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Novel immobilized calixarenes and related compounds and process for their productionRelated Patent Categories: Stock Material Or Miscellaneous Articles, Composite (nonstructural Laminate), Of Aldehyde Or Ketone Condensation ProductNovel immobilized calixarenes and related compounds and process for their production description/claimsThe Patent Description & Claims data below is from USPTO Patent Application 20050255332, Novel immobilized calixarenes and related compounds and process for their production. Brief Patent Description - Full Patent Description - Patent Application Claims
BACKGROUND OF THE INVENTION [0001] This invention relates to calixarenes and related compounds immobilized onto the surface of a substrate and to a novel method for the production of such products. The substrate may be silica or another inorganic oxide substrate. [0002] Calixarenes are cyclic oligomers of phenol and substituted phenols with formaldehyde, and are characterized by the general structure 1 [0003] in which n is a value of 3-16, preferably 3 or an even number, most preferably 3, 4, 6 or 8. General information about such molecules can be found, for example in Bauer et al., JACS 107, 6053 (1985) and the texts "Calixarenes" by C. David Gutsche, which is part of the Monographs in Supramolecular Chemistry (J. Fraser Stoddart, ed.; Royal Society of Chemistry, 1989) and "Calixarenes Revisited" by the same author (1998). [0004] Calixarenes are in the form of a cyclical oligomer having a "basket" shape, where the cavity can serve as a binding site for numerous guest species, including ions and molecules. The group R may be hydrogen, or may be any of a number of functional groups including alkyl, alkenyl, alkynyl, allyl, aryl, heteroaryl, alcohol, sulfonic acid, phosphine, phosphonate, phosphonic acid, thiol, ketone, aldehyde, ester, ether, amine, quaternary ammonium, imine, amide, imide, imido, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, acetal, ketal, boronate, cyanohydrin, hydrazone, oxime, oxazole, oxazoline, oxalane, hydrazide, enamine, sulfone, sulfide, sulfenyl and halogen. Substituent R typically represents a single substituent at the position para to the hydroxyl group. However, the class of calixarene compounds as known in the art includes calix[n]resorcinarenes, which comprise resorcinol moieties that are joined to each other, and typically possess phenoxy groups in a different arrangement around the ring. [0005] Other substances exist that have structures analogous to calixarenes, but which, for example include phenolic groups having bridging moieties other than the methylene bridges shown above in the calixarene structure. These include thiacalixarenes, azacalixarenes, silicacalixarenes and oxacalixarenes, in which some or all of the phenols are bridged by sulfur, nitrogen, silicon and oxygen, respectfully, and calixarenes in which some or all phenol groups are linked by C.sub.2 and larger groups, for example by cyclobutyl. Some other types of analogues of calixarenes have been synthesized with a metal atom such as platinum as the spacer bridging phenols [Rauter et al., J. Am. Chem. Soc. 116, 616 (1994)]. Other analogous compounds are discussed below. These types of compounds, and others, as known in the art, are referred to here as "calixarene-related compounds". [0006] There has been much interest in using calixarenes and related compounds as designable hosts for the specific adsorption of small molecule guests. Although protic solvents such as water and alcohols offer an optimum environment for host-guest interactions in this case, calixarenes have generally poor solubility in these solvents, which has required the use of organic solvents in studies of adsorption. However, use of these solvents tends to result in relatively weak binding. Immobilization of calixarenes and related compounds offers a route to circumvent host solubility limitations, but thus far it has required rather laborious syntheses of calixarene derivatives that contain reactive functional groups for polymerization to a surface (e.g. capable of sol-gel hydrolysis and condensation) or other type of surface binding (e.g. via a thiol or sulfide for anchoring on a gold surface). These groups are typically linked to the lower rim of the calixarene or other compound via flexible tethers. [0007] Such flexible tethers usually consisted of ether or thioether groups. For example, Healy et al, Anal. Lett. 31 (9), 1543 (1998) produced calixarenes immobilized onto silica particles through dipropylthio linkers. Schierbaum et al., Science 265, 1413 (1994) used dialkylthio linkers to immobilize calixarenes on gold. Friebe et al., J. Chromat. Sci. 33, 282 (1995) produced calixarenes immobilized on silica gels through an unspecified hydrophilic spacer. These tethers, however, tend to decrease the conformational rigidity of the anchored binding site and limit the maximum attainable site density for the calixarenes. Multicavitand complexes that contain stable linkages between a tetrahedral silicon atom and three calixarene phenolic oxygens on the lower rim are known from work reported by Delaigue, et al. Tetrahedron Lett. 1993, 34, 3285-3288, Tetrahedron Lett. 1993, 34, 7561-7564, and Tetrahedron Lett. 1994, 35, 1711-1714. These, however, are free-standing molecules; they are not immobilized onto a substrate. SUMMARY OF THE INVENTION [0008] This invention relates to the immobilization of calixarenes and calixarene-related compounds to a substrate without the need for derivatization of the calixarene compound with a flexible tether. When the substrate has been modified, e.g. by treatment with a polyhalide or polyalkoxide as described herein, the process is carried out in essentially a single step. This method can achieve the anchoring of monolayers of calixarenes or related compounds onto a silicate glass with the highest site densities on a per-gram-of material basis reported to date. It further provides a new class of materials comprising calixarenes and calixarene-related compounds immobilized on an inorganic oxide surface. These new materials will have widespread uses in fundamental studies as well as in technological applications, including catalysis, adsorption, and sensing. [0009] In brief, in one aspect the invention comprises a process for immobilizing a calixarene or a calixarene-related compound on an inorganic oxide substrate containing one or more metallic or non-metallic elements, said method comprising either: [0010] (a) contacting the calixarene or calixarene-related compound with a substrate that has been surface-modified by reaction with one or more polyhalides and/or polyalkoxides of an element capable of forming a stable aryloxide species with the substrate, or [0011] (b) reacting the substrate with a calixarene or calixarene-related compound that has been previously modified or derivatized by reaction with said one or more polyhalides and/or polyalkoxides. [0012] More particularly, in one aspect, this invention comprises a process for immobilizing a calixarene or a calixarene-related compound on a substrate containing one or more metallic or non-metallic oxides comprising; [0013] (a) reacting a polyhalide or polyalkoxide of one or more elements selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum or iron, or another element that forms a stable aryloxide with the substrate, forming a modified substrate; and [0014] (b) contacting the modified substrate with a calixarene or calixarene-related compound so as to immobilize the calixarene or calixarene-related compound to the substrate through at least one phenolic oxygen linkage. [0015] In another aspect this invention comprises a process for immobilizing a calixarene or a calixarene-related compound on a substrate containing one or more metallic or non-metallic oxides comprising; [0016] (a) reacting the calixarene or calixarene-related compound with a polyhalide or polyalkoxide of one or more elements selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum or iron, or another element that forms a stable aryloxide with the substrate, forming a modified calixarene or calixarene-related compound, respectively; and [0017] (b) contacting the modified calixarene or calixarene-related compound with the substrate so as to immobilize the calixarene or related compound to the substrate through at least one phenolic oxygen linkage. [0018] In another aspect this invention comprises a calixarene or calixarene-related compound immobilized on a substrate, preferably a substrate comprising an inorganic oxide or oxides, via bonding between a polyvalent metallic or non-metallic atom and at least one phenolic oxygen atom of the calixarene or calixarene-related compound. BRIEF DESCRIPTION OF THE DRAWINGS [0019] FIG. 1 represents a schematic illustration of the immobilization of p-tert-butylcalixarene onto silica according to this invention, and the subsequent use of the anchored site for small molecule adsorption. [0020] FIG. 2 represents a .sup.13C CP/MAS NMR spectrum of the immobilized calixarene illustrated in FIG. 1, collected at a spinning rate of 6 kHz and a CP contact time of 1.0 ms. The inset shows the .sup.1H MAS NMR spectrum of the immobilized calixarene collected at a spinning rate of 10.0 kHz. [0021] FIG. 3 depicts Barrett-Joyner-Halenda (BJH) pore size distributions for the immobilized calixarene of FIG. 1 (solid) and for the silica support (dashed) and nitrogen adsorption/desorption isotherms of the immobilized calixarene (b) and of the silica support (c). Continue reading about Novel immobilized calixarenes and related compounds and process for their production... Full patent description for Novel immobilized calixarenes and related compounds and process for their production Brief Patent Description - Full Patent Description - Patent Application Claims Click on the above for other options relating to this Novel immobilized calixarenes and related compounds and process for their production patent application. ###  How KEYWORD MONITOR works... a FREE service from FreshPatents1. Sign up (takes 30 seconds). 2. Fill in the keywords to be monitored. 3. Each week you receive an email with patent applications related to your keywords. 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