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|Publication number
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|Mar 2, 2010
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|Jul 12, 2006
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|Jul 7, 2003
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|Stanislaus S. Wong, Sarbajit Banerjee
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|The Research Foundation Of State University Of New York
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|Patent Citations (6), Non-Patent Citations (23), Referenced by (6), Classifications (50), Legal Events (1)
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This application is a divisional application of U.S. application Ser. No. 10/615,492 filed on Jul. 7, 2003 now U.S. Pat. No. 7,169,329. The entire disclosure of the aforementioned application is incorporated herein by reference.
This invention was made with Government support under Grant No. 22245 by the Petroleum Research Fund, and Grant No. 24027 by Sigma Xi.
The present invention relates to the art of nanotechnology, and in particular, to carbon nanotube technology, its function and structure.
A carbon nanotube is a single graphene sheet in the form of a seamless cylinder. The ends of a nanotube typically have hemispherical caps. The typical diameter of a nanotube ranges from about 1 nm to 10 nm. The length of a nanotube potentially can be millions of times greater than its diameter.
Since their discovery in the early 1990s, carbon nanotubes have been the focus of intense study due to their very desirable and unique combination of physical properties. They are chemically inert, thermally stable, highly strong, lightweight, flexible and electrically conductive. In fact, carbon nanotubes may potentially be stiffer and stronger than any other known material.
Carbon nanotubes are currently being proposed for numerous applications, such as, for example, catalyst supports in heterogeneous catalysis, high strength engineering fibers, sensory devices and molecular wires for the next generation of electronics devices.
There has been particularly intense study of the electrical properties of nanotubes, and their potential applications in electronics. Metallic carbon nanotubes have conductivities and current densities that meet or exceed the best metals; and semiconducting carbon nanotubes have mobilities and transconductance that meet or exceed the best semiconductors.
Carbon nanotubes are grown by combining a source of carbon with a catalytic nanostructured material such as iron or cobalt at elevated temperatures. At such temperatures, the catalyst has a high solubility for carbon. The carbon links up to form graphene and wraps around the catalyst to form a cylinder. Subsequent growth occurs from the further addition of carbon.
Current methods of producing carbon nanotubes yield aggregations of nanotubes. Such aggregations are referred to as bundles (or ropes). Bundles typically range in diameter from about 20 nm to 300 nm. Each nanotube in a bundle has its own individual physical properties. For example, the electric property of any given nanotube in a bundle may vary from the extremes of superconducting to insulating. Different end use applications of nanotubes require particular physical properties. Accordingly, it is critical to be able to isolate individual nanotubes and determine their physical properties. Also, the manipulation and tailoring of individual nanotubes are necessary for end use applications. To these ends, methods of exfoliating bundles by dissolving bundles in solvents have been explored.
Raw carbon nanotubes are essentially insoluble in organic and aqueous solvents. Current methods of increasing the solubility of nanotubes are by the derivatization of the nanotubes. For example, acid-shortened carbon nanotubes which have been derivatized with thionyl chloride and octadecylamine were shown to be soluble in several organic solvents (Chen et al. Science 282:95 (1998)). Solubilization has also been achieved by attaching tubes to highly soluble poly(propionylethylenimine-co-ethylenimine) (Riggs et al. J. Am. Chem. Soc. 122:5879 (2000)). Sidewall derivatization with fluorine and alkanes also appears to render tubes soluble in a number of different organic solvents including chloroform and methylene chloride (Boul et al. Chem. Phys. Lett. 310:367 (1999)). Recently, water solubilization has been achieved by derivatization of carbon nanotubes with glucosamine and gum arabic (Bandyopadhyaya et al. Nano Lett. 2:25 (2002)).
The current methods for exfoliating carbon nanotube bundles, and for increasing the solubility of nanotubes, involve time-consuming, complex processes. Also, the range of solvents in which increased solubility has been achieved, and the degree of solubility achieved, are limited. Moreover, current methods of derivatization of nanotubes, in particular sidewall derivatization, destroy the structural integrity of nanotubes, thereby potentially interfering with desirable physical properties. For example, the electrical properties of nanotubes may be eliminated upon such derivatization. These shortcomings of current methods present obstacles for actualizing the utility of carbon nanotubes for end use applications. Moreover, the derivatized nanotubes provided by current methods would require additional synthetic steps in order to use the nanotubes in catalysis or as catalytic supports.
Accordingly, there remains a need for a simple method of exfoliating carbon nanotubes. Also, there is a need for carbon nanotubes which exhibit a high degree of solubility in a wide range of solvents. Moreover, for various end use applications, there remains a need for a method of increasing the solubility of nanotubes without interfering with their intrinsic physical properties.
The present invention provides adducts comprising a carbon nanotube and a transitional metal coordination complex. A metal of the complex is attached by a covalent linkage to at least one oxygen moiety on the nanotube. Preferably the covalent linkage is a coordinative linkage.
The oxygen moiety on the nanotube is a carboxyl group, a hydroxyl group, an aldehyde group or a ketone group. Preferably, the transitional metal coordination complex is a Wilkinson's complex, [Ag(NH3)2]+, [Cu(NH3)4]2+, [Fe(CN)6]4−, [Fe(CN)6]3−, [Co(NH3)6]3+, [Pt(NH3)2Cl2], [Cr(ethylenediamine)3]3+, [Pt(NH3)4]2+, Fe(C5H5)2, Ni(C5H5)2, [PdCl4]2−, Cr(CO)6, [Ni(NH3)6]2+, [CoF6]3−, [Pt(ethylenediamine)2Cl2]Br2, [Co(NH3)4 (SCN)Br]Cl, [Fe(H2O) 6]3+, [CeCl6]2−, [La(acetylacetone)3 (H2O)2], [Nd(H2O)9]3+, [Er(NCS)6], [Lu(2,6-dimethylphenyl)4]−, [Ho(tropolonate)4]−. or mixtures thereof. The transitional metal can be in the form of a nitrate, a halide, or a salt.
The adducts have high degree of solubility in organic or aqueous solvents. Examples of organic solvents include dimethylsulfoxide (DMSO), tetrahydrofuran (THF) or dimethylformamide (DMF). methanol, ethanol, 2-propanol, acetone, o-dichlorobenzene (ODCB), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate, benzene and dimethylformamide (DMF).
The invention also provides methods of producing a plurality of carbon nanotubes with increased solubility. The method comprises adding a solution comprising a transitional metal coordination complex to a carbon nanotube dispersion to form a resultant dispersion comprising carbon nanotube-metal adducts. Fifty to 99 wt % of the carbon nanotube-metal adduct dispersion comprises nanotubes. The method can further comprising precipitating the adduct from the solution.
The invention also provides a method of catalyzing a reaction of an unsaturated hydrocarbon. The method comprises providing a catalyst system comprising a carbon nanotube-transitional metal coordination complex adduct in an organic solvent; and contacting a reactant and an unsaturated hydrocarbon with said catalyst system. After catalysis, the adduct can be recovered from the catalyst system.
The reaction which can be catalyzed with the system include a hydrogenation, a hydroformylation, an epoxidation, an olefin metathesis, a hydrosilylation, and an alkene (Ziegler-Natta) polymerization.
The invention also provides a catalyst support comprising a plurality of the adducts.
The invention also provides a method of exfoliating a plurality of carbon nanotube bundles, comprising contacting a carbon nanotube dispersion with transitional metal coordination complexes.
The present invention also provides an adduct comprising a carbon nanotube and a macrocyclic molecule. The macrocyclic molecule can be a coronand, a corand, a cryptand, a spherand, a cryptaspherand, a hemisspherand, a podand, a cavitand, a carcerand, and derivatives thereof.
The macrocyclic molecule forms a cavity which is about 0.5 to 10 Angstroms. In one embodiment, within the cavity is a metal ion, such as, a lithium ion, a potassium ion, a calcium ion, a mercury ion, a zinc ion, a strontium ion, and a magnesium ion.
The macrocyclic molecule and said carbon nanotube can be covalently linked, or ionically linked to one another.
The macrocyclic molecule adduct have a high degree of solubility in an organic solvent or an aqueous solvent. Examples of such organic solvent include methanol, ethanol, 2-propanol, acetone, o-dichlorobenzene (ODCB), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate, benzene and dimethylformamide (DMF).
The invention also provides a method of producing a plurality of carbon nanotubes with increased solubility. The method comprising providing a plurality of carbon nanotubes in the form of bucky paper; and dispersing the bucky paper in a solution of macrocyclic molecules. The macrocyclic molecule solution can comprise a mixture of different macrocyclic molecules.
The invention also provides a method of exfoliating a plurality of carbon nanotube bundles. Bucky paper is contacted with a solution comprising functionalized macrocyclic molecules.
The nanotube adducts, and methods of making the same, of the present invention provide several advantages over the current technology.
For example, unlike current methods of exfoliating carbon nanotubes bundles which involve complicated, time-consuming processes, the present invention provides methods of exfoliating nanotube bundles by simple chemical processes. Also, unlike prior art derivatized nanotubes, the nanotubes adduct of the present invention exhibit increased solubility in a wide variety of aqueous and organic solvents. Moreover, unlike prior art derivatized nanotubes, in one embodiment of the present invention, the nanotubes adducts have metallo-organic chemistry. Such chemistry allows for the use of the adducts, without further synthetic steps, in catalysis and as catalytic supports.
For a better understanding of the present invention, reference is made to the following description, taken in conjunction with the accompanying drawings, and the scope of the invention set forth in the claims.
An adduct of the present invention comprises a carbon nanotube covalently linked, such as coordinatively linked, to at least one transitional metal coordination complex, or a carbon nanotube attached to at least one macrocyclic molecule.
The carbon nanotubes of the adducts comprise graphene in cylindrical form. The nanotubes preferably have open ends. Alternatively, the nanotubes can have one or two hemispherical caps on their ends. In addition to the hexagonal carbon rings of graphene, the caps can comprise pentagonal rings of carbon. The carbon nanotube can be a semi-conducting nanotube or a metallic nanotube. (A metallic nanotube has no band gap.)
The carbon nanotube can be either single-walled nanotubes (SWNTs) or multi-walled nanotubes (MWNTs). A SWNT comprises only one nanotube. A MWNT comprises more than one nanotube each having a different diameter. Thus, the smallest diameter tube is encapsulated by a larger diameter tube, which in turn, is encapsulated by another larger diameter nanotube.
SWNTs typically have a diameter of about 0.7 to about 2.5 nm, and a length of up to about one mm. MWNTs typically have a diameter of about 3 to about 30 nm, and a length of up to about one mm.
SWNTs and MWNTs are produced, typically, as bundles. A bundle comprises a plurality of SWNTs or MWNTs. The diameter of a bundle of SWNTs is typically about 10 to 20 nm. The diameter of a bundle of MWNTs is typically about 2.5 to 250 nm.
The carbon nanotubes can be prepared by methods known in the art. For example, carbon nanotubes can be prepared by the laser vaporization. (Thess et al. Science 273: 483 (1996)). Also, carbon nanotubes can be prepared by arc discharge (Ishigami, M. et al. Chem. Phys. Lett. 319:457 (2000); Su, M. et al. Chem. Phys. Lett. 322:321 (2000); Journet, C. et al. Nature 388:756 (1997); Colbert et al. Science 266:1218, (1994)); Shi, Z. et al. Carbon 37:1449 (1999) and Ebbeson, T. et al. Nature 358:220 (1992)). The carbon nanotubes can be prepared by catalytic chemical vapor deposition (Kukovitsky, E. F. et al. Chem. Phys. Lett. 317:65 (2000); Su, M. et al. Chem. Phys. Lett. 322:321 (2000); Li et al. Science 274:1701 (1996); and Pan, Z. et al. Chem. Phys. Lett. 299:97 (1999)).
The carbon nanotubes may optionally be doped with other elements, for example, with metals, such as boron or nitrogen; or gases, such as ammonia and oxygen, by methods known in the art.
In one embodiment, an adduct of the present invention comprises a carbon nanotube and a transitional metal coordination complex. The metal of the coordination complex can be any transitional metal. Transitional metals include elements 21 through 29 (scandium through copper), 39 through 47 (yttbrium through silver), 57 through 79 (lanthanum through gold), and all known elements from 89 (actinium) on.
Preferred examples of transitional metal coordination complexes include RhCl(PPh3)3 (also known as the Wilkinson's complex, wherein Ph stands for phenyl), [Ag(NH3)2]+, [Cu(NH3)4]2+, [Fe(CN)6)4, [Fe(CN)6]3−, [Co(NH3)6]3+, [Pt(NH3)2Cl2], [Cr(ethylenediamine)3]3+, Pt(NH3)4]2+, Fe(C5H5)2, Ni(C5H5)2, [PdCl4]2−, Cr(CO)6, [Ni(NH3)6]2+, [CoF6]3−, [(ethylenediamine)2Cl2]Br2, [Co(NH3)4 (SCN)Br]Cl, [Fe(H2O)6]3+, [CeCl6]2−, [La(acetylacetone)3 (H2O)2], [Nd(H2O)9]3+, [Er(NCS)6], [Lu(2,6-dimethylphenyl)4]−, [Ho(tropolonate)4]−. Nitrates, halides, or salts of transition metals also can be used.
The metal of the complex is attached to at least one oxygen moiety, i.e., oxygen functional group, on the nanotube by a covalent linkage. Oxygen moieties include a carboxyl, a hydroxyl, an aldehyde or a ketone functional group.
A covalent linkage is the sharing of electrons by a pair of atoms. The covalent linkage can be via a single bond, i.e. one pair of electrons shared, or a double bond, i.e. two pairs of electrons shared. Preferably, the covalent linkage is a coordinative linkage. A coordinative linkage comprise a pair of electrons donated by only one of the two atoms that are joined. The covalent linkages can also be polar covalent bonds (hybrid bonds). Such bonds are partially ionic in nature; that is, the electrons are not shared equally.
Transitional metals exhibit a variety of oxidation states. Depending on the particular metal used in an adduct, the oxidation states of a metal in the adduct can vary from +1 to +7. For example, in the embodiment wherein the metal complex is a Wilkinson's complex, the oxidation state of rhodium within an adduct is preferably three or two. As another example, in the embodiment wherein the metal complex is [Pt(NH3)4]2+, the oxidation state of platinum within an adduct is preferably two or four.
The spatial arrangement of a particular adduct can be, for example, a tetracoordinate structure, pentacoordinate structure, a hexacoordinate structure, septacoordinate structure, octacoordinate structure etc. The arrangement depends upon the particular transitional metal complex, the number of ligands held by the metal, and the number of attachments the metal makes with the nanotube. For example, in the embodiment in which the Wilkinson's complex is used, preferably the adduct has a hexacoordinate structure.
An adduct can comprise one or more than one transitional metal complex. The number of metal complexes attached is governed by the quantity of oxygen moieties on the surface of a nanotube. About 3 to 4% of the carbon atoms on a nanotube have oxygen moieties. Of these moieties, all or about one third, for example, has a metal complex attached. In one embodiment, an adduct can comprise a mixture of different types of metal complexes.
The adducts of the invention exhibit a high degree of solubility in organic or aqueous solvents. That is, a plurality of adducts readily dissolve in solvents, and remain dissolved upon prolonged standing. For the purposes of this specification, prolonged standing includes standing for several hours, several weeks, several months, or standing for an indefinite period of time. As the quantity of metal complexes on a nanotube increases, the solubility of the nanotube increases.
Examples of organic solvents in which solubility is increased include dimethylsulfoxide (DMSO), tetrahydrofuran (TMF), dimethylformamide (DMF), methanol, ethanol, 2-propanol, acetone, o-dichlorobenzene (ODCB), ethyl acetate, and benzene.
For example, a adduct comprising a Wilkinson's complex exhibits a solubility of greater than 250 mg/L in DMSO, and a solubility of greater than 75 mg/L in THF or DMF.
Also, the adducts exhibit strong intrinsic luminescence when placed in an organic solvent.
In another aspect, the present invention provides methods of making the nanotube-metal complex adducts described above.
The production of the adducts of the present invention are preferably based on the presence of oxygen functional groups on a nanotube by which to allow the covalent linkage with a transitional metal complex. The oxygen functional groups can be anywhere on the outer surfaces of the nanotubes. Preferably, the groups are at the tips of open-ended nanotubes.
During the formation of a carbon nanotube, oxygen moieties can arise on the nanotube. In another embodiment, carbon nanotubes with oxygen moieties are produced by oxidation processes. Alternatively, carbon nanotubes with oxygen moieties are obtained from an outside source.
Processes for oxidizing nanotubes are well known in the art. For example, raw SWNT bundles can be oxidized according to existing procedures involving acidic potassium permanganate solution and hydrochloric acid. See for example Hiura et al. Adv. Mater 7:275 (1995). Also, for example, MWNT samples prepared via arc discharge can be purified by oxidizing the carbon nanotubes at 700� C. in the presence of air until approximately 2% of the original mass remained. SWNT samples can be prepared via arc discharge, pulsed laser vaporization, or chemical vapor deposition. The SWNT samples can be purified by sonication and filtration through 0.8 micron pore membranes. See for example, Bonard et al. Adv. Mat., 9, 827 (1997), K. Tohji et al. J. Phys. Chem. B, 101, 1974 (1997), and K. Tohji et al., Nature, 383, 679, (1996).
Optionally, the carbon nanotubes can be shortened. Techniques by which to shorten nanotubes include acid etching, ion beam milling, ball milling, and gas etching.
The nanotubes, which comprise oxygen moieties, are placed in an organic solvent to form a carbon nanotube dispersion. Preferably, the organic solvent is, for example, DMSO, THF or DMF. The dispersion may optionally be sonicated. To this dispersion is added a solution comprising transitional metal coordination complexes to form a resultant dispersion. The complexes are as described above. In one embodiment, the transitional metal coordination complex solution can comprise a mixture of different complexes.
Preferably, the addition of the metal complex solution to the carbon nanotube dispersion takes place in an inert atmosphere at room temperature. The addition is preferably effected in a gradual fashion, for example, in a dropwise fashion. During the addition, the resultant dispersion is preferably stirred vigorously. Once the addition is complete, the resultant dispersion is preferably stirred for approximately a day, more preferably two days, most preferably for three days, and optimally for four days at an elevated temperature. The elevated temperature is preferably about 40 to 75� C., more preferably about 50 to 65� C., and most preferably about 55 to 60� C.
The resultant dispersion comprises carbon nanotube-metal complex adducts, as described above. Preferably, the resultant dispersion comprises from about 50 to 99 wt % of carbon nanotubes, more preferably from about 80 to 99 wt % of carbon nanotubes, and most preferably from about 96 to 99 wt % of carbon nanotubes.
In one embodiment, the adducts are recovered from the resultant dispersion. Preferably, recovery is effected by precipitating the adduct from the solution by the addition of a salt solution, such as, for example, and aqueous sodium chloride solution. Recovery can also be effected by the addition of liquid which is nonsoluble in the resultant dispersion. For example, a solvent or solution could be added that would preferentially dissolve the adduct or the products of the reaction, such that the catalyst can be separated from the product.
While not wishing to be bound by theory, it is believed that the fact that the tubes can be precipitated out upon the addition of a salt solution suggests that the tubes are charged to some extent in solution and that the observed solubility occurs by means of electric double-layer stabilization. The presence of charge likely originates in carboxylate anion-like species, formed during the purification procedure, coordinating to the metal of the complexes.
In one aspect of the present invention, a plurality of the adducts can be used as catalyst systems. In particular, the nanotubes of the adducts supports, and immobilizes, transitional metal complexes, wherein the complexes function as catalysts. The catalyses effected by the catalyst systems can be carried out at room temperature.
Depending upon the particular complex used in the adducts, the catalyst systems can catalyze various reactions. For example, the catalyst system can be used to catalyze any reaction of an unsaturated hydrocarbon. Examples of such reactions include hydrogenation, hydroformylation, epoxidation, olefin metathesis, hydrosilylation, and alkene (Ziegler-Natta) polymerization. These reactions are well known in the art. Some of the transitional metal complexes need to be modified in order to perform some of the catalytic reactions, as is well known to a skilled artisan. For example, changing a single triphenylphosphine ligand to a CO on the Wilkinson's complex would result in a hydroformylation vis-�-vis a hydrogenation.
Further guidance on catalytic reactions can be found in Cotton, F. A.; Wilkinson, G., Murillo, C. A., Bochmann, M., Advanced Inorganic Chemistry, John Wiley and Sons (New York), 1999; Crabtree, Robert, Organometallic Chemistry of the Transition metals, John Wiley and Sons (New York), 2000; and Miessler, G. L. and Tarr, D. A., Inorganic Chemistry, Prentice Hall (New Jersey), 1991.
Examples of unsaturated hydrocarbons include alkenes, acetylene, alkadienes, cycloolefins, cycloacetylene, cycloalkenes, alkynes, cyclohexene or aromatic compounds.
In one embodiment, the catalyst systems allow for homogeneous catalysis; that is, the reactants and the metal complex catalyst are all in the same phase. In this embodiment, the catalyst system comprises a carbon nanotube-transitional metal coordination complex adduct in an organic solvent. The organic solvent can be any organic solvent or mixture of solvents, including, for example, the organic solvents listed above. Preferred examples of organic solvents include halogenated organic solvents. An example of a halogenated organic solvent is CHCl3.
Most unsaturated hydrocarbons are in a liquid phase, and are introduced into the catalyst system along with other liquid reactants, such as hydrides. Alternatively, hydrogen can be introduced as hydrogen gas. The hydrogen gas dissolves into the solvent. Once catalysis is complete, the adducts can be recovered from the catalyst system. The recovery can comprise precipitating the adduct from the catalyst system by the addition of a high-ionic strength solution, i.e. a salt solution.
In an alternative embodiment, the catalyst system is a solid state system; that is, the system is not in solution. In such embodiment, the reactants in the gas phase are flowed over the nanotube-metal complex adducts. In particular, some unsaturated hydrocarbons are in the gas phase, such as, for example, some of the lower olefins. Such olefins along with hydrogen gas are flowed over the catalyst system.
In another aspect of the invention, a method of exfoliating a plurality of carbon nanotubes, is provided. Exfoliation is the separation, isolation or dispersing of a plurality nanotubes, i.e. nanotube bundles, into either smaller bundles or into single nanotubes.
In this aspect, a carbon nanotube dispersion is contacted with a solution comprising transitional metal coordination complexes. The nanotube dispersion comprises a plurality of nanotube bundles wherein the bundles have an average first diameter. Upon addition of a transitional metal coordination complex solution, the bundles are exfoliated. The exfoliated bundles have an average second diameter. The average second diameter is 10-80% or 30-50% of the average first diameter. The exfoliated bundles have an average diameter of 15 to 20 nm. About 30% to 70% of the nanotubes in the original dispersion are exfoliated to a single nanotubes.
While not wishing to be bound by theory, it is believed that the bulky metal complexes spread along the length of carbon nanotubes, lead to disruption of the molecular interactions between the nanotubes, thereby causing the nanotubes to stay apart in solution. In fact, the metal complexes essentially substitute for the pre-existing intertube and inter bundle van der Waals interactions, and provide for a favorable interface to the solvent.
Another aspect of the invention is a method of providing single carbon nanotubes, and carbon nanotube bundles with a selected diameter. In this aspect, a carbon nanotube dispersion is contacted with a solution comprising a transitional metal coordination complex to form a resultant dispersion. Adducts are preferentially formed with small bundles and with single nanotubes. For the purposes of this specification, a small bundle has a diameter of less than about 10 nanometers. The adducts are then precipitated from the resultant dispersion.
In another embodiment of the present, an adduct comprises a carbon nanotube and a macrocyclic molecule. The macrocyclic molecule can be any macrocyclic molecule. Preferably, a functional group attaches the macrocyclic molecule to the nanotube.
Examples of macrocyclic molecules include coronands, such as crown ethers; corands (modified crown ethers); cryptands; spherands; cryptaspherands; hemisspherands; podands; cavitands, carcerands and derivatives thereof. All these structures have cavities that are 0.5 to 10 Angstroms in diameter.
Coronands, cryptands, corands, podands and cavitands act as hosts of guest entities, i.e. anions, cations or neutral species. The guests define cavities within the molecules, and bind within the cavities.
A coronand is a macrocyclic molecule which has only one ring, thus one cavity. A coronand comprises any type of heteroatom. Examples of heteroatoms include sulfur atoms, oxygen atoms and nitrogen atoms. A crown ether is a coronand which comprises only oxygen heteroatoms in the ring.
The cavity size of crown ethers is determined by the coordination number of the ether and the size of a guest, i.e. a metal ion. Preferably, the cavity size of the crown ethers used in the adducts range from about 0.99 to about 8.05 Angstroms in diameter; more preferably the diameters range from about 1.7 to 3.9 Angstroms. For example, a 18-crown-6 has a diameter range from 2.6 to 3.5 Angstroms. The diameter values are derived from CPK (Corey-Kuhn-Pauling) molecular models, as would be known by a skilled artisan.
Preferably, the rings of the crown ethers of the adducts have about 12 to 60 atoms; more preferably, the rings have about 15 to 44 atoms. Preferably, the rings of the crown ethers have about 3 to 20 oxygen atoms. More preferably, the rings have about 5 to 11 oxygen atoms.
Examples of crown ethers for use in the adducts include 12-crown-4, 15-crown-5, 18-crown-6, 27-crown-9, 30-crown-10, and dicyclohexano-18-crown-6.
A corand is a modified crown ether, such as a crown ether with pendant groups. Examples of pendant groups include alkyl groups, ether groups, keto groups, amine groups, ester groups, carboxyl groups and thiol groups.
A cryptand is a macrocyclic molecule which has two or more rings and contains any type of heteroatom. Cryptands can be defined by their number of binding sites. Preferably, the crytands in the nanotube adducts have about 5 to 15 binding sites. Examples of cryptands for use in the adducts include Cryptand 2.2.1, Cryptand 2.2.1N, oxacryptand 3.3.3, Cryptand 2.2.2, Oxacryptand 3.3.3, Oxacryptand 3.3.4, and Dimethyloxacryptand 3.3.4. The numbering represents the number of donor heteroatoms on each branch.
A podand is an open chain molecule with two or more binding sites. Based on the number of arms a podand has, the molecule can be classified as a mono, di, and tri podand. Each of the arms bears an 'n' number of donor atoms to bind to a guest. Preferably, the podands in the nanotube adducts have about 1-4 arms wherein each arm has about 2 to 10 donor atoms. Preferred examples of podands include 11,10-Dimethyl<O4podand-4>, <(8)Quinolino, O5(8)quinolinopodand-7>, and 16-Methyl-1,19-diphenyl {3}<O2NO2N<S(7)-podand-7>.
A cavitand is a synthetic organic compounds with enforced concave cavities large enough to bind complementary organic compounds or ions. They are named as [n] cavitands, depending on the number of repeating units that are cyclized (usually the same as the number of phenyl groups in the interior rings). Preferably, the cavitands in the nanotube adducts range from [1] cavitands to [7] cavitands. Cavitands which are variously substituted with organic sidechains are also preferred.
A spherand is similar to crown ether and cavitands in that they have binding sites to hold guests. However, they differ in that their structure is not conferred by the binding of a guest. That is, they are preorganized ligand systems. Hence, on binding the guest, no substantial structural reorganization is needed. The cavities of spherands are fixed and are usually spherical. The cavity sizes of the spherands for use in the adducts can preferably range from about 1 to 8.5 Å in terms of CPK models.
A hemispherand and a cryptaspherand are hybrid structures. A hemispherand is a hybrid of a spherand and a coronand. A cryptaspherand is a hybrid of a spherand and a cryptand. The cavities of these structures are partially preorganized ligand systems. That is, a part of these structures changes according to guest binding, while another part is prefigured into a particular orientation. The sizes of these hybrid structures are similar to their respective parent structures.
Carcerands are closed surface hosts with fixed-size interiors. They are large enough to imprison guests of the size of ordinary solvent molecules in covalently bonded cage. These are thus molecular containers, which trap molecules inside of them. A large number of these are based on linking two cavitands by four linkers; The size of these containers can be varied to trap various solvent molecules, such as DMF and DMSO as well as gases such as Xe and CF4.
Examples of macrocyclic molecules used in the adducts can be found in Donald J. Cram, Nobel Lecture, University of California (Dec. 8, 1987); Donald J. Cram, Journal of Inclusion Phenomena, 6(4):397 (1988); "Crown ethers and cryptands" by George W. Gokel (Royal Society of Chemistry, 1991) and "Crown ethers and analogous compounds" by Michio Hiraoka (edited) (Elsevier Science, 1992).
An adduct can comprise one type of macrocyclic molecule, or different types of macrocyclic molecules.
Examples of guest entities within the macrocyclic molecules include metal ions. Preferred metal ions include, for example, a lithium ion, a potassium ion, a calcium ion, a mercury ion, a zinc ion, a strontium ion, a silver atom, a cesium atom and a magnesium ion.
In one embodiment, the macrocylic molecule and the nanotube are linked to one another covalently. Covalent linkages are described above. Examples of covalent linkages include amide linkages, ester linkages, anhydride linkages, cysteine linkages and thioester linkages.
In another embodiment, the macrocylic molecule and the nanotube are linked to one another ionically. For example, in one embodiment, an amino functional group is on the macrocyclic molecule and an oxygenated moiety is on the nanotube. In another embodiment, an amino functional group is on the nanotube and an oxygenated moiety is on the macrocyclic molecule.
While not wishing to be bound by a theory, it is believed that the attachment of the amino functional group to the oxygenated moiety is by an ionic attachment between a protonated amine and an oxyanion. (See
The functional group can be directly attached to the macrocyclic molecule. Alternatively, the adduct can further comprise an organic molecule linker between the functional group and the macrocyclic molecule. The linker preferably comprises less than about twenty carbon atoms. Preferred examples of linkers include an ethyl group, and a methyl group. Other examples of organic molecule linkers are bifunctional amines. Examples of bifunctional amines are alkyl or aryl diamine derivatives. Examples of diamine derivatives are ethylenediamine and semicarbazide.
The macrocylic molecule adducts of the invention exhibit a high degree of solubility in organic or aqueous solvents. That is, a plurality of adducts readily dissolve in solvents. As the quantity of macrocylic molecules on a nanotube increases, the solubility of the nanotube increases.
Examples of organic solvents in which solubility is increased include dimethylsulfoxide (DMSO), tetrahydrofuran (THF), dimethylformamide (DMF), methanol, ethanol, 2-propanol, acetone, o-dichlorobenzene (ODCB), ethyl acetate, and benzene. For example, Table 1 lists the solubilities of a 2-aminomethyl-18-crown-6-nanotube adducts in various solvents.
Concentrations of SWNTs in the Form of Solubilized 2-aminomethyl-18-
crown-6-nanotube Adducts for Selected Solventsa
Concentration of SWNTs in
solubilized adduct (in mg/L)
aValues are within a �10% error range.
In another aspect, the present invention provides methods of making the nanotube-macrocyclic molecule adducts described above.
In one embodiment, the production of the adducts of the present invention are preferably based on the presence of oxygenated moieties on a nanotube by which to allow the attachment of a macrocyclic molecule. The oxygenated moieties can be anywhere on the outer surfaces of the nanotubes. Preferably, the oxygenated moieties are at the tips of open-ended nanotubes. Methods to obtain, and form such nanotubes are described above.
A plurality of carbon nanotubes, which have carboxyl and/or hydroxyl functional groups, are provided in the form of bucky paper. Bucky paper is a free standing film comprising bundles of nanotubes. The bucky paper is ground up and dispersed in liquid macrocyclic molecules, or in macrocyclic molecules in solution, to form a resultant dispersion. The macrocyclic molecules are as described above. In one embodiment, the solution can comprise a mixture of different macrocyclic molecules. The ratio of the amount of bucky paper to the amount of macrocyclic molecules varies depending upon the specific macrocyclic molecules used. As an example, in the embodiment wherein the macrocylic molecule is a 2-aminomethyl-18-crown-6-ether, the ratio of the crown ether to the bucky paper is about three to one.
The resultant dispersion comprises a plurality of nanotube-macrocyclic molecule adducts. The resultant dispersion has a highly viscous consistency, and can be referred to as black paste. The resultant dispersion preferably comprises from about 50 to 99 wt % of carbon nanotubes, more preferably from about 80 to 99 wt % of carbon nanotubes, and most preferably from about 96 to 99 wt % of carbon nanotubes.
Preferably, during the production of the adducts, the black paste is purified. For example, the black paste can be mixed with distilled deionized water. The mixture can then be swirled, sonicated, and allowed to stand for about a few minutes to few hours. Preferably, after standing, distilled water can again be added followed by vigorous stirring.
In one embodiment, the adducts are recovered from the resultant dispersion. Preferably, recovery is effected by precipitating the adducts from the solution by the addition of a high ionic strength solution, such as, for example, a salt solution.
While not wishing to be bound by theory, it is believed that the fact that the tubes can be precipitated out upon the addition of a high ionic strength solution suggests that the tubes are charged to some extent in solution and that solubility occurs by means of electric double-layer stabilization.
In another embodiment, the oxygenated moiety is on the macrocyclic molecule. In this embodiment, any oxygenated moiety on the nanotube is converted to a functional group which would react with the oxygenated moiety on the macrocyclic molecule, such as, for example, an amino group.
In another embodiment, any of the following functional groups can be either on the nanotube or macrocylic molecule: an amino group, a keto group, an aldehyde group, an ester group, an hydroxyl group, a carboxyl group, or a thiol group. The functional group on the macrocyclic molecule is required to reactive with the functional group on the nanotube. If the two groups are not reactive with each other, an appropriate bifunctional linker can be used, as would be known by a skilled artisan.
In another aspect of the invention, a method of exfoliating a plurality of carbon nanotubes is provided. A plurality of carbon nanotubes in the form of bucky paper is contacted with a solution comprising macrocyclic molecules, as described above. The nanotube bundles in the bucky paper have an average first diameter. Upon addition of the macrocyclic molecule solution, the bundles are exfoliated. The exfoliated bundles have an average second diameter. The average second diameter is about 10-80% or 40-65% of the average first diameter. The exfoliated bundles have an average diameter of about 30 to 200 nm. About 1 to 50% of the nanotubes in the original dispersion are exfoliated to a single nanotubes.
The derivatization process occurs as a result of salt formation initiated by a complementary attractive, zwitterionic interaction between carboxylic groups located at the ends, sidewalls, and defect sites of the oxidized SWNTs and amine moieties dangling from the side chain of the crown ether. This so-called ionic (charge-transfer) functionalization enhances the stability of SWNT solutions by effectively preventing nanotubes from aggregating in the solution state, though it does not necessarily prevent them from clumping together upon drying
In another aspect of the invention, methods of modifying a physical property of a carbon nanotube are provided. The methods comprise forming adducts from the carbon nanotube, as described above. The adducts comprise a carbon nanotube covalently linked to at least one transitional metal coordination complex, or a carbon nanotube attached to at least one macrocyclic molecule.
The physical property which is modified is, for example, electronic properties, electrical properties, electromechanical properties, optical properties, chemical properties, mechanical properties, structural properties, thermal properties and thermoelectric properties.
The electrical property which is modified can be, for example, conductance, resistivity, carrier mobility, transport properties, permittivity, and charge transfer properties. The modification of conductance can be, for example, a tunability in conductance.
The structural property which is modified can be, for example, elasticity, and ease of composite formation.
In another aspect of the invention, a device comprising the adducts of the invention is provided. The device can be, for example, sensors, a device used in molecular electronics, solar cells, a device used in optoelectronics, a device used in nanocatalysis, and scanning probe microscopy tips.
Nanotube Synthesis and Purification. Raw SWNTs (
Generally, solvents, such as dimethylformamide and tetrahydrofuran (Acros Fisher), were used after distillation and were stored over 4 Å molecular sieves. All other reagents were obtained commercially and used without further purification.
Synthesis of SWNT-Wilkinson's Adduct. In a typical synthesis, the reaction was carried out in a Schlenk setup. To a briefly sonicated nanotube dispersion in DMSO was added, dropwise, 10 mL of a 10 mM solution of Wilkinson's catalyst in DMSO solution under vigorous stirring, in an inert Ar atmosphere. The reaction mixture was then stirred at 55-60� C. for a period of 80 h. It was observed that a substantial portion of the nanotubes dissolve into a visually, nonscattering solution. The reaction mixture was filtered over a 0.2-μm Nylon membrane, after which undispersed chunks of unreacted bucky paper were removed, and the remaining solid was then successively washed with DMSO, ethanol, and water.
The dissolved tubes in solution could be salted or precipitated out by adding in a saturated aqueous NaCl solution. These were purified by filtering over a 0.2-μm Nylon membrane and washing in an analogous manner as previously described. In terms of solubility behavior, the synthesized adducts could be readily redissolved in DMSO by mild stirring, demonstrating the reversibility of the dissolution process, and the resultant product was stable, even after four months. The product is not particularly air-sensitive, but if left out in the ambient atmosphere for extended periods of time, oxidation of some of the triphenylphosphine groups to triphenylphosphine oxide is inevitable. Dissolution of the adducts in THF and DMF was also observed, but the derivatized tubes tended to precipitate out of solution within a day.
Catalysis with SWNT-Wilkinson's Adduct. The adduct-mediated hydrogenation reaction of cyclohexene was carried out in a DMSO/CHCl3 mixed solvent system by bubbling in a mixture of hydrogen gas in argon under Schlenk conditions for a period of 3 days at room temperature. Typically, 1 mL of a saturated solution of the supported catalyst in DMSO was stirred with 3 mL of CHCl3 and 3 mL of cyclohexene. The reaction was monitored by 1H NMR spectroscopy through the appearance of cyclohexene peaks at ˜1.52 ppm. The reaction yield obtained was approximately 30%, but it is expected that a higher yield is likely with further optimization of the solvent system and with an improved hydrogenation apparatus.
Electron Microscopy. Samples for TEM were obtained by drying sample droplets from an ethanolic or DMSO solution onto a 300 mesh Cu grid with a lacey carbon film. All the micrographs were taken at an accelerating voltage of 120 kV on a Philips CM 12 TEM, equipped with EDAX capabilities. SEM images were obtained on Cu grids as well at accelerating voltages of 1-2 kV at a 2-mm working distance using a Leo 1550 field emission instrument.
Atomic Force Microscopy. AFM height images were taken in Tapping mode in air at resonant frequencies of 50-75 kHz with oscillating amplitudes of 10-100 nm. The samples were spin coated onto a mica substrate, and imaged with Si tips (k=1-5 N/m) using a Multimode Nanoscope IIIa (Digital Instruments, Santa Barbara, Calif.).
Nuclear Magnetic Resonance. Deuterated solvents, including CDCl3, d6-DMF, d6-DMSO, and d7-THF, were purchased from Aldrich and used without further purification. All NMR spectra were obtained on a Bruker AC-250 multinuclear FT-NMR at 298 K. The 31P and 13C NMR data were proton decoupled. 31P NMR results are referenced to an external phosphoric acid standard.
X-ray Diffraction. Powder X-ray diffraction spectra were collected on a Scintag diffractometer, operating in the Bragg configuration using Cu Kα radiation (λ=1.54 Å). A Soonerveld background subtraction was performed to remove low Q diffuse reflections. Parameters used for slit widths and accelerating voltage, as well as Savitzky-Golay smoothing algorithms, were identical for all the samples.
Optical Spectroscopy. UV spectra were obtained at high resolution on a ThermoSpectronics UVI using quartz cells with a 10-mm path length. NIR spectra were obtained on a Nicolet Nexus 670 spectrophotometer with a CaF2 beam splitter and an InGaAs room-temperature detector using a 5-mm path length quartz cell. All spectra collected were corrected to account for a background of the appropriate solvent. Fluorescence data were obtained on a Jobin Yvon Spex Fluorolog 3.22, equipped with a 450-W xenon source and configured with double monochromators for both emission and excitation, with a 1-s integration time, to provide for stray light rejection while maintaining high light throughput. The experiments were performed using front face collection optics to collect the emission most efficiently.
Microscopy. Electron microscopy (
X-ray Diffraction. The powder XRD pattern for a solid, functionalized adduct sample shows recovery of the nanotube lattice peaks (
NMR Spectroscopy. NMR spectroscopy confirmed the coordination of the complex onto the oxidized tubes. In particular, 31P, 1H, and 13C NMR spectra of the adduct were obtained. Comparison of the 31P and 1H NMR data with that of the starting material, RhCl(PPh3) 31, is shown in
Second, as noted with other types of functionalizations performed, the NMR peaks of nanotubes tend to broaden upon derivatization. Since the large nanotubes move relatively slowly on the NMR time scale of measurement, observed broadening of the NMR peaks is indicative of the localization and immobilization, through restriction of the degrees of conformational freedom, of metal complex molecules onto the oxygenated surface sites of the tube with the accompanying loss of symmetry. Indeed, this same broadening trend is observed for all nuclei, including 31P, 1H, and 13C. While inhomogeneities in the local magnetic field induced by the diameter and helicity-dependent diamagnetism of the SWNTs themselves and the partial alignment of the tubes in the magnetic field of the NMR magnet are expected to contribute to peak broadening, in the present case, the broadening is likely a result not only of slow tumbling and motion of the tubes in solution, preventing rotational averaging, but also of a slow rate of ligand exchange upon complexation to the tubes.
Providing more evidence for the localization mechanism postulated, it is noted that in pristine Wilkinson's complex, the loss of a triphenylphosphine moiety is facile and indeed a vital step in its catalytic behavior. In DMSO solvent, for the starting material, exchange involving triphenylphosphine takes place very rapidly, such that all the phosphines in the 31P NMR spectra become equivalent (unlike in CH2Cl2 or in benzene.), which is similar to phenomena noted at higher temperatures; also, coupling of the P nucleus to the Rh nucleus is removed. The fact that the phosphine peaks are broadened upon the addition of and reaction with SWNTs suggests the presence of a slower rate of exchange and the inequivalence of the phosphine ligands. Hence, this phenomenon is steric in nature, arising from reduced accessibility of the metal center for the phosphine ligands due to complexation with the nanotube. Essentially, the nanotube itself can be considered as a bulky, sterically encumbering ligand. Not surprisingly, on increasing the concentration of nanotubes, the 1H NMR spectra, like the 31P NMR data, similarly broaden.
The 13C solution NMR spectrum for the adduct contains broad resonances centered at δ=128.6, 128.8, 131.4, 131.5, and 132 ppm. DEPT spectra confirmed that all these are C—H aromatic carbons, originating from phosphine groups. No resonances were seen, however, for the nanotube carbons. Nanotube resonances have not as yet been observed in solution NMR studies of these materials, even upon substantial isotopic enrichment with 13C (up to 20 times the natural abundance). Among the reasons cited for this situation include the relatively long relaxation times of nanotube carbons, as well as the low concentrations of nanotubes present, even upon saturation, which cannot be readily detected by 13C solution NMR.
Optical Spectroscopy. The UV-visible spectra collected for pure Wilkinson's complex, RhCl(PPh3)3, in DMSO show evidence of increased peak structure (apparent upon normalization of intensity) with the addition of 0.01 M PPh3, as the dissociation equilibrium is shifted to monomeric, undissociated species. (
The featureless absorbance spectrum of the adduct corresponds to the presence of a large number of absorbing and emitting species. Indeed, a large number of chromophores would account for the absence of any clear isosbestic points in the electronic spectra. The adduct is, in fact, fluorescent; the strong fluorescence prevented any detection of a Raman signal at 752-nm laser excitation, despite repeated efforts.
Rh complexes are known to have charge-transfer transitions at higher energies; however, interference from solvent DMSO lower than 300 nm makes monitoring these transitions an unreliable task. The DMSO solution of derivatized nanotubes can be readily diluted by organic solvents, such as methanol, DMF, chloroform, and toluene, without precipitating the tubes and with little change in the electronic spectrum of the diluted solutions. Similar optical behavior was reported for SWNT-aniline solutions. Upon dilution with acetone, however, a new peak at 330 nm is observed, which could be indicative of the presence of charge-transfer phenomenon in the adduct.
In general, the near-IR of dried, commercially available SWNTs in air show three characteristic optical absorptions at 0.67, 1.3, and 1.9 eV (approximately at 5400; 10,000 and 16,000 cm−1, respectively), which can be attributed to optical transitions between van Hove singularities of the density of electronic states of these tubes; the first two transitions are assigned to semiconducting tubes, whereas the feature at 1.9 eV can be attributed to the first pair of such singularities in metallic tubes. The observed peaks are due to overlapping van Hove transitions from all nanotube sizes that are present.
The presence of bands in the near-IR spectra of the functionalized nanotubes (
Of particular significance is the presence of substructure and resolution of some of these peaks in the adduct spectrum, where only broad, unresolved humps had been seen for the raw, underivatized nanotubes. Because the width of the features in the NIR spectrum originates from the overlap of transitions from tubes of different diameters and helicities, the greater spectral resolution of peaks observed shows that certain discrete diameter distributions of nanotubes are preferentially solubilized. In other words, there is a degree of size and diameter selectivity, associated with the derivatization reaction and accompanying solubilization process.
Spectra for two different concentrations of the adduct are shown in
To demonstrate the presence of "metallicity" in the adducts, fluorescence data was obtained on these structures. In the present systems, the origin of luminescence is attributed to the existence of extensive conjugated electronic structures and the excitation-energy trapping associated with defects in the nanotubes. The luminescence studies (
Functionalization facilitates the manifestation of the intrinsic luminescence, emanating from these tubes, through dispersion of these nanotubes as well as trapping of the excitation energy on the nanotube surface itself. The slow motion of the tubes in solution suggests that this energy is not lost rapidly, and thus, the observed quenching and corresponding deactivation rate through molecular motion is slower.
Furthermore, the emission spectrum upon excitation at 385 nm (
Adduct Comprising Carbon Nanotube and Crown Ethers
Nanotube Purification and Bucky Paper Synthesis. Raw SWNTs (HiPco: average diameters of 0.7 to 1.1 nm) were purified by a mild nitric acid reflux followed by filtration using a polycarbonate membrane with a pore diameter of 0.2 μm. This process generates surface functionalities, particularly carboxylic acids at nanotube ends and sidewall defect sites. The bucky paper mat thereby obtained was then redispersed in 12.1 N HCl and briefly sonicated to remove the metal catalyst. Upon the second filtration, the precipitate was washed thoroughly with large amounts of deionized water and placed in a vacuum oven at 180� C.
To create the derivatized adduct, the purified bucky paper was initially ground up with a 3:1 mass excess of 2-aminomethyl-18-crown-6 ether (Aldrich) (CE), a clear yellow, viscous liquid, to form a black paste; CE readily moistened and permeated the bucky paper. Next, 1 mL of distilled deionized water was added. The mixture was swirled, sonicated for 1 s, and then allowed to stand for 1 h, after which an additional 9 mL of distilled water was added followed by vigorous stirring. The resultant mixture was filtered by a polycarbonate membrane to separate out unfunctionalized or partially functionalized SWNT precipitate, yielding a dark-brown solution, which could be further dried by heating under an Ar flow to form a black paste, the SWNT-CE adduct.
The paste could then be dissolved in many organic solvents such as methanol, ethanol, 2-propanol, acetone, o-dichlorobenzene (ODCB), dimethylformamide (DMF), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), ethyl acetate, and benzene. Excess, unreacted CE could be removed from the adduct by washing with diethyl ether. Prior to characterization, the solutions were, passed through a column packed with glass wool to remove excess solid particulate matter in order to obtain an optically clear solution. The resultant solutions were visually nonscattering and were appropriately diluted for optical measurements.
The optical characteristics of SWNTs in solution were monitored by the absorbance at 500 nm; the derivatized crown ether does not absorb beyond that value. Quantitative concentrations were calculated using optical absorption data fitted to a Beer-Lambert plot. Representative solubility values are listed in Table 1.
Results Crown ethers containing an amino functionality attached to a pendant methylene side chain on the macrocyclic ring were attached to the nanotube. The amino group of 2-aminomethyl-18-crown-6 interacts with oxygenated groups, particularly the carboxylic acid sites, at the ends of the purified tubes as well as at oxidized defect sites scattered along the sidewalls. The crown ether's maerocyclic ring dangles from the SWNT. Evidence that it does comes from 1H NMR data (
To further ascertain the conformational nature of SWNT-CE bonding within the adduct, the adduct was incubated with a solution of lithium chloride to observe the Li cation movement; 7Li NMR was performed on the adduct mixture in MeOH. In a solution of pure crown ether, because of the fast exchange kinetics between the Li+ complexed within the cavity of the crown ether and the free, solvated cation, only one 7Li peak is visible. In a solution of the SWNT-CE adduct, a single narrow Li peak was observed, similarly implying the presence of fast exchange between Li cations residing in the crown ether cavities within the SWNT-CE adduct and those free in solution. Whereas exchange between CE and the oxygenated sites on the SWNTs may be possible, the fact that only one Li peak was observed shows, supported by 1H NMR, that the macrocyelic ring is tethered to the SWNT through an interaction involving the aminomethyl side chain and that the ring freely dangles. Thus, the crown ether can readily complex with the Li cation.
Optically, the presence of a sharp peak at 1105 cm−1 in the mid-IR range (
The emission peak is wider in the SWNT-CE adduct, an effect arising from slower tumbling of the larger nanotubes in solution, which would thereby slow self-quenching of the fluorescence due to molecular motion. These results further show the SWNT-CE adduct formation.
The SWNT-CE adduct arises from a zwitterionic interaction between a protonated amine on CE and an oxyanion from a carboxylic acid group, creating a COO−NH3 + ionic bond.
The exfoliation of nanotube ropes into individual tubes can be ascertained by means of microscopy. Compared with the raw tubes, the AFM and TEM images (
The macrocycles may preferentially orient and align relative to each other, projecting outward and parallel to the tubular axis, thereby facilitating the formation of larger bundles. In addition, it has been shown that oxidative derivatization can cause smaller tubes to associate into larger bundles because of H-bonding between carboxyl groups attached to the walls of functionalizing tubes, thereby adding to the overall stacking effect.
Thus, while there have been described what are presently believed to be the preferred embodiments of the present invention, other and further embodiments, modifications, and improvements will be known to those skilled in the art, and it is intended to include all such further embodiments, modifications, and improvements and come within the true scope of the claims as set forth below.
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|U.S. Classification
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Jacqui Adler '17
Bend, OR
"I've learned that people will forget what you said, people will forget what you did, but people will never forget how you made them feel." - Maya Angelou
Major: Sociology
Many memories ago, Jacqui arrived at CC with dreams of majoring in Biology and becoming a surgeon, but quickly fell even more in love with the social sciences. After a year and a half of studying Political Science, Jacqui happily landed in the Sociology department where she enjoys studying everything that's wrong with the world, and plotting how to fix it. She plans to follow her long-time passion for culinary arts following graduation. When Jacqui is not studying, mentoring students in the community, or babysitting her (four-year-old) best friend, she is cooking, baking, or watching dramatic television shows.
Activities: middle school teacher aide, student mentor, theater, spoken word poetry, Taste of the World, Queer Community Coalition
Will Baird '17
Denver, CO
"Don't count the days. Make the days count." - Muhammad Ali
Major: Sociology
Born and raised in Denver Colorado, Will was not ready to leave the Rocky Mountains. As an avid ski and mountain bike enthusiast, Will was able to utilize his love for the outdoors while at the same time taking full advantage of CC's liberal arts opportunities. After taking 12 distinctly different courses at CC, Will is now happily pursuing a degree in Sociology with a minor in Spanish language. Will's academic interests also include economics and finance and he hopes to find his niche in the economics of Higher Education. Additionally, Will studied abroad in Salamanca and Madrid and enjoys connecting with people from all parts of the world, whether he understands them or not. He is also a member of the New Student Orientation Leadership Program because "what could be better than meeting new people and camping with them for a week?" Will hopes to bring his open-minded and enthusiastic attitude into the admissions fellowship.
Activities: Colorado College Men's Lacrosse, CC Show of Talents Committee, Intramurals, Sarcasm, NSO Leader, American Diabetes Association Ambassador, Lacrosse Coach, Chess Club
Joel Fisher-Katz '17
Northampton, Massachusetts
"That which builds is better than that which is built." - Ralph Waldo Emerson
Major: Philosophy
Born and raised in Northampton Massachusetts, Joel left a community of passion and art after graduating from Pioneer Valley Performing Arts High School. Joel moved to Colorado for the climbing but ended up staying for Colorado College after discovering a passion for philosophy during a year at Piles Peak Community College. He is pursuing a philosophy major along with an English minor. When not philosophizing, Joel plays Ultimate Frisbee for Colorado College Wasabi and takes part in numerous IM sports including being a 2015 Broom Ball champion. Joel plans on continuing his education after CC and eventually teaching at the college level. Along with his admissions work Joel helps to construct sets for the theater department under the tutelage of CC's technical director Paul Martin and spends as much time as possible exploring the innumerable beauties of the Southern Frontrange. As a Junior and a transfer, Joel hopes to bring an energetic and motivated spirit to the job of admission fellow and to offer his experience of CC as a resource for prospective students.
Activities: Colorado College Men's Frisbee, IM participant, Spoken Word Performance, Rock Climbing, Scene shop employee, General Enjoyment of the South Platte
DeAira Hermani '17
Chicago, IL
"When you've worked hard and done well, and walked through that door of opportunity...you do not slam it shut behind you...you reach back, and you give other folks the same chances that helped you succeed." - Michelle Obama
Major: Independently Designed Major: Performance and Identity (Anthropology, Theater, and Race, Ethnicity, and Migration Studies)
The windy city blew DeAira all the way to Colorado College where she originally thought she would be on a pre-med track. However, DeAira has now created her own major that combines Theater, Anthropology, and Race, Ethnicity and Migration Studies. Outside of the classroom DeAira is heavily involved in theater through the department as well as with a group called Women In Comedy and takes part in many on campus organizations that mentors, supports, and feeds students such as the BSU, Carnivore Club, SAIL Program, and as a Residential Advisor. DeAira joined the Office of Admission as a leader and a teacher looking to help students decide or discover if Colorado College can help them on their own intellectual adventure.
Activities: Women In Comedy, Black Student Union (BSU), Carnivore Club, SAIL Program
Madelene Travis '17
Fort Worth, TX
"We don't see things as they are, we see them as we are." - Anaïs Nin
Major: Sociology
Minor: Nonviolence
After a fairly nomadic childhood that led her from Roswell, NM to an island in Michigan to Fort Worth, TX Madelene chose to settle down for a four-year academic adventure at Colorado College. Madelene tried to declare a Sociology major after her very first course at CC but was advised to give it some time, which changed nothing and she eventually did it anyways while adding a Nonviolence minor. A two-year Resident Advisor and a huge fan of Rastall's tater tots, Madelene makes the most out of every experience and opportunity CC provides. She recently returned from a semester in Rwanda where she studied post-genocide reconciliation and met at least one hippopotamus. Madelene is excited to join admissions so she can finally have an outlet for her endless questions.
Activities: New Student Orientation leader, First Year Experience mentor, Resident Advisor, student researcher, hiker, eater, and sleeping enthusiast
Maya Williamson '17
London, UK
"Forgiveness and compassion are always linked: how do we hold people accountable for wrongdoing and yet at the same time remain in touch with their humanity enough to believe in their capacity to be transformed?" - bell hooks
Majors: Anthropology, French
Born in Seattle and raised in London, Maya spent almost her entire academic life at competitive girls' schools in the UK. After graduating from high school, she came to Colorado College in search of the Liberal Arts and a change of pace. Maya is a double major in French and Anthropology, and spent the fall semester of her junior year in Senegal studying French language, and West African culture. After finishing her semester abroad, Maya was awarded a Venture Grant to extend her stay and study the impacts of the French education system on Senegalese national identity. Maya cites the Keller Family Venture Grants as one of her favorite things about CC, with another one of her research projects taking her to Japan, where she studied the effects of kawaii (cuteness) on gender expression and gender roles. Outside of class, Maya can be found climbing on rocks in Garden of the Gods, eating ramen noodles, or taking her bunny for a walk on the quads.
Activities: State of the Rockies research fellow, First Year Experience Mentor, Ritt Kellogg Climbing Gym monitor, Climbers Association of Colorado College, EQUAL for queer and questioning students, Student Anthropology Society
Michael Zijing Wu '17
Shanghai, China
"Our greatest glory is not in never falling, but in rising every time we fall." - Confucius
Major: International Political Economy
Minors: Music & Education
Born and raised in the largest city in the world by population – Shanghai, China – Michael came to Colorado to pursue peace and explore nature. After taking classes in more than ten departments at CC, Michael realized that he wanted to learn more about this world before living a peaceful life. After exploring CC for a year and a half, Michael decided to major in International Political Economy, along with two other minors: Music and Education. In order to know the world better, Michael took full advantage of CC's study abroad programs, and went abroad three times to Spain, Germany, and Central Europe. Besides exploring the world, Michael enjoys skateboarding around CC, snowboarding, boxing, playing poker, as well as playing piano and Erhu.
Activities: CCSGA Finance Representative, President's Council, Phi Gamma Delta, NSO Leader, ISO Leader, Chinese Student Association Co-chair, Honors Concert, Music at Midday, Mighty Math, Intramural Sports


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Questions have been raised about the Nurburgring's ability to continue to operate in the long-term amid serious financial losses following an attempt to expand it into a non-motorsport attraction, but the Mercedes-Benz motorsport boss is certain that the problems can be overcome.
"The hiring of the track and so on is very successful," said Haug. "I think that should continue and there will be solutions in place.
"DTM will take place in August so the circuit will continue. This does not mean that there will be no racing. It is obviously a concern, but to my knowledge the normal business goes on.
"It's a shame, what is happening, because the region there is really dependent on motorsport.
"The basic idea was a good one. The plan was to create some attractions and obviously it did not work according to plan. The plan was supposed to be a positive one but not enough people outside motorsport came."
Haug is unsure as to what effect the Nurburgring's plight could have on the future of the German Grand Prix, but is confident that the event will continue.
Currently, the race alternates between Hockenheim and the Nurburgring, with neither track able to hold the race every year. With Hockenheim very unlikely to take over the race full-time, it could lead to the race being held in alternate years, possibly sharing a slot with the Belgian Grand Prix, which might also have to switch to running biennially.
"It's too early to say," said Haug of what Nurburgring's problems mean for Mercedes's home grand prix. "The news only came on Wednesday. We will see what the next steps will be.
"Germany is still very interested in motorsport in general and F1. It's still huge and I'm sure that a solution can be found."
* Read Dieter Rencken's in-depth analysis of the Nurburgring's financial situation on AUTOSPORT Plus.


text:
Community and forum dedicated to the books and films of the J.R.R. Tolkien series
Eol may have been an intriguing character, but for my money he was a bad seed whose mother should never have let him see the light of day, let alone the dark of night.
Users browsing this forum: No registered users and 2 guests


text:
The Tank supports emerging choreographers, dancers, improvisers, and cross-disciplinary performers whose work celebrates or challenges the current field of contemporary dance and movement. We present premieres of full-length works, tours, and more.
Past dancers and choreographers who have performed at The Tank over the years include:
Project Limb | Hattie Mae Williams | AUNTS | Kyle Abraham | Tiffany Rea Fischer | Erick Montes | Danielle Russo | Peter Chamberlain | MariaColacoDance | and hundreds more!
Our current signature dance program is XYZ, NYC, Three to four choreographers are chosen randomly each month, and the remaining dancers make up their teams. Every month has a different theme that must be be woven into the nascent dances. The public performance one week later is a competition between the pieces. After each dance, a prominent guest judge provides feedback with the goal of expanding the audience's vocabulary for talking about what they just saw, and the audience ultimately picks the winner. All dancers who apply to participate are welcomed on stage, promoting an unparalleled level of accessibility to performing and viewing dance. For more information about the show or how to apply to perform or choreograph, visit the XYZ NYC Tumblr. Curated by Jill Rousseau.
Current dance curators are: Jill Rousseau and Olney Edmondson.
Do a show here! As with all of our programming, we operate with an ongoing open submissions process. Click HERE for application instructions!
151 West 46th Street / 8th Fl. / New York, NY 10036


text:
Top Definition
A self administered dirty sanchez.
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Two sexual partners go to get mexican food. Then, because of their uncontrollable bowels they have anal sex. Diarihha sprays onto the man's cock. In his anger he sticks a straw in his ass and puts the other end up the girls nose and sprays more diarihha threw it.
Dude, after the mexican, she shit on my dick so I gave her a dirty raul.
by Emoney627 July 26, 2006
A dirty raul is when you fuck the shit out of a bitch then take a huge dump on her chest
Dude i gave yo momma a wicked dirty raul last night
by Mowdollars23 June 10, 2006


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Handmade Wreaths for All Seasons: 14 Wreath Tutorials
Bonus: Get our newsletter & special offers for free. We will not share or sell your email address. View our Privacy Policy
Delia Randall
We are adding the project to your Holiday Projects.
The project was added to your Holiday Projects.
Click here to view your Holiday Projects.
Hi! I'm Delia. I'm a wife and stay at home mom to two boys and a new baby girl.
I am the type of girl who likes to work with my hands and see if I can do it myself. I am a self-taught sewer, crocheter, cook, photographer and I love to craft with my children. In fact, it's become quite a passion for me. I love learning and growing more in the art of all things domestic and crafty and I share all my creations on my blog: deliacreates.blogspot.com. I hope you come by and say hi.
Delia's Links:
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Delia's Projects on AllFreeHolidayCrafts:
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text:
Trapped Orcas!
Over a year ago
IDK if there is anything that we can do.
But the video is so sad.
These whales obviously want to survive, be free
They are trying so hard to survive and keep from being enclosed by the ice
I can only imagine how tiring these efforts must be… with such little room and so many..
I will have them in my thoughts…


text:
Lemon Recipes | I'm Lovin' It
Some sizzling hot temps here in the midwest still! What could be more refreshing and perfect than the tangy goodness of a lemon. There's more to a lemon than lemonade…….not that there's anything wrong with lemonade, but oh there's SO much more when you sprinkle in a little sugary goodness, your taste buds will explode!!
Lemon is my favorite summertime flavor so how about a round up of recipes from some of the top food bloggers!
Lemon Recipes
- Lemon Curd from Smith Bites
- Lemon Cake Roll from Crazy for Crust
- Raspberry Lemon Cupcakes from My Baking Addiction
- Lemon Burst Cookies from TidyMom
- Limoncello Cocktail from Dine and Dish
- Strawberry Basil Lemonade from What's Gaby Cooking
- Honey Ginger Lemonade from Gourmande in the Kitchen
- Homemade Lemon Raspberry Soda from Eat Good 4 Life
- Lemon Blueberry Bars from Two Peas and their Pod
- Lemonade Pie from TidyMom
- Lemonade Cake from Bake at 350
- Lemon Meringue Cookies from Confessions of a Cookbook Queen
- Lemon Curd from Ladles and JellySpoons
- Lemonade Cake with Lemon Cream Cheese Frosting at Cookies and Cups
- Lemon Frozen Yogurt from Food For My Family
- Lemon Coconut Cupcakes with Lemon Buttercream from Good Life Eats
Do you like lemon? What's your favorite lemon recipe?
I'm Lovin…. anything and everything Lemon!
Now it's your turn! Please remember to link back to http://Tidymom.net
What is I'm Lovin' It Fridays? get all the info, how to's trouble shoot and button here
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53 comments
Cheryl…thanks so much for adding my cake to your round up! I want to make EVERY one of those recipes!!!
I love lemon too! I'm resisting the urge to link up all my lemon recipes and instead just put two of my favorites – Lemon Sherbet and Lemon Chicken. Last year my original blog name (Heidi's Full Plate) was swiped and I changed it to Heidi's Recipes. To help process my pain I wrote a series of blog entries on "When life gives you lemons, make. . . " lemon pie, lemon bundt cake, lemon vinaigrette. . . Can't wait to check out all of your lemony goodness!
Pingback: Coffee Ice Cream with Mud Pie Mojo
Wow! Look at all the lemon recipes. My mom is a huge lemon fan… she'd go nuts for just about any of these!
I love LEMON! I already found two I need to try!!! Yumm!
oh I love lemon things, too! those lemon cookies look SO good! Thanks for hosting.
Great, now I'm craving all things lemon! Lemon bars are one of my favorite summer treats.
Those lemon burst cookies look delish!
Thanks for all the lemony goodness and for hosting the linky!
I love lemon! Great round up! thanks for including our lemon blueberry bars!
this is a really neat collection of pretty, tasty recipes…THANKS!
Oh my goodness! My husband's going to be loving it that you posted all of these lemon recipes. Totally his favorite.
This week, I'm linking up my dream closet makeover (just a bit proud, can you tell? :)). #94.
Thanks for hosting, Cheryl!
Hi Cheryl
I've posted a recipe for a no bake Lemon Date Bar and a no bake Orange Slice, where lemon could be substituted. Just ideal for that long hot summer you're having.
Anne @ Domesblissity
When life gives you lemons, visit Tidy Mom! Thanks for another awesome party!!!
What an awesome round-up! Lemon Lovers Unite!
I am loving those cupcakes from good life eats! They look amazing.
Thanks for hosting the party!
Cheryl I love your lemon round up!! Your lemon burst cookies look amazing!!
i love everything with lemon. nice blog. regards from croatia
Love Lemons! These definately going on my baking to do list!
Just added my Lemon Ricotta Cookies & Blueberry Lemon Muffins 🙂
Oh my goodness, I LOVE lemon! Can't wait to try some of these. 🙂
What a fabulous round up!!
Pingback: Don't Be So Pushy!
Love seeing my lemon burst cookies make an appearance again! I think I need to make them soon!
I just love lemon! great recipes!
Great lemon round up! I really love lemon curd, but recently I made lemon cakes baked in a jar which I really enjoyed:)
Cheryl, I recently purchased an iPad. I am on the road with it and can't compose/edit in blogger. Do you happen to know a good app for blogger(even though you are not on blogger)? I know you have an iPad, so I thought perhaps you might be able to help me in my ineptitude! I can't even send an email(only reply) or I would have done that. I joined the linky party and can't edit the post to add your link:( Thanks for any help you can lend~I know you're busy!
Oh. My. Yum. I'm hungry now! My fave is the Pioneer Woman's Lemon Chicken Pasta….with a little extra lemon! It's sooooo good!
WOW! What a wonderful collection of lemony recipes!!! Thanks for hosting, Cheryl!
I'm totally in awe of your lemon wrangling skills – I need more lemons to make Gaby's lemonade, lemon frozen yogurt and all those cakes and cookies – THANK YOU – oh and my fav lemon Eaton Mess…
Pingback: Lemon Drops |
Lemon is one of my fav flavors. Love the roundup!
So excited to actually have a recipe this week that matches the theme!! You will LOVE these pancakes.
Love these! And love lemon everything so thank you for all of the links.
I love all lemon desserts. I mean, really, you can't go wrong with citrus. My favorite though is lemonade donuts!
All the lemon recipes look wonderful. Today I am bringing Easy No-Machine Ice Cream. You don't need an ice cream maker. You will find 3 recipes and suggestions for many variations. Thanks for hosting this party. I am off to check out all those links.
the lemon collages look FABULOUS Cheryl!!! i LOVE lemon ANYTHING!!
LOVE lemon and this one one has great links all around. Some are on my instant list of try!
Hello Cheryl, thank you for this beautiful collection of delicious lemon recipes! I was visiting Cornwall until today and a couple of days ago I spotted a fantastic café in Penzance who served a superb lemon and lime cheesecake. When I get back home I'll try crazily to obtain the recipe.
Your blog is delicious, fantastic work you got here btw 🙂
Those all look so refreshing and delicious! I'm sharing Creamy Lemon Crumb Bars. So amazingly simple and addicting.
Thank you so so much for hosting, Chery!!! All of those lemon recipes are making my mouth water!!! Gotta try some…) Hope you have a great weekend!
I love lemon!! I think I might need to try your cookies… or one of those yummy drinks!
Thanks for hosting, Cheryl!
Pingback: Lemon Burst Cake Mix Cookies | TidyMom
Pfewf! I think I did it! (added to this week's I'm Lovin' It). Thanks for your help. (duh me).
These lemon recipes are making me want to bake! Thanks for all the lemony goodness!
i love good ol simple lemonade & lemon tarts 🙂
Pingback: Craft Party DIY Ideas | TidyMom
Oh boy do these lemon recipes look good…lemon is one of my favorite things and especially in the summer when it's so hot. I'm late to the party but glad to be able to hook up my Week in the Life post. Thanks for hosting as always Cheryl, fondly, Roberta
You are a wealth of info, Cheryl and I love learning from you. Some of those lemon recipes are now on my "to do" list!
Sweet! I like the lemon blueberry bars, it's somehow prepared like refrigerated cake. It can go with the lemon yogurt. Hmmm… yummy! 🙂
I love lemon! These all look fantabulous! Thank you!
I have died and am floating on a cloud of meringue in Lemon Heaven! Thank you for provided such sweet inspiration.
Pingback: Zucchini Cookies | Angel's Homestead


text:
Have you noticed the pace of business accelerating? That makes partnerships between technology providers more essential than ever to delivering interoperable and optimized solutions that help customers not only survive but thrive. For HDS, strategic alignment and active engagement with our Alliance Partners means efficiency gains and increased predictability. It also means unmatched performance for our customers as they use these leading technology platforms and business applications to take their companies to the next level.
Hitachi Data Systems and Intel® partner to define and create information management and Internet of Things solutions. The combination of Hitachi expertise and resources with Intel's rich experience and leadership in compute and innovative technologies enables us to deliver flexible solutions that improve business outcomes, simplify the lives of mobile workers and accelerate real-time decision making. Hitachi Data Systems solutions with Intel Xeon® processors provide the performance and scalability you need to collect, analyze and store big data.INTEL WEBSITE
Hitachi Data Systems and Microsoft® have been strategic partners since 1990, working together to provide our mutual customers with tightly integrated Hitachi server, network and storage solutions for the Microsoft ecosystem. HDS is a Microsoft OEM and Gold Certified Partner, offering tightly integrated solutions for Microsoft Windows®, Hyper-V®, System Center, Microsoft Business Applications and the Microsoft Azure™ Cloud. Hitachi solutions are designed to work with Microsoft environments, and enable customers of all sizes to implement scalable, available and reliable architectures in a cost-effective way.MICROSOFT WEBSITE
Hitachi, Ltd. is one of only 11 Oracle Global Diamond Partners and has been collaborating with Oracle for more than 20 years. Our alliance integrates two industry-leading portfolios, with Hitachi providing an agile, secure and cost-effective set of solutions to support Oracle's database and application software. Our solutions are designed to meet the most demanding requirements for performance and resilience to ensure that customers' most valuable applications and data are always available. From storage, compute and converged infrastructure systems to data protection and automation solutions, and services and support delivered by Oracle experts, our alliance ensures that businesses are ready for what's next.ORACLE WEBSITE
For over 20 years, Hitachi Data Systems and SAP have helped customers find new ways to achieve their business goals through tailored technology solutions. This strategic alliance takes advantage of our combined leadership and resources in enterprise-class infrastructure, Internet of Things, and cloud solutions. Hitachi Data Systems and SAP offer integrated and certified solutions that enable simplicity, agility and value across the SAP landscape. Whether striving to create personalized customer experiences, optimize operations or launch innovations, the combined Hitachi Data Systems and SAP solutions enable smarter decisions at the speed of business.SAP WEBSITE
Hitachi Data Systems and VMware have been collaborating on technology integration since 2002 to deliver industry-leading solutions. HDS is an Elite-level member of VMware's Technology Alliance Partner program and a global OEM, as well as a VMware Consulting and Integration Partner. Hitachi provides a true, deep integrated foundation that spans almost all VMware technologies and environments, from virtualization, converged, storage, networking, adaptors, SDDC and more. Combining the reliability, scalability and innovation of Hitachi with the flexibility and agility of VMware solutions simplifies and automates virtualized environments while reducing cost.VMWARE WEBSITE


text:
- Report: #1054
Report - Rebuttal - Arbitrate
Complaint Review: Cruise Planners Inc. Franchising
Cruise Planners Inc. Franchising3300 University Drive #602 , Florida U.S.A.
Cruise Planners Inc. Florida Travel Agency ripping-off consumers Nationwide
*REBUTTAL Owner of company: Amicable Agreement Reached
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Updated 12/29/99
Cruise Planners Inc. in Florida ripping off many
people across the country
I am an ex agent of Cruise Planners Inc. in Coral Springs Florida. I have clients that are due $1,525.00 in refunds from this company and they refuse to pay.
They say that they in fact never received payments from these
people for their cruise. This is a lie, all checks from these clients were made out to Cruise Planners and sent directly to them by me and they were allcashed by this company.
I have sent them a payment schedule and they still refuse to send
moneys. They have a gripe with me and other ex agents for leaving
their company and they say that they are going to sue me.
It has been nearly 3 months since I have left them and they still
have not filed any action against me or the others who are in the same situation as I am.
They are not only holding client refunds but also all our
commissions as well. We feel that this company is playing games and we are fed up with it. I am a California resident and have also filed a complaint with the state attorney generals office here.
We need some resolution as soon as possible!
Thank You,
Teresa York
I would like to thank the Rip Off Report for the help they have provided me to date.
Since this posting (September 20,1999) I would like to report that Cruise Planners Inc. has paid all refunds due to my clients. However Cruise Planners Inc. still refuses to pay me thousands of dollars in commission due me.
Cruise Planners Inc. still has not served me with any law suit, nor to the best of my knowledge even filed a law suit. I have sent letters and called Cruise Planners Inc. and their Attorney, Mark Abzug (who is the son-in-law of Lynn Korn, the president of the company) to try to resolve this matter.They refuse to respond to me. I have received one letter from Mr. Abzug to retract all statements made on this web site as well as any other web sites I have postings regarding this matter.
I have stated is the truth and there is nothing libelous in my posting.
(Teresa York)
This report was posted on Ripoff Report on 12/29/1999 12:00 AM and is a permanent record located here: http://www.ripoffreport.com/r/Cruise-Planners-Inc-Franchising/Florida/Cruise-Planners-Inc-Florida-Travel-Agency-ripping-off-consumers-Nationwide-1054. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year.
Ripoff Report has an exclusive license to this report. It may not be copied without the written permission of Ripoff Report.
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#1 REBUTTAL Owner of company
Amicable Agreement Reached
AUTHOR: Lynn - (U.S.A.)
SUBMITTED: Friday, October 03, 2003POSTED: Friday, October 03, 2003
Are you an owner, employee or ex-employee with either negative or positive information about the company or individual, or can you provide "insider information" on this company?
Advertisers above have met our
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text:
Quam's Carpet Cleaning
Posted on under North CarolinaMorris Carpet Cleaning are specialists in Residential and Commercial Carpet Cleaning.
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We also offers a wide array of cleaning services that include Oriental and Specialty Area Rugs, Upholstery, Duct and HVAC Systems, Hard Surfaced Floors, Automobile Interiors, Teflon Protector, and Green Cleaning.
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Our fully staffed 24-hour Client Service Department can meet all your needs around the clock.
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We recommend that you research any company through the Better Business Bureau website, Consumers.
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text:
- Report: #1072942
Report - Rebuttal - Arbitrate
Complaint Review: The Scotts Company LLC
The Scotts Company LLCMarysville, Ohio USA
The Scotts Company LLC topsoil ripoff .it's not topsoil Marysville Ohio
Ripoff Report
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on the Internet.
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willing to make a
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customer satisfaction
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Fix it the right way.
Corporate Advocacy Program™
I recently purchased , August 2013 ,thru WalMart, a bag of Scotts Premium Topsoil...my complaint is that it does not even remotely resemble topsoil or dirt ..it's not even compost ...it's shredded bark pieces ...big and small. Scotts is guilty of fraud and deliberate misrepresentation of a product. Do Not buy this product if you are genuinely looking for true topsoil/ dirt.
This report was posted on Ripoff Report on 08/04/2013 12:05 PM and is a permanent record located here: http://www.ripoffreport.com/r/The-Scotts-Company-LLC/Marysville-Ohio/The-Scotts-Company-LLC-topsoil-ripoff-its-not-topsoil-Marysville-Ohio-1072942. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year.
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