WO1998009913A1 - Liaison covalente reversible de fullerenes a des supports insolubles - Google Patents

Liaison covalente reversible de fullerenes a des supports insolubles Download PDF

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Publication number
WO1998009913A1
WO1998009913A1 PCT/US1996/014555 US9614555W WO9809913A1 WO 1998009913 A1 WO1998009913 A1 WO 1998009913A1 US 9614555 W US9614555 W US 9614555W WO 9809913 A1 WO9809913 A1 WO 9809913A1
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Prior art keywords
support
moiety
fullerene
insoluble support
composition
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PCT/US1996/014555
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English (en)
Inventor
Vincent Rotello
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University Of Massachusetts
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Priority to PCT/US1996/014555 priority Critical patent/WO1998009913A1/fr
Priority to AU70180/96A priority patent/AU7018096A/en
Publication of WO1998009913A1 publication Critical patent/WO1998009913A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3253—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3255—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment

Definitions

  • Fullerenes and their derivatives posses a number of potentially useful magnetic, electronic, biological, and chemical properties. Recent advances in fullerene production have made crude fullerenes available in large quantities. However, one major limit to the use of fullerenes is the high cost of purification of the different fullerenes from each other and from byproducts, such as soot, that are formed during the fullerene synthesis. Current methodologies for the purification of fullerenes rely upon chro atographic techniques to separate the individual fullerenes and the undesired byproducts. For example, fullerenes have been purified by chromatography on columns, eluting with conventional solvents (see, e.g., Mittelbach, A.
  • Fullerenes have been purified by a cycle of hydrogenation and dehydrogenation to separate non-fullerene impurities (see, e.g., Shigematsu, K.; Abe, K. (1991) Japanese Patent Application Serial No. 91246509). This method requires several steps and the use of hydrogenation catalysts, which are often expensive. Polymeric supports for covalent modification of fullerenes have also been reported
  • the present invention relates to methods for reversibly attaching fullerenes to solid supports.
  • the invention provides solid supports suitable for covalent attachment of fullerenes, methods for preparing solid supports suitable for covalent attachment of fullerenes, and methods for purifying fullerenes using the solid supports of the invention.
  • the invention provides a composition comprising a conjugated diene moiety covalently bonded to an insoluble support selected from the group consisting of silica, alumina, titania, and zirconia.
  • the invention provides a method for preparing a composition comprising a diene moiety covalently bonded to an insoluble support selected from the group consisting of silica, alumina, titania, and zirconia. The method comprises the step of reacting the insoluble support with a diene moiety under conditions such that the diene moiety becomes covalently bonded to the solid support, to form the composition comprising a diene moiety covalently bonded to an insoluble support.
  • the invention provides a method of preparing a composition comprising a diene moiety covalently bonded to a sol-gel silica support.
  • the method includes the steps of providing a compound comprising a diene moiety and an orthosilicate; and hydrolyzing the orthosilicate such that a sol-gel silica support is formed to obtain the composition comprising a diene moiety covalently bonded to a silica support.
  • the invention provides a composition comprising a covalent adduct of a fullerene and an insoluble support, wherein the insoluble support is selected from the group consisting of silica, alumina, titania, and zirconia.
  • Figure 1 is a reaction scheme which depicts the synthesis of an exemplary insoluble support for reversible covalent attachment of fullerenes.
  • Figure 2 shows HPLC chromatograms of fullerene extracts before and after reversible covalent attachment to an insoluble support according to the invention.
  • Figure 3 is a reaction scheme showing the synthesis of a silica sol-gel support with a covalently bonded diene suitable for reversible covalent attachment of fullerenes.
  • the present invention provides methods for reversible covalent attachment of fullerenes to insoluble supports.
  • the reversible covalent attachment methods of the invention are useful, e.g., as a means of fullerene purification.
  • fullerene is art-recognized, and as used herein refers to all-carbon species such as C Q. 70, -j , C ⁇ g, Cg_ ⁇ , carbon nanotubes, and the like, as well as derivatives thereof.
  • derivatives can include covalent adducts (for a review, see Diederich, F and Thilgen, C. (1996) Science 271 :317) as well as non-covalent compounds such as inclusion compounds (see, e.g., Hirsch, A. "The Chemistry of the Fullerenes” (Thie e. Stuttgart. 1994)).
  • the invention provides insoluble supports capable of undergoing reaction with fullerenes to provide a covalent adduct between the insoluble support and the fullerene.
  • Such supports include solid functionalized inorganic supports such as silica (e.g., silica gel, controlled-pore glass, and the like), alumina, zirconia, titania, and the like.
  • silica e.g., silica gel, controlled-pore glass, and the like
  • Other inorganic supports useful as supports, e.g., for chromatography are contemplated for use in the invention.
  • Other preferred insoluble supports include functionalized sol-gels, such as silicate sol-gels, e.g., as described infra.
  • the insoluble support will generally be functionalized with a functional group capable of undergoing a covalent bond-forming reaction with fullerenes.
  • Fullerenes are known to undergo a variety of covalent bond-forming reactions (see Diederich, F and Thilgen, C, supra).
  • a preferred class of covalent bond-forming reactions is cycloadditions. Cycloadditions include the Diels-Alder reaction, ene reaction, 1,3-dipolar additions, [2+2] cycloadditions, and the like (see, e.g., March, J. (1985) "Advanced Organic Chemistry," 3rd Ed., John Wiley & Sons).
  • an olefm covalently bonded to a solid support can react (e.g., thermal or by photochemical initiation, optionally in the presence of a photosensitizer) with a fullerene in a [2+2] cycloaddition to yield a covalent adduct.
  • Cycloreversion of the adduct regenerates the original fullerene.
  • a preferred cycloaddition is the Diels-Alder reaction.
  • Fullerenes can react as dienophiles with reactive dienes to form covalent adducts. Accordingly, any diene capable of reaction with a fullerene in a Diels-Alder reaction is contemplated for use in the invention. Such dienes are generally conjugated dienes. Any diene capable of acting as a diene in a Diels-Alder reaction may be useful in the present invention.
  • Exemplary diene moieties include 1 ,3-butadienyl, furanyl, cyclopentadienyl and anthracenyl, and derivatives thereof, and the like.
  • the invention provides a composition comprising a conjugated diene moiety covalently bonded to an insoluble support selected from the group consisting of silica, alumina, titania, and zirconia.
  • the insoluble support is a solid silica support or a silica sol-gel support.
  • the conjugated diene moiety is covalently bonded to a linker moiety, as described below.
  • the linker moiety comprises a C2 to C12 alkylene moiety or a phenylene moiety.
  • the linker moiety is covalently bonded to the insoluble support through an orthosilicate moiety.
  • the conjugated diene moiety is selected from the group consisting of cyclopentadienyl, furanyl, and anthracenyl, and derivatives thereof.
  • the diene moiety can be selected so that covalent attachment of a fullerene, and subsequent cleavage of the fullerene, occur under appropriate conditions.
  • a highly reactive diene will generally react with a fullerene to form a covalent adduct at a lower temperature than will a less reactive diene.
  • an adduct of a reactive diene and a fullerene will more readily undergo cleavage, e.g., will be cleaved at a lower temperature.
  • One of ordinary skill in the art will be able to select appropriate dienes with no more than routine experimentation.
  • the diene moiety can be provided with a linker moiety for covalently bonding the diene moiety to the support.
  • the support can be modified with a linker moiety for attachment to the diene.
  • the linker moiety serves to functionalize the support or the diene moiety for covalent linkage, and provides a spacer unit.
  • the propylene linker of modified silica gel 2 joins the cyclopentadienyl functionality (through a carbon-carbon bond) to the silica support (through an orthosilicate functionality).
  • linking moieties can be chosen to be selectively cleavable (e.g., a linking moiety containing an ester functionality can be cleaved by hydrolysis).
  • linkers include C2 to C12 alkylene moieties, or phenylene, e.g., p-phenylene, moieties.
  • the invention provides a method for preparing a composition comprising a diene moiety covalently bonded to an insoluble support selected from the group consisting of silica, alumina, titania, and zirconia.
  • the method comprises reacting the insoluble support with a diene-containing moiety under conditions such that the diene moiety becomes covalently bonded to the solid support, to form the composition comprising a diene moiety covalently bonded to an insoluble support.
  • the support can be functionalized with a moiety which does not contain a diene group, but which can be converted to a diene group by suitable manipulations.
  • the insoluble support is a silica support.
  • the method comprises, prior to the reacting step, the step of reacting the insoluble support with a linker moiety under conditions such that the linker moiety becomes covalently bonded to the insoluble support.
  • a covalently-bonded composition comprising a support and a diene moiety, joined by a linking moiety, can be prepared by reacting a support with a linking reagent such that the linking reagent is covalently bonded to the support, followed by reaction with a diene- containing reagent to provide a diene moiety covalently bonded to the linking moiety.
  • the linking moiety when bound to the support, can include an electrophilic moiety (e.g., an alkyl halide, alkyl tosylate, enone, epoxide, ketone, acid chloride, or the like) for reaction with a nucleophile (e.g., a carbanion, amine, thiol, hydroxyl, or the like) to form a covalent bond.
  • an electrophilic moiety e.g., an alkyl halide, alkyl tosylate, enone, epoxide, ketone, acid chloride, or the like
  • a nucleophile e.g., a carbanion, amine, thiol, hydroxyl, or the like
  • the linking moiety can be covalently joined to the diene moiety, and the linking moiety then covalently bonded to the support.
  • the invention provides a method for preparing a composition comprising a diene moiety covalently bonded to a sol-gel silica support.
  • the the method comprises the steps of providing a compound comprising a diene moiety and an orthosilicate; and hydrolyzing the orthosilicate such that a sol-gel silica support is formed, to form the composition comprising a diene moiety covalently bonded to a silica support.
  • the hydrolyzing step comprises treating the orthosilicate with acid. This process is described in more detail in Example 3, infra.
  • the sol-gel supports formed according to the methods of the invention can be provided as surfaces, or as discrete particles and can be cast or formed, as is known in the art.
  • the sol-gel supports of the invention can provided greater porosity than other supports, and therefore can have greater accessibility to fullerene species and higher capacity for covalent attachment of fullerenes. It has been found that dienes covalently bonded to insoluble supports such as silica have advantages compared to similar dienes covalently bonded to polymeric (e.g., resin) supports.
  • the silica supports of the invention provide improved stability compared to polymeric supports (see, e.g., Nie, B. and Rotello, V. (1996) J. Org. Chem. 6_1_:1870).
  • the silica-based supports can be re-used repeatedly (i.e., repeated cycles of fullerene attachment and regeneration are possible without sugnificant loss of support capacity or activity toward fullerenes).
  • polymeric supports can degrade with repeated use, and degradation products can contaminate the fullerenes, making purification difficult.
  • the silica- based support 2 releases the fullerene at lower temperature than the resin-based polymeric supports. Without being bound by any theory, it is believed that the difference in release temperature is due, at least in part, to interactions between the polymeric resin and the immobilized diene and/or fullerene. Such interactions are decreased or absent in the silica- based support.
  • the diene-containing supports of the invention can be used to separate fullerenes from mixtures.
  • fullerenes can be separated from byproducts of fullerene synthesis, such as soot, as described in Example 2, infra.
  • different fullerene species can be separated from other fullerenes.
  • C 0 and C70 can be separated from each other with the compositions of the invention, as described below.
  • the invention provides a method for separating, e.g., purifying, fullerenes from a mixture, e.g., from a reaction mixture, e.g., a mixture formed by the synthesis of fullerenes or fullerene derivatives.
  • a mixture can include, for example, any fullerene and either a non-fullerene material or a different fullerene.
  • the methods of the invention can be used to selectively purify mixtures of two or more fullerenes to obtain a purified fullerene or a mixture enriched in a particular fullerene.
  • the method includes contacting the mixture with a diene moiety covalently bonded to an insoluble support, under conditions such that the fullerene becomes covalently bound to the insoluble support.
  • the insoluble support is then separated from at least a portion of the mixture.
  • the fullerene is cleaved from the solid support so that the fullerene is separated from the mixture.
  • the insoluble support is selected from the group consisting of silica, alumina, titania, and zirconia.
  • Silica sol-gel supports arc also preferred insoluble supports.
  • conditions for attaching fullerenes to the support can be very mild.
  • C ⁇ o rapidly undergoes a Diels-Alder reaction with the support 2 ( Figure 1) at room temperature in toluene.
  • the conditions will be selected so that covalent bonding of the fullerene to the support occurs readily, preferably under conditions where the fullerene is not cleaved from the support at a significant rate.
  • the conditions can include the use of a solvent, to suspend the support and suspend or dissolve the fullerene.
  • Inert solvents are preferred, and inert aromatic solvents such as benzene, toluene, and the like are particularly preferred.
  • the covalent bond- forming reaction can be conducted under an inert atmosphere such as nitrogen or argon gas.
  • the conditions for attaching fullerenes to the support include reaction temperature less than about 100°C, more preferably less than 50°C, and more preferably less than 30°C. Conditions suitable for covalent attachment of fullerenes to the support will be selected according to the fullerene and the support, and selection of such conditions will be routine to one of ordinary skill in the art.
  • the insoluble support can be separated from at least a portion of the mixture by methods known in the art.
  • the insoluble support, bearing the covalently- attached fullerene can be filtered, e.g., with filter paper, a membrane, a frit, or the like, to remove solvent and soluble components of the mixture.
  • the separated support can be washed or otherwise freed of excess solvent or impurities, and can then be suspended in fresh solvent for cleavage of the fullerenes from the support.
  • the support can be treated to cleave the fullerenes without use of solvent.
  • the isolated fullerene-bcaring support can be heated to cleave the covalently-bonded fullerenes (e.g.. through a retro-Diels-Alder reaction), and the fullerenes can be isolated by sublimation without solvent.
  • the fullerenes are preferably cleaved from the support under conditions suitable to effect fullerene cleavage without degrading the fullerenes. It will be appreciated that conditions suitable for cleavage of fullerenes to the support will be selected according to the fullerene and the support, and selection of such conditions will be routine to one of ordinary skill in the art. For example, a covalent adduct of a fullerene with a solid support can be cleaved by heating of the support containing the adduct. For example, fullerene- containing support 3a undergoes retro-Diels-Alder reaction at about 100°C.
  • the fullerene (or fullerenes) is cleaved by heating to a temperature of less than about 200°C, more preferably less than about 150°C, and still more preferably less than about 100°C.
  • a preferred range of temperatures is from about 20°C to about 150°C.
  • the cleavage reaction can be performed with or without a solvent, optionally under an inert atmosphere. It will be appreciated that different fullerenes can be differentially cleaved from a support. This differential release permits the selective cleavage of one fullerene from the support in the presence of another fullerene, thus providing selective separation of the fullerenes, as shown in Example 1, infra.
  • heating of an adduct of a mixture of fullerenes with a solid support can result in release of one fullerene at a lower temperature, followed by release of another fullerene at a higher temperature.
  • the separation process can be carried out in a single vessel, e.g., a column, e.g., a chromatographic column.
  • the fullerenes can be cleaved from the solid support by heating the column or the eluting solvent; or, the process can be performed at a temperature such that the formation and cleavage of the fullerene:diene compound both occur in an equilibrium process.
  • the covalent adduct of the fullerene and the support need not be isolated; formation, separation, and cleavage of the adduct occur simultaneously.
  • the contacting step comprises loading the mixture onto a column, and the separating step comprises eluting the portion of the mixture from the column.
  • the invention provides a composition comprising a covalent adduct of a fullerene and an insoluble support, wherein the insoluble support is selected from the group consisting of silica, alumina, titania, and zirconia.
  • the insoluble support is a silica sol-gel.
  • the fullerene will generally be covalently bound through an adduct of the fullerene and a diene moiety covalent bonded to the solid support.
  • Example 1 The invention is further illustrated by the following non-limiting examples.
  • Example 1 The invention is further illustrated by the following non-limiting examples.
  • fullerenes to functionalized silica gel 2 is readily reversible and selective for Cg ⁇ : heating of the mixed fullerene-functionalized material in toluene to 100°C for 5 h releases 93.7% of the bound C 60 and 41.1% of the bound C 70 ( Figure 1 ).
  • the release process was fully reproducible, and the fullerenes were completely rcabsorbed (i.e., covalently attached to the functionalized silica gel) upon cooling of the solution.
  • the difference in release provides fullerenes significantly enriched in Cg : the initial Cg ⁇ /C ⁇ ratio was 90: 10, the final ratio was 96:4. This selectivity is comparable to that observed from a single iteration of the calixarenc-based C ⁇ purification strategy.
  • Example 3 A functionalized silicate sol-gel support is made according to the following procedure, depicted in Figure 3.
  • (3-chloropropyl)trimethoxysilane 4 (aldrich Chemical Co., Milwaukee, WI) is reacted with lithium cyclopentadienylide 5 to yield the (3- cyclopentadienylpropyl)trimethoxysilane 6.
  • This orthosilicate is hydrolyzed, e.g., in the presence of aqueous acid to intermediate 7, followed by polycondensation to form a sol-gel 8, which can be aged to complete the polymerization, and dried to remove excess solvent.
  • sol-gel technology see Hench, L.; West, J. (1990) Chem. Rev. 90:33.
  • Cyclopentadiene-functionalized silica gel 2 (100 mg) was added to an extract of fullerene-containing soot (MER, Tuscon, AZ) in toluene (initial concentrations Cg ⁇ , 1.283 mM, C7 , 0.136 mM). The mixture was gently shaken at room temperature for 3.5 h, then filtered, and washed with toluene (20mL) to provide 102 mg of the mixed functionalized silica gel.
  • MER fullerene-containing soot
  • Fullerene uptake was determined via HPLC, using a reversed-phase C18 column (Rainin Instruments, Woburn, MA). The fullerenes were eluted using a 70:30 methylene chloride/acentonitrile solvent system and were detected at 265 nm, using pyrene as an internal standard.

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Abstract

L'invention a trait à des techniques visant à séparer des fullerènes d'un mélange par le biais d'une liaison covalente à un support insoluble. Elle concerne également des compositions utilisées dans le cadre de ces techniques ainsi que des procédés de préparation de ces compositions.
PCT/US1996/014555 1996-09-06 1996-09-06 Liaison covalente reversible de fullerenes a des supports insolubles WO1998009913A1 (fr)

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PCT/US1996/014555 WO1998009913A1 (fr) 1996-09-06 1996-09-06 Liaison covalente reversible de fullerenes a des supports insolubles
AU70180/96A AU7018096A (en) 1996-09-06 1996-09-06 Reversible covalent attachment of fullerenes to insoluble supports

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Cited By (9)

* Cited by examiner, † Cited by third party
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WO2003037937A1 (fr) * 2001-10-18 2003-05-08 The Dow Chemical Company Supports de catalyseurs fonctionnalises par un diene et compositions catalysantes supportees
WO2004043857A2 (fr) * 2002-11-13 2004-05-27 Kim Bolton Manipulation de nanotubes de carbone derivatises
WO2007075257A1 (fr) 2005-12-20 2007-07-05 3M Innovative Properties Company Compositions dentaires comprenant un composant labile thermiquement et leur utilisation
EP1841523A2 (fr) * 2005-01-03 2007-10-10 Luna Innovations, Inc. Procede de separation chimique pour fullerenes
EP2043952A2 (fr) * 2006-07-06 2009-04-08 Solenne B.V. i.o. Mélanges de dérivés de fullerène et leurs utilisations dans des dispositifs électroniques
US7776940B2 (en) 2005-12-20 2010-08-17 3M Innovative Properties Company Methods for reducing bond strengths, dental compositions, and the use thereof
US7896650B2 (en) 2005-12-20 2011-03-01 3M Innovative Properties Company Dental compositions including radiation-to-heat converters, and the use thereof
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EP0952110A1 (fr) * 1998-04-21 1999-10-27 Ulf Dr. Menyes Procédé de séparation de fullérènes par chromatographie
US6943133B2 (en) 2000-10-20 2005-09-13 Univation Technologies, Llc Diene functionalized catalyst supports and supported catalyst compositions
WO2003037937A1 (fr) * 2001-10-18 2003-05-08 The Dow Chemical Company Supports de catalyseurs fonctionnalises par un diene et compositions catalysantes supportees
WO2004043857A2 (fr) * 2002-11-13 2004-05-27 Kim Bolton Manipulation de nanotubes de carbone derivatises
WO2004043857A3 (fr) * 2002-11-13 2005-01-27 Kim Bolton Manipulation de nanotubes de carbone derivatises
EP1841523A2 (fr) * 2005-01-03 2007-10-10 Luna Innovations, Inc. Procede de separation chimique pour fullerenes
EP1841523A4 (fr) * 2005-01-03 2009-03-25 Luna Innovations Inc Procede de separation chimique pour fullerenes
US8026296B2 (en) 2005-12-20 2011-09-27 3M Innovative Properties Company Dental compositions including a thermally labile component, and the use thereof
WO2007075257A1 (fr) 2005-12-20 2007-07-05 3M Innovative Properties Company Compositions dentaires comprenant un composant labile thermiquement et leur utilisation
US7776940B2 (en) 2005-12-20 2010-08-17 3M Innovative Properties Company Methods for reducing bond strengths, dental compositions, and the use thereof
US7896650B2 (en) 2005-12-20 2011-03-01 3M Innovative Properties Company Dental compositions including radiation-to-heat converters, and the use thereof
EP2043952A2 (fr) * 2006-07-06 2009-04-08 Solenne B.V. i.o. Mélanges de dérivés de fullerène et leurs utilisations dans des dispositifs électroniques
EP2043952A4 (fr) * 2006-07-06 2013-03-20 Solenne B V I O Mélanges de dérivés de fullerène et leurs utilisations dans des dispositifs électroniques
US8435713B2 (en) 2006-07-06 2013-05-07 Solenne Bv Blends of fullerene derivatives, and uses thereof in electronic devices
US8945807B2 (en) 2006-07-06 2015-02-03 Solenne Bv Blends of fullerene derivatives, and uses thereof in electronic devices
US8362163B2 (en) 2007-03-07 2013-01-29 Dow Global Technologies, Llc Tethered supported transition metal complex

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