 20, 2012International Business Machines CorporationOptical tandem photovoltaic cell panelsUS8232134Sep 11, 2009Jul 31, 2012Stion CorporationRapid thermal method and device for thin film tandem cellUS8563850Mar 12, 2010Oct 22, 2013Stion CorporationTandem photovoltaic cell and method using three glass substrate configurationUS8569613Sep 28, 2009Oct 29, 2013Stion CorporationMulti-terminal photovoltaic module including independent cells and related systemUS8889468 *Feb 18, 2011Nov 18, 2014Stion CorporationMethod and structure for thin film tandem photovoltaic cellUS8907206Jul 24, 2011Dec 9, 2014Stion CorporationMulti-junction solar cell devicesUS20110143487 *Feb 18, 2011Jun 16, 2011Stion CorporationMethod and Structure for Thin Film Tandem Photovoltaic CellWO1990004142A1 *Oct 13, 1989Apr 19, 1990Solar Energy Applic IncSolar electric conversion unit and systemWO2003058725A1 *Jan 2, 2003Jul 17, 2003Reveo IncPhotovoltaic cell and method of manufacture of photovoltaic cells* Cited by examinerClassifications U.S. Classification136/249, 257/433, 257/E25.007, 257/E31.118, 136/244International ClassificationH01L25/04, H01L31/052, H01L31/0203, H01L31/02, H01L31/048Cooperative ClassificationH01L31/043, H01L2924/0002, H01L31/02008, Y02E10/52, H01L31/048, H01L31/0203, H01L31/052European ClassificationH01L31/0203, H01L25/04C4C, H01L31/02E2B, H01L31/052, H01L31/048Legal EventsDateCodeEventDescriptionJun 27, 1995FPExpired due to failure to pay maintenance feeEffective date: 19950419Apr 16, 1995LAPSLapse for failure to pay maintenance feesNov 22, 1994REMIMaintenance fee reminder mailedSep 10, 1990FPAYFee paymentYear of fee payment: 4Jun 3, 1985ASAssignmentOwner name: CHEVRON RESEARCH COMPANY SAN FRANCISCO CA A CORP OFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MC LEOD, PAUL S.;CAPE, JOHN A.;FRAAS, LEWIS M.;AND OTHERS;REEL/FRAME:004423/0630Effective date: 19850603RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services

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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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"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. Commun. pp. 8-9 (1990).40 *Pessi 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. Commun. pp. 8 9 (1990).41Rajac, "A Polyarylmethyl Carbotetraanion", J.Am.Chem. Soc. 5889-5890 (1990).42 *Rajac, A Polyarylmethyl Carbotetraanion , J.Am.Chem. Soc. 5889 5890 (1990).43Rajca, "Synthesis of 1,3-Connected Polyarylmethanes", J.Org. Chem. 56:2557-2563 (1991).44 *Rajca, Synthesis of 1,3 Connected Polyarylmethanes , J.Org. Chem. 56:2557 2563 (1991).45Rengan and Engel, "Phosphonium Cascasde Molecules", J.Chem. Soc. Chem. Commun. pp. 1084-1085 (1990).46 *Rengan and Engel, Phosphonium Cascasde Molecules , J.Chem. Soc. Chem. Commun. pp. 1084 1085 (1990).47Ringsdorf et al., "Molecular Architecture/Function of Polymeric Oriented Systems: Models for Study of Org., Surface Recognition and Dynamics of Biomembranes", Angew Chem. Ed. Engl. 27:113-158 (1988).48 *Ringsdorf et al., Molecular Architecture/Function of Polymeric Oriented Systems: Models for Study of Org., Surface Recognition and Dynamics of Biomembranes , Angew Chem. Ed. Engl. 27:113 158 (1988).49 *Saunders et al. Planta 1981, 152, 272 281.50Saunders et al. Planta 1981, 152, 272-281.51Shahlai et al., "Supertriptycene . . . " J.Am.Chem.Soc., 112:3678-3688 (1990).52 *Shahlai et al., Supertriptycene . . . J.Am.Chem.Soc., 112:3678 3688 (1990).53 *Shinaki, S. et al., J. Am. Chem. Soc. 1986, 108, 2409; Brooker et al., J. Am. Chem. Soc. 1941, 63, 3214.54Singh et al. "Extensions of Bicycloalkyne . . . " J.Org.Chem. 55:3412.55 *Singh et al. Extensions of Bicycloalkyne . . . J.Org.Chem. 55:3412.56Tanford, C. "Micelles" The Hydrophobic Effect: Formation of Micelles and Biological Membranes, 2nd Ed., Wiley-Interscience New York, pp. 42-59 (1980).57 *Tanford, C. Micelles The Hydrophobic Effect: Formation of Micelles and Biological Membranes, 2nd Ed., Wiley Interscience New York, pp. 42 59 (1980).58Tomalia et al., "Dendritic Macromolecules: Synthesis of Starburst Dendrimers" Macromolecules, 19:2466-2468 (1986).59Tomalia et al., "Starburst Dendrimers. 3.The Importance of Branch Junction Symmetry in the Dev. of Topological Shell Molecules" J.Am.Chem.Soc., 109:1601-1603 (1987).60 *Tomalia et al., Dendritic Macromolecules: Synthesis of Starburst Dendrimers Macromolecules, 19:2466 2468 (1986).61 *Tomalia et al., Starburst Dendrimers. 3.The Importance of Branch Junction Symmetry in the Dev. of Topological Shell Molecules J.Am.Chem.Soc., 109:1601 1603 (1987).62Tomalia, "Conformational Calculations on Plly-di-n-hexylsilane" Macromolecules, 20:1167-1169 (1987).63 *Tomalia, Conformational Calculations on Plly di n hexylsilane Macromolecules, 20:1167 1169 (1987).64Uchida, "General Strategy for Systematic Synthesis of Oligosiloxanes. 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


text:
PM's claims supermarkets overcharge for food to fund cut-price booze dubbed 'nonsense' by retail group | Mail Online
Prime Minister said 'good evidence' supermarkets are subsidising low alcohol price with higher food pricesBritish Retail Consortium dismissed the claims By
05:08 EST, 15 December 2012
07:07 EST, 15 December 2012
Claims by David Cameron that supermarkets are funding cheap alcohol by overcharging shoppers for food have been branded 'nonsense'. The Prime Minister said yesterday there was 'good evidence' that supermarkets were subsidising low prices on wine, beer and cider by increasing the cost of everyday food. The British Retail Consortium have rejected the claims and demanded to know on what evidence it was based. Mr Cameron was quoted in the Daily Telegraph as saying: 'There is some evidence, pretty good evidence, that what some supermarkets are doing is actually pushing up the price of food to heavily pay for the very discounted, very cheap alcohol.'He was speaking to a group of factory workers in north Wales yesterday about the Government's proposals to introduce a minimum price of alcohol of 45p a unit to tackle Britain's binge drinking problem. The Prime Minister said the proposals would prevent strong lager being sold for as little as 25p a can. However, supermarkets have denied they are overcharging for food to fund cheap alcohol. More...
Andrew Opie, from the British Retail Consortium, told the Daily Telegraph: 'This is nonsense. What evidence? The Government's own figures show alcohol prices rising at exactly the same rates as food prices.'Downing Street told the newspaper Mr Cameron's comments were based on research by Newcastle University liver specialist Dr Chris Record in 2009.
The 45p-a-unit rule would slap an extra 70p on the price of some bottles of wine and an additional £1.30 on a two-litre bottle of cider.Last month, the European Commission warned Mr Cameron that his plan of putting a minimum price on alcohol is illegal. A nine-page letter from Brussels to the Prime Minister said the scheme would break laws governing the free movement of goods.The average family drinks bill could soar by almost £100 a year under the Government's plan. Bottles of wine could not be sold for less than about £4.05 each, beer will be at least 90p a can and a bottle of vodka will cost at least £11.70. Share or comment on this article

value: This website is the website of the Daily Mail, a newspaper in the United Kingdom, and of its sister paper The Mail on Sunday. MailOnline is a division of dmg media, which is owned by Daily Mail and General Trust plc.


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Carpinteria Eyelash Extensions - Deals in Carpinteria, CA | Groupon
Welcome to Groupon! Discover the local deals that make Santa Barbara unique!
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MIUMIU purse (with Coin Pocket) Embossing Leather | eBay
May 14, 2019, 12:43:21 PM PDT
kyounokura-japan (5240 )
Details about MIUMIU purse (with Coin Pocket) Embossing Leather
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Andrea Garolla - Semantic Scholar
Carlo Foresta244
Alberto Ferlin184
Eberhard Nieschlag48
Riccardo Selice43
Niels E Skakkebaek42
238Carlo Foresta
184Alberto Ferlin
56Riccardo Selice
49Andrea Lenzi
46Frank Tüttelmann
A novel circulating hormone of testis origin in humans.
C Foresta, Andrea Bettella, +4 authors Alberto Ferlin
Insulin-like factor 3 (INSL3) is a member of the relaxin-insulin family, and it is expressed in pre- and postnatal Leydig cells of the testis. This peptide affects testicular descent during embryonic… (More)
Androgens stimulate endothelial progenitor cells through an androgen receptor-mediated pathway.
C Foresta, Daniela Zuccarello, Luca De Toni, Andrea Garolla, Nicola Caretta, Alberto Ferlin
BACKGROUND AND OBJECTIVE Testosterone (T) treatment has recently been shown to induce an increase in the number of endothelial progenitor cells (EPCs) through a possible effect on bone marrow.… (More)
Daniela Zuccarello, Alberto Ferlin, +6 authors C Foresta
Genetic abnormalities among severely oligospermic men who are candidates for intracytoplasmic sperm injection.
C Foresta, Andrea Garolla, Lucia Bartoloni, Andrea Bettella, Alberto Ferlin
Recent reports suggest that children born after intracytoplasmic sperm injection performed for male factor infertility are at increased risk of congenital malformations and chromosome aberrations. To… (More)

value: This website is an artificial-intelligence backed search engine for academic publications developed at the Allen Institute for AI and publicly released in November 2015. It uses advances in natural language processing to provide summaries for scholarly papers.